The influence of citric acid,EDTA, and fulvic acid on U(VI) sorption onto kaolinite

Uranium(VI) sorption onto kaolinite was investigated as a function of pH (3–12), sorbate/sorbent ratio (1 × 10^?6–1 × 10^?4 M U(VI) with 2 g/L kaolinite), ionic strength (0.001–0.1 M NaNO₃), and pCO₂ (0–5%) in the presence or absence of 1 × 10^?2–1 × 10^?4 M citric acid, 1 × 10^?2–1 × 10^?4 M EDTA, and 10 or 20 mg/L fulvic acid. Control experiments without-solids, containing 1 × 10^?6–1 × 10^?4 M U(VI) in 0.01 M NaNO₃ were used to evaluate sorption to the container wall and precipitation of U phases as a function of pH. Control experiments demonstrate significant loss (up to 100%) of U from solution. Although some loss, particularly in 1 × 10^?5 and 1 × 10^?4 M U experiments, is expected due to precipitation of schoepite, adsorption on the container walls is significant, particularly in 1 × 10^?6 M U experiments. In the absence of ligands, U(VI) sorption on kaolinite increases from pH ～3 to 7 and decreases from pH ～7.5 to 12. Increasing ionic strength from 0.001 to 0.1 M produces only a slight decrease in U(VI) sorption at pH < 7, whereas 10% pCO₂ greatly diminishes U(VI) sorption between pH ～5.5 and 11. Addition of fulvic acid produces a small increase in U(VI) sorption at pH < 5; in contrast, between pH 5 and 10 fulvic acid, citric acid, and EDTA all decrease U(VI) sorption. This suggests that fulvic acid enhances U(VI) sorption slightly via formation of ternary ligand bridges at low pH, whereas EDTA and citric acid do not form ternary surface complexes with the U(VI), and that all three ligands, as well as carbonate, form aqueous uranyl complexes that keep U(VI) in solution at higher pH.     

Metal binding to dissolved organic matter and adsorption to ferrihydrite in shallow peat groundwaters: Application to diamond exploration in the James Bay Lowlands,Canada

The speciation and solubility of kimberlite pathfinder metals (Ni, Nd, Ba and K) in shallow peat groundwaters is investigated over the Yankee, Zulu and Golf kimberlites in the Attawapiskat region, James Bay Lowlands, Canada. The purpose of this study is to examine the relationship between dissolved organic matter (DOM) complexation with kimberlite pathfinder metals and determine the spatial distribution of those metals in shallow peat groundwaters along sampling transects over subcropping kimberlites. Nickel, Nd, Ba and K complexation with DOM and the adsorption of these metals onto ferrihydrite were calculated using Visual MINTEQ 3.0 and the NICA-Donnan database. Calculations predict almost 100% of soluble Nd, Ni and Ba form complexes with DOM at sampling sites with little to no contribution from upwelling groundwater (i.e., dissolved organic C (DOC) concentrations = 40–132 mg/L, pH = 3.9–5.5, and log ionic strength ??3). In only the most ombrotrophic peat groundwater conditions does a majority fraction of K bind to DOM. By contrast, under conditions with large contributions from upwelling groundwaters (i.e., DOC concentrations ?40 mg/L, pH = 5.5–6.5, and log ionic strength = ?3 to ?2), as little as 10% of Nd and Ni, and 0% K and Ba are predicted to complex with DOM. The modeling calculations suggest the dominant control on metal–DOM complexation, particularly with respect to Ni and Nd, is competitive effects for DOM binding sites due to elevated ionic strength where there is evidence of strong groundwater upwelling. Visual MINTEQ modeling of metal adsorption on ferrihydrite surfaces predicts that under strong upwelling conditions, Ni and Nd are scavenged from solution due to increased ferrihydrite precipitation and decreased fractions of metals complexed with DOM. Analytical geochemical data are consistent with model predictions of metal adsorption on ferrihydrite. Total dissolved Ni and Nd concentrations at sites of strong upwelling are up to five times lower than waters with little to no upwelling and log ferrihydrite saturation indices (logSI_ferr) indicate precipitation (values up to 5) at sites of strong groundwater upwelling. Where the majority of Ni and Nd complex with DOM and ferrihydrite is highly under saturated (logSI_ferr = ?18 to ?5), the concentrations of total Ni and Nd are elevated compared to other sites along sampling transects. Metal complexation with DOM effectively inhibits metal scavenging from solution via adsorption and/or from forming secondary mineral precipitates. Also, because alkaline earth metals do not compete strongly with Ni and Nd for adsorption sites on ferrihydrite surfaces, but do compete strongly for insoluble organic sites, Ni and Nd are more likely to adsorb onto ferrihydrite.     

Effect of silicic acid on arsenate and arsenite retention mechanisms on 6-L ferrihydrite: A spectroscopic and batch adsorption approach

The competitive adsorption of arsenate and arsenite with silicic acid at the ferrihydrite–water interface was investigated over a wide pH range using batch sorption experiments, attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, extended X-ray absorption fine structure (EXAFS) spectroscopy, and density functional theory (DFT) modeling. Batch sorption results indicate that the adsorption of arsenate and arsenite on the 6-L ferrihydrite surface exhibits a strong pH-dependence, and the effect of pH on arsenic sorption differs between arsenate and arsenite. Arsenate adsorption decreases consistently with increasing pH; whereas arsenite adsorption initially increases with pH to a sorption maximum at pH 7–9, where after sorption decreases with further increases in pH. Results indicate that competitive adsorption between silicic acid and arsenate is negligible under the experimental conditions; whereas strong competitive adsorption was observed between silicic acid and arsenite, particularly at low and high pH. In situ, flow-through ATR-FTIR data reveal that in the absence of silicic acid, arsenate forms inner-sphere, binuclear bidentate, complexes at the ferrihydrite surface across the entire pH range. Silicic acid also forms inner-sphere complexes at ferrihydrite surfaces throughout the entire pH range probed by this study (pH 2.8–9.0). The ATR-FTIR data also reveal that silicic acid undergoes polymerization at the ferrihydrite surface under the environmentally-relevant concentrations studied (e.g., 1.0 mM). According to ATR-FTIR data, arsenate complexation mode was not affected by the presence of silicic acid. EXAFS analyses and DFT modeling confirmed that arsenate tetrahedra were bonded to Fe metal centers via binuclear bidentate complexation with average As(V)-Fe bond distance of 3.27 Å. The EXAFS data indicate that arsenite forms both mononuclear bidentate and binuclear bidentate complexes with 6-L ferrihydrite as indicated by two As(III)–Fe bond distances of ∼2.92–2.94 and 3.41–3.44 Å, respectively. The As–Fe bond distances in both arsenate and arsenite EXAFS spectra remained unchanged in the presence of Si, suggesting that whereas Si diminishes arsenite adsorption preferentially, it has a negligible effect on As–Fe bonding mechanisms.     

Trace metal adsorption onto urban stream suspended particulate matter (Auckland region,New Zealand)

Trace metal adsorption to suspended particulate matter (SPM) influences bioavailability and toxicity of trace metals in natural waters. For highly contaminated urban catchments in the greater Auckland (New Zealand) area, trace metal adsorption to SPM was assessed and compared to similar data from non-urban catchments in the Auckland region, to determine whether there was any difference in the ability of the SPM to adsorb Cu, Pb and Zn. The degree of trace metal adsorption onto the SPM was assessed by way of adsorption edge experiments. It was found that the ability of the Auckland urban SPM to adsorb trace metals decreased in the order Pb > Cu > Zn. Little difference in adsorption was observed between the non-urban Waikato and Kaipara River SPM and urban SPM, or between urban SPM from different flow regimes and seasons, despite some compositional differences in the SPM. This suggests that on the basis of a single surface-binding site, metal adsorption onto SPM could be readily predicted across a range of urban and non-urban catchments in the Auckland region. Adsorption edges were modelled with a diffuse layer, surface complexation model to assess the role of Fe-oxide in adsorption. The MINTEQA2 model was used, assuming Fe-oxide (as HFO) was the only adsorbing surface. There was generally good agreement between observed and modelled adsorption for Pb, indicating the importance of Fe-oxide surfaces for Pb adsorption. However, the model did not predict Zn or Cu adsorption as well. The TOC content of the SPM, and presence of dissolved ligands and organic matter in the water column, appeared to play an important role in Cu adsorption to the SPM. For Zn, the presence of adsorbing surfaces other than HFO appeared to influence adsorption.     

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.     

Dissolution kinetics of Devonian carbonates at circum-neutral pH, 50 bar pCO2, 105 °C,and 0.4 M: The importance of complex brine chemistry on reaction rates

The dissolution kinetics of carbonate rocks sampled from the Keg River Formation in Northeast British Columbia were measured at 50 bar pCO₂ and 105 °C, in both natural and synthetic brines of 0.4 M ionic strength. Natural brines yielded reaction rates of −12.16 ± 0.11 mol cm⁻² s⁻¹ for Log R_Ca, and −12.64 ± 0.05 for Log R_Mg. Synthetic brine yielded faster rates of reaction than natural brines. Experiments performed on synthetic brines, spiked with 10 mmol of either Sr or Zn, suggest that enhanced reaction rates observed in synthetic brines are due to a lack of trace ion interaction with mineral surfaces. Results were interpreted within the surface complexation model framework, allowing for the discrimination of reactive surface sites, most importantly the hydration of the >MgOH surface site. Dissolution rates extrapolated from experiments predict that CO₂ injected into the Keg River Formation will dissolve a very minor portion of rock in contact with affected formation waters.     

Changes of environments and human activity at the Sannai-Maruyama ruins in Japan during the mid-Holocene Hypsithermal climatic interval

Sannai-Maruyama is one of the most famous and best-researched mid-Holocene (mid-Jomon) archaeological sites in Japan, because of a large community of people for a long period. Archaeological studies have shown that the Jomon people inhabi1ted the Sannai-Maruyama site from 5.9 to 4.2 ± 0.1 cal kyr BP However, a continuous record of the terrestrial and marine environments around the site has not been available. Core KT05-7 PC-02, was recovered from Mutsu Bay, only 20 km from the site, for the reconstruction of high-resolution time series of environmental records, including sea surface temperature (SST). C₃₇ alkenone SSTs showed clear fluctuations, with four periods of high (8.4–7.9, 7.0–5.9, 5.1–4.1, and 2.3–1.4 cal kyr BP) and four of low (?8.4, 7.9–7.0, 5.9–5.1, and 4.1–2.3 cal kyr BP) SST. Thus, each SST cycle lasted 1.0–2.0 kyr, and the amplitude of fluctuation was about 1.5–2.0 °C. Total organic carbon (TOC) and C₃₇ alkenone contents, and the TOC/total nitrogen ratio indicate that marine biogenic production was low before 7.0 cal kyr BP, but was clearly increased between 5.9 and 4.0 cal kyr BP, because of stronger vertical mixing. During the period when the community at the site prospered (between 5.9 and 4.2 ± 0.1 cal kyr BP), the terrestrial climate was relatively warm. The high relative abundance of pollen of both Castanea and Quercus subgen. Cyclobalanopsis supports the interpretation that the local climate was optimal for human habitation. Between 5.9 and 5.1 cal kyr BP, in spite of warm terrestrial climates, the C₃₇ alkenone SST was low; this apparent discrepancy may be attributed to the water column structure in the Tsugaru Strait, which differed from the modern condition. The evidence suggests that at about 5.9 cal kyr B.P, high productivity of marine resources such as fish and shellfish and a warm terrestrial climate led to the establishment of a human community at the Sannai-Maruyama site. Then, at about 4.1 ± 0.1 cal kyr BP, abrupt marine and terrestrial cooling, indicated by a decrease of about 2 °C in the C₃₇ alkenone SST and an increase in the pollen of taxa of cooler climates, led to a reduced terrestrial food supply, causing the people to abandon the site. The timing of the abandonment is consistent with the timing (around 4.0–4.3 cal kyr BP) of the decline of civilizations in north Mesopotamia and along the Yangtze River. These findings suggest that a temperature rise of ～2 °C in this century as a result of global warming could have a great impact on the human community and especially on agriculture, despite the advances of contemporary society.     

Crustal structure of the Gujarat region,India: New constraints from the analysis of teleseismic receiver functions

In this study, receiver function analysis is carried out at 32 broadband stations spread all over the Gujarat region, located in the western part of India to image the sedimentary structure and investigate the crustal composition for the entire region. The powerful Genetic Algorithm technique is applied to the receiver functions to derive S-velocity structure beneath each site. A detail image in terms of basement depths and Moho thickness for the entire Gujarat region is obtained for the first time. Gujarat comprises of three distinct regions: Kachchh, Saurashtra and Mainland. In Kachchh region, depth of the basement varies from around 1.5 km in the eastern part to 6 km in the western part and around 2–3 km in the northern part to 4–5 km in the southern part. In the Saurashtra region, there is not much variation in the depth of the basement and is between 3 km and 4 km. In Gujarat mainland part, the basement depth is 5–8 km in the Cambay basin and western edge of Narmada basin. In other parts of the mainland, it is 3–4 km. The depth of Moho beneath each site is obtained using stacking algorithm approach. The Moho is at shallower depth (26–30 km) in the western part of Kachchh region. In the eastern part and epicentral zone of the 2001 Bhuj earthquake, large variation in the Moho depths is noticed (36–46 km). In the Saurashtra region, the crust is more thick in the northern part. It varies from 36–38 km in the southern part to 42–44 km in the northern part. In the mainland region, the crust is more thick (40–44 km) in the northern and southern part and is shallow in Cambay and Narmada basins (32–36 km). The large variations of Poisson’s ratio across Gujarat region may be interpreted as heterogeneity in crustal composition. High values of σ (∼0.30) at many sites in Kachchh and few sites in Saurashtra and Mainland regions may be related to the existence of high-velocity lower crust with a mafic/ultramafic composition and, locally, to the presence of partial melt. The existing tectono-sedimentary models proposed by various researchers were also examined.     

Kaolinite and smectite dissolution rate in high molar KOH solutions at 35° and 80°C

Experiments measuring kaolinite and smectite dissolution rates were carried out using batch reactors at 35° and 80°C. No potential catalysts or inhibitors were present in solution. Each reactor was charged with 1 g of clay of the ≤2 μm fraction and 80, 160 or 240 ml of 0.1–4 M KOH solution. An untreated but sized kaolinite from St. Austell and two treated industrial smectites were used in the experiments. One smectite is a nearly pure montmorillonite, while the second has a significant component of beidellitic charge (35%). The change in solution composition and mineralogy was monitored as a function of time. Initially, the 3 clays dissolved congruently. No new formed phases were observed by XRD and SEM during the pure dissolution stage. The kaolinite dissolution is characterized by a linear release of silica and Al as a function of the log of time. This relationship can be explained by a reaction affinity effect which is controlled by the octahedral layer dissolution. Far from equilibrium, dissolution rates are proportional to a^0.56±0.12_OH⁻ at 35°C and to a^0.81±0.12_OH⁻ at 80°C. The activation energy of kaolinite dissolution increases from 33±8 kJ/mol in 0.1 M KOH solutions to 51±8 kJ/mol in 3 M KOH solutions. In contrast to kaolinite, the smectites dissolve at much lower rates and independently of the aqueous silica or Al concentrations. The proportionality of the smectite dissolution rate constant at 35 and 80°C was a^0.15±0.06_OH⁻. The activation energy of dissolution appears to be independent of pH for smectite and is found to be 52±4 kJ/mol. The differences in behavior between the two kinds of minerals can be explained by structural differences. The hydrolysis of the tetrahedral and the octahedral layer appears as parallel reactions for kaolinite dissolution and as serial reactions for smectite dissolution. The rate limiting step is the dissolution of the octahedral layer in the case of kaolinite, and the tetrahedral layer in the case of smectite.     

The nature and distribution of Cu,Zn, Hg,and Pb in urban soils of a regional city: Lithgow,Australia

This study investigates the concentration and spatial distribution of Cu, Zn, Hg and Pb in the surface (0–2 cm) soils of a regional city in Australia. Surface soils were collected from road sides and analysed for their total Cu, Zn, Hg and Pb concentrations in the <180 μm and <2 mm grain size fractions. The average metal concentration of surface soils, relative to local background soils at 40–50 cm depth, are twice as enriched in Hg, more than three times enriched in Cu and Zn, and nearly six times as enriched in Pb. Median surface soil metal concentration values were Cu – 39 mg/kg (682 mg/kg max), Zn – 120 mg/kg (4950 mg/kg max), Hg – 44 μg/kg (14,900 μg/kg max) and Pb – 46 mg/kg (3490 mg/kg max). Five sites exceeded the Australian NEPC (1999) 300 mg/kg guideline for Pb in residential soils. Strong positive correlations between Cu, Zn and Pb, coupled with the spatial distribution of elevated soil concentrations towards the city centre and main roads suggest traffic and older housing as major sources of contamination. No spatial relationships were identified between elevated metal loadings and locations of past or present industries.     

Late Archaean granulite facies metamorphism in the Vestfold Hills,East Antarctica

Granulites of the Vestfold Hills record a pulsed end-Archaean to early Palaeoproterozoic M1–M2 evolution that is distinct from other Archaean areas in East Antarctica and cratonic domains placed adjacent to East Antarctica in Gondwana reconstructions. Pressure and temperature conditions of the end-Archaean to earliest Palaeoproterozoic (2501–2496 Ma) M1 granulite facies metamorphism in the Vestfold Hills have been constrained from mineral assemblages and thermobarometry of Fe-rich paragneisses. Reintegrated compositions of exsolved subcalcic clinopyroxenes and pigeonites in a metaironstone yield temperatures of 895 ± 35 °C, whilst reintegrated compositions of perthitic feldspars in semipelitic paragneisses give minimum estimates of 860 ± 30 °C. These results rule out the extreme ultrahigh temperature (UHT) conditions previously proposed for M1 in the Vestfold Hills. Pressures of metamorphism during M1 are estimated as 8.1 ± 0.9 kb at 850 ± 40 °C from hercynite + sillimanite + almandine + corundum and retrieved Fe–Mg–Al relations in orthopyroxene coexisting with garnet. A second metamorphic event, M2, occurred at 600–660 °C and 6–8 kb based on thermometry of recrystallised pyroxene neoblasts and thermobarometry applied to M2 garnet–quartz symplectites formed on orthopyroxene and garnet. The intervening emplacement of the magmatic Crooked Lake Gneiss Group precursors occurred at similar or shallower pressures prior to D2–M2, an event that caused tectonic interleaving and reactivation of the Vestfold Hills basement at mid-crustal depths in the earliest Palaeoproterozoic, prior to its unroofing to shallower levels (3–5 kb) by 2470 Ma. The lack of correlative Archaean histories in areas that were formerly adjacent in Gondwanan reconstructions is consistent with the Vestfold Hills region either being exotic to the East Antarctic Shield until the final (Neoproterozoic to Cambrian) amalgamation of Gondwana, or being accreted to part of East Antarctica in a Proterozoic event distinct from the Rayner–Eastern Ghats tectonism that united much of India with Antarctica at 1000–900 Ma.     

Trace metals in Antarctic ecosystems: Results from the Larsemann Hills,East Antarctica

Sediments, mosses and algae, collected from lake catchments of the Larsemann Hills, East Antarctica, were analysed to establish baseline levels of trace metals (Ag, As, Cd, Co, Cr, Cu, Ni, Sb, Pb, Se, V and Zn), and to quantify the extent of trace metal pollution in the area. Both impacted and non-impacted sites were included in the study. Four different leaching solutions (1 M MgCl₂, 1 M CH₃COONH₄, 1 M NH₄NO₃, and 0.3 N HCl) were tested on the fine fraction (<63 μm) of the sediments to extract the mobile fraction of trace metals derived from human impact and from weathering of basement lithologies. Results of these tests indicate that dilute HCl partly dissolves primary minerals present in the sediment, thus leading to an overestimate of the mobile trace metal fraction. Concentrations of trace metals released using the other 3 procedures indicate negligible levels of anthropogenic contribution to the trace metal budget. Data derived from this study and a thorough characterisation of the site allowed the authors to define natural baseline levels of trace metals in sediments, mosses and algae, and their spatial variability across the area. The results show that, with a few notable exceptions, human activities at the research stations have contributed negligible levels (lower than natural variability) of trace metals to the Larsemann Hills ecosystem. This study further demonstrates that anthropogenic sources of trace metals can be correctly identified and quantified only if natural baselines, their variability, and processes controlling the mobility of trace metals in the ecosystem, have been fully characterised.     

Early Mesozoic retrograded eclogite and mafic granulite from the Badu Complex of the Cathaysia Block,South China: Petrology and tectonic implications

The high-grade metamorphic terrane in the Badu region along the northeastern Cathaysia Block in South China preserves retrograded eclogites and mafic granulites. Here we present the petrology, mineral phase equilibria and P-T conditions based on pseudosection computations, as well as zircon U-Pb ages of these rocks. Mineral textures and reaction relationships suggest four metamorphic stages for the retrograded eclogite as follows: (1) eclogite facies stage (M1), (2) clinopyroxene retrograde stage (M2), (3) amphibole retrograde stage (M3), and (4) chlorite retrograde stage (M4). For the mafic granulite, three stages are identified as: (1) plagioclase-absent stage (M1), (2) granulite facies stage (M2) and (3) amphibolite facies stage (M3). Metamorphic evolution of both of the rock types follows clockwise P-T path. Conventional geothermometers and geobarometers in combination with phase equilibria modelling yield metamorphic P-T conditions for each metamorphic stage for the eclogite as 500–560 °C, 23–24 kbar (M1), 640–660 °C, 14–16 kbar (M2), 730–750 °C, and 11–13 kbar (M3). The chlorite retrograde stage (M4) is inferred to have occurred at lower amphibolite to greenschist facies conditions. Phase equilibria modelling of the mafic granulite shows P-T conditions for each metamorphic stage as 600–720 °C, > 13 kbar (M1) and 860–890 °C, 5–6 kbar (M2) and M3 at amphibolite facies conditions. LA-ICPMS zircon U-Pb dating and trace element analysis show that the high pressure metamorphism occurred at 245–251 Ma. Protolith age of the mafic granulite is 997 Ma, similar to that of the mafic to ultramafic rocks widely distributed in the Cathaysia Block and also along the Jiangnan belt. Subduction of ancient oceanic lithospheric materials (or crustal thickening) during Mesozoic and formation of eclogites suggest that the Cathaysia Block was perhaps in the Tethyan oceanic domain at this time. The granulite formation might have been aided by Mesozoic mafic magma underplating associated with lithospheric delamination, heating and retrogression of the eclogite accompanied by rapid uplift.     

Experimental study of octanol–water partition coefficients for2,4,6-trichlorophenol and pentachlorophenol: Derivation of an empirical model of chlorophenol partitioning behaviour

The octanol–water partition coefficients (log K_ow) of 2,4,6-trichlorophenol and pentachlorophenol were determined as functions of pH, ionic strength and aqueous metal content. For both chlorophenols, the log K_ow exhibits pH dependence in the range pK_a−1<pH<pK_a+3. At lower and higher pH values, the behaviour of the chlorophenols is independent of pH. The present data, in conjunction with that of pre-existing data, indicate that a linear relationship exists between log K_ow and log ionic strength of the aqueous solution for pentachlorophenol, and the data also suggest that aqueous metal–chlorophenolate complexation can significantly alter the partitioning behaviour. The data reported here was used to obtain an empirical model of the partitioning behaviour based on speciation of the aqueous chlorophenol. The model requires knowledge of the low pH partitioning behaviour, as well as the acidity constant for the particular chlorophenol of interest. Although K_ow values have been measured as a function of pH and/or ionic strength for only pentachlorophenol, the input parameters for our empirical model are readily accessible in the literature for many chlorophenols. The model greatly expands our ability to quantify the hydrophobicity of chlorophenols, enabling accurate estimations of the pH and ionic strength dependencies of the partitioning behaviour over a wide range of pH and ionic strength values of environmental interest.     

Tube fossils from gossanites of the Urals VHMS deposits,Russia: Authigenic mineral assemblages and trace element distributions

The occurrence, types, morphology, and mineralogical characteristics of tube microfossils were studied in gossanites from twelve VHMS deposits of the Urals. Several types of tube microfossils were recognized, including siboglinids, polychaetes and calcerous serpulids, replaced by a variety of minerals (e.g. hematite–quartz, hematite–chlorite, carbonate–hematite) depending on the nature of the substrate prior to the formation of the gossanites. Colonial hematite tube microfossils (~ 150 μm across,1–2 mm long) are composed of hematitic outer and inner walls, and may exhibit a cellular structure within their cavities. Spherical forms are saturated with Fe-oxidizing bacteria inside the tubes – probably analogues of trophosomes. Colloform stromatolitic outer wall surfaces are characterized by the presence of numerous interlaced filaments of hematite (2–3 μm diameter, up to 1–2 mm long). Between tube microfossils, the hematitized cement contains bundles of hematitized filaments with structures similar to the hyphae of fungi. Hematite–chlorite tube microfossils are scattered in gossanites, mostly as biological debris. They are typically 30 to 300 μm in diameter and 1 to 5 mm long. The layered structure of their tube walls is characterized by hematite–quartz and chlorite layers. Abundant filamentous bacteria coated by glycocalix and chlorite stromatolite are associated with hematite–chlorite tubes. The carbonate–hematite tube microfossils (up to 300 μm across, 2–3 mm long) occur in carbonate-rich gossanites. The tubes are characterized by fine (~ 10 μm thick) walls of hematite and cavities dominated by relatively dark carbonate or hematite. Carbonates may be present both in walls and cavities. Stromatolite-like leucoxene or hematite–carbonate aggregates were also found in association with tubes. Randomly oriented filaments are composed of ankerite. Single filaments are composed of individual cells, typically smaller than 100 nm across, similar to that of magnetotactic bacteria.Three dimensional tomographic images of all types of tube microfossils demonstrate a clear wavy microlayering from outer and inner walls, which may reflect segmentation of the tube worms. The traces of burrowing or fragments of glycocalix with relict spheres are typical of tube microfossils from gossanites.The carbon isotopic composition of carbonates associated with tube microfossils from hematite–quartz, hematite–carbonate, and hematite–chlorite gossanites average − 7.2, − 6.8, –22.8‰, PDB, respectively. These values are indicative of a biogenic origin for the carbonates. The oxygen isotopic composition of these carbonates is similar in all three gossanite types averaging + 13.5, + 14.2, + 13.0‰ (relative to SMOW), and indicative of active sulfate reduction during the diagenetic (and anadiagenetic) stages of the sediments evolution. The trace element characteristics of hematite from tube microfossils are characterized by high contents of following trace elements (average, ppm): Mn (1529), As (714), V (540), W (537), Mo (35), and U (5). Such high contents are most likely the result of metal and metalloid sorption by fine particles of precursor iron hydroxides during the oxidation of sulfides and decomposition of hyaloclasts via microbially-mediated reactions.     

The genesis of metal zonation in the Weilasituo and Bairendaba Ag–Zn–Pb–Cu–(Sn–W) deposits in the shallow part of a porphyry Sn–W–Rb system,Inner Mongolia,China

The Weilasituo and Bairendaba Zn–Pb–Ag–Cu–(Sn–W) sulphide deposits are located in the southern part of Great Xing'an Range of Inner Mongolia in China. The deposits are located at shallow depths in the newly discovered Weilasituo porphyry hosting Sn–W–Rb mineralization. The mineralization at Weilasituo and Bairendaba consist of zoned massive sulphide veins within fractures cutting the Xilinhot Metamorphic Complex and quartz diorite. The Weilasituo deposit gradually zones from the Cu-rich Zn–Cu sulphide mineralization in the west to Zn-rich Zn–Cu sulphide mineralization in the east. The Bairendaba deposit has a Cu-bearing and Zn-rich core through a transitional zone devoid of copper to an outer zone of Zn–Pb–Ag mineralization. Three main veins contain more than 50 wt.% of the contained metal in the two deposits with their metal ratios displaying a systematic and gradual increase in Zn/Cu, Pb/Zn and Ag/Zn ratios from the western part of Weilasituo to the eastern part of Bairendaba.Three stages of vein-type mineralization are recognized. Early, sub-economic mineralization consists of a variable proportion of euhedral arsenopyrite, pyrite, quartz, and rare wolframite, scheelite, cassiterite, magnetite and cobaltite. This was succeeded by main stage mineralization with economic concentration of zoned Cu, Zn, Pb and Ag sulphide minerals along strike within the veins. The zones consist of the assemblages: (1) pyrrhotite–Fe-rich sphalerite–chalcopyrite(–quartz–fluorite) at west Weilasituo; (2) pyrrhotite–Fe-rich sphalerite–chalcopyrite(–galena–tetrahedrite–quartz–fluorite) at east Weilasituo; (3) pyrrhotite–Fe-rich sphalerite–chalcopyrite(–galena–tetrahedrite–quartz–fluorite) in the centre of Bairendaba; (4) pyrrhotite–Fe-rich sphalerite–galena(–chalcopyrite–tetrahedrite–quartz–fluorite) in the transition zone of Bairendaba; and (5) pyrrhotite–Fe-rich sphalerite–galena–tetrahedrite(–chalcopyrite–falkmanite–argentite–pyrargyrite–quartz–fluorite) in the outer zone at Bairendaba. Post-main ore stage is devoid of sulphides and characterized overprinting of fluorite, sericite, chlorite, illite, kaolinite and calcite.Zircon SHRIMP U–Pb dating, Zircon LA–ICP–MS U–Pb dating, molybdenite Re–Os isochron dating, and muscovite Ar–Ar dating indicate the Beidashan granitic batholith was intruded at 140 ± 3 Ma (MSWD = 3.3), the porphyritic monzogranite from marginal facies of the Beidashan batholith was intruded at 139 ± 2 Ma (MSWD = 0.75), the mineralized quartz porphyry was intruded at 135 ± 2 Ma (MSWD = 0.91), the greisen mineralization occurred at 135 ± 11 Ma (MSWD = 7.2), and the post-main ore stage muscovite deposited at 129.5 ± 0.9 Ma. The new geochronology data show the porphyry Sn–W–Rb and vein-type sulphide mineralization are contemporaneous with granitic magmatism in the region.The metal zonation at the Weilasituo and Bairendaba deposits is a result of progressive metal deposition. This was during the evolution of a metal-bearing fluid along the strike of the veins and during the main stage of ore formation at the upper part of the deep-seated porphyry Sn–W–Rb system. This progressive zonation indicates that the deposits represent end-numbers formed from one ore-forming fluid, which moved from west to east from the porphyry. The metal zonation patterns of the major veins are consistent with metal-bearing fluid entering the system with the precipitation of chalcopyrite proximally and sphalerite, galena and Ag-bearing minerals more distally. We show that the mechanism of metal deposition is therefore controlled by thermodynamic conditions resulting in the progressive separation of sulphides from the metal-bearing fluid. The temperature gradient between the inflow zone and the outflow zone appears to be one of the key parameters controlling the formation of the metal zonation pattern. The sulphide precipitation sequence is consistent with a low fS₂ and low fO₂ state of the acidic metal-bearing fluid. The metal zonation pattern provides helpful clues from which it is possible to establish the nature of fluid migration and metal deposition models to locate a possible porphyry mineralization at depth in the Great Xing'an Range, which is consistent with the geology of the newly discovered porphyry Sn–W–Rb system.     

Backarc mafic–ultramafic magmatism in Northeastern Vietnam and its regional tectonic significance

The geology of Northern Vietnam offers critical clues on the convergence history between the South China and Indochina blocks. We constrain the tectonic evolution of the South China and Indochina blocks using geochemical, mineral chemical and geochronological data collected from mafic–ultramafic rocks exposed in the Cao Bang area, Northeastern Vietnam. These rocks show significant enrichment in large ionic lithophile elements (LILEs) such as Cs, Rb, Ba, Th, U, and Pb and depletion in high field strength elements (HFSEs) such as Nb, Ta, Zr, and Ti showing [Nb/La]_N between 0.28–0.41, [La/Yb]_N = 3.94–10.00 and Zr/Y = 2.0–4.4. These geochemical features as well as the petrology and mineral chemistry of the Cao Bang mafic–ultramafic magmas are comparable to those of magmatic complexes formed in a back-arc environment. The basalts yield Rb–Sr whole rock ages of 263 ± 15 Ma, that are consistent with the zircon U–Pb and K–Ar ages reported in previous studies from the same area. The spatial and temporal distribution of the arc magmas within the Indochina block and along the southern margin of the South China block suggest that the Permo-Triassic mafic–ultramafic magmas formed during a tectonic event that is different from the subduction and collision event between the Indochina and South China blocks.     

Significance of trace elements in syntaxial quartz cement,Haushi Group sandstones,Sultanate of Oman

Trace element contents and distributions in authigenic quartz cement in deeply buried (2500–4000 m) Haushi Group sandstones from wells in Oman have been investigated in order to determine the factors that control trace element uptake during precipitation.Scanning electron microscope-cathodoluminescence images show well developed growth zones within the quartz cement, which correlate with chemical zonations observed in electron microprobe Al distribution maps. The most abundant trace elements are Al (50–3000 μg g^?1), Li (1–100 μg g^?1), Na (1–40 μg g^?1), and Ge (0.3–5 μg g^?1) with a strong linear correlation between Li and Al and a weaker one between Ge and Al. The molar concentration of Li (+ Na) accounts only for ~ 15% of the charge compensation for Al³⁺ substitution of Si⁴⁺. Though H was not measured in this study, these data indicate a major role of H in charge balancing Al³⁺. The samples belong to the same stratigraphic unit and have similar petrography, but show considerable variability in absolute trace element concentrations between different wells. This variability does not correlate with either sample depth or temperature and shows no regional pattern, but seems to reflect petrophysical and tectonic differences within the sedimentary basin.Petrographic observations of the cogenetic mineral assemblages and hydrochemical modelling indicate that a change from the equilibrium assemblage quartz–kaolinite (–dolomite) to quartz–illite (–dolomite) reflects a decrease in the CO₂ concentration and concurrent variations of the Al concentration. It is concluded that changes in the CO₂ concentrations are responsible for fluctuations in fluid Al concentrations and thus likely also in the investigated quartz cements.     

Structural evolution of the Mokrsko-West,Mokrsko-East and Čelina gold deposits,Bohemian Massif,Czech Republic: Role of fluid overpressure

The studied Mokrsko-West (90–100 t Au), Mokrsko-East (30 t Au) and Čelina (11 t Au) deposits represent three spatially and genetically interrelated deposits of supposed affiliation to the intrusion-related gold deposit type. The deposits differ in their dominant host rocks, which are represented by ca 354 Ma old biotite tonalite (Mokrsko-West) and Neoproterozoic volcanic and volcanosedimentary rocks (Mokrsko-East, Čelina). Another difference lies in the style of veining — densely spaced networks of 0.1–5 mm thin veins (Q₂) within the tonalite, compared to thick (usually 5–20 cm; Q_1–2) and widely spaced veins within the Neoproterozoic rocks.Five generations of quartz veins, referred to as Q₀ through Q₄ were distinguished: Q₀ veins are the oldest and ore-barren, Q₁ veins mark the onset of the Au-ore formation, Q₂ veins its culmination and Q₃ veins its fading. Late quartz gangue (Q₄) is associated with uneconomic Ag–Pb–Zn vein-type ores hosted by calcite–barite–(quartz) veins.Quartz vein thickness (~ 0.3 to ~ 300 mm), spacing (~ 3 mm to ~ 500 mm), distribution, and related extensional strain (ca. 3–25%) evolve systematically across the studied ore district, reflecting both the major host rock and other tectonic factors. Detailed study of vein dimension parameters (thickness, length, width, aspect ratios) allowed estimation of the probable depth of the fluid source reservoir (~ 2 km or ~ 4 km) below the present surface. The depth to the fluid source seems to increase through time, being the shallowest for the Q₀ veins and the deepest for the Q₂ veins. Two independent methods of estimating fluid overpressure are discussed in the paper. Fluid overpressure during vein formation decreases from the Q₀ through the Q₂ veins, from 10 to 4 MPa or from 26 to 10 MPa, depending on the assumed tensile strength of the tonalite (5.5 and 15 MPa, respectively).The origin of joints and veins is discussed in terms of the stress orientation and crack-seal and crack-jump mechanisms. Field relationships unambiguously indicate that the veins hosted by Neoproterozoic rocks originated by reopening of the pre-existing extension joints (J₁) due to fluid overpressure. The origin of the densely-spaced thin veins (Q₂) hosted by the tonalite at the Mokrsko-West deposit is, however, less certain. It is probable that the tonalite was already affected by microfracturing analogous to the J₁ joints prior to the formation of quartz veins.The formation of the Q_1–2 veins at the Mokrsko-East deposit was constrained by the Re–Os dating of molybdenite to 342.9 ± 1.4 Ma. The ore-bearing hydrothermal system is thus ca 12 Ma younger than the tonalite that hosts the Mokrsko-West deposit. A similar ca 15–2 Ma difference between the age of the host-intrusion and the age of the hydrothermal event was encountered in several other gold deposits in the vicinity of the Central Bohemian Plutonic Complex. Two hypotheses to explain this are discussed in the paper.     

Contrasting mineralogical and processing potential of two mineralization types in the platinum group element and Ni-bearing Kapalagulu Intrusion,western Tanzania

The Kapalagulu layered ultramafic and mafic intrusion is emplaced between the Paleoproterozoic Ubendian basement and overlying Neoproterozoic Itiaso Group metasedimentary rocks, located near the western shore of Lake Tanganyika. High-grade platinum group element (PGE) mineralization (1–6 g/t Pt + Pd + Au) is associated with chromitite and sulfide-bearing harzburgite within the southeastern extension of the intrusion, known as the Lubalisi Zone, which is covered by a layer of nickel-rich (0.2–2%Ni) laterite regolith that contains linear areas of PGE mineralization.In the Lubalisi Zone, the mineralization may be divided into several significant geometallurgical domains: (a) high-grade PGE mineralization (1–6 g/t Pt + Pd + Au) associated with stratiform PGE reefs and chromitite seams within a harzburgite unit; (b) high-grade PGE mineralization (up to 12 g/t Pt + Pd + Au) associated with small bodies and veins of nickel massive sulfide within harzburgite below PGE-bearing reefs and chromitite seams; (c) low-grade PGE mineralization (0.1–0.5 g/t Pt + Pd + Au) associated with a sulfide-mineralized harzburgite unit above the PGE-bearing reefs; (d) laterite style residual PGE mineralization (0.2–4 g/t Pt + Pd + Au) associated with chromite concentrations in the saprolite and overlying red clay horizons of the laterite regolith; and (e) supergene Ni associated with the saprock and overlying saprolite clay.Mineralogical study of three samples from the PGE reef consisting of high grade PGE chromitite and harzburgite indicate that this mineralization will give a good metallurgical response to conventional grinding and floatation due to the relatively coarse-grained nature of the PGM (P80 from ∼37 to 52 µm), association with base metal sulfides, and unaltered gangue minerals (Wilhelmij and Cabri, 2016). In contrast, mineralogical and metallurgical study of the Ni and PGE mineralized laterite indicate that it cannot be processed using conventional mineral processing techniques but that a hydrometallurgical route should be used to recover the base and precious metals. Because any process is very much deposit-controlled, significant metallurgical and geometallurgical testing of mineralized samples, as well as pilot plant testing, will be required to arrive at feasibility studies.