Mineralogy and geochemistry of laterites from the Morro dos Seis Lagos Nb (Ti,REE) deposit (Amazonas,Brazil)

The Morro dos Seis Lagos niobium deposit (2897.9 Mt at 2.81 wt% Nb₂O₅) is associated with laterites formed by the weathering of siderite carbonatite. This iron-rich lateritic profile (>100 m in thickness) is divided into six textural and compositional types, which from the top to the base of the sequence is: (1) pisolitic laterite, (2) fragmented laterite, (3) mottled laterite, (4) purple laterite, (5) manganiferous laterite, and (6) brown laterite. All the laterites are composed mainly of goethite (predominant in the lower and upper varieties) and hematite (predominant in the intermediate types, formed from goethite dehydroxylation). The upper laterites were reworked, resulting in goethite formation. In the manganiferous laterite (10 m thick), the manganese oxides (mainly hollandite, with associated cerianite) occur as veins or irregular masses, formed in a late event during the development of the lateritic profile, precipitated from a solution with higher oxidation potential than that for Fe oxides, closer to the water table. Siderite is the source for the Mn. The main Nb ore mineral is Nb-rich rutile (with 11.26–22.23 wt% Nb₂O₅), which occurs in all of the laterites and formed at expense of a former secondary pyrochlore, together with Ce-pyrochlore (last pyrochore before final breakdown), Nb-rich goethite and minor cerianite. The paragenesis results of lateritization have been extremely intense. Minor Nb-rich brookite formed from Nb-rich rutile occurs as broken spherules with an “oolitic” (or Liesegang ring structure). Nb-rich rutile and Nb-rich brookite incorporate Nb following the [Fe³⁺ + (Nb, Ta) for 2Ti] substitution and both contain up to 2 wt% WO₃. The laterites have an average Nb₂O₅ content of 2.91 wt% and average TiO₂ 5.00 wt% in the upper parts of the sequence. Average CeO₂ concentration increases with increasing depth, from 0.12 wt% in the pisolitic type to 3.50 wt% in the brown laterite. HREE concentration is very low.     

Geochemical and isotopic variations in shallow groundwater in areas of the Fayetteville Shale development,north-central Arkansas

Exploration of unconventional natural gas reservoirs such as impermeable shale basins through the use of horizontal drilling and hydraulic fracturing has changed the energy landscape in the USA providing a vast new energy source. The accelerated production of natural gas has triggered a debate concerning the safety and possible environmental impacts of these operations. This study investigates one of the critical aspects of the environmental effects; the possible degradation of water quality in shallow aquifers overlying producing shale formations. The geochemistry of domestic groundwater wells was investigated in aquifers overlying the Fayetteville Shale in north-central Arkansas, where approximately 4000 wells have been drilled since 2004 to extract unconventional natural gas. Monitoring was performed on 127 drinking water wells and the geochemistry of major ions, trace metals, CH₄ gas content and its C isotopes (δ¹³C_CH4), and select isotope tracers (δ¹¹B, ⁸⁷Sr/⁸⁶Sr, δ²H, δ¹⁸O, δ¹³C_DIC) compared to the composition of flowback-water samples directly from Fayetteville Shale gas wells. Dissolved CH₄ was detected in 63% of the drinking-water wells (32 of 51 samples), but only six wells exceeded concentrations of 0.5 mg CH₄/L. The δ¹³C_CH4 of dissolved CH₄ ranged from −42.3‰ to −74.7‰, with the most negative values characteristic of a biogenic source also associated with the highest observed CH₄ concentrations, with a possible minor contribution of trace amounts of thermogenic CH₄. The majority of these values are distinct from the reported thermogenic composition of the Fayetteville Shale gas (δ¹³C_CH4 = −35.4‰ to −41.9‰). Based on major element chemistry, four shallow groundwater types were identified: (1) low (<100 mg/L) total dissolved solids (TDS), (2) TDS > 100 mg/L and Ca–HCO₃ dominated, (3) TDS > 100 mg/L and Na–HCO₃ dominated, and (4) slightly saline groundwater with TDS > 100 mg/L and Cl > 20 mg/L with elevated Br/Cl ratios (>0.001). The Sr (⁸⁷Sr/⁸⁶Sr = 0.7097–0.7166), C (δ¹³C_DIC = −21.3‰ to −4.7‰), and B (δ¹¹B = 3.9–32.9‰) isotopes clearly reflect water–rock interactions within the aquifer rocks, while the stable O and H isotopic composition mimics the local meteoric water composition. Overall, there was a geochemical gradient from low-mineralized recharge water to more evolved Ca–HCO₃, and higher-mineralized Na–HCO₃ composition generated by a combination of carbonate dissolution, silicate weathering, and reverse base-exchange reactions. The chemical and isotopic compositions of the bulk shallow groundwater samples were distinct from the Na–Cl type Fayetteville flowback/produced waters (TDS ∼10,000–20,000 mg/L). Yet, the high Br/Cl variations in a small subset of saline shallow groundwater suggest that they were derived from dilution of saline water similar to the brine in the Fayetteville Shale. Nonetheless, no spatial relationship was found between CH₄ and salinity occurrences in shallow drinking water wells with proximity to shale-gas drilling sites. The integration of multiple geochemical and isotopic proxies shows no direct evidence of contamination in shallow drinking-water aquifers associated with natural gas extraction from the Fayetteville Shale.     

Provenance and origins of a Late Paleozoic accretionary complex within the Khangai–Khentei belt in the Central Asian Orogenic Belt,central Mongolia

We have investigated the petrography, geochemistry, and detrital zircon U–Pb LA-ICPMS dating of sandstone from the Gorkhi Formation of the Khangai–Khentei belt in the Ulaanbaatar area, central Mongolia. These data are used to constrain the provenance and source rock composition of the accretionary complex, which is linked to subduction of the Paleo-Asian Ocean within the Central Asian Orogenic Belt during the Middle Devonian to Early Carboniferous. Field and microscopic observations of the modal composition of sandstone and constituent mineral chemistry indicate that the sandstone of the Gorkhi Formation is feldspathic arenite, enriched in saussuritized plagioclase. Geochemical data show that most of the sandstone and shale were derived from a continental margin to continental island arc setting, with plutonic rocks being the source rocks. Detrital zircon ²⁰⁶Pb/²³⁸U ages of two sandstones yields age peaks of 322 ± 3 and 346 ± 3 Ma. The zircon ²⁰⁶Pb/²³⁸U age of a quartz–pumpellyite vein that cuts sandstone has a weighted mean age of 339 ± 3 Ma. Based on these zircon ages, we infer that the depositional age of sandstone within the Gorkhi Formation ranges from 320 to 340 Ma (i.e., Early Carboniferous). The provenance and depositional age of the Gorkhi Formation suggest that the evolution of the accretionary complex was influenced by the intrusion and erosion of plutonic rocks during the Early Carboniferous. We also suggest that spatial and temporal changes in the provenance of the accretionary complex in the Khangai–Khentei belt, which developed aound the southern continental margin of the Siberian Craton in relation to island arc activity, were influenced by northward subduction of the Paleo-Asian Ocean plate.     

Uraniferous paleoplacers of the Mesoarchean Mahagiri Quartzite,Singhbhum craton,India: Depositional controls,nature and source of > 3.0 Ga detrital uraninites

The quartz-pebble conglomerate (QPC)-hosted detrital uranium mineralization is unique in character in terms of their restricted distribution before 2.2 Ga atmosphere during pre-Great Oxidation Event (pre-GOE). Such QPC paleoplacer deposits over the world are good targets for moderate to high tonnage and low grade uranium deposits and more importantly for their gold content. The Mahagiri Quartzite, dated c. 3.02 Ga for their youngest detrital zircon population, is developed unconformably over the Mesoarchean Singhbhum Granite (3.44 Ga to 3.1 Ga). The Mahagiri Quartzite includes a conglomerate-pebbly sandstone dominated subaerial alluvial fan to coastal braided plain sequence in the lower parts and shallow marine mature quartz arenite in the upper parts. The alluvial fan-braided plain deposits in the lower parts host a number of pyritiferous and uraniferous conglomerate and pebbly sandstone beds. The uraninite grains are rounded to subrounded in outline suggesting mechanical transport and detrital origin. Together with detrital pyrite and uraninite constitute the example of > 3.0 Ga paleoplacer closely comparable to the Witwatersrand Au–U deposits. EPMA and SEM-EDS studies suggest that the uraninite grains are rich in Th (> 4 wt.%), S and REE-Y. Chemical formula calculations from EPMA analyses suggest uraninite grains belong to two populations with different oxidation states as revealed from Y/REE and cation U^4 +: U^6 + [apfu] ratios. The U contents of the detrital uraninite grains from Mahagiri are significantly lower than that of the ideal stoichiometric composition of UO₂. This is mainly due to higher amount of heterovalent cationic substitution by Th, REE, Y, Pb, and Ca in Mahagiri QPC uraninite structures, and partial alteration and metamictization of uraninites. Alteration due to metamictization resulted in elevated concentration of Si, Al, P, and Ca in more altered and metamict uraninite grains. The REE pattern is typically flat with comparable LREE–HREE concentration. The high Th content flat REE-pattern suggests that the uraninitere presents high temperature phases (> 350 °C) and are magmatic in origin. The Mahagiri detrital uraninite grains suggest existence of highly felsic and K-rich (richer than TTG) granodiorite–granite–monzogranite suites (GGM) of rocks older than 3.1 Ga in the Singhbhum craton.     

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.     

Geology and geochemistry of the sediment-hosted Cheshmeh-Konan redbed-type copper deposit,NW Iran

The several-hundred-m-thick Miocene Upper Red Formation in northwestern Iran hosts stratiform and fault-controlled copper mineralization. Copper enrichment in the percent range occurs in dm-thick carbonaceous sandstone and shale units within the clastic redbed sequence and consists of fine-grained disseminated copper sulfides (chalcopyrite, bornite, chalcocite) and supergene alteration minerals (covellite, malachite and azurite). The copper mineralization formed after calcite cementation of the primary rock permeability. Copper sulfides occur mainly as replacement of diagenetic pyrite, which, in turn, replaced organic matter. Electron microprobe analysis on bornite, chalcocite and covellite identifies elevated silver contents in these minerals (up to 0.12, 0.72 and 1.21 wt%, respectively), whereas chalcopyrite and pyrite have only trace amounts of silver (<0.26 and 0.06 wt%, respectively). Microthermometric data on fluid inclusions in authigenic quartz and calcite indicate that the Cu mineralization is related to a diagenetic fluid of moderate-to low temperature (Th = 96–160 °C) but high salinity (25–38 wt% CaCl₂ equiv.). The range of δ³⁴S in pyrite is −41.9 to −16.4‰ (average −31.4‰), where framboidal pyrite shows the most negative values between −41.9 and −31.8‰, and fine-grained pyrite has relatively heavier δ³⁴S values (−29.2 to −16.4‰), consistent with a bacteriogenic derivation of the sulfur. The Cu-sulfides (chalcopyrite, bornite and chalcocite) show slightly heavier values from −14.6 to −9.0‰, and their sulfur sources may be both the precursor pyrite-S and the bacterial reduction of sulfate-bearing basinal brines. Carbonates related to the ore stage show isotopically light values of δ¹³C_V-PDB from −8.2 to −5.1‰ and δ¹⁸O_V-PDB from −10.3 to −7.2‰, indicating a mixed source of oxidation of organic carbon (ca. −20‰) and HCO₃⁻ from seawater/porewater (ca. 0‰). The copper mineralization is mainly controlled by organic matter content and paleopermeability (intragranular space to large fracture patterns), enhanced by feldspar and calcite dissolution. The Cheshmeh-Konan deposit can be classified as a redbed-type sediment-hosted stratiform copper (SSC) deposit.     

Charging time of tight gas in the Upper Paleozoic of the Ordos Basin,central China

The Upper Paleozoic section contains a tight gas sandstone reservoir (of 2.75 × 10¹² m³) in the Ordos Basin, central China. The measured porosities (< 10%) and permeabilities (generally < 1 mD) are the result of significant mechanical and chemical compaction and precipitation of carbonate, quartz and authigenic clay cements. Fluid inclusion geochemistry and kinetic modeling (generation of gaseous components and δ¹³C₁) were integrated to constrain the timing of gas charge into the tight reservoir. The modeling results indicate that the natural gases in the present reservoir are similar to gases liberated from quartz inclusions in both composition and stable carbon isotope values and also similar to gas generated from Upper Paleozoic coal. The similar geochemistry suggests that an important phase of quartz cementation must have occurred after gas emplacement in the reservoirs during regional uplift at the end of the Cretaceous. The latest carbonate cement, postdating quartz cementation, consumed most of the late CO₂ generated from coal at high maturity (R_O > 1.7%) and reduced the reservoir quality dramatically. On the contrary, tight sandstones from non-producing areas have fluid inclusions that were trapped in quartz cements much earlier. These data indicate that natural gas migrated into the Upper Paleozoic reservoir when it still retained high porosity and permeability. The reservoir continued to experience porosity and permeability reduction from continued quartz and carbonate cementation after gas charging due to low gas saturation. Comparison of the relative timing of gas charging with that of sandstone cementation can help to predict areas of risk during tight gas exploration and development.     

Remarkably uniform oxygen isotope systematics for co-existing pairs of gem-spinel and calcite in marble,with special reference to Vietnamese deposits

Oxygen isotope systematics for co-existing pairs of gem-spinel and calcite in marble from Vietnam and other worldwide deposits have been determined in order to characterize the O-isotope fractionation between calcite and spinel. In Vietnam, the Δ¹⁸O_cc–sp (= 3.7 ± 0.1‰ for six samples from the An Phu and Cong Troi deposits) is remarkably constant. The combination of these data with those obtained on calcite–spinel pairs of Paigutan (Nepal, n = 2), Ipanko (Tanzania, n = 1), and Mogok (Myanmar, = 2) are also consistent with an overall Δ¹⁸O_cc–sp of 3.6 ± 0.3‰ for all the spinel samples (n = 11). The straight line correlation δ¹⁸O_cc = 0.96 δ¹⁸O_sp + 4.4 is excellent despite their worldwide geographic spread. The increment method of calculating oxygen isotope fractionation gave a geologically unreasonable temperature of formation for both minerals at 1374 °C when compared to temperatures obtained by mineral assemblage equilibrium of these marble type deposits, between 610 and 750 °C. The constant Δ¹⁸O_cc–sp reflects a constant temperature for this amphibolite facies assemblage, whose current best estimate is calculated at 620 ± 40 °C, but unquantified uncertainties remain.     

Recognizing OIB and MORB in accretionary complexes: A new approach based on ocean plate stratigraphy,petrology and geochemistry

We present a new approach for recognizing the origin of accreted basaltic rocks based on ocean plate stratigraphy (OPS), and on the petrology and geochemistry of basalts from mid-oceanic ridges (MORB) and oceanic islands (OIB) using examples from four accretionary complexes (AC) in SW Japan: Akiyoshi, Mino–Tamba, Chichibu and Shimanto. The key to the problem is the model of OPS, which includes an association of igneous and sedimentary rocks that form on an oceanic plate during its travel from a mid-oceanic ridge to a subduction zone. We propose the reconstruction of the tectonic settings of basalts according to their relationships with associated OPS sediments, their petrogenesis and their geochemical features. Five types of OPS are recognized in the accretionary complexes of SW Japan: (1) sandstone/shale; (2) sandstone/shale and chert; (3) sandstone/shale, chert and MORB; (4) sandstone/shale, chert, MORB and gabbro (± peridotite); (5) seamount OPS including OIB, cap carbonates, slope clastics and basal shale/chert. The alkaline, tholeiitic or calc-alkaline composition of basaltic melts, which are typical of oceanic islands, mid-oceanic ridges and island-arcs, respectively, can be identified by the sequence in crystallization of their major phenocrysts, i.e. olivine (ol), clinopyroxene (cpx) and plagioclase (pl), and by their compositions. Alkaline and calc-alkaline mafic lavas are characterized by an ol → cpx → pl succession, whereas tholeiitic melts by their ol → pl ± cpx succession. Titanium-rich minerals, e.g., Ti–augite, kaersutite, Ti–biotite, are typical of alkaline lavas. The application of geochemistry-based tectonic discrimination diagrams is also a powerful tool, if not supported by geological and petrological data, may result in confusion due to magma contamination, post-magmatic alteration, and secular change of mantle thermal conditions. We propose that a direct comparison of normalized multi-element patterns and key binary plots from older volcanic rocks with their modern analogues provides a more viable and reliable method of basalt discrimination. Our OPS–petrology–geochemistry method allows us to confirm the above conclusions that the lavas of the Akiyoshi, Mino–Tamba and Southern Chichibu AC formed in oceanic islands, because they are associated with seamount OPS sediments, crystallized from ol to cpx and pl, contain Ti–augite and kaersutite and are enriched in TiO₂, LREE and Nb. In this paper we present geochemical data from the Inuyama basalts of the Mino–Tamba AC and from the Toba complex in the huge Mikabu greenstone belt of the Chichibu AC. The Inuyama basalts are in contact with Jurassic pelagic cherts, but their geochemical features are confusing; they contain phenocrysts of ol, Ti–augite and kaersutite and therefore probably formed in seamounts. The Toba volcanic rocks are a part of the huge ophiolite belt; they have flat to slightly LREE-enriched REE patterns, are characterized by an ol → cpx succession of phenocrysts and they plot in the OIB field in binary plots suggesting they formed in an oceanic plateau.     

Geology,mineralization, stable isotope,and fluid inclusion characteristics of the Vostok-2 reduced W-Cu skarn and Au-W-Bi-As stockwork deposit,Sikhote-Alin,Russia

The large (>180 Kt WO₃ and at least 10–15 t Au) Vostok-2 deposit is situated in a metallogenic belt of W, Sn-W, Au, and Au-W deposits formed in late to post-collisional tectonic environment after cessation of active subduction. The deposit is related to an ilmenite-series high-K calc-alkaline plutonic suite that, by its petrologic signatures, is transitional between those at W-dominant and Au-dominant reduced intrusion-related deposits. Consistently, besides large W-Cu skarns of the reduced type, the deposit incorporates quartz stockworks with significant Au-W-Bi mineralization also formed in a reduced environment. The hydrothermal stages include prograde and retrograde, essentially pyroxene skarns, hydrosilicate (amphibole, chlorite, quartz) alteration, and phyllic (quartz, sericite, albite, apatite, and carbonate) alteration assemblages. These assemblages contain abundant scheelite associated with pyrrhotite, chalcopyrite and, at the phyllic stage, also with Bi minerals, As-Bi-Sb-Te-Pb-Zn sulfides and sulfosalts, as well as Au mineralization. The fluid evolution included hot, high-pressure (420–460 °C, 1.1–1.2 kbar), low-salinity (5.4–6.0 wt% NaCl-equiv.) aqueous fluids at the retrograde skarn stage, followed by lower temperature cyclic releases of high-carbonic, low salinity to non-carbonic moderate-salinity aqueous fluids. At the hydrosilicate stage, a high-carbonic, CH₄-dominated, hot (350–380 °C) low salinity fluid was followed by cooler (300–350 °C) non-carbonic moderate-salinity (5.7–14.9 wt% NaCl-equiv.) fluid. At the phyllic stage, a high-carbonic, CO₂-dominated, moderately-hot (330–355 °C, 0.9 kbar) low salinity fluid was followed by cooler (230–265 °C) non-carbonic moderate-salinity (6.6–12.0 wt% NaCl-equiv.) fluid. A homogenized magmatic source of water (δ¹⁸O_H2O = +8.3 to +8.7‰), and a sedimentary source of sulfur (δ³⁴S = −6.9 to −6.2‰) and carbon (δ¹³C_fluid = −20.1 to −14.9‰) at the hydrosilicate stage are suggested. A magmatic source of water (δ¹⁸O = +8.6 to +9.2‰) and a sedimentary source of sulfur (δ³⁴S = −9.3 to −4.1‰) but a magmatic (mantle- to crustal-derived) source of carbon (δ¹³C_fluid = −6.9 to −5.2‰) are envisaged for fluids that formed the early mineral assemblage of the phyllic stage. Then, the role of sedimentary carbon again increased toward the intermediate (δ¹³C_fluid = −16.4 to −14.5‰) and late (δ¹³C_fluid = −16.3 to −14.7‰) phyllic mineral assemblages. The magmatic differentiation was responsible for the fluid enrichment in W, whereas Au and Bi could also have been sourced from mafic magma. The decreasing temperatures, together with elevated Ca content in non-boiling fluids, promoted scheelite deposition at the early hydrothermal stages. The most intense scheelite deposition at the phyllic stage was caused by CO₂ removal due to boiling of CO₂-rich fluids; further cooling of non-boiling fluids favoured joint deposition of scheelite, Bi and Au.     

Physical properties of selected block Argonne Premium bituminous coal related to CO2, CH4, and N2 adsorption

CO₂, CH₄, and N₂ adsorption and gas-induced swelling were quantified for block Blind Canyon, Pittsburgh #8 and Pocahontas Argonne Premium coals that were dried and structurally relaxed at 75 °C in vacuum. Strain measurements were made perpendicular and parallel to the bedding plane on ~ 7 × 7 × 7 mm³ coal blocks and gravimetric sorption measurements were obtained simultaneously on companion coal blocks exposed to the same gaseous environment. The adsorption amount and strain were determined after equilibration at P  ≤ 1.8 MPa. There is a strong non-linear correlation between strain and the quantity of gas adsorbed and the results for all gases and coals studied follow a common pattern. The dependence of the coal matrix shrinkage/swelling coefficient (C_gc) on the type and quantity of gas adsorbed is seen by plotting the ratio between the strain and the adsorbate concentration against the adsorbate concentration. In general, C_gc increases with increasing adsorbate concentration over the range of ~ 0.1 to 1.4 mmol/g. Results from the dried block coals are compared to CO₂ experiments using native coals with an inherent level of moisture as received. The amount of CO₂ adsorbed using native coals (assuming no displacement of H₂O by CO₂) is significantly less than the dried coals. The gas-induced strain (S) and adsorption amount (M) were measured as a function of time following step changes in CO₂, CH₄, and N₂ pressure from vacuum to 1.8 MPa. An empirical diffusion equation was applied to the kinetic data to obtain the exponent (n) for time dependence for each experiment. The data for all coals were pooled and the exponent (n) evaluated using an ANOVA statistical analysis method. Values for (n) near 0.5 were found to be independent on the coal, the gas or type of measurement (e.g., parallel strain, perpendicular strain, and gas uptake). These data support the use of a Fickian diffusion model framework for kinetic analysis. The kinetic constant k was determined using a unipore diffusion model for each experiment and the data were pooled for ANOVA analysis. For dry coal, statistically significant differences for k were found for the gases (CO₂ > N₂ > CH₄) and coals (Pocahontas >Blind Canyon > Pittsburgh #8) but not for the method of the kinetic measurement (e.g., strain or gas uptake). For Blind Canyon and Pittsburgh #8 coal, the rate of CO₂ adsorption and gas-induced strain for dry coal was significantly greater than that of the corresponding native coal. For Pocahontas coal the rates of CO₂ adsorption and gas-induced strain for dry and native coal were indistinguishable and may be related to its low native moisture and minimal amount of created porosity upon drying.     

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.     

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.     

Primary to re-equilibrated fluids and geochemical signatures for the evolution of the Nagthat siliciclastics in the Tons valley,Lesser Himalaya,India

Medium to coarse-grained Neo-Proterozoic Nagthat siliciclastic rocks form a part of the Krol Formation in the Lesser Himalayan geotectonic zone. Fluid inclusion and geochemical studies have been carried out on the Nagthat siliciclastics from the Tons valley to determine their provenance during the Proterozoic and their recrystallisation during maximum burial to uplift. Fluid inclusion studies have been carried out on detrital, recrystallised quartz grains and quartz overgrowths. Major and trace element analyses of the siliciclastics, the relationships of SiO₂ with various trace elements, and the association of various trace elements with mineral species suggest a granitic source for these siliciclastics. Primary Q1 aqueous brine inclusions and Q3 H₂O–CO₂ fluid with 0.9 gm/cm³ CO₂ density in detrital quartz grains characterised the protolith of the sandstone as granite or metamorphic rocks. H₂O–NaCl fluids participated in the cementation history, temperatures of quartz overgrowth from 198 to 232 °C show the effect of maximum burial. The re-equilibration of the primary fluid due to elevated internal pressure > confining pressure is evident from features like ‘C’ shaped cavities, stretching of the inclusions, their migration, decrepitation clusters, etc. During recrystallisation these inclusions were equilibrated at 187 ° and 235 °C in a restricted fluid of aqueous, moderately saline composition. The observed inclusion morphology is attributed to a decrease in external pressure related to isothermal decompression uplift.     

Geochemistry,radiocarbon ages,and paleorecharge conditions along a transect in the central High Plains aquifer,southwestern Kansas,USA

Water samples from short-screen monitoring wells installed along a 90-km transect in southwestern Kansas were analyzed for major ions, trace elements, isotopes (H, B, C, N, O, S, Sr), and dissolved gases (He, Ne, N₂, Ar, O₂, CH₄) to evaluate the geochemistry, radiocarbon ages, and paleorecharge conditions in the unconfined central High Plains aquifer. The primary reactions controlling water chemistry were dedolomitization, cation exchange, feldspar weathering, and O₂ reduction and denitrification. Radiocarbon ages adjusted for C mass transfers ranged from <2.6 ka (¹⁴C) B.P. near the water table to 12.8 ± 0.9 ka (¹⁴C) B.P. at the base of the aquifer, indicating the unconfined central High Plains aquifer contained a stratified sequence of ground water spanning Holocene time. A cross-sectional model of steady-state ground-water flow, calibrated using radiocarbon ages, is consistent with recharge rates ranging from 0.8 mm/a in areas overlain by loess to 8 mm/a in areas overlain by dune sand. Paleorecharge temperatures ranged from an average of 15.2 ± 0.7 °C for the most recently recharged waters to 11.6 ± 0.4 °C for the oldest waters. The temperature difference between Early and Late Holocene recharge was estimated to be 2.4 ± 0.7 °C, after taking into account variable recharge elevations. Nitrogen isotope data indicate NO₃ in paleorecharge (average concentration=193 μM) was derived from a relatively uniform source such as soil N, whereas NO₃ in recent recharge (average concentration=885 μM) contained N from varying proportions of fertilizer, manure, and soil N. Deep water samples contained components of N₂ derived from atmospheric, denitrification, and deep natural gas sources. Denitrification rates in the aquifer were slow (5 ± 2× 10⁻³ μmol N L⁻¹ a⁻¹), indicating this process would require >10 ka to reduce the average NO₃ concentration in recent recharge to the Holocene background concentration.     

Tillage and farm manure affect root growth and nutrient uptake of wheat and rice under semi-arid conditions

Tillage systems affect soil properties, crop growth and nutrient uptake under various agro-ecological conditions. The uptake of water and nutrients are largely dependent on the root systems of wheat (Triticum aestivum L.) and rice (Oryza sativa L.). The application of manure has direct influence on the nutrient uptake by the crop plants. A 2 year field experiment was conducted to evaluate the impact of tillage and farm manure on root growth by measuring the root length density on a sandy clay loam (Typic calciargid soil). Three tillage systems were used; (i) minimum tillage (MT), (ii) deep tillage (DT) and (iii) conventional tillage (CT). Three farm manure levels were used; (i) FM₀ (only chemical fertilizers), (ii) FM₁₅ (farm manure at 15 Mg ha^?1) and (iii) FM₃₀ (farm manure at 30 Mg ha^?1). The incorporation of farm manure into soil markedly improved the root length density (RLD) of both wheat and rice crops. For wheat, the application of FM₃₀ increased RLD by 16% and 9% in cases of deep tillage and minimum tillage, respectively. For rice, the increase in RLD at the same farm manure rate (FM₃₀) was 13% and 17%, during first and second year, respectively. Averaged across tillage, the trend of RLD for both wheat and rice was DT > CT > MT. The incorporation of FM has increased the uptake of N, P and K significantly (P < 0.05), thereby increasing the agronomic parameters. The manure may be used to ameliorate the deleterious effects of tillage for sustainable crop yield.     

Orogenesis vs. diagenesis: Can we use organic-rich shales to interpret the tectonic evolution of a depositional basin?

Black shales from the southern Appalachian Basin and the southwest Welsh Basin have anomalous U–Pb and Nd model ages suggesting syn- and post-depositional resetting of the Sm–Nd and U–Pb isotopic systems. This alteration to the primary detrital signature of these two shale sequences is indicative of black shale diagenetic/depositional processes that obscure paleo-environmental and provenance information recorded prior to and during deposition. The trace element and isotopic signatures of these two shale sequences reveal a syn-/post-depositional history that is de-coupled from the coeval orogenic history of the region making it difficult to reconstruct the tectonic and oceanographic conditions present at the time of deposition.Both the Ordovivian Welsh Basin and the Devonian Appalachian Basin sequences host REE- and U-bearing diagenetic phosphate minerals that play a critical role in the whole rock REE and U budgets. In the Welsh Basin shales, early diagenetic apatite and a later monazite phase dominate the REE budget and cause the redistribution of REE early in the basin's history (ca. 460 Ma). This redistribution is recorded by the Sm–Nd system (450 ± 90 Ma) and the Nd model ages that are anomalously old by as much as 20% (T_DM > 2.0 Ga). This early history is complicated by a Permo-Triassic fluid event affecting the whole rock U-budget and resetting the U–Pb isotopic system at 193 ± 45 Ma. The Appalachian Basin sequence appears to have a much less complicated history yet still records a significant disturbance in both the Sm–Nd isotopic system (392 ± 76 Ma) and the Pb isotopic system (340 ± 50 Ma) at about the time of deposition (ca. 365 Ma).These two sequences suggest a pattern of diagenetic disturbance common to black shales. These processes are unique to black shales and must be considered when interpreting provenance and paleo-environmental information from the black shale sequences. Although these rocks are susceptible to alteration, the alteration may provide extensive information on the post-depositional history of the basin while still retaining some primary depositional information. If black shale processes are considered during the interpretation of isotopic and trace element signatures from organic-rich shales, it may be possible to recover an extensive basin history.     

Composition,nucleation, and growth of iron oxide concretions

Iron oxide concretions are formed from post depositional, paleogroundwater chemical interaction with iron minerals in porous sedimentary rocks. The concretions record a history of iron mobilization and precipitation caused by changes in pH, oxidation conditions, and activity of bacteria. Transport limited growth rates may be used to estimate the duration of fluid flow events. The Jurassic Navajo Sandstone, an important hydrocarbon reservoir and aquifer on the Colorado Plateau, USA, is an ideal stratum to study concretions because it is widely distributed, well exposed and is the host for a variety of iron oxide concretions.Many of the concretions are nearly spherical and some consist of a rind of goethite that nearly completely fills the sandstone porosity and surrounds a central sandstone core. The interior and exterior host-rock sandstones are similar in detrital minerals, but kaolinite and interstratified illite–smectite are less abundant in the interior. Lepidocrocite is present as sand-grain rims in the exterior sandstone, but not present in the interior of the concretions.Widespread sandstone bleaching resulted from dissolution of early diagenetic hematite grain coatings by chemically reducing water that gained access to the sandstone through fault conduits. The iron was transported in solution and precipitated as iron oxide concretions by oxidation and increasing pH. Iron diffusion and advection growth time models place limits on minimum duration of the diagenetic, fluid flow events that formed the concretions. Concretion rinds 2 mm thick and 25 mm in radius would take place in 2000 years from transport by diffusion and advection and in 3600 years if transport was by diffusion only. Solid concretions 10 mm in radius would grow in 3800 years by diffusion or 2800 years with diffusion and advection.Goethite (α-FeO (OH)) and lepidocrocite (γ-FeO (OH)) nucleated on K-feldspar grains, on illite coatings on sand grains, and on pore-filling illite, but not on clean quartz grains. Model results show that regions of detrital K-feldspar in the sandstone that consume H⁺ more rapidly than diffusion to the reaction site determine concretion size, and spacing is related to diffusion and advection rates of supply of reactants Fe²⁺, O₂, and H⁺.     

Pioneering assessment of carbon stocks in polder soils developed in inter-dune landscapes in a semiarid climate,Lake Chad

In semiarid Sahelian region, the dynamics of soil organic carbon (SOC) and water are key to sustainable land management. This work focuses on the behaviour of carbon. A total of 33 soil profiles in four polders, ranging from 10 to 65 years in age, were sampled, analysed (0–1 m), and matched with marsh soil profiles in recent sediments considered as reference (t₀) for carbon stocks determination. SOC and soil inorganic carbon (SIC) stocks show a spatial variability between polders. SOC stocks were t₀ 200 ± 0.8; t₆₀ 183 ± 34; and t₆₅ 189 ± 1.1 MgC·ha^?1, whereas the SIC stocks were negligible. These results show the highest stocks of soil carbon observed for this climatic region. The SOC stocks were also calculated for the equivalent soil mass at a defined depth (0–0.3 m); the corrected calculation of SOC stocks (S_corr) for 2450 Mg·ha^?1 of equivalent soil mass is t₀ 64 ± 1.9, t₆₀ 59 ± 9.8, and t₆₅ 53 ± 2.2 MgC·ha^?1; the stocks decrease by ?7.8% and ?17.2% from t₀ to t₆₀ and t₆₅. Carbon was inherited from the pre-existing·marsh and the polders have conserved high stock values.     

Soil formation in Phobjikha Valley,Central Bhutan with special regard to the redistribution of loessic sediments

Soil development and landscape evolution were studied in the basin-shaped Phobjikha Valley at 2900–3200 m a.s.l., to the west of the Black Mountain Range, West Central Bhutan. The local environmental setting with strong along-valley winds, frequent freeze–thaw cycles, extensive dry periods and sparse vegetation cover seems to encourage the generation and short-distance transport of silt-sized particles. The effects of this process are evidenced in the smooth valley morphology and in the nature of the examined pedons. Their involvement in continuing redistribution of local sediments is reflected by a homogeneous silty-clayey and stone-free texture, varying profile depths, buried topsoils and weakly developed recent A horizons. In protected locations, in situ weathering of metamorphic parent materials results in alu-andic features with bulk densities <0.9 g cm^?3, (Al_o + ½Fe_o) > 2%, and phosphate retention >95%. Dominance by Al-hydroxy interlayered clay minerals and large amounts of well-crystallised iron oxides indicate an advanced stage of weathering. In areas of preferred eolian deposition, argic and ferralic features emerge, with clay contents of up to 60% and surface areas of >50 m² g^?1. Under forest, umbric horizons can develop. CEC_eff is below 10 cmol_c kg^?1 at all sites. Cluster and factor analyses of soil chemical and physical parameters confirm the redistribution of local sediments as a dominant factor behind the measured variables. No clear indication of glacial activities in the area was found, whereas the massive silty sediments in the lower parts of most profiles, the presence of debris slopes, and the asymmetric cross sections of the side valleys suggest periglacial conditions. Buried topsoils dated at about 2000 conventional ¹⁴C years BP indicate a weakening or absence of sediment influx under wetter conditions towards the end of the Holocene climate optimum. Charcoal on top of paleosols suggests that human activities of deforestation, grazing and arable agriculture may have contributed to the reactivation of local sediment redistribution until today.