Evaluation of radiation dose due to naturally occurring radionuclides in rock samples of different origins collected from Azad Kashmir

The state of Azad Kashmir is rich in three types of rocks, namely, sedimentary, metamorphic, and igneous rocks. These rocks contain extensive deposits of graphite, marble, limestone, quartzite, granite, dolerite, and sandstone, which are widely used for the construction of dwellings in Azad Kashmir and Pakistan. Therefore, knowledge about the presence of natural radioactivity in these materials is desirable to assess the radiological hazards associated with it. In this context, 30 rock samples were collected from different geologic formations of the Muzaffarabad Division, Azad Kashmir. After processing the samples, the specific activities of ²²⁶Ra, ²³²Th, and ⁴⁰ K in them were measured using a P-type coaxial high-purity germanium detector. The observed highest dose rate values for sedimentary, metamorphic, and igneous rocks have been found to be 83.16 ± 1.08, 135.87 ± 1.18, and 115.98 ± 1 nGy ⋅ h^–1, respectively. The radium equivalent activity (Ra_eq) varied from 23.76 ± 1.15 for dolerite sample (igneous rock) to 293.69 ± 2.60 Bq ⋅ kg^–1 for marble (metamorphic rock). The Ra_eq values of all rock samples are lower than the limit mentioned in the Organization for Economic Cooperation and Development (OECD, 1979) report (370 Bq ⋅ kg^–1, equivalent to γ-dose of 1.5 mSv ⋅ y^–1). The values of external (H_ex) and internal hazard indices (H_in) are less than unity. The mean outdoor and indoor annual effective dose equivalents are 0.073 mSv ⋅ y^–1 and 0.29 mSv ⋅ y^–1, respectively. The mean (over all types of rock samples) annual effective dose equivalent is reported as 0.36 mSv ⋅ y^–1.     

Using pyroxene microphenocrysts to determine cosmogenic 3He concentrations in old volcanic rocks: an example of landscape development in central Gran Canaria

Determinations of cosmogenic ³He exposure ages and erosion rates in volcanic rocks older than a few hundred thousand years are complicated by the presence of radiogenic He in addition to the magmatic and cosmogenic He, in phenocryst minerals. However, by analysing microphenocrysts (that crystallised on or immediately prior to eruption) that have not trapped magmatic He, the three-component problem can be eliminated and accurate determinations of cosmogenic ³He made. In this study, we perform three experiments using pyroxene microphenocrysts in basaltic clasts in the Pliocene Ayacata Formation breccias, Gran Canaria, that demonstrate they are free of magmatic He. Exposure ages and erosion rates calculated from the cosmogenic ³He concentrations are combined with a geomorphological study, to produce a tentative interpretation of landscape evolution in the mountainous interior of Gran Canaria. Long-term steady-state erosion rates of 14–24 mm ka⁻¹ are recorded from bedrock erosional surfaces on a high plateau. Headwall retreat rates for a major drainage system of 1.6 m ka⁻¹ have been constrained from the ca 225 ka exposure age of a boulder emplaced on slopes beneath the headwall. Strath terraces and boulders in a small canyon system yield much younger exposure ages of 47–43 ka.     

Lithium elemental and isotopic variations in rock-melt interaction

Despite the occurrence of highly variable lithium (Li) elemental distribution and isotopic fractionation in mantle mineral, the mechanism of Li heterogeneity and fractionation remains a controversial issue. We measured Li contents and isotopic compositions of olivine and clinopyroxene xenocrysts and phenocrysts from kamafugite host lavas, as well as minerals in melt pockets occurring as metasomatic products in peridotite xenoliths from the Western Qinling, central China. The olivine xenocrysts in the kamafugites show compositional zonation. The cores have high Mg# (100 × Mg/(Mg+Fe); 91.0–92.2) and Li abundances (5.63–21.7 ppm), low CaO contents (≤0.12 wt%) and low δ⁷Li values (−39.6 to −6.76‰), which overlap with the compositional ranges of the olivines in the melt pockets as well as those in peridotite xenoliths. The rims of the olivine xenocrysts display relatively low Mg# (85.9–88.2), high CaO contents (0.19–0.38 wt%) and high δ⁷Li values (18.3–26.9‰), which are comparable to the olivine phenocrysts (Mg#: 86.4–87.1; CaO: 0.20–0.28 wt%; Li: 12.4–36.8 ppm; δ⁷Li: 18.1–26.0‰) and the silicate-melt metasomatized olivines. The clinopyroxene phenocrysts and clinopyroxenes in the melt pockets have no distinct characteristics with respect to the Li abundances and δ⁷Li values, but show higher and lower CaO contents, respectively, than the clinopyroxenes from silicate and carbonatite metasomatized samples. These features indicate that Li concentration and isotopic signatures of the cores of the xenocrysts recorded carbonatite melt-peridotite reaction (carbonatite metasomatism) at mantle depth, and the variations in the rims probably resulted from xenocryst–host magma interaction during ascent. Our results reveal that the interaction with carbonatite and silicate melts gave rise to an increase in Li abundance in minerals of peridotite xenoliths at mantle depth or during transportation. In terms of δ⁷Li, the carbonatite and silicate melts produced remarkably contrasting δ⁷Li variations in olivine. Based on the systematic variations of Li abundances and Li isotopes in olivines, we suggest that the δ⁷Li value of olivine is a more important indicator than that of clinopyroxene in discriminating carbonatite and silicate melt interaction agents with peridotites.     

Petrology,geochemistry and geochronology of the magmatic suite from the Jianzha Complex,central China: Petrogenesis and geodynamic implications

The intermediate–mafic–ultramafic rocks in the Jianzha Complex (JZC) at the northern margin of the West Qinling Orogenic Belt have been interpreted to be a part of an ophiolite suite. In this study, we present new geochronological, petrological, geochemical and Sr–Nd–Hf isotopic data and provide a different interpretation. The JZC is composed of dunite, wehrlite, olivine clinopyroxenite, olivine gabbro, gabbro, and pyroxene diorite. The suite shows characteristics of Alaskan-type complexes, including (1) the low CaO concentrations in olivine; (2) evidence of crystal accumulation; (3) high calcic composition of clinopyroxene; and (4) negative correlation between FeO^tot and Cr₂O₃ of spinels. Hornblende and phlogopite are ubiquitous in the wehrlites, but minor orthopyroxene is also present. Hornblende and biotite are abundant late crystallized phases in the gabbros and diorites. The two pyroxene-bearing diorite samples from JZC yield zircon U–Pb ages of 245.7 ± 1.3 Ma and 241.8 ± 1.3 Ma. The mafic and ultramafic rocks display slightly enriched LREE patterns. The wehrlites display moderate to weak negative Eu anomalies (0.74–0.94), whereas the olivine gabbros and gabbros have pronounced positive Eu anomalies. Diorites show slight LREE enrichment, with (La/Yb)_N ratios ranging from 4.42 to 7.79, and moderate to weak negative Eu anomalies (Eu/Eu¹ = 0.64–0.86). The mafic and ultramafic rocks from this suite are characterized by negative Nb–Ta–Zr anomalies as well as positive Pb anomalies. Diorites show pronounced negative Ba, Nb–Ta and Ti spikes, and typical Th–U, K and Pb peaks. Combined with petrographic observations and chemical variations, we suggest that the magmatism was dominantly controlled by fractional crystallization and crystal accumulation, with limited crustal contamination. The arc-affinity signature and weekly negative to moderately positive ε_Nd(t) values (−2.3 to 1.2) suggest that these rocks may have been generated by partial melting of the juvenile sub-continental lithospheric mantle that was metasomatized previously by slab-derived fluids. The lithologies in the JZC are related in space and time and originated from a common parental magma. Geochemical modeling suggests that their primitive parental magma had a basaltic composition. The ultramafic rocks were generated through olivine accumulation, and variable degrees of fractional crystallization with minor crustal contamination produced the diorites. The data presented here suggest that the subduction in West Qinling did not cease before the early stage of the Middle Triassic (∼242 Ma), a back-arc developed in the northern part of West Qinling during this period, and the JZC formed within the incipient back-arc.     

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.     

Coupled lithium- and iron isotope fractionation during magmatic differentiation

In this study, we investigated Fe and Li isotope fractionation between mineral separates of olivine pheno- and xenocrysts (including one clinopyroxyene phenocryst) and their basaltic hosts. Samples were collected from the Canary Islands (Teneriffa, La Palma) and some German volcanic regions (Vogelsberg, Westerwald and Hegau). All investigated bulk samples fall in a tight range of Li and Fe isotope compositions (δ⁵⁶Fe_wr = 0.06–0.17‰ and δ⁷Li_ma = 2.5–5.2‰, assuming δ⁷Li of the olivine-free matrix is virtually identical to that of the bulk sample for mass balance reasons). In contrast, olivine phenocrysts display highly variable, but generally light Fe and mostly light Li isotope compositions compared to their respective olivine-free basaltic matrix, which was considered to represent the melt (with δ⁵⁶Fe_ol = ? 0.24 to 0.14‰ and δ⁷Li_ol = ? 10.5 to + 6.5‰, respectively). Single olivine crystals from one sample display even a larger range of δ⁵⁶Fe_ol between ? 0.7 and + 0.1‰. One single clinopyroxene phenocryst displays the lightest Li isotope composition (δ⁷Li_cpx = ? 17.7‰), but no Fe isotope fractionation relative to melt. The olivine phenocrysts show variable Mg# and Ni (correlated in most cases) that range between 0.89 and 0.74 and between 300 and 3000 μg/g, respectively. These olivines likely grew by fractional crystallization in an evolving magma. One sample from the Vogelsberg volcano contained olivine xenocrysts (Mg# > 0.89 and Ni > 3000 μg/g), in addition to olivine phenocrysts. This sample displays the highest Li- and the second highest Fe-isotope fractionation between olivine and melt (Δ⁷Li_ol-melt = ? 13; Δ⁵⁶Fe_ol-melt = ? 0.29).Our data, i.e. the variable olivine- at constant whole rock and matrix isotope compositions, strongly indicate disequilibrium, i.e. kinetic Fe and Li isotope fractionation between olivine and melt (for Li also between cpx and melt) during fractional crystallization. Δ⁷Li_ol-melt is correlated with the Li partitioning between olivine and melt (i.e. with Li_ol/Li_melt), indicating Li isotope fractionation due to preferential (faster) diffusion of ⁶Li into olivine during fractional crystallization. Olivine with low Δ⁷Li_ol-melt, also have low Δ⁵⁶Fe_ol-melt, indicating that Fe isotope fractionation is also driven by diffusion of isotopically light Fe into olivine, potentially, as Fe–Mg inter-diffusion. The lowest Δ⁵⁶Fe_ol-melt (? 0.40) was observed in a sample from Westerwald (Germany) with abundant magnetite, indicating relatively oxidizing conditions during magma differentiation. This may have enhanced equilibrium Fe isotope fractionation between olivine and melt or fine dispersed magnetite in the basalt matrix may have shifted its Fe isotope composition towards higher δ⁵⁶Fe. The decoupling of Li- and Fe isotope fractionation in cpx is likely due to faster diffusion of Li relative to Fe in cpx, implying that the large investigated cpx phenocryst resided in the magma for only a short period of time which was sufficient for Li- but not for Fe diffusion. The absence of any equilibrium Fe isotope fractionation between the investigated cpx phenocryst and its basaltic host may be related to the similar Fe^3 +/Fe^2 + of cpx and melt. In contrast to cpx, the generally light Fe isotope composition of all investigated olivine separates implies the existence of equilibrium- (in addition to diffusion-driven) isotope fractionation between olivine and melt, on the order of 0.1‰.     

Geochemical characteristics of the high- and low-Ti basaltic rocks from the uplifted shoulder of the Ohře (Eger) Rift,Western Bohemia

High-Ti melanephelinite (3.8–5.9 wt% TiO₂), medium-Ti (phono)tephrite (2.7–3.1 wt% TiO₂), and low-Ti olivine melanephelinite/basanite (1.9–2.3 wt.% TiO₂) are subordinate rock types in the central European Cenozoic Volcanic Province. A contrasting melanephelinite to (phono)tephrite series occurs in the Lou?ná–Oberwiesenthal Volcanic Centre (37–28 Ma) and also as satellite volcanic bodies (26–12 Ma) together with olivine melanephelinite/basanite (17–20 Ma) on the southwestern periphery of the Kru?né hory mountains (Erzgebirge). The volcanic rocks intrude the Variscan basement of the uplifted shoulder of the Oh?e/Eger Rift in the Kru?né hory mountains of the Bohemian Massif. Low Mg# (44–59) and Cr, Ni contents and enrichment of LILE, Zr, Hf, Nb, Ta, U, Th and LREE in the high-Ti melanephelinites contrast with the composition of primitive low-Ti olivine melanephelinites/basanites displaying high Mg# (63–74) and high contents of compatible elements. The high-Ti melanephelinites reveal a wide range in initial ⁸⁷Sr/⁸⁶Sr of ca. 0.7034–0.7038 and ε_Nd of 2.4–4.9. The low-Ti melanephelinites show an overlapping range of initial ⁸⁷Sr/⁸⁶Sr of ca. 0.7035–0.7036 and ε_Nd of 4.3–5.5. The large variation in initial ⁸⁷Sr/⁸⁶Sr ratios at similar ε_Nd values in those rock types is interpreted as evidence for melting of metasomatized lithospheric mantle sources comprising K-bearing phases with radiogenic Sr. Modification of the olivine-free alkali basaltic magmas by differentiation or crustal contamination could give rise to the medium-Ti (phono) tephrites. The initial isotope ratios of all samples are consistent with HIMU-mantle sources and contributions from lithospheric mantle. The olivine-free melanephelinitic rocks often contain alkali pyroxenite–ijolite xenoliths with initial ⁸⁷Sr/⁸⁶Sr ratios of ca. 0.7036 and ε_Nd of 3.0. We interpret these xenoliths as samples of an intra-crustal alkali complex derived from similar mantle sources as those for the basaltic volcanic rocks.     

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.     

Petrogenesis and tectonic significance of the ∼ 850 Ma Gangbian alkaline complex in South China: Evidence from in situ zircon U–Pb dating,Hf–O isotopes and whole-rock geochemistry

The Gangbian alkaline complex in the southeastern Yangtze Block (South China) is composed of Si-undersaturated pyroxene syenites and Si-saturated to -oversaturated syenites and quartz monzonites. SIMS zircon U–Pb analyses indicate that the complex was emplaced at 848 ± 4 Ma, during a previously-recognized interval of magmatic quiescence between the ca 1.0–0.89 Ga Sibaoan orogenic magmatism and the ca 0.83–0.78 Ga magmatic flare-up. The Gangbian rocks are characterized by wide, coherent variations in major and trace elements (SiO₂ = 47.6–68.4%, K₂O + Na₂O = 4.5–10.5%, K₂O/Na₂O = 0.4–1.2, MgO = 1.2–8.5%, Cr = 4.5–239 ppm, and Ni = 4.5–143 ppm) and by enrichment in LIL and LREE and depletion in Nb, Ta and P in trace element spidergrams. Their whole-rock εNd(T) (? 6.5 to ? 0.4) and εHf(T) (? 10.7 to 0.4) are positively correlated, suggesting involvement of both metasomatized mantle and continental crust materials in their genesis. In situ zircon Hf–O isotopic measurements for the most evolved quartz monzonite sample yield a binary mixing trend between the mantle- and supracrustal-derived melts. It is suggested that the pyroxene syenites were derived by partial melting of metasomatized, phlogopite-bearing lithospheric mantle, and the parental magma experienced extensive fractionation of pyroxene and olivine associated with varying degrees of crustal contamination. Subsequent fractional crystallization of hornblende and minor amounts of plagioclase from the alkali basaltic magmas, accompanied by crustal contamination, produced the Si-saturated to -oversaturated syenites and quartz monzonites. These ca. 0.85 Ga alkaline rocks and neighboring contemporaneous dolerite dykes are the products of the anorogenic magmatism after the Sibao Orogeny. They post-date the final amalgamation between the Yangtze and Cathaysia Blocks, most likely manifesting the initial rifting of South China within the Rodinia supercontinent.     

Helium–carbon relationships in geothermal fluids of western Anatolia,Turkey

We investigate the helium, carbon and oxygen–hydrogen isotopic systematics and CO₂/³He ratios of 8 water and 6 gas samples collected from 12 geothermal fields in western Anatolia (Turkey). ³He/⁴He ratios of the samples (R) normalized to the atmospheric ³He/⁴He ratio (R_A = 1.39 × 10^? 6) range from 0.27 to 1.67 and are significantly higher than the crustal production value of 0.05. Fluids with relatively high R / R_A values are generally found in areas of significant heat potential (K?z?ldere and Tuzla fields). CO₂/³He ratios of the samples, ranging from 1.6 × 10⁹ to 2.3 × 10¹⁴, display significant variation and are mostly higher than values typical of an upper mantle source (2 × 10⁹). The δ¹³C (CO₂) and δ¹³C (CH₄) values of all fluids vary from ? 8.04 to + 0.35‰ and ? 25.80 to ? 23.92‰ (vs. PDB), respectively. Stable isotope values (δ¹⁸O–δD) of the geothermal waters are conformable with the Mediterranean Meteoric Water Line and indicate a meteoric origin. The temperatures calculated by gas geothermometry are significantly higher than estimates from chemical geothermometers, implying that either equilibrium has not been attained for the isotope exchange reaction or that isotopic equilibration was disturbed due to gas additions en route to the surface.Evaluation of He–CO₂ abundances indicates that hydrothermal degassing and calcite precipitation (controlled probably by adiabatic cooling due to degassing) significantly fractionate the elemental ratio (CO₂/³He) in geothermal waters. Such processes do not affect gas phase samples to anywhere near the same extent. For the gas samples, mixing between mantle and various crustal sources appears to be the main control on the observed He–C systematics: however, crustal inputs dominate the CO₂ inventory. Considering that limestone is the main source of carbon (～ 70 to 97% of the total carbon inventory), the carbon flux from the crust is found to be at least 20 times that from the mantle. As to the He-inventory, the mantle-derived component is found to vary up to 21% of the total He content and is probably transferred to the crust by fluids degassed from deep mantle melts generated in association with the elevated geotherm and adiabatic melting accompanying current extension. The range of ³He/enthalpy ratios (0.000032 to 0.19 × 10^? 12 cm³ STP/J) of fluids in western Anatolia is consistent with the release of both helium and heat from contemporary additions of mantle-derived magmas to the crust. The deep faults appear to have facilitated the deep circulation of the fluids and the transport of mantle volatiles and heat to the surface.     

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.     

Crustal contamination of Late Neogene basalts in the Dien Bien Phu Basin,NW Vietnam: Some insights from petrological and geochronological studies

Early Pliocene (Zanclean) basalts in the Dien Bien Phu pull-apart basin in NW Vietnam, associated with the presently sinistral Dien Bien Phu Fault Zone, have been dated by the K–Ar method at 4.4–4.9 and 5.4–5.2 Ma. Rapid migration of basaltic magma to the surface in the Dien Bien Phu Fault Zone may be due to Pliocene transtension of the crust in this region, resulting from asthenospheric upwelling induced by lateral displacement of the mantle. The basalts are moderately phyric ( < 10%) and consist of olivine (hyalosiderite), plagioclase (bytownite–labradorite) and orthopyroxene (bytownite–labradorite) phenocrysts, and a fine-grained crystalline matrix (olivine–hortonolite, plagioclase–labradorite, clinopyroxene–pigeonite and augite, K-feldspar). The presence of Fe-rich olivine and orthopyroxene phenocrysts indicates that the basalts are SiO₂-saturated/oversaturated olivine tholeiites which formed under water-undersaturated conditions. The Dien Bien Phu basalts contain both mantle-derived (pyroxenites, dunites, gabbros) and crustal (sillimanite/mullite + Mg–Fe spinel), wallrock xenoliths, indicative of crustal contamination during the ascent of the basaltic magma. The basalts show selective enrichment in some mobile elements (K, Rb, Sr and Th), a feature considered to be a result of metasomatism. These rocks, classified on the basis of their normative composition as quartz tholeiites, could represent primary olivine tholeiites/basalts, in which the geochemical signatures were modified by the processes of contamination.     

Petrogenesis of coexisting high-silica aluminous and peralkaline rhyolites from Yunshan (Yongtai), southeastern China

The Late Cretaceous bimodal Yunshan (Yongtai) volcanics in Fujian province contain peralkaline rhyolites, the only presence of such rhyolites in southeastern China. Whole-rock and mineral chemical compositions are analyzed for the coexisting aluminous (metaluminous to weakly peraluminous)-peralkaline high-silica rhyolites from the Yunshan volcanics. They are sparsely porphyritic, and contain K-feldspar, ferromagnesian minerals, quartz, magnetite, and titanomagnetite phenocrysts, as well as accessory minerals such as fayalite, chevkinite, apatite and zircon. The mineral assemblage indicates an oxidizing pre-eruption condition. These rhyolites exhibit diagnostic geochemical features of A-type granites, such as elevated 10⁴ * Ga/Al (mostly greater than 2.6) and FeO^T/(FeO^T + MgO) ratios, enrichment in high field strength elements (HFSE) such as Zr (>400 ppm) and Nb, and strong depletion in Al₂O₃ (<13 wt%), CaO, Ba and Sr. On the basis of their petrographic and geochemical characteristics, it is suggested that the rhyolite magmas are derived from partial melting of H₂O-poor (meta) granitic igneous rocks in the deep crust, and cannot be fractionated from the coeval Yunshan mafic magmas. Geochemical variations of major and trace elements indicate the possible fractionation of K-feldspar, calcium-rich pyroxene, Fe–Ti oxides and minor chevkinite during the magma evolution. In peralkaline rhyolites, we found that the pre-existing Fe–Ti oxide and hedenbergite phenocrysts had been transformed into aegirine + oxide and aegirine + oxide + fluorite assemblages, respectively. These mineral assemblages are the products of the subsolidus reaction of pre-existing phenocrysts and extraneous Na–F-rich fluids. Such Na–F-rich fluids may be derived from the degassing of the subvolcanic rocks. The reactions indicate that the Yunshan peralkaline rhyolites could be generated through the reaction of highly fractionated aluminous silica magmas and Na–F-rich fluids.     

Modelling the petroleum generation and migration of the third member of the Shahejie Formation (Es3) in the Banqiao Depression of Bohai Bay Basin,Eastern China

The mudstones in the third member of the Shahejie Formation (Es3) are the primary source rocks in the Banqiao Depression of Bohai Bay Basin. They are rich in organic matter with Total Organic Carbon (TOC) content up to 3.5%. The sandstones in the Es3 member are the deepest proven hydrocarbon reservoir rocks with measured porosity and permeability values ranging from 3.6% to 32.4% and from 0.01 md to 3283.7 md, respectively. One, two and three-dimensional basin modelling studies were performed to analyse the petroleum generation and migration history of the Es3 member in the Banqiao Depression based on the reconstruction of the burial, thermal and maturity history in order to evaluate the remaining potential of this petroleum province. The modelling results are calibrated with measured vitrinite reflectance (R_o), borehole temperatures and some drilling results of 63 wells in the study area. Calibration of the model with thermal maturity and borehole temperature data indicates that the present-day heat flow in the Banqiao Depression varies from 59.8 mW/m² to 61.7 mW/m² and the paleo-heat flow increased from 65 Ma to 50.4 Ma, reached a peak heat-flow values of approximately 75 mW/m² at 50.4 Ma and then decreased exponentially from 50.4 Ma to present-day. The source rocks of the Es3 member are presently in a stage of oil and condensate generation with maturity from 0.5% to 1.8% R_o and had maturity from 0.5% to 1.25% R_o at the end of the Dongying Formation (Ed) deposition (26 Ma). Oil generation (0.5% R_o) in the Es3 member began from about 37 Ma to 34 Ma and the peak hydrocarbon generation (1.0% R_o) occurred approximately from 30 Ma to 15 Ma. The modelled hydrocarbon expulsion evolution suggested that the timing of hydrocarbon expulsion from the Es3 member source rocks began from 31 Ma to 10 Ma with the peak hydrocarbon expulsion shortly after 26 Ma. Secondary petroleum migration pathways in the Es3 member of the Banqiao Depression are modelled based on the structure surfaces at 26 Ma and present-day, respectively. The migration history modelling results have accurately predicted the petroleum occurrences within the Es3 member of the Banqiao Depression based on the calibration with drilling results of 10 oil-producing wells, one well with oil shows and 52 dry holes. Six favorable zones of oil accumulations in the Es3 member of the Banqiao Depression are identified especially oil accumulation zones I and II due to their proximity to the generative kitchens, short oil migration distances and the presence of a powerful drive force.     

Marine radiocarbon reservoir corrections (∆R) for Chesapeake Bay and the Middle Atlantic Coast of North America

Radiocarbon dates from known age, pre-bomb eastern oyster (Crassostrea virginica) shells provide local marine reservoir corrections (?R) for Chesapeake Bay and the Middle Atlantic coastal area of eastern North America. These data suggest subregional variability in ?R, ranging from 148 ± 46 ¹⁴C yr on the Potomac River to ? 109 ± 38 ¹⁴C yr at Swan Point, Maryland. The ?R weighted mean for the Chesapeake's Western Shore (129 ± 22 ¹⁴C yr) is substantially higher than the Eastern Shore (? 88 ± 23 ¹⁴C yr), with outer Atlantic Coast samples falling between these values (106 ± 46 and 2 ± 46 ¹⁴C yr). These differences may result from a combination of factors, including ¹⁴C-depleted freshwater that enters the bay from some if its drainages, ¹⁴C-depleted seawater that enters the bay at its mouth, and/or biological carbon recycling. We advocate using different subregional ?R corrections when calibrating ¹⁴C dates on aquatic specimens from the Chesapeake Bay and coastal Middle Atlantic region of North America.     

Base metal mineral segregation and Fe-Mg exchange inducing extreme compositions of olivine and chromite from the Xiadong Alaskan-type complex in the southern part of the Central Asian Orogenic Belt

The Xiadong Alaskan-type complex shares much in common with typical Alaskan-type complexes worldwide, while showing some unique features in terms of mineral compositions. Olivine from the Xiadong dunites is characterized by extremely high Fo component of 91.7–96.7 and anomalously negative correlation of Fo with NiO, while chromite is featured by high 100 × Fe³⁺/(Fe³⁺ + Cr + Al) (>70), high 100 × Fe²⁺/(Fe²⁺ + Mg) (>70), high 100 × Cr/(Cr + Al) (>90), low MnO (<0.6 wt%) and TiO₂ contents (<0.5 wt%). To investigate these particular features, we conducted petrographic observation and mineral composition analyses for the Xiadong dunite. A number of Fe and/or Ni sulfides and alloys occurring as inclusions in olivine and chromite indicate that base metal mineral segregation took place prior to crystallization of olivine and chromite and probably induced Fe and Ni depletions in olivine. The FeO and MgO variations in profile analyses from chromite to adjacent olivine are compatible with Fe-Mg exchange. The diffusion mechanism of Fe from olivine to chromite and Mg from chromite to olivine may have elevated both Fo of olivine and 100 × Fe²⁺/(Mg + Fe²⁺) ratio of chromite and further enhanced the decoupling of Fo and NiO in olivine. We thus suggest that base metal mineral segregation and Fe-Mg exchange play important roles in the extreme compositions of the Xiadong dunite. The Ni depletion of olivine and degree of Fe-Mg exchange between olivine and chromite may be used as indicators of mineralization in mafic-ultramafic intrusions.     

Hydrothermal He and CO2 at Wudalianchi intra-plate volcano,NE China

Chemical and isotopic compositions have been measured for CO₂-rich bubbling gases discharging from cold springs in Wudalianchi intra-plate volcanic area, NE China. Observed ³He/⁴He ratios (2–3 R_A) and δ¹³C values of CO₂ (−5‰ to −3‰) indicate the occurrence of a mantle component released and transferred to the surface by the Cenozoic extension-related magmatic activities. The CO₂/³He ratios are in wide range of (0.4–97 × 10⁹). Based on the apparent mixing trend in a ³He/⁴He and δ¹³C of CO₂ diagram from all published data, the extracted magmatic end-member in the Wudalianchi Volcano has ³He/⁴He, δ¹³C and CO₂/³He value of ∼3.2 R_A, ∼−4.6‰ and ∼6 × 10¹⁰, respectively. These values suggest that the volatiles originate from the sub-continental lithospheric mantle (SCLM) in NE China and represent ancient fluids captured by prior metasomatic events, as revealed by geothermal He and CO₂ from the adjacent Changbaishan volcanic area.     

Mineralogical and microfabric characteristics of magnetite in the Wuyang Precambrian BIFs,southern North China Craton: Implications for genesis and depositional processes of the associated BIFs

Precambrian Banded Iron Formations (BIFs) are widely distributed in the North China Craton (NCC). Among them, the Wuyang BIFs located in the southern margin of NCC occur in the Late Archaean Tieshanmiao Formation and can be subdivided in two different sub-types: (i) quartz–magnetite BIFs (QMB), consisting of magnetite, fine-microcrystalline quartz and minor calcite and (ii) pyroxene–magnetite BIFs (PMB), composed of pyroxene, fine-microcrystalline quartz and subordinate feldspars. Both sub-types display apparent discrepancies in terms of petrography and mineral composition.As shown in Electron BackScattered Diffraction (EBSD) images and micrographs, magnetite grains from the QMB range in size from tens up to hundreds of μm, whereas magnetite crystals from the PMB can be up to a few tens of μm across. The X-ray diffraction (XRD) structural data indicate that magnetite from both BIF sub-types is equiaxed (cubic) and was generated by sedimentary metamorphic processes. The cell parameters of magnetite in the QMB are a = b = c = 8.396 Å and Z = 8, which deviate slightly from these of magnetite in the PMB: a = b = c = 8.394 Å and Z = 8. The analytical results of Raman spectroscopy analysis revealed micro-structural signatures of both magnetite (Raman shifts near 552 cm⁻¹ and 673 cm⁻¹) and hematite (Raman shifts near 227 cm⁻¹, 295 cm⁻¹ and 413 cm⁻¹). In magnetite from both QMB and PMB, the crystallinity degree is similar for magnetite micro-structures but varies significantly for hematite micro-structures. Oxygen fugacity (fO₂) conditions fluctuated during the recrystallization of magnetite in the QMB, whereas no evident variation of fO₂ occurred during the formation of magnetite in the PMB. Analytical results of laser ablation inductively-coupled plasma mass spectrometry (LA-ICP-MS) show that the Si, Al and Mg abundances are higher in magnetite from the QMB, whereas the Ti and Mn contents are more elevated in magnetite from the PMB. Magnetite composition also denotes that both BIF sub-types are sedimentary-metamorphic origin, whereas the deposition of PMB was also affected by volcanic activities. Overall data indicate that the differences in the depositional environment of each BIF sub-type are due to the involvement of volcanic eruption processes in the genesis of the PMB. Thus, this paper indicated that the QMB was deposited by chemical deposition at the long-term interval of volcanic eruptions, and the PMB were the product of chemical deposition affected by the volcanic eruption.     

An experimental model approach of biologically-assisted silicate dissolution with olivine and Escherichia coli – Impact on chemical weathering of mafic rocks and atmospheric CO2 drawdown

Chemical weathering of Mg, Ca-silicates and alumino-silicates contributes significantly to the drawdown of atmospheric CO₂ over long time scales. The present work focuses on how this mode of weathering may change in the presence of free-living bacteria in oligotrophic waters, which compose most of the surface freshwaters of the Earth. Forsterite (Fo90) was reacted for 1 week with a stable Escherichia coli population in water maintained at 37 °C and neutral pH in a batch reactor. Control samples with suspensions of pure olivine powders and E. coli cells in pure water were also used for reference. Olivine controls reproduce the Mg, Si and Fe release in solutions predicted from rates published in the literature with pH shifts of less than 0.5 unit. After 1 week, under abiotic conditions, weathered surfaces are enriched in Fe and Fe³⁺ relative to the initial composition of the mineral. Bacterial controls (without minerals) show decreasing Eh with increasing cell concentrations (−50 mV with 7 × 10⁷ cells/mL and −160 mV with 8 × 10⁸ cells/mL). Magnesium concentrations in bacterial control solutions are in the μg/L range and can be accounted for by the release of Mg from dead cells. More than 80% of the cells were still alive after 1 week. The solutions obtained in the experiments in which olivine reacts in the presence of cells show Mg and Si concentrations a few tens of percent lower than in the mineral control samples, with a prominent depletion of Fe(III) content of the mineral surfaces. Magnesium mass balance discounts both significant bacterial uptake and inhibition of the Mg dissolution rates as a consequence of changing pH and Eh. Coating by bacterial cell layers is also negligible. E. coli reduces the chemical weathering of olivine. This study infers that the presence of free-living Proteobacteria, a prevalent group of subsurface bacteria, should decrease the amount of riverine Mg released by chemical weathering of mafic rocks.     

Microstructural and experimental constraints on the rheology of partially molten gabbro beneath oceanic spreading centers

Flow laws for high-temperature creep of olivine, plagioclase, and diabase are used to place constraints on the rheology of partially molten lower oceanic crust. This analysis is motivated by the observation of olivine lattice preferred orientations and subgrain microstructures in oceanic gabbros that lack evidence for dislocation creep in coexisting plagioclase and pyroxene. Extrapolation of experimental flow laws indicates that at temperatures above 1100°C and stresses less than 10 MPa, olivine may be the weakest phase in rocks with gabbroic composition. By accounting for variations in the melt fraction (0–10%) and grain size of partially molten plagioclase aggregates we can constrain the rheological conditions where olivine deforms by dislocation creep while plagioclase deforms by diffusion creep. Calculated effective viscosities range from 10¹⁵ to 10¹⁹ Pa s; based on observations of the geometry of the partially molten zone beneath the East Pacific Rise and the microstructural and experimental constraints we favor a value of ∼10¹⁸ Pa s. This value approaches estimates for the viscosity of the upper mantle beneath ridge axes, but is significantly higher than previously suggested for the partially molten lower crust. Such high viscosities are inconsistent with ridge evolution models that require large amounts of lower crustal flow to accommodate melt redistribution. However, the results are compatible with recent models that favor local magma replenishment from the mantle at closely spaced intervals along the spreading center axis in a 2D, ‘sheet-like’ fashion.