He–Ar and Nd–Sr isotopic compositions of late Pleistocene felsic plutonic back arc basin rocks from Ulleungdo volcanic island, South Korea: Implications for the genesis of young plutonic rocks in a back arc basin

We report analyses of noble gases and Nd–Sr isotopes in mineral separates and whole rocks of late Pleistocene (< 0.2 Ma) monzonites from Ulleungdo, South Korea, a volcanic island within the back arc basin of the Japan island arc. A Rb–Sr mineral isochron age for the monzonites is 0.12 ± 0.01 Ma. K–Ar biotite ages from the same samples gave relatively concordant ages of 0.19 ± 0.01and 0.22 ± 0.01 Ma. ⁴⁰Ar/³⁹Ar yields a similar age of 0.29 ± 0.09 Ma. Geochemical characteristics of the felsic plutonic rocks, which are silica oversaturated alkali felsic rocks (av., 12.5 wt% in K₂O + Na₂O), are similar to those of 30 alkali volcanics from Ulleungdo in terms of concentrations of major, trace and REE elements. The initial Nd–Sr isotopic ratios of the monzonites (⁸⁷Sr/⁸⁶Sr = 0.70454–0.71264, ¹⁴³Nd/¹⁴⁴Nd = 0.512528–0.512577) are comparable with those of the alkali volcanics (⁸⁷Sr/⁸⁶Sr = 0.70466–0.70892, ¹⁴³Nd/¹⁴⁴Nd = 0.512521–0.512615) erupted in Stage 3 of Ulleungdo volcanism (0.24–0.47 Ma). The high initial ⁸⁷Sr/⁸⁶Sr values of the monzonites imply that seawater and crustally contaminated pre-existing trachytes may have been melted or assimilated during differentiation of the alkali basaltic magma.A mantle helium component (³He/⁴He ratio of up to 6.5 RA) associated with excess argon was found in the monzonites. Feldspar and biotite have preferentially lost helium during slow cooling at depth and/or during their transportation to the surface in a hot host magma. The source magma noble gas isotopic features are well preserved in fluid inclusions in hornblende, and indicate that the magma may be directly derived from subcontinental lithospheric mantle metasomatized by an ancient subduction process, or may have formed as a mixture of MORB-like mantle and crustal components. The radiometric ages, geochemical and Nd–Sr isotopic signatures of the Ulleungdo monzonites as well as the presence of mantle-derived helium and argon, suggests that these felsic plutonic rocks evolved from alkali basaltic magma that formed by partial melting of subcontinental lithospheric mantle beneath the back arc basin located along the active continental margin of the southeastern part of the Eurasian plate.     

Zircon U–Pb ages, Hf and O isotopes constrain the crustal architecture of the ultrahigh-pressure Dabie orogen in China

The crustal structure of the Dabie orogen was reconstructed by a combined study of U–Pb ages, Hf and O isotope compositions of zircons from granitic gneiss from North Dabie, the largest lithotectonic unit in the orogen. The results were deciphered from metamorphic history to protolith origin with respect to continental subduction and exhumation. Zircon U–Pb dating provides consistent ages of 751 ± 7 Ma for protolith crystallization, and two group ages of 213 ± 4 to 245 ± 17 Ma and 126 ± 4 to 131 ± 36 Ma for regional metamorphism. Majority of zircon Hf isotope analyses displays negative ε_Hf(t) values of − 5.1 to − 2.9 with crust Hf model ages of 1.84 to 1.99 Ga, indicating protolith origin from reworking of middle Paleoproterozoic crust. The remaining analyses exhibit positive ε_Hf(t) values of 5.3 to 14.5 with mantle Hf model ages of 0.74 to 1.11 Ga, suggesting prompt reworking of Late Mesoproterozoic to Early Neoproterozoic juvenile crust. Zircon O isotope analyses yield δ¹⁸O values of − 3.26 to 2.79‰, indicating differential involvement of meteoric water in protolith magma by remelting of hydrothermally altered low δ¹⁸O rocks. North Dabie shares the same age of Neoproterozoic low δ¹⁸O protolith with Central Dabie experiencing the Triassic UHP metamorphism, but it was significantly reworked at Early Cretaceous in association with contemporaneous magma emplacement. The Rodinia breakup at about 750 Ma would lead to not only the reworking of juvenile crust in an active rift zone for bimodal protolith of Central Dabie, but also reworking of ancient crust in an arc-continent collision zone for the North Dabie protolith. The spatial difference in the metamorphic age (Triassic vs. Cretaceous) between the northern and southern parts of North Dabie suggests intra-crustal detachment during the continental subduction. Furthermore, the Dabie orogen would have a three-layer structure prior to the Early Cretaceous magmatism: Central Dabie in the upper, North Dabie in the middle, and the source region of Cretaceous magmas in the lower.     

Dehydration and melting during continental collision: Constraints from element and isotope geochemistry of low-T/UHP granitic gneiss in the Dabie orogen

A combined study of petrography, whole-rock major and trace elements as well as Rb?Sr and Sm?Nd isotopes, and mineral oxygen isotopes was carried out for two groups of low-T/UHP granitic gneiss in the Dabie orogen. The results demonstrate that metamorphic dehydration and partial melting occurred during exhumation of deeply subducted continent. Zircon δ¹⁸O values of ? 2.8 to + 4.7‰ for the gneiss are all lower than normal mantle values of 5.3 ± 0.3‰, consistent with ¹⁸O depletion of protolith due to high-T meteoric-hydrothermal alteration at mid-Neoproterozoic. Most samples have extremely low ⁸⁷Sr/⁸⁶Sr ratios at t₁ = 780 Ma, but very high ⁸⁷Sr/⁸⁶Sr ratios at t₂ = 230 Ma. This suggests intensive fluid disturbance due to the hydrothermal alteration of protoliths during Neoproterozoic magma emplacement and the metamorphic dehydration during Triassic continental collision. Rb–Sr isotopes, Th/Ta vs. La/Ta and Th/Hf vs. La/Nb relationships suggest that Group I gneiss experienced lower degrees of hydrothermal alteration, but higher degrees of dehydration, than Group II gneiss. The two groups of gneiss have similar patterns of REE and trace element partition. Group I gneiss displays good correlations between Nb and LREEs but no correlations between Nb and LILEs (Rb, Ba, Pb, Th and U), indicating differential mobilities of LILEs during the dehydration. Thus the correlation between Nb and LREEs is inherited from protolith rather than caused by metamorphic modification. Relative to Group I gneiss, Group II gneiss has stronger negative Eu anomaly, lower contents of Sr and Ba but higher contents of Rb, Th and U. In particular, Nb correlates with LILEs (e.g., Rb, Sr, Ba, Th and U), but not with LREEs (La and Ce). This may indicate decoupling between the dehydration and LILEs transport during continental collision. Furthermore, dehydration melting may have occurred due to breakdown of muscovite during “hot” exhumation. Group II gneiss has extremely low contents of FeO + MgO + TiO₂ (1.04 to 2.08 wt.%), high SiO₂ contents of 75.33 to 78.23 wt%, and high total alkali (Na₂O + K₂O) contents (7.52 to 8.92 wt.%), comparable with compositions predicted from partial melting of felsic rocks by experimental studies. Almost no UHP metamorphic minerals survived; felsic veins of fine-grain minerals occurs locally between coarse-grain minerals, resulting in a kind of metatexite migmatites due to dehydration melting without considerable escape of felsic melts from the host gneiss. In contrast, Group I gneiss only shows metamorphic dehydration. Therefore, the two groups of gneiss show contrasting behaviors of fluid–rock interaction during the continental collision.     

Chemical weathering of carbonates and silicates in the Han River basin,South Korea

A detailed investigation of the fluvial geochemistry of the Han River system allows to estimate the rates of chemical weathering and the consumption of CO₂. The Han River drains approximately 26,000 km² and is the largest river system in South Korea in terms of both water discharge and total river length. It consists of two major tributaries: the North Han River (NHR) and the South Han River (SHR). Distinct differences in basin lithology (silicate vs. carbonate) between the NHR and SHR provide a good natural laboratory in which to examine weathering processes and the influence of basin geology on water quality. The concentrations of major elements and the Sr isotopic compositions were obtained from 58 samples collected in both summer and winter along the Han River system in both 2000 and 2006. The concentrations of dissolved loads differed considerably between the NHR and SHR; compared with the SHR, the NHR had much lower total dissolved solids (TDS), Sr, and major ion concentrations but a higher Si concentration and ⁸⁷Sr/⁸⁶Sr ratio. A forward model showed that the dissolved loads in the NHR came primarily from silicate weathering (55 ± 11%), with a relatively small portion from carbonates (30 ± 14%), whereas the main contribution to the dissolved loads in the SHR was carbonate weathering (82 ± 3%), with only 11 ± 4% from silicates. These results are consistent with the different lithologies of the two drainage basins: silicate rocks in the NHR versus carbonate rocks in the SHR. Sulfuric acid derived from sulfide dissolution in coal-containing sedimentary strata has played an important role in carbonate weathering in the SHR basin, unlike in the NHR basin. The silicate weathering rate (SWR) was similar between the NHR and SHR basins, but the rate of CO₂ consumption in the SHR basin was lower than in the NHR basin due to an important role of sulfuric acid derived from pyrite oxidation.     

Using ALSM to map sinkholes in the urbanized covered karst of Pinellas County,Florida—1, methodological considerations

Comparison of a database of interpreted sinkholes made using airborne laser swath mapping (ALSM) with databases of sinkholes made from interpretation of aerial photographs reveals substantial disagreement. The discrepancies involve the location, number, areas, and circularity of interpreted sinkholes. Methodological factors that contribute to the discrepancies include blockage of ALSM laser returns in thick vegetation, multi-path reflections, and misrepresentation of the true extent of sinkholes. Comparison of two ALSM-derived databases made (1) independently from versus (2) in combination with earlier air photo analysis in undeveloped regions had the following result: one-fourth of the sinkholes interpreted by using the composite method were missed by the independent analysis, and one-third of the sinkholes that were interpreted from the independent analysis were not interpreted as sinkholes using the composite method. Subjective interpretation leads to a high level of uncertainty such that the results of the remote sensing studies are suspect, if not invalid.     

Estimation of groundwater recharge using the soil moisture budget method and the base-flow model

A detailed characterization of the site is crucial to designing an efficient method of managing the risks associated with tailings from abandoned mines. Therefore, samples collected from various depths within tailings in Guryong mine, Korea, were analyzed for their chemical, physical and mineralogical characteristics. All samples of the Guryong tailings had acid-generating potential. However, in the oxidation zone, the net acid generation (NAG) was low (30 kg H₂SO₄ t⁻¹) although the acid neutralization potential (ANP) was less than zero. The ANP values in the unoxidation zone were higher (> −56.0 kg CaCO₃ t⁻¹) than in the other zones. As a result, the amount of alkali ions that are needed to neutralize the acid needs to be considered. In this experiment G3, G4 and G6 drill cores containing fine tailings particles near the unoxidation zone were observed to contain calcite (CaCO₃) with acid-neutralizing capacity. A low pH (2−4) in the oxidation zone of the tailings changed to a neutral pH in the unoxidation zone of the tailings. These results suggest that the acid-neutralizing capacity of the tailings was controlled by particle and mineral composition of tailings.     

Late Palaeozoic hydrocarbon migration through the Clair field, West of Shetland, UK Atlantic margin

Geochemical analysis of bitumen- and hydrocarbon-bearing fluid inclusions from the Devonian-Carboniferous Clair field indicates that the reservoirs contain a mixture of oils from different marine and lacustrine sources. Reconstruction of the Clair field oil-charge history using fluid inclusion petrography show that oil-charging occurred at times of K-feldspar, quartz and calcite cementation. Temperature–composition–time data yielded from the integration of fluid inclusion microthermometry with high-resolution Ar–Ar dating, date hydrocarbon-bearing K-feldspar overgrowths at 247 ± 3.3 Ma. These data show that in order for oil to be trapped within primary fluid inclusions in K-feldspar overgrowths, hydrocarbon migration throughout the UK Atlantic margin must have been taking place during the Late Palaeozoic and as such, current industry oil-play models based solely on oil charging from Jurassic-Cretaceous marine sources are clearly incomplete and need revision. Apatite fission track analysis and vitrinite reflectance data were used to reconstruct thermal burial histories and assess potential oil generation from Middle Devonian lacustrine source rocks. Thermal history data from wells along The Rona Ridge adjacent to the Clair field show that the Palaeozoic section was heated to greater than 100 °C at some time between 270 and 230 Ma, confirming that Devonian source rocks were mature and expelling oil during the Late Palaeozoic at the time that authigenic K-feldspar overgrowths were growing in the Clair field.     

The composition and crystallinity of the near-surface regions of weathered alkali feldspars

Our ability to identify thin non-stoichiometric and amorphous layers beneath mineral surfaces has been tested by undertaking X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) work on alkali feldspars from pH 1 dissolution experiments. The outcomes of this work were used to help interpret XPS and TEM results from alkali feldspars weathered for <10,000 years in soils overlying the Shap Granite (north-west England). The chemistry of effluent solutions indicates that silica-rich layers a few nanometers in thickness formed during the pH 1 experiments. These layers can be successfully identified by XPS and have lower Al/Si, Na/Si, K/Si and Ca/Si values than the outermost ∼9 nm of unweathered controls. Development of Al-Si non-stoichiometry is coupled with loss of crystal structure to produce amorphous layers that are identifiable by TEM where >∼2.5 nm thick, whereas the crystallinity of albite is retained despite leaching of Na to depths of tens to hundreds on nanometers. Integration of XPS data over the outermost 6-9 nm of naturally weathered Shap feldspars shows that they have stoichiometric Al/Si and K/Si ratios, which is consistent with findings of previous TEM work on the same material that they lack amorphous layers. There is some XPS evidence for loss of K from the outermost couple of nanometers of Shap orthoclase, and the possibility of leaching of Na from albite to greater depths cannot be excluded using the XPS or TEM results. This study demonstrates that the leached layer model, as formulated from laboratory experiments, is inapplicable to the weathering of alkali feldspars within acidic soils, which is an essentially stoichiometric reaction.     

Comparison of arsenic concentrations in simultaneously-collected groundwater and aquifer particles from Bangladesh,India, Vietnam,and Nepal

One of the reasons the processes resulting in As release to groundwater in southern Asia remain poorly understood is the high degree of spatial variability of physical and chemical properties in shallow aquifers. In an attempt to overcome this difficulty, a simple device that collects groundwater and sediment as a slurry from precisely the same interval was developed in Bangladesh. Recently published results from Bangladesh and India relying on the needle-sampler are augmented here with new data from 37 intervals of grey aquifer material of likely Holocene age in Vietnam and Nepal. A total of 145 samples of filtered groundwater ranging in depth from 3 to 36 m that were analyzed for As (1–1000 μg/L), Fe (0.01–40 mg/L), Mn (0.2–4 mg/L) and S (0.04–14 mg/L) are compared. The P-extractable (0.01–36 mg/kg) and HCl-extractable As (0.04–36 mg/kg) content of the particulate phase was determined in the same suite of samples, in addition to Fe(II)/Fe ratios (0.2–1.0) in the acid-leachable fraction of the particulate phase. Needle-sampler data from Bangladesh indicated a relationship between dissolved As in groundwater and P-extractable As in the particulate phase that was interpreted as an indication of adsorptive equilibrium, under sufficiently reducing conditions, across 3 orders of magnitude in concentrations according to a distribution coefficient of 4 mL/g. The more recent observations from India, Vietnam and Nepal show groundwater As concentrations that are often an order of magnitude lower at a given level of P-extractable As compared to Bangladesh, even if only the subset of particularly reducing intervals characterized by leachable Fe(II)/Fe >0.5 and dissolved Fe >0.2 mg/L are considered. Without attempting to explain why As appears to be particularly mobile in reducing aquifers of Bangladesh compared to the other regions, the consequences of increasing the distribution coefficient for As between the particulate and dissolved phase to 40 mL/g for the flushing of shallow aquifers of their initial As content are explored.