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.     

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.     

Numerical modeling of rainstorm-induced shallow landslides in saturated and unsaturated soils

For the assessment of shallow landslides triggered by rainfall, the physically based model coupling the infinite slope stability analysis with the hydrological modeling in nearly saturated soil has commonly been used due to its simplicity. However, in that model the rainfall infiltration in unsaturated soil could not be reliably simulated because a linear diffusion-type Richards’ equation rather than the complete Richards’ equation was used. In addition, the effect of matric suction on the shear strength of soil was not actually considered. Therefore, except the shallow landslide in saturated soil due to groundwater table rise, the shallow landslide induced by the loss in unsaturated shear strength due to the dissipation of matric suction could not be reliably assessed. In this study, a physically based model capable of assessing shallow landslides in variably saturated soils is developed by adopting the complete Richards’ equation with the effect of slope angle in the rainfall infiltration modeling and using the extended Mohr–Coulomb failure criterion to describe the unsaturated shear strength in the soil failure modeling. The influence of rainfall intensity and duration on shallow landslide is investigated using the developed model. The result shows that the rainfall intensity and duration seem to have similar influence on shallow landslides respectively triggered by the increase of positive pore water pressure in saturated soil and induced by the dissipation of matric suction in unsaturated soil. The rainfall duration threshold decreases with the increase in rainfall intensity, but remains constant for large rainfall intensity.     

Oxidation of pyrite during extraction of carbonate associated sulfate

The sulfur isotopic composition of carbonate associated sulfate (CAS) has been used to investigate the geochemistry of ancient seawater sulfate. However, few studies have quantified the reliability of δ³⁴S of CAS as a seawater sulfate proxy, especially with respect to later diagenetic overprinting. Pyrite, which typically has depleted δ³⁴S values due to authigenic fractionation associated with bacterial sulfate reduction, is a common constituent of marine sedimentary rocks. The oxidation of pyrite, whether during diagenesis or sample preparation, could thus adversely influence the sulfur isotopic composition of CAS. Here, we report the results of CAS extractions using HCl and acetic acid with samples spiked with varying amounts of pyrite. The results show a very strong linear relationship between the abundance of fine-grained pyrite added to the sample and the resultant abundance and δ³⁴S value of CAS. This data represents the first unequivocal evidence that pyrite is oxidized during the CAS extraction process. Our mixing models indicate that in samples with much less than 1 wt.% pyrite and relatively high δ³⁴S_pyrite values, the isotopic offset imparted by oxidation of pyrite should be much less than ? 4‰. A wealth of literature exists on the oxidation of pyrite by Fe³⁺ and we believe this mechanism drives the oxidation of pyrite during CAS extraction, during which the oxygen used to form sulfate is taken from H₂O, not O₂. Consequently, extracting CAS under anaerobic conditions would only slow, but not halt, the oxidation of pyrite. Future studies of CAS should attempt to quantify pyrite abundance and isotopic composition.     

Controls on porphyroblast size along a regional metamorphic field gradient

Garnet-bearing schists from the Waterville Formation of south-central Maine provide an opportunity to examine the factors governing porphyroblast size over a range of metamorphic grade. Three-dimensional sizes and locations for all garnet porphyroblasts were determined for three samples along the metamorphic field gradient spanning lowest garnet through sillimanite grade, using high-resolution X-ray computed tomography. Comparison of crystal size distributions to previous data sets obtained by stereological methods for the same samples reveals significant differences in mode, mean, and shape of the distributions. Quantitative textural analysis shows that the garnets in each rock crystallized in a diffusion-controlled nucleation and growth regime. In contrast to the typical observation of a correlation between porphyroblast size and position along a metamorphic field gradient, porphyroblast size of the lowest-grade specimen is intermediate between the high- and middle-grade specimens’ sizes. Mean porphyroblast size does not correlate with peak temperatures from garnet-biotite Fe-Mg exchange thermometry, nor is post-crystallization annealing (Ostwald Ripening) required to produce the observed textures, as was previously proposed for these rocks. Robust pseudosection calculations fail to reproduce the observed garnet core compositions for two specimens, suggesting that these calc-pelites experienced metasomatism. For each of these two specimens, Monte Carlo calculations suggest potential pre-metasomatism bulk compositions that replicate garnet core compositions. Pseudosection analyses allow the estimation of the critical temperatures for garnet growth: ∼481, ∼477, and ∼485°C for the lowest-garnet-zone, middle-garnet-zone, and sillimanite-zone specimens, respectively. Porphyroblast size appears to be determined in this case by a combination of the heating rate during garnet crystallization, the critical temperature for the garnet-forming reaction and the kinetics of nucleation. Numerical simulations of thermally accelerated, diffusion-controlled nucleation, and growth for the three samples closely match measured crystal size distributions. These observations and simulations suggest that previous hypotheses linking the garnet size primarily to the temperature at the onset of porphyroblast nucleation can only partially explain the observed textures. Also important in determining porphyroblast size are the heating rate and the distribution of favorable nucleation sites.     

Shear strength characterization of municipal solid waste at the Suzhou landfill, China

The current practice of slope stability analysis for a municipal solid waste (MSW) landfill usually overlooks the dependence of waste properties on the fill age or embedment depth. Changes in shear strength of MSW as a function of fill age were investigated by performing field and laboratory studies on the Suzhou landfill in China. The field study included sampling from five boreholes advanced to the bottom of the landfill, cone penetration tests and monitoring of pore fluid pressures. Twenty-six borehole samples representative of different fill ages (0 to 13 years) were used to perform drained triaxial compression tests. The field and laboratory study showed that the waste body in the landfill can be sub-divided into several strata corresponding to different ranges of fill age. Each of the waste strata has individual composition and shear strength characteristics. The triaxial test results showed that the MSW samples exhibited a strain-hardening and contractive behavior. As the fill age of the waste increased from 1.7 years to 11 years, the cohesion mobilized at a strain level of 10% was found to decrease from 23.3 kPa to 0 kPa, and the mobilized friction angle at the same strain level increasing from 9.9° to 26°. For a confinement stress level greater than 50 kPa, the shear strength of the recently-placed MSW seemed to be lower than that of the older MSW. This behavior was consistent with the cone penetration test results. The field measurement of pore pressures revealed a perched leachate mound above an intermediate cover of soils and a substantial leachate mound near the bottom of the landfill. The measurements of shear strength properties and pore pressures were utilized to assess the slope stability of the Suzhou landfill.     

Assessment of disaster resilience capacity of hillslope communities with high risk for geological hazards

This study presents a novel preparedness assessment method for assessing hazard mitigation and environmental planning of hillslope communities. A professional questionnaire was utilized to weight each indicator. Communities in Hsinchu, Taichung and Nantou counties with debris flow hazards were taken as study samples. Debris flow risk and landslide susceptibility for each community were determined using Geographic Information System (GIS) technology and logistic regression analysis. Thus, a novel risk assessment method for evaluating disaster resilience capacity of hillslope communities was established. This method was then applied to assess casualties caused by Typhoon Herb in 1996 and Typhoon Mindulle in 2004. Additionally, the analytical results generated by this assessment method were discussed with the aim of developing references for implementation of risk analysis, increasing the effectiveness of disaster mitigation, and reducing future loss of life and property.     

Surface complexation of U(VI) on goethite (α-FeOOH)

Sorption of U(VI) to goethite is a fundamental control on the mobility of uranium in soil and groundwater. Here, we investigated the sorption of U on goethite using EXAFS spectroscopy, batch sorption experiments and DFT calculations of the energetics and structures of possible surface complexes. Based on EXAFS spectra, it has previously been proposed that U(VI), as the uranyl cation , sorbs to Fe oxide hydroxide phases by forming a bidentate edge-sharing (E2) surface complex, >Fe(OH)₂UO₂(H₂O)_n. Here, we argue that this complex alone cannot account for the sorption capacity of goethite (α-FeOOH). Moreover, we show that all of the EXAFS signal attributed to the E2 complex can be accounted for by multiple scattering. We propose that the dominant surface complex in CO₂-free systems is a bidentate corner-sharing (C2) complex, (>FeOH)₂UO₂(H₂O)₃ which can form on the dominant {101} surface. However, in the presence of CO₂, we find an enhancement of UO₂ sorption at low pH and attribute this to a (>FeO)CO₂UO₂ ternary complex. With increasing pH, U(VI) desorbs by the formation of aqueous carbonate and hydroxyl complexes. However, this desorption is preceded by the formation of a second ternary surface complex (>FeOH)₂UO₂CO₃. The three proposed surface complexes, (>FeOH)₂UO₂(H₂O)₃, >FeOCO₂UO₂, and (>FeOH)₂UO₂CO₃ are consistent with EXAFS spectra. Using these complexes, we developed a surface complexation model for U on goethite with a 1-pK model for surface protonation, an extended Stern model for surface electrostatics and inclusion of all known UO₂-OH-CO₃ aqueous complexes in the current thermodynamic database. The model gives an excellent fit to our sorption experiments done in both ambient and reduced CO₂ environments at surface loadings of 0.02-2.0 wt% U.     

Silicon isotope fractionation in bamboo and its significance to the biogeochemical cycle of silicon

A systematic investigation on silica contents and silicon isotope compositions of bamboos was undertaken. Seven bamboo plants and related soils were collected from seven locations in China. The roots, stem, branch and leaves for each plant were sampled and their silica contents and silicon isotope compositions were determined. The silica contents and silicon isotope compositions of bulk and water-soluble fraction of soils were also measured. The silica contents of studied bamboo organs vary from 0.30% to 9.95%. Within bamboo plant the silica contents show an increasing trend from stem, through branch, to leaves. In bamboo roots the silica is exclusively in the endodermis cells, but in stem, branch and leaves, the silica is accumulated mainly in epidermal cells. The silicon isotope compositions of bamboos exhibit significant variation, from −2.3‰ to 1.8‰, and large and systematic silicon isotope fractionation was observed within each bamboo. The δ³⁰Si values decrease from roots to stem, but then increase from stem, through branch, to leaves. The ranges of δ³⁰Si values within each bamboo vary from 1.0‰ to 3.3‰. Considering the total range of silicon isotope composition in terrestrial samples is only 7‰, the observed silicon isotope variation in single bamboo is significant and remarkable. This kind of silicon isotope variation might be caused by isotope fractionation in a Rayleigh process when SiO₂ precipitated in stem, branches and leaves gradually from plant fluid. In this process the Si isotope fractionation factor between dissolved Si and precipitated Si in bamboo (α_pre-sol) is estimated to be 0.9981. However, other factors should be considered to explain the decrease of δ³⁰Si value from roots to stem, including larger ratio of dissolved H₄SiO₄ to precipitated SiO₂ in roots than in stem. There is a positive correlation between the δ³⁰Si values of water-soluble fractions in soils and those of bulk bamboos, indicating that the dissolved silicon in pore water and phytoliths in soil is the direct sources of silicon taken up by bamboo roots. A biochemical silicon isotope fractionation exists in process of silicon uptake by bamboo roots. Its silicon isotope fractionation factor (α_bam-wa) is estimated to be 0.9988. Considering the distribution patterns of SiO₂ contents and δ³⁰Si values among different bamboo organs, evapotranspiration may be the driving force for an upward flow of a silicon-bearing fluid and silica precipitation. Passive silicon uptake and transportation may be important for bamboo, although the role of active uptake of silicic acid by roots may not be neglected. The samples with relatively high δ³⁰Si values all grew in soils showing high content of organic materials. In contrast, the samples with relatively low δ³⁰Si values all grew in soil showing low content of organic materials. The silicon isotope composition of bamboo may reflect the local soil type and growth conditions. Our study suggests that bamboos may play an important role in global silicon cycle.     

Low-oxygen and chemical kinetic constraints on the geochemical niche of neutrophilic iron(II) oxidizing microorganisms

Neutrophilic iron oxidizing bacteria (FeOB) must actively compete with rapid abiotic processes governing Fe(II) oxidation and as a result have adapted to primarily inhabit low-O₂ environments where they can more successfully compete with abiotic Fe(II) oxidation. The spatial distribution of these microorganisms can be observed through the chemical gradients they affect, as measured using in situ voltammetric analysis for dissolved Fe(II), Fe(III), O₂, and FeS_(aq). Field and laboratory determination of the chemical environments inhabited by the FeOB were coupled with detailed kinetic competition studies for abiotic and biotic oxidation processes using a pure culture of FeOB to quantify the geochemical niche these organisms inhabit. In gradient culture tubes, the maximum oxygen levels, which were associated with growth bands of Sideroxydans lithotrophicus (ES-1, a novel FeOB), were 15-50 μM. Kinetic measurements made on S. lithotrophicus compared biotic/abiotic (killed control) Fe oxidation rates. The biotic rate can be a significant and measurable fraction of the total Fe oxidation rate below O₂ concentrations of approximately 50 μM, but biotic Fe(II) oxidation (via the biotic/abiotic rate comparison) becomes difficult to detect at higher O₂ levels. These results are further supported by observations of conditions supporting FeOB communities in field settings. Variablity in cell densities and cellular activity as well as variations in hydrous ferrous oxide mineral quantities significantly affect the laboratory kinetic rates. The microbial habitat (or geochemical niche) where FeOB are active is thus largely controlled by the competition between abiotic and biotic kinetics, which are dependent on Fe(II) concentration, P_O2, temperature and pH in addition to the surface area of hydrous ferric oxide minerals and the cell density/activity of FeOB. Additional field and lab culture observations suggest a potentially important role for the iron-sulfide aqueous molecular cluster, FeS_(aq), in the overall cycling of iron associated with the environments these microorganisms inhabit.