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.     

Geochemistry and mineralogy of arsenic in (natural) anaerobic groundwaters

Here new data from field bioremediation experiments and geochemical modeling are reported to illustrate the principal geochemical behavior of As in anaerobic groundwaters. In the field bioremediation experiments, groundwater in Holocene alluvial aquifers in Bangladesh was amended with labile water-soluble organic C (molasses) and MgSO₄ to stimulate metabolism of indigenous SO₄-reducing bacteria (SRB). In the USA, the groundwater was contaminated by Zn, Cd and SO₄, and contained <10 μg/L As under oxidized conditions, and a mixture of sucrose and methanol were injected to stimulate SRB metabolism. In Bangladesh, groundwater was under moderately reducing conditions and contained ∼10 mg/L Fe and ∼100 μg/L As. In the USA experiment, groundwater rapidly became anaerobic, and dissolved Fe and As increased dramatically (As > 1000 μg/L) under geochemical conditions consistent with bacterial Fe-reducing conditions. With time, groundwater became more reducing and biogenic SO₄ reduction began, and Cd and Zn were virtually completely removed due to precipitation of sphalerite (ZnS) and other metal sulfide mineral(s). Following precipitation of chalcophile elements Zn and Cd, the concentrations of Fe and As both began to decrease in groundwater, presumably due to formation of As-bearing FeS/FeS₂. By the end of the six-month experiment, dissolved As had returned to below background levels. In the initial Bangladesh experiment, As decreased to virtually zero once biogenic SO₄ reduction commenced but increased to pre-experiment level once SO₄ reduction ended. In the ongoing experiment, both SO₄ and Fe(II) were amended to groundwater to evaluate if FeS/FeS₂ formation causes longer-lived As removal. Because As-bearing pyrite is the common product of SRB metabolism in Holocene alluvial aquifers in both the USA and Southeast Asia, it was endeavored to derive thermodynamic data for arsenian pyrite to better predict geochemical processes in naturally reducing groundwaters. Including the new data for arsenian pyrite into Geochemist’s Workbench, its stability field completely dominates in reducing Eh–pH space and “displaces” other As-sulfides (orpiment, realgar) that have been implied to be important in previous modeling exercises and reported in rare field conditions.     

Impact of lightning on organic matter-rich soils: influence of soil grain size and organic matter content on underground fires

A detailed study was carried out on a piece of land that had been struck by lightning during the violent rainstorm that raged over the Island of S?o Miguel (Azores Archipelago) in late October 2006. Temperature and gas measurements (CO₂, CO, H₂S and CH₄) were performed in four study trenches, dug in an area of ∼3 m², where an underground fire had been initiated by the impact with a lightning stroke, followed by the emission of a column of gases and smoke. The soil under study was originally a well-pedogenized about 80 cm thick bed, made of volcanic clayey to silty tephra fallouts and contained 5.5–9.7% of organic matter. The underground fire was monitored for one week and revealed a peak release of 404 ppm CO and 3.4% CO₂ originating from a horizon located about 45 cm under the soil surface. Measurements of temperature, performed one week after the impact, indicated a maximum value of 326°C inside the soil, while 516.5°C were measured on the surface of a lava block interred about 20 cm under the surface. Subsequently, a stratigraphic and sedimentologic study proved the role of the grain-size of the soil and of the organic matter content of the different horizons of the impact area, in determining the ratio between anoxic/oxidised combustion conditions and in the progress of the process itself. It was also noticed that combustion was not total all over in the soil bed and that the process had slightly migrated toward SW during the observation period. The combustion process went on for about ten days, in spite of several other violent rainstorms, until it was artificially extinguished through the excavations made to obtain study trenches. This particular circumstance evidenced the potential natural hazard represented by this kind of atmospheric event, especially in a land where the volcanic nature of the soil may easily mislead inexperienced observers and, consequently, delay proper action.     

青藏高原西部赛利普中新世火山岩源区:地球化学及Sr-Nd同位素制约

青藏高原拉萨地块西部赛利普地区新生代火山岩依据主量元素可划分为超钾质、钾质和钙碱性系列,主要的岩石类型为粗面安山岩、粗面岩,一个超钾质岩石的40Ar-39Ar年龄为17.58Ma,指示出火山活动为中新世.超钾质、钾质和钙碱性火山岩都显示出富集LREE及LILE(Th、U)、亏损HFSE(Nb、Ta、Ti)的特征.超钾质火山岩具有较高的K2O(6.31%～8.55%)、MgO(6.75%～8.96%)、Cr(270.7×10-6～460.4×10-6)、Ni(142.3×10-6～233.9×10-6)含量,较高的(87Sr/86Sr)i(0.71883～0.72732)和较低的εNd(-14.78～-15.37),指示可能起源于一个前期亏损并经后期俯冲作用改造的富钾的方辉橄榄岩富集地幔源区.钾质火山岩具有比超钾质火山岩低的K2O、MgO、Cr、Ni含量以及高的Ba、Sr含量,初始87Sr/86Sr为0.71553～0.71628,初始143Nd/144Nd为0.51197～0.51198,在空间上与超钾质火山岩共生,可能是前者母岩浆的演化产物.钙碱性火山岩具有较高的Sr(881.7×10-6～1309.2×10-6)、Sr/Y比值(50～108)和较低的Y(12.05×10-6～18.02×10-6),明显亏损重稀土Yb(0.93×10-6～1.30×10-6),类似于典型的埃达克质岩成分特征但相对高钾,并具有相对低的(87Sr/86Sr);(0.70928～0.71374)以及高的εNd(-7.90～-10.91),指示起源于富钾增厚下地壳物质的部分熔融.区域上拉萨地块超钾质岩、钾质岩与N-S向地堑系在空间上共存、时间上相吻合,由此本文认为拉萨地块中新世钾质.超钾质岩和南北向地堑系的形成可能与中新世早期北向俯冲的印度大陆岩石圈断离有关.     

青藏高原东南木里地区二叠纪苦橄岩的Os-Sr-Nd同位素地球化学研究

本文报道了在青藏高原东南木里地区发现的二叠纪苦橄岩和与其共生玄武岩的主微量元素地球化学特征以及Os-Sr-Nd同位素组成。苦橄岩和与其共生玄武岩受地壳混染作用影响较小。根据苦橄岩的Ti/Y比值和初始的Os同位素组成,将木里苦橄岩分为两类:高Ti/Y型苦橄岩和低Ti/Y型苦橄岩,其中高Ti/Y型苦橄岩具有高的γ_(Os)= 5.3～ 10.7和ε_(Nd)= 5.9～ 6.4,与全球典型洋岛玄武岩的Os和Nd同位素组成接近,代表了地幔柱源区的同位素特征;而低Ti/Y型苦橄岩具有低的γ_(Os)=-4.1～ 1.2和ε_(Nd)= 3.2～ 5.0,可能表明受到了SCLM(大陆岩石圈地幔)源区物质的混染。与其共生的玄武岩具有低的γ_(Os)=-3.5～-1.6和ε_(Nd)=-0.6～ 0.7,表明其来自于不同于低Ti/Y型苦橄岩也有异于高Ti/Y型苦橄岩的地幔源区,但是也可能受到了SCLM物质的混染。基于Nd-Os同位素的地幔柱与SCLM的二端元混合模型显示:低Ti/Y型苦橄岩可能是SCLM物质组分与地幔柱起源的苦橄质原始岩浆混合形成的;与苦橄岩共生的玄武岩可能是由地幔柱来源的玄武质岩浆与SCLM小比例熔融的熔体混合形成的。