Rb-Sr and K-Ar systems of biotite in surface environments regulated by weathering processes with implications for isotopic dating and hydrological cycles of Sr isotopes

Biotite is widely used for Rb-Sr and K-Ar isotopic dating and influences Sr isotope geochemistry of hydrological regimes. The isotopic system of biotite behaves diversely in response to surface weathering; i.e. the complete preservation of original Rb-Sr and K-Ar isotopic ages or dramatic reduction. In this study, we have explored the relation between the behavior of isotopic systems and complex weathering processes of biotites in the weathering profiles distributed on the Mesozoic granitoids in South Korea. In the lower parts of the profiles, biotite in the early stages of weathering was transformed into either oxidized biotite or hydrobiotite, with a mass release of ⁸⁷Sr and ⁴⁰Ar forced by the rapid oxidation of ferrous iron. During the transformation to oxidized biotite, ⁸⁷Sr and ⁴⁰Ar were preferentially released relative to Rb and K, respectively, via solid-state diffusion through the biotite lattice, resulting in a drastic reduction of original isotopic age. The reduction of Rb-Sr age was greater than that of K-Ar age because K was preferentially released over Rb whereas ⁸⁷Sr and ⁴⁰Ar were released proportionally to each other. However, during the transformation of biotite to hydrobiotite (i.e., to regularly interstratified biotite-vermiculite), ⁸⁷Sr, Rb, ⁴⁰Ar, and K were completely retained in the alternating biotite interlayer, and thus the original isotopic age can be preserved. In the upper parts of the profiles, where iron oxidation was almost completed, ⁸⁷Sr, Rb, ⁴⁰Ar, and K were gradually and proportionally released, with no further significant change in isotopic age during the gradual transformation of the early-formed oxidized biotite into hydrobiotite and vermiculite or during their final decomposition to kaolinite. The ratios and amounts of isotopes released from weathered biotites are dependent upon the degree of iron oxidation and the pathways of mineralogical transformation. Regional and local variations in isotopic systems affected by particular weathering processes should be considered when dating biotite or biotite-bearing rocks in weathering environments, modeling the transfer of Sr isotopes to hydrologic regimes, and tracking the provenance of sediments.     

Evaluation of heavy metal contamination and implication of multiple sources from Hunchun basin, northeastern China

Present concentrations and distributions of heavy metals through profiles, surface soil, and stream sediment samples in the Hunchun area, north-eastern China, were investigated to determine the elemental background values. This study also aims to characterize potentially toxic materials such as pulverized fly ash (PFA) from power stations or ash and slag from coal used domestically in urban areas, agrochemicals applied inappropriately, and urban sewage sludges from Hunchun City, as well as to ascertain the possibility of natural enrichment through site characterization by mineralogical and geochemical investigation. The distribution of contaminants in the alluvial soils (fluvisol) of this area has been influenced by several interacting factors. The parent alluvial materials from weathered products of amphiboles have made coatings such as ferrihydrite, goethite, and hematite. This natural inheritance factor is supported by the fact that the concentrations of weak acid-extractable (plant-available) heavy metals are very low, except for Fe and Mn. However, in agricultural soils and adjacent stream sediments, an anthropogenic input of Cd, Pb, Ni and Cr by agrochemicals is strongly suggested. Also, F contamination by coal combustion and the dissolution of F-bearing minerals could cause some future problems. Wide distribution and significantly high concentrations of Cd, Fe, Mn, and F in soils throughout the combination of pollutants originating from lithogenic and the anthropogenic sources pose potential problems in utilizing water resources. Received: 14 June 1999 · Accepted: 27 December 1999     

Adsorption of Cu(II) to Bacillus subtilis: A pH-dependent EXAFS and thermodynamic modelling study

Bacteria are very efficient sorbents of trace metals, and their abundance in a wide variety of natural aqueous systems means biosorption plays an important role in the biogeochemical cycling of many elements. We measured the adsorption of Cu(II) to Bacillus subtilis as a function of pH and surface loading. Adsorption edge and XAS experiments were performed at high bacteria-to-metal ratio, analogous to Cu uptake in natural geologic and aqueous environments. We report significant Cu adsorption to B. subtilis across the entire pH range studied (pH ∼2-7), with adsorption increasing with pH to a maximum at pH ∼6. We determine directly for the first time that Cu adsorbs to B. subtilis as a (CuO₅H_n)ⁿ⁻⁸ monodentate, inner-sphere surface complex involving carboxyl surface functional groups. This Cu-carboxyl complex is able to account for the observed Cu adsorption across the entire pH range studied. Having determined the molecular adsorption mechanism of Cu to B. subtilis, we have developed a new thermodynamic surface complexation model for Cu adsorption that is informed by and consistent with EXAFS results. We model the surface electrostatics using the 1pK basic Stern approximation. We fit our adsorption data to the formation of a monodentate, inner-sphere RCOOCu⁺ surface complex. In agreement with previous studies, this work indicates that in order to accurately predict the fate and mobility of Cu in complex biogeochemical systems, we must incorporate the formation of Cu-bacteria surface complexes in reactive transport models. To this end, this work recommends log K RCOOCu⁺ = 7.13 for geologic and aqueous systems with generally high B. subtilis-to-metal ratio.     

Mineralogical and geochemical characterization of precipitates on stream receiving acid mine water, Korea

Seasonal variations of water chemistry occurred in acid mine drainage receiving mine and leachate water. Sulfate and metal concentrations were low in winter but high in spring and summer. Mine waters were highly acidic (up to pH 3.4) in nature with high concentrations of manganese, copper and zinc but high electrical conductivity and sulfate in leachate. The blue and brownish yellow precipitates were formed under different chemical environments of acid mine drainage. Brownish yellow (Munsell color 7.5YR 8/12), blue (Munsell color 2.5B 9/7) and light blue (Munsell color 2.5B 9/3) precipitates deposited on the stream bottom receiving acid mine water. The brownish yellow precipitates formed in the acid mine water, whereas the blue and light blue precipitates formed in the leachate water. The brownish yellow precipitates consisted mainly of ferrihydrite, whereas the blue and light blue precipitates consisted of glaucocerinite and/or woodwardite.     

Comparison of the Ordovician-Carboniferous Boundary Between Korea and NE China: Implications for Correlation and Tectonic Evolution

There is a great hiatus between Ordovician and Carboniferous strata in the Northeast China and Korean Peninsula. In order to understand geology and tectonic evolution, and to find out the similarities and differences in both regions, two sections in the Western Hill near Beijing in NE China and several sections in the Korean Peninsula were selected to examine their geologic boundaries between Lower and Upper Paleozoic strata to compare their characteristic features. At four sites in the two sections in the Western Hill near Beijing were examined their contact relations. The Hui Yu section is the same horizon where one site is top of a quarry hill and the other of down hill. Mid-Carboniferous Qingshuijian Formation rests on the Ordovician Majiagou Formation. Limestone beds are more commonly intercalated with shale and sandstone at site 2 of the Hui Yu section, while at site 1, conglomerate beds are dominant. Site 1 of the Se Shu Fen section shows eroded and concealed karst topography and conglomerate beds are intercalated within shale beds. Silurian and Devonian strata are absent in these areas. In the Korean Peninsula, most O-C contacts occur between Ordovician limestone formation and Carboniferous strata, although Silurian strata occur beneath the Carboniferous strata in the Jeongseon area and Pyeongnam Basin. Most contact relations are parallel unconformity and angular unconformity is rarely seen. The O-C relations in both regions are similar to each other, and these indicate that the Korean Peninsula was located near or belonged to the Sino-Korean paraplatform during Paleozoic time.     

Simultaneous stabilization of arsenic, lead, and copper in contaminated soil using mixed waste resources

In the present study, stabilization treatment using waste resource stabilizers was performed for soil contaminated with As and heavy metals (Pb and Cu). Calcined oyster shell (COS) and coal mine drainage sludge (CMDS) were used as a mixed stabilizing agent for a wet-curing duration of 28 days. After the stabilization treatment, the treatment process efficiency was evaluated by the results of various batch- and column-leaching tests. Neutral and weak acid extraction methods, such as water-soluble extraction and SPLP, did not exhibit satisfactory results for heavy metal stabilization, even if they showed very low leachability. On the other hand, TCLP and 0.1 M HCl extraction showed that the stabilizers significantly reduced the amount of heavy metals leached from the soil, which strongly supports the thesis that the stabilization treatment is efficient in the acidic leaching conditions that were explored. Specifically, in the 0.1 M HCl extraction, the reduction efficiencies of As, Pb, and Cu leachings were more than 90 %, compared with control experiments. This study demonstrates that the application of waste resources for the stabilization of As and heavy metals is feasible. However, some limitations observed in the experiments should be considered in future studies, such as the mobilization of alkali-soluble elements, and in particular, exchangeable fractions of Cu. In addition, the treatment efficiency can be evaluated by different leaching methods, which suggests that multidirectional approaches are required for the proper evaluation of stabilization treatment.     

New dinosaur tracks from Korea, Ornithopodichnus masanensis ichnogen. et ichnosp. nov. (Jindong Formation, Lower Cretaceous): implications for polarities in ornithopod foot morphology

Twelve trackways of ornithopods from Lower Cretaceous lacustrine margin deposits of the Jindong Formation represent new dinosaur trackways described from Korea. The site, discovered during highway construction, was rescued by removing the most important trackways to the Korean Natural Heritage Center in Daejeon, where they are on permanent display. The new ichnotaxon Ornithopodichnus masanensis ichnogen. et ichnosp. nov. is recognized as a distinctive robust tridactyl track, slightly wider than long (l/w ratio = 0.91), with positive (inward) rotation. The toe prints are very thick, broad and U-shaped, resulting in a trefoil outline with a smoothly rounded hind margin. Digit III is short and projects anteriorly much less than digit II and IV (= weak mesaxony). Divarication of digits II-IV is about 70° with interdigital angle II-III larger than III-IV. Trackway width is narrow and the stride length/track length ratio is about 4.2–4.6. The Ornithopodichnus trackways evidently represent gregarious blunt-toed Iguanodon-like bipedal ornithopods, although poorly preserved manus traces are discerned in a few trackways. Ornithopodichnus is distinct from other well known iguanodontid tracks that display much stronger mesaxony and indicates a polarity in ornithopod foot morphology that can be verified by reference to known foot skeletons.     

Effects of natural and calcined oyster shells on Cd and Pb immobilization in contaminated soils

In Korea, soils adjacent to abandoned mines are commonly contaminated by heavy metals present in mine tailings. Further, the disposal of oyster shell waste by oyster farm industries has been associated with serious environmental problems. In this study, we attempted to remediate cadmium (Cd)- and lead (Pb)-contaminated soils typical of those commonly found adjacent to abandoned mines using oyster shell waste as a soil stabilizer. Natural oyster shell powder (NOSP) and calcined oyster shell powder (COSP) were applied as soil amendments to immobilize Cd and Pb. The primary components of NOSP and COSP are calcium carbonate (CaCO₃) and calcium oxide (CaO), respectively. X-ray diffraction, X-ray fluorescence and scanning electron microscope analyses conducted in this study revealed that the calcination of NOSP at 770°C converted the less reactive CaCO₃ to the more reactive CaO. The calcination process also decreased the sodium content in COSP, indicating that it was advantageous to use COSP as a liming material in agricultural soil. After 30 days of incubation, we found that the 0.1 N HCl-extractable Cd and Pb contents in soil decreased significantly as a result of an increase in the soil pH and the formation of metal hydroxides. COSP was more effective in immobilizing Cd and Pb in the contaminated soil than NOSP. Overall, the results of this study suggest that oyster shell waste can be recycled into an effective soil ameliorant.     

Aerobic oxidation of mackinawite (FeS) and its environmental implication for arsenic mobilization

Oxidation of mackinawite (FeS) and concurrent mobilization of arsenic were investigated as a function of pH under oxidizing conditions. At acidic pH, FeS oxidation is mainly initiated by the proton-promoted dissolution, which results in the release of Fe(II) and sulfide in the solution. While most of dissolved sulfide is volatilized before being oxidized, dissolved Fe(II) is oxidized into green rust-like precipitates and goethite (α-FeOOH). At basic pH, the development of Fe(III) (oxyhydr)oxide coating on the FeS surface inhibits the solution-phase oxidation following FeS dissolution. Instead, FeS is mostly oxidized into lepidocrocite (γ-FeOOH) via the surface-mediated oxidation without dissolution. At neutral pH, FeS is oxidized via both the solution-phase oxidation following FeS dissolution and the surface-mediated oxidation mechanisms. The mobilization of arsenic during FeS oxidation is strongly affected by FeS oxidation mechanisms. At acidic pH (and to some extent at neutral pH), the rapid FeS dissolution and the slow precipitation of Fe (oxyhydr)oxides results in arsenic accumulation in water. In contrast, the surface-mediated oxidation of FeS at basic pH leads to the direct formation of Fe (oxyhydr)oxides, which provides effective adsorbents for As under oxic conditions. At acidic and neutral pH, the solution-phase oxidation of dissolved Fe(II) accelerates the oxidation of the less adsorbing As(III) to the more adsorbing As(V). This study reveals that the oxidative mobilization of As may be a significant pathway for arsenic enrichment of porewaters in sulfidic sediments.