Historical tsunamis and storms recorded in a coastal lowland,Shizuoka Prefecture,along the Pacific Coast of Japan

Four sand units deposited by tsunamis and one sand unit deposited by storm surge(s) were identified in a muddy marsh succession in a narrow coastal lowland along the Pacific coast of central Japan. Tsunamis in ad 1498, 1605, 1707 and 1854 that were related to large subduction‐zone earthquakes along the Nankai Trough, and storm surges in 1680 and/or 1699 were responsible for the deposition of these sand units. These sand units are distinguished by lithofacies, sedimentary structures, grain‐size and mineral composition, and radiocarbon ages; their ages are supported by events in local historical records. The tsunami deposits in the study area are massive or parallel‐laminated sands, with associated intraclasts, gravels, draping mud layers and, rarely, a return‐flow subunit. The storm surge deposits are devoid of these characteristics, and are composed of groups of thin, current ripple‐laminated sand layers. The differences in sedimentary structures between the tsunami and storm surge deposits are attributed to the different characteristics of tsunami and storm waves.     

Reinterpretation of an archaeological pebble culture from the Middle Mekong River valley,Cambodia

In 1963, E. Saurin and J.‐P. Carbonnel discovered the Sre Sbov site on an alluvial terrace of the Mekong River in central Cambodia. Saurin described a lithic typology dating to the Lower/Middle Pleistocene from this site. Although the original lithic assemblage has been lost, this typology has been used continuously as a reference by Southeast Asian prehistorians. In 2007, a Khmer–French team conducted excavations at Sre Sbov that yielded numerous pebbles and cobbles showing apparently convincing handmade removals, as Saurin had previously described. However, an in‐depth study of this assemblage, combined with a geological survey of the area, led to the conclusion that the stones were, in fact, of natural origin, and that for this reason their typology should be disregarded. Using satellite imagery and geological surveys, we explain how such a misinterpretation may have occurred and define a “buffer zone,” corresponding to the maximal extent of the proto‐Mekong River, where fluvially reworked pebbles and cobbles resembling artifacts may be recovered. © 2009 Wiley Periodicals, Inc.     

Laser ablation of stream-sediment pebble coatings for simultaneous multi-element analysis in geochemical exploration

Laser ablation of the Fe and Mn oxide coatings on stream sediments has been tested as a means of rapidly introducing this highly sorptive geochemical exploration medium into an inductively coupled plasma emission spectrometer (ICP) for simultaneous multielement analysis.Training data were obtained by selectively leaching coatings on about ten 1-cm diameter pebbles from 50 sites in the Allen drainage system, Southwest England. The Pb, Zn, Fe and Mn concentrations of the resulting leachates were determined by atomic absorption spectrophotometry. This procedure is relatively rapid and economical, but the leachate is suitable only for the determination of a restricted range of elements (mainly heavy metals). The laser-microprobe testing data were obtained by vaporizing approximately 1 μg of coating from one pebble from each sample site with a laser pulse, producing a crater in the coating 150–200 μm in diameter and 30–50 μm deep. The ablation was effected within a cell which the laser beam penetrates via a quartz window and the vaporized material quickly condenses into an aerosol which is carried in a flow of argon passing through the cell to the ICP, for simultaneous determination of up to 36 elements.Training and testing data for the elements determined were normalized by ratioing to Fe or Mn following a preliminary statistical inspection of the data to ascertain predominant correlations. In the Allen drainage basin, where a narrow and impersistent galena vein with subordinate sphalerite occupies a north-south-trending fracture, Pb determinations on coatings correlate well with the Fe content of coatings, while Zn correlates with Mn. The Pb/Fe dispersion patterns produced by the training and testing procedures are essentially similar, as are the Zn/Mn patterns from each of the procedures, demonstrating the potential of the novel laser microprobe technique.Anomalous Pb/Fe and Zn/Mn ratios in pebble coatings occur in the vicinity of the mineralized fracture. These compare favourably in terms of anomaly contrast and length of dispersion trains (especially their extension beyond major confluences) with the Pb and Zn anomalies detected by the more conventional analysis of the minus 200 μm fraction of the stream sediment. The low levels of potential pathfinder elements associated with mineralization do not lend themselves readily to determination in leachates derived from pebble coatings. Laser microprobe data, however, revealed a low-order but punctual As/Fe anomaly in a tributary, where this cuts the mineralized vein.     

Biogeochemistry of nitrous oxide in groundwater in a forested ecosystem elucidated by nitrous oxide isotopomer measurements

The biological and physical controls on microbial processes that produce and consume N₂O in soils are highly complex. Isotopomer ratios of N₂O, with abundance of ¹⁴N¹⁵N¹⁶O, ¹⁵N¹⁴N¹⁶O, and ¹⁴N¹⁴N¹⁸O relative to ¹⁴N¹⁴N¹⁶O, are promising for elucidation of N₂O biogeochemistry in an intact ecosystem. Site preference, the nitrogen isotope ratio of the central nitrogen atom minus that of the terminal nitrogen atom, is useful to distinguish between N₂O via hydroxylamine oxidation and N₂O via nitrite reduction.We applied this isotopomer analysis to a groundwater system in a temperate coniferous-forested ecosystem. Results of a previous study at this location showed that the N₂O concentration in groundwater varied greatly according to groundwater chemistry, i.e. NO₃⁻, DOC, and DO, although apportionment of N₂O production to nitrification or denitrification was ambiguous. Our isotopic analysis (δ¹⁵N and δ¹⁸O) of NO₃⁻ and N₂O implies that denitrification is the dominant production process of N₂O, but definitive information is not derived from δ¹⁵N and δ¹⁸O analysis because of large variations in isotopic fractionations during production and consumption of N₂O. However, the N₂O site preference and the difference in δ¹⁵N between NO₃⁻ and N₂O indicate that nitrification contributes to total N₂O production and that most measured N₂O has been subjected to further N₂O reduction to N₂. The implications of N₂O biogeochemistry derived from isotope and isotopomer data differ entirely from those derived from conventional concentration data of DO, NO₃⁻, and N₂O. That difference underscores the need to reconsider our understanding of the N cycle in the oxic-anoxic interface.     

Origin of manganese carbonates in Jurassic red shale, central Japan

Manganese carbonate deposits in Japanese Jurassic sedimentary rocks were studied petrogeochemically. The deposits are characteristically composed of spheroidal micronodules, up to 1 mm in diameter, and always contain well-preserved radiolarian shells. Chemical elemental composition and mineralogical characteristics indicate that the micronodules contain rhodochrosite in a mixed carbonate phase composition (Mn_86.7?92.2Ca_2.2?2.9Mg_2.6?6.7Fe_2.6?5.6)CO₃ Carbon and oxygen isotope values, which range from ?7.99 to ?4.78‰ and ?4.05 to 0.28‰ relative to PDB, respectively, suggest that the manganese carbonate was precipitated in a suboxic zone. The micronodules closely resemble agglutinated benthic foraminifera in shape. We suggest that agglutinated foraminiferal tests composed of radiolarian shells accumulated selectively on the sediment surface during redeposition of bottom sediments and were replaced by manganese carbonate in suboxic diagenetic conditions of manganese reduction.     

新疆和田籽玉的开采与玉龙喀什河流域生态环境

本文从探讨玉龙喀什河的历史和源流入手,试图从地理和生态上构勒出玉龙喀什河(以下简称玉河)与和田绿洲唇齿相依的共生关系.并从环境角度,针对近年来愈演愈烈的籽玉疯采现象,分析了所谓"玉石经济"产生的背景状况.描述了不当开采对资源的影响、对玉河的损害、对绿洲生态的破坏.提示人们脆弱生态需要呵护,以牺牲长远利益换取眼前利益的做法,后患无穷.呼吁人们珍惜资源,合理开发、保护环境.     

大宝山多金属矿区土壤-植被稀土元素生物地球化学特征

为研究采矿对土壤-植被REE生物地球化学特征的影响,采集大宝山多金属矿区及背景区土壤及优势植物芒萁、马尾松叶片,测量REE含量.对比分析样品中REE分布模式、∑REE、δEu、δCe及四重效应等地球化学特征.结果表明:受采矿活动影响,矿区土壤REE含量均值达284.99 mg/kg,显著高于背景区,且表土层REE含量明显高于心土层;相对于背景区,矿区土壤和植被轻重稀土分馏更弱;研究区土壤和植被都为Eu亏损,大都为Ce富集,马尾松与土壤REE含量呈正相关,REE富集植物芒萁在背景区富集系数反而更高;矿区环境抑制植物对REE正常的迁移和分异,对植被生长不利,植被REE分布分异特征是其对生长环境的反映和适应.      

Types and genesis of manganese oxide ores in Guangxi, Southwest China

Systematic studies are diven to the genesis and spatial distribution of manganese oxide deposits in Guangxi,Southwest China.The deposits are classified as 3 types and 7 subtypes among which the karst depression type is regionally characteristic an of reat potential.A genetic model is presented for the mineralization on the basis of proto-rock,tectonic background,topographic features and climatic and hydrogeological conditions.     

Geochemical behaviour of iron and manganese ions in the Ningyo-Toge uranium deposit district, southwest Japan

The Ningyo-Toge uranium deposit is one of the typical sedimentary uranium deposits in Japan. In general, during weathering, U is removed from the basal granite through underground water. The underground water in this area is rich in U, and has a comparatively high concentration of Fe and Mn.

In this area, three types of Fe minerals can be recognized in different modes of occurrence: (1) in the oxide zone brownish Fe-hydroxide mineral with ferric ion, i.e. goethite (-FeOOH); (2) in the reduced zone of the mine gallery pale-blue Fe-hydroxide mineral with some ferrous ion, i.e. lepidocrocite (γ-FeOOH); and (3) Fe-sulphate minerals such as melanterite (FeSO₄·7H₂O), etc. Some uranyl sulphate minerals, uranopilite and zippeite, are closely associated with these Fe-sulphate minerals. Under weakly alkaline conditions of the oxidizing environment, Mn-hydroxide (MnOOH) coexists with goethite as alternative thin laminae with shale, or coprecipitates resembling a marine Mn nodule, in the size of 0.5 cm in diameter. Radioactive anomalies have been recognized frequently for these Mn sediments due to absorption of Ra by the sediments.     

Theory of electronic structures of chemisorption on oxide surfaces

Surface electronic structures of metal oxides such as MgO, TiO₂, SrTiO₃, ReO₃ and transition-metal monoxides are discussed based on the first-principles DV-Xα cluster and slab methods. Particular attention is paid to the origin and properties of intrinsic and extrinsic surface states. A close correlation between the surface structure and electronic states is confirmed. Some exotic properties of polar oxide surfaces, for example the formation of a two-dimensional metallic band, are predicted.     

Biogeochemistry, a prospecting tool in the search for mercury mineralization

Summary of biogeochemical prospecting for mercury mineralization in the Pinchi Fault is given. One thousand two hundred and eight plant samples were collected and analyzed for mercury. In mineralized areas the typical mercury content of dried plants was not less than 0.2 and 0.4 μg/g and even concentrations between 0.6 and 1.6 μg/g were observed. In nonmineralized zones at least 90% of the plants contained no more than 0.15 μg/g of mercury. Analytical and sampling procedures are described.     

Hydrogen isotopic composition of MnO(OH) minerals from manganese oxide and massive sulfide (Kuroko) deposits in Japan

The hydrogen isotopic composition of structural water in MnO(OH) minerals from manganese oxide and massive sulfide deposits (Kuroko) in Tertiary formations fall within a narrow range from -261 to -275 permil relative to standard mean ocean water (SMOW). The δD of two manganites from manganese deposits in Paleozoic formations were -236 and -298 permil, indicating a wider range than in those of Tertiary manganese deposits. The MnO(OH) minerals are more deuterium-depleted. than any other hydrothermal minerals reported to date. Hydrogen isotopic fractionation factors between manganite and water were experimentally determined to be 0.7894, 0.7958, and 0.8078 at 150°, 200°, and 250° C, respectively, under hydrothermal conditions at 500 bars. The present experimental results indicate that if manganites were formed at temperatures below 250° C under isotopic equilibrium conditions, then most manganite mineralization in the ore deposits must have precipitated from meteoric hydrothermal solutions.     

Precipitation of iron,manganese, zinc,and copper on clean,ceramic surfaces in a stream draining a polymetallic sulfide deposit

Acid-cleaned ceramic plates placed upstream and downstream from a Cu-Zn-Pb sulfide deposit (Magruder mine) developed a precipitate of Fe-Mn oxides in a 36-day period. Copper and Zn concentrations on the coated surface, normalized to surface area and ratios with Fe and/or Mn, are distinctly anomalous for a distance of 2 km downstream from the mine.The major source of metals in the coatings is interpreted to be groundwater percolating into the stream bed. Anomalous concentrations of Cu and Zn in groundwater from the Magruder mine area, due to oxidation of sulfide minerals, probably accounts for the anomaly identified on the ceramic plates.     

Redox cycling of iron and manganese in sediments of the Kalix River estuary, Northern Sweden

Iron and manganese redox cycling in the sediment — water interface region in the Kalix River estuary was investigated by using sediment trap data, pore-water and solid-phase sediment data. Nondetrital phases (presumably reactive Fe and Mn oxides) form substantial fractions of the total settling flux of Fe and Mn (51% of Fe_total and 84% of Mn_total). A steady-state box model reveals that nondetrital Fe and Mn differ considerably in reactivity during post-depositional redox cycling in the sediment. The production rate of dissolved Mn (1.6 mmol m^–2 d^–1) exceeded the depositional flux of nondetrital Mn (0.27 mmol m^–2 d^–1) by a factor of about 6. In contrast, the production rate of upwardly diffusing pore-water Fe (0.77 mmol m^–2 d^–1) amounted to only 22% of the depositional flux of nondetrital Fe (3.5 mmol m^–2 d^–1). Upwardly diffusing pore-water Fe and Mn are effectively oxidized and trapped in the oxic surface layer of the sediment, resulting in negligible benthic effluxes of Fe and Mn. Consequently, the concentrations of nondetrital Fe and Mn in permanently deposited, anoxic sediment are similar to those in the settling material. Reactive Fe oxides appear to form a substantial fraction of this buried, non-detrital Fe. The in-situ oxidation rates of Fe and Mn are tentatively estimated to be 0.51 and 0.16–1.7 mol cm^–3 d^–1, respectively.     

Impacts of hydrous manganese oxide on the retention and lability of dissolved organic matter

Minerals constitute a primary ecosystem control on organic C decomposition in soils, and therefore on greenhouse gas fluxes to the atmosphere. Secondary minerals, in particular, Fe and Al (oxyhydr)oxides—collectively referred to as “oxides” hereafter—are prominent protectors of organic C against microbial decomposition through sorption and complexation reactions. However, the impacts of Mn oxides on organic C retention and lability in soils are poorly understood. Here we show that hydrous Mn oxide (HMO), a poorly crystalline δ-MnO₂, has a greater maximum sorption capacity for dissolved organic matter (DOM) derived from a deciduous forest composite O_i, O_e, and O_a horizon leachate (“O horizon leachate” hereafter) than does goethite under acidic (pH 5) conditions. Nonetheless, goethite has a stronger sorption capacity for DOM at low initial C:(Mn or Fe) molar ratios compared to HMO, probably due to ligand exchange with carboxylate groups as revealed by attenuated total reflectance-Fourier transform infrared spectroscopy. X-ray photoelectron spectroscopy and scanning transmission X-ray microscopy–near-edge X-ray absorption fine structure spectroscopy coupled with Mn mass balance calculations reveal that DOM sorption onto HMO induces partial Mn reductive dissolution and Mn reduction of the residual HMO. X-ray photoelectron spectroscopy further shows increasing Mn(II) concentrations are correlated with increasing oxidized C (C=O) content (r = 0.78, P < 0.0006) on the DOM–HMO complexes. We posit that DOM is the more probable reductant of HMO, as Mn(II)-induced HMO dissolution does not alter the Mn speciation of the residual HMO at pH 5. At a lower C loading (2 × 10² μg C m^?2), DOM desorption—assessed by 0.1 M NaH₂PO₄ extraction—is lower for HMO than for goethite, whereas the extent of desorption is the same at a higher C loading (4 × 10² μg C m^?2). No significant differences are observed in the impacts of HMO and goethite on the biodegradability of the DOM remaining in solution after DOM sorption reaches steady state. Overall, HMO shows a relatively strong capacity to sorb DOM and resist phosphate-induced desorption, but DOM–HMO complexes may be more vulnerable to reductive dissolution than DOM–goethite complexes.     

The distribution of manganese and iron between ilmenite and granitic magma in the Ôsumi Peninsula,Japan

Manganoan ilmenite with a variable manganese content occurs as an early accessory constituent of granitic rocks in the Ôsumi Peninsula, southern Kyushu. Electron probe micro-analysis of a grain containing highest manganese gives the structural formula (Fe _1.23 ²⁺ Mn _0.81 ²⁺ ) (Ti_1.97) O₆, if all of the manganese and iron are in the divalent state. The manganese content of manganoan ilmenite increases with an increase of the differentiation index of host rocks, however, the amount of ilmenite tends to decrease with the increase of the same index. The mode of occurrence of the ilmenite suggests that it is the first mafic mineral to precipitate from the magma. The average value of the distribution coefficient of manganese and ferrous iron between ilmenite and granitic magma is 5.5, if the Mn/Fe ratio of the granitic rocks represents that of granitic magma. The variation in the FeO and MnO contents against the differentiation index for granitic rocks of the Ôsumi Peninsula, and the value of the distribution coefficient, show that high manganoan ilmenite is stable in the most differentiated granitic rock of the Ôsumi Peninsula.     

The kinetics of iodide oxidation by the manganese oxide mineral birnessite

The kinetics of iodide (I⁻) and molecular iodine (I₂) oxidation by the manganese oxide mineral birnessite (δ-MnO₂) was investigated over the pH range 4.5-6.25. I⁻ oxidation to iodate proceeded as a two-step reaction through an I₂ intermediate. The rate of the reaction varied with both pH and birnessite concentration, with faster oxidation occurring at lower pH and higher birnessite concentration. The disappearance of I⁻ from solution was first order with respect to I⁻ concentration, pH, and birnessite concentration, such that −d[I⁻]/dt = k[I⁻][H⁺][MnO₂], where k, the third order rate constant, is equal to 1.08 ± 0.06 × 10⁷ M⁻² h⁻¹. The data are consistent with the formation of an inner sphere I⁻ surface complex as the first step of the reaction, and the adsorption of I⁻ exhibited significant pH dependence. Both I₂, and to a lesser extent, sorbed to birnessite. The results indicate that iodine transport in mildly acidic groundwater systems may not be conservative. Because of the higher adsorption of the oxidized I species I₂ and , as well as the biophilic nature of I₂, redox transformations of iodine must be taken into account when predicting I transport in aquifers and watersheds.     

Biogeochemistry of acetate in anoxic sediments of Skan Bay,Alaska

The role of acetate in the biogeochemical cycling of organic matter in contemporary marine anoxic sediments of Skan Bay, Alaska was investigated with inhibition and quasi in situ turnover experiments. The turnover time for acetate oxidation in the upper 30 cm of the sediment column is ca. 1 hr. A molybdate inhibition experiment indicated that sulfate reducing bacteria were responsible for more than 95% of acetate oxidation. However, measured acetate oxidation rates exceeded sulfate reduction rates indicating that acetate oxidation rates are overestimated. Values for acetate concentration calculated from sulfate reduction rates (0.3–3.4 μM) were considerably lower than directly measured acetate concentrations (3.1–10.8 μM). Much of the chemically measured acetate may be microbially unavailable, perhaps in the form of a soluble or colloidal complex. A sorption experiment indicates that 10% to 40% of added acetate associates with Skan Bay sediment particles. Production of methane from acetate was detected only at 2 m depth.