分光光度法测定钼矿石中钼不确定度评定

对分光光度法测定钼矿石中钼质量分数的不确定度进行评估,建立了数学模型,评定测量过程中不确定度主要来源于曲线拟合,以及重复实验产生的不确定度。当矿石中钼质量分数为0.054%时,评定其扩展不确定度为0.003 0%（k=2）。     

Rapid colorimetric determination of phosphorus in geochemical survey samples

A colorimetric method for the determination of phosphorus in batches of geochemical survey samples is described. The powdered material is digested with a nitric-perchloric acid mixture, excess of acid is evaporated off and the residue is leached with water. Aliquots of the leachate are treated with vanadomolybdate reagent and the yellow phosphorus complex is extracted into isobutyl methyl ketone. The colour in the organic phase, which is stable for many days, is matched against a series of similarly prepared standards. Iron, other coloured ions, and titanium do not interfere. Standard deviations of ±0.02% about a mean value of 0.20% P₂ O₅ and ±0.4% about a mean of 11.6% P₂ O₅ were obtained. At least 40 powdered samples may be analysed per working day per person.     

环境样品中钼的测定方法进展

根据多年来国内对钼的测定方法的研究报道,对环境样品中钼的主要测定方法进行总结,常用方法有分光光度法、催化极谱法、原子吸收分光光度法、ICP—AES法及ICP-MS等,分析了它们的优缺点,有利于选择适宜的测定方法。     

Speciation of naturally-accumulated uranium in an organic-rich soil of an alpine region (Switzerland)

Very high concentrations of uranium (up to 4000 ppm) were found in a natural soil in the Dischma valley, an alpine region in the Grisons canton in Switzerland. The goal of this study was to examine the redox state and the nature of uranium binding in the soil matrix in order to understand the accumulation mechanism. Pore water profiles collected from Dischma soil revealed the establishment of anoxic conditions with increasing soil depth. A combination of chemical extraction methods and spectroscopy was applied to characterize the redox state and binding environment of uranium in the soil. Bicarbonate extraction under anoxic conditions released most of the uranium indicating that uranium occurs predominantly in the hexavalent form. Surprisingly, the uranium redox state did not vary greatly as a function of depth. X-ray absorption near edge spectroscopy (XANES), confirmed that uranium was present as a mixture of U(VI) and U(IV) with U(VI) dominating. Sequential extractions of soil samples showed that the dissolution of solid organic matter resulted in the simultaneous release of the majority of the soil uranium content (>95%). Extended X-ray absorption fine structure (EXAFS) spectroscopy also revealed that soil-associated uranium in the soil matrix was mainly octahedrally coordinated, with an average of 1.7 axial (at about 1.76 Å) and 4.6 to 5.3 equatorial oxygen atoms (at about 2.36 Å) indicating the dominance of a uranyl-like (UO₂²⁺) structure presumably mixed with some U(IV). An additional EXAFS signal (at about 3.2 Å) identified in some spectra suggested that uranium was also bound (via an oxygen atom) to a light element such as carbon, phosphorus or silicon. Gamma spectrometric measurements of soil profiles failed to identify uranium long-life daughter products in the soil which is an indication that uranium originates elsewhere and was transported to its current location by water. Finally, it was found that the release of uranium from the soil was significantly promoted at very low pH values (pH 2) and increased with increasing pH values (between pH 5 and 9).     

对壤中钒、硒、钼测量方法的观察与思考

本文简要介绍了钒、硒、钼的地球化学性质。根据我国西北业已查实的3个层间氧化带砂岩型铀矿床中钒、硒、钼与铀的展布特征,认为,按已知铀矿床中铀与钒、硒、钼的存在及相互关系,试图用壤中钒、硒、钼测量对层间氧化带砂岩型铀矿实施伴生元素找矿或进行“空间定位”的依据尚不足。     

硫氰酸盐光度法快速测定铅锌矿中钼

通过硝酸-硫酸混合溶液对铅锌矿进行前处理,用抗坏血酸-硫氰酸盐分光光度法测定铅锌矿中钼含量,在选定的条件下,该方法的ρ(Mo)检出限为0.0763 μg·mL-1,ρ(Mo)线性范围为0.4～6.768μg·mL-1,加标回收率为94%～99%,用此法测定铅锌矿中钼含量,结果满意.     

金的野外现场快速分析

利用甲基异丁基酮的易挥发性,从富集了金的磷酸三丁酯-甲基异丁基酮组合萃取剂中自然挥发除去甲基异丁基酮后,使金高度富集在不易挥发的磷酸三丁脂少量有机相中.加入硫代米蚩酮显色剂,可以野外现场目视比色测定金.方法的精密度(RSD,n=10)< 9%.     

Diagenesis of dissolved aluminum in organic-rich estuarine sediments

The sedimentary geochemistry of dissolved Al is complicated by a number of different reactions. In this study we show that complexation by organic matter, adsorption to Fe-oxyhydroxides, and reaction with Si in solution have important effects on the distribution of dissolved Al in sediments. In the absence of physical resuspension of sediment into overlying waters, dissolved Al is rapidly consumed at the sediment-water interface and is subsequently released upon reduction of Fe-oxyhydroxides. This release does not cause noticeable perturbations in dissolved Al concentrations in sediments because of rapid consumption reactions which mask the true mobility of Al. Results suggest that one of the consumption reactions may be due to formation of an Fe-Al-silicate. The amount of authigenic aluminosilicate formed in estuarine sediments must be very small relative to the detrital component. In the deep-sea, however, the long residence time of Fe-oxyhydroxides at the sediment-water interface, with resulting greater accumulation of adsorbed Al may explain the abundance of Al in Fe-smectites reported from many different areas.     

催化极谱法连续测定化探样品中的钨、钼

本方通过催化极谱法连续测定化探样品中的的钨、钼的试验,研究了测量过程的共存干扰离子的消除、指示剂用量的选择、酸度影响、底液各组分用量等主要影响因素,选择了最佳实验条件．．并确定了钨、钼的质量浓度与电流呈线性关系的范围。在进行回收率、精密度、栓出限试验,均能满足化探找矿的要求,测定结果经国家一级标准物质验证,测定结果与标准值相符。     

全量萃取火焰原子吸收法测定岩石、土壤中微量钼的研究

本文研究了测定时的萃取酸度,有机相与水相的体积比,酒石酸、抗坏血酸、硫氰酸钾和硝硫混酸用量对测定结果的影响,做了萃取分离后共存元素干扰测定,经与国家一级标准物质对比分析,验证结果与标准相符。     

Volatile fatty acid cycling in organic-rich marine sediments

Volatile fatty acid (VFA) apparent turnover rates were determined by measuring whole sediment VFA concentrations and the corresponding reaction rate constants. The following ranges of VFA concentrations were measured in Cape Lookout Bight, N.C. sediments (μmole·l_s^?1): acetate 54–660, propionate 1–24, butyrate <0.5–22, iso-butyrate <0.5–6. Apparent turnover rates measured over a one-year period ranged from 18–600 μmole·l_s^?1·h^?1 for acetate and 0.7–7 μmole·l_s^?1·h^?1 for the carboxyl carbon of propionate. Methane production was observed only with acetate and only in sulfatedepleted sediments; total acetate turnover attained approximately the same maximum value in both sulfate-reducing and sulfate-depleted sediments.Apparent turnover rates for acetate and propionate appeared to be controlled by similar factors: in sulfate-reducing (surface) sediments the turnover rates were stimulated by autumn storm-mediated deposition/resuspension events; in deeper sulfate-depleted sediments the turnover rates followed changes in the ambient temperature. Changes in VFA poolsizes were proportionally much larger than changes in corresponding rate constants. The ratio of CO₂ to CH₄ produced from acetate vs. depth suggested that non-methanogenic bacteria accounted for 60% of the acetate turnover in sulfate-depleted sediments.VFA concentrations were much lower in N.C. continental slope mud than in Cape Lookout sediments; acetate was the only VFA detectable throughout the top 40 cm of the slope sediments. The estimated production rate of CO₂ from acetate decreased rapidly with depth. The surface rate was approximately 20 times less than that measured at similar temperatures in sulfate-reducing Cape Lookout sediments.     

Palaeogeography of radiolarite and organic-rich deposits in Mesozoic Tethys

Siliceous and marine organic-rich deposits are sometimes associated, sometimes separate in space and time; however, both are generally accepted to be the result of high planktonic productivity. Among the siliceous marine deposits, the phtanite family facies is distinguished from the radiolarite family facies by several characteristics: They contain organic material and as a result are blackish (vs red/green for radiolarite facies), their time of deposition corresponds with strong faunal modifications and they are deposited generally in shallower environments. A palaeogeographic analysis of locations of Tethyan biosiliceous and marine organic-rich rocks, both resulting from a high planktonic palaeoproductivity, for three Mesozoic high sea-level intervals, Toarcian, Kimmeridgian and Cenomanian, show: (a) during Jurassic times these Tethyan deposits were dissociated, the siliceous deposits being closer to open ocean waters than the organic-rich ones. This is a common disposition in modern upwelling systems and suggests a common process; (b) during Cretaceous times these Tethyan deposits were often associated, i.e. both occur at the same site, and are probably the result of a different process from that in the Jurassic.     

焦石坝地区页岩各向异性及其影响的分析研究

黑色富含有机质页岩由于沉积方式的特殊性,一般具有较强的各向异性.但现有大部分研究是基于各向同性理论开展页岩储层预测工作,这与页岩的实际地质特点不符.文中联合利用实验室岩石力学测试数据以及各向异性参数经验公式计算焦石坝地区页岩的各向异性参数,并进一步探讨了各向异性对页岩岩石速度、储层AVO响应特征以及岩石力学参数计算的影响.结果表明,各向异性对页岩速度、脆性指数预测结果影响较大,在地层倾角较大时进行速度分析及页岩可压性预测时应考虑各向异性参数的影响;同时,AVO正演结果表明地震反射入射角小于40°时,各向异性算法与各向同性算法计算的页岩AVO响应差异较小,利用各向同性叠前反演方法进行页岩储层预测具有可行性.     

Application of formaldoxime colorimetric method for the determination of manganese in the pore water of anoxic estuarine sediments

The formaldoxime colorimetric method for manganese, previously utilized for freshwater and seawater samples of large volume, has been modified for the analysis of small volume, iron-rich sediment pore water samples. Using as little as 3 ml of sample and the addition of EDTA to destroy the Fe-formaldoxime interference (at concentrations of 9 μM Mnl^?1), a precision of 3% is obtained.     

Sulfur isotope fractionation during bacterial sulfate reduction in organic-rich sediments

Isotope fractionation during sulfate reduction by natural populations of sulfate-reducing bacteria was investigated in the cyanobacterial microbial mats of Solar Lake, Sinai and the sediments of Logten Lagoon sulfuretum, Denmark. Fractionation was measured at different sediment depths, sulfate concentrations, and incubation temperatures. Rates of sulfate reduction varied between 0.1 and 37 micromoles cm-3 d-1, with the highest rates among the highest ever reported from natural sediments. The depletion of 34S during dissimilatory sulfate reduction ranged from 16% to 42%, with the largest 34S-depletions associated with the lowest rates of sulfate reduction and the lowest 34S-depletions with the highest rates. However, at high sulfate reduction rates (>10 micromoles cm-3 d-1) the lowest fractionation was 20% independent of the rates. Overall, there was a similarity between the fractionation obtained by the natural populations of sulfate reducers and previous measurements from pure cultures. This was somewhat surprising given the extremely high rates of sulfate reduction in the experiments. Our results are explained if we conclude that the fractionation was mainly controlled by the specific rate of sulfate reduction (mass cell-1 time-1) and not by the absolute rate (mass volume-1 time-1). Sedimentary sulfides (mainly FeS2) were on average 40% depleted in 34S compared to seawater sulfate. This amount of depletion was more than could be explained by the isotopic fractionations that we measured during bacterial sulfate reduction. Therefore, additional processes contributing to the fractionation of sulfur isotopes in the sediments are indicated. From both Solar Lake and Logten Lagoon we were able to enrich cultures of elemental sulfur-disproportionating bacteria. We suggest that isotope fractionation accompanying elemental sulfur disproportionation contributes to the 34S depletion of sedimentary sulfides at our study sites.     

江苏某材料厂周边农田土壤钼污染特征及农作物健康风险评价（84）

为了解江苏某材料厂金属冶炼活动引发的重金属污染风险,采集周围农田土壤、小麦和水稻籽实样品,确定Mo含量及其在土壤中的形态,采用地质累积指数和富集因子指标评价土壤中钼的污染风险,采用健康风险指数评价小麦、稻米中Mo的健康风险。结果表明,农田土壤中Mo含量在0.50～63.2 mg/kg之间,其平均值5.70 mg/kg远高于全省平均值0.65 mg/kg,表层土壤出现了中度—高度富集,近70%的样点受到不同程度的钼污染,污染范围距该厂300 m,污染深度>1.5 m。土壤中的Mo具有较高的生物有效性,在小麦、水稻籽实中显著富集,主要与土壤具有较高的全Mo含量以及土壤呈碱性有关。基于EPA的健康风险评估方法,食用当地稻米、小麦会产生较大的健康风险。     

Influence of geochemistry on toughening behavior of organic-rich shale

Our research objective is to understand the influence of geochemistry on the fracture behavior of organic-rich shale at multiple length-scales. Despite an increasing focus on the fracture behavior of organic-rich shale, the relationships between geochemistry and fracture behavior remain unclear and there is a scarcity of experimental data available. To this end, we carry out 59 mesoscale scratch-based fracture tests on 14 specimens extracted from 7 major gas shale plays both in the USA and in France. Post-scratch testing imaging reveals fractures with a small crack width of about 411–660 nm. The fracture toughness is evaluated using the energetic size effect law, which is extended to generic axisymmetric probes. A nonlinear anisotropic and multiscale fracture behavior is observed. In addition, a positive correlation is found between the fracture toughness and the presence of kerogen, clay and calcite. Moreover, the geochemistry is found to influence the timescale and the regime of propagation of the hydraulic fracture at the macroscopic length-scale. In particular, shale systems rich in total organic content, clay and calcite are more likely to exhibit high values of the fluid lag and a low hydraulic crack width. Our findings highlight the need for advanced constitutive models for organic-rich shale systems and advanced hydraulic fracturing solutions that can fully integrate the complex fracture response of organic-rich shale materials.

     

渝东南地区下古生界富有机质页岩有机岩石学特征

渝东南下古生界主要发育牛蹄塘组和五峰-龙马溪组两套富有机质页岩:五峰-龙马溪组岩心样品显微组分总含量TMC值为0.6%~1.2%,牛蹄塘组岩样TMC值为0.7%~2.2%。页岩富氢显微组分主要为腐泥组和壳质组,其中矿物沥青基质、藻类体和壳屑体是下古生界页岩主要生烃组分,对油气生成贡献最大渝东南下古生界富有机质页岩热演化程度处于过成熟—极高过成熟阶段,等效镜质体反射率(VR_O)为2.25%~5.18%。本文应用全岩有机岩石学分析技术,系统研究了2套页岩的显微组分组成、分布特征、主要组分对生烃的贡献以及有机质热演化程度,希望为该区页岩气的勘探与开发提供进一步的证据支持。     

土壤样品中碱解氮测定不确定度评定

通过容量法测定土壤样品中碱解氮,重复测定11次,计算实验标准差,同时对测试过程系统效应产生的不确定度分量进行评估。经评定,不确定度主要由盐酸标准溶液标定、样品重复性试验和样品制备所产生。当土壤样品中碱解氮质量分数为58.4、73.4、95.1、169 mg/kg时,其扩展不确定度分别为2.0、2.4、3.4、5.0 mg/kg。测定不确定度越小,用测定值表示真值的可靠性越高。     

Sulphur cycling in organic-rich marine sediments from a Scottish fjord

In this study, the biogeochemical transformations of sulphur in organic‐rich marine sediments in a Scottish fjord are investigated by a combination of pore water and sediment geochemistry with sulphide diffusive gradient thin‐film probes and sulphate isotopic data (δ³⁴S and δ¹⁸O). Particular attention is paid to sulphur cycling in the upper sediment profile where sulphate reduction occurs but free sulphide is below the detection limits of conventional pore water geochemical analysis but quantifiable by sulphide diffusive gradient thin film. In the uppermost part of the sediment core, δ¹⁸O sulphate decreased from near‐sea water values to +7‰, indicating that anoxic sulphide oxidation dominated during this interval. Sulphate δ³⁴S remained unchanged as there was no net sulphate reduction (i.e. reduction was balanced by re‐oxidation). Below 4 cm depth, there was a slight increase in sulphate δ³⁴S from 20‰ to 23‰ associated with minor accumulation of iron sulphide. The δ¹⁸O of the sulphate also increased, to around +10‰ at 10 cm depth, as a result of the isotopic exchange of sulphate–oxygen with pore water and/or sulphur disproportionation reactions mediated during sulphur cycling. These processes continued to increase the δ¹⁸O of the sulphate to 14‰ at 20 cm depth with no further change in the δ³⁴S of the sulphate. Below 20 cm depth, free sulphide is detectable in pore waters and both the δ³⁴S of the sulphate and sulphide increase with depth with an offset controlled by kinetic fractionation during bacterial sulphate reduction. The δ³⁴S of the sedimentary organic fraction shifted towards lower, more bacteriogenic, values with depth in the profile, without any increase in the size of this sulphur pool. Thus, the organic sulphur fraction was open to interaction with bacteriogenic sulphide without the occurrence of net addition. Therefore, caution should be exercised when using sulphur isotopic compositions to infer simple net addition of bacteriogenic sulphide to the organic sulphur fraction.