Simultaneous Determination of Total Carbon, Nitrogen, Hydrogen and Sulfur in Twenty-seven Geological Reference Materials by Elemental Analyser

The contents of total carbon, hydrogen, nitrogen and sulfur in twenty-seven geological reference materials, issued by five producer organisations (USGS, CCRMP, ANRT, NIST and GSJ) were determined using an automated simultaneous elemental analyser following combustion. In order to complete gasification of C and N in some geological materials, the combustion temperature needed to be greater than 1150 °C. The calibrator prepared from known amounts of reagent material was not adopted for more than 1.2% m/m of H. Unrealistically high values in certain materials supposed to contain less than 1000 μg g⁻¹ S may be due mainly to memory effects. The limit of detection was 50 μg g⁻¹ for C and N, 500 μg g⁻¹ for H and 1000 μg g⁻¹ for S. Although the blank value of C and N was always stable and less than one third of the detection limit, it had a slightly higher value for N and S. By repeating long-term analysis, high reproducibility for each of the four elements was verified. The method has been applied satisfactorily to a variety of geological reference materials, and recommended values for C, H and N for most of the reference materials studied have been tabulated.     

Hydrogen Isotopic Compositions of Pyroxenes in Nushan Peridotite Xenoliths,SE China

Hydrogen isotopic compositions of pyroxenes in peridotite xenohths from the Nushan volcano, Anhui Province, SE China have been obtained using an ion probe (Cameca 1270). D/H ratios are constant within a single grain and among the different grains from the same sample. The lack of correlation between the D/H ratios and the hydrogen contents indicates that the hydrogen isotopic compositions are inherited from their mantle source. Combining with the δD values of coexisting amphiboles, it is inferred that the Nushan mantle experienced at least a two-stage metasomatic event.One was responsible for formation of amphiboles with extremely variable δD values, and the other was probably responsible for the high δD values (up to -20‰) of some clinopyroxenes from peridotites, clinopyroxene and mica megacrysts. High δD values point to a subduction-related fluid being involved in one metasomatic event. The primary δD values (-90‰ to -140‰) of the Nushan pyroxenes, together with data gleaned from the literature, suggest that the D/H ratios of the nominally anhydrous mineral reservoir might have differed from that of the other mantle hydrogen in being relatively depleted in D.     

渝东南断裂型碳酸盐岩地热水的形成特征

通过水化学法和同位素示踪法对渝东南断裂型碳酸盐岩地热水的地球化学特征及其水资源的形成进行研究。结果表明:郁山断裂以西地热水的水化学类型为Cl-Na型,断裂以东地热水以SO4-Ca?Mg型为主。根据Gibbs图,郁山断裂以西、以东的地热水分别受到蒸发浓缩和岩石风化作用的影响;断裂以西地热水的γNa+/γCl-接近1,表明地热水中高浓度的Cl-和Na+主要是源于地层中岩盐的溶解;断裂以东地热水的γ（Ca2++Mg2+）/γ（HCO_3^-+ SO〖_4^(2-)〗）接近1,表明地热水中高浓度的Ca2+和SO〖_4^(2-)〗主要来源于地层中膏岩的溶解。地热水的δD和δ18O值分别为-64.7‰~-50‰和-9.17‰~-7.89‰,分布在当地大气降水线两侧,表明补给来源主要为大气降水。地热水水源平均补给高程为1 278 m,这很可能来自附近岩溶中山地区。其热储温度为41~90 ℃,平均热储温度为66℃;循环深度为1 000~3 500 m,平均值为2 300 m。大气降水到达地表后,在重力（地形）作用下向深部径流,接受地球内部的热传导形成地热水,由西北向东南流动,沿着断裂带上涌,并接受冷水的混入。      

唐山曹妃甸浅层地下水水化学特征及咸化成因

为了查明曹妃甸浅层地下水水化学及咸化成因,采集研究区河水、地下淡水、微咸水、咸水、卤水、雨水和海水等不同类型水样,对其水化学组成、离子比、Piper三线图、吉布斯图、氢氧同位素组成及14C测年结果进行了分析。结果表明：(1)曹妃甸浅层地下水包括全新世沉积层潜水和晚更新世沉积层微承压水,且非原始封存在地层中而是形成于全新世中晚期。(2)地下潜水向海方向分布有淡水、微咸水、咸水水质类型,微承压水以咸水和卤水为主要水质类型;近冲洪积扇前缘水化学特征主要受岩石风化作用控制,围填海区及河口处水化学特征受海水混合作用控制,滨海平原区水化学特征主要受蒸发/结晶作用控制。(3)曹妃甸浅层地下水咸化过程主要是晚更新世以来海侵海退时期形成海洋蒸发盐经大气降水和河水多期溶滤所致,其盐分来源于海水蒸发盐,河口及围填海区地下潜水盐分主要来源于现代海水入侵。     

川东北飞仙关组鲕滩天然气地球化学特征与成因

四川盆地东北部下三叠统飞仙关组鲕滩气藏天然气烃类气体以甲烷为主,含量主要分布在75%～90%之间,C2 含量很少,为0%～0.15%,干燥系数为0.997 0～0.999 8,是典型的干气;非烃气体以H2S和CO2为主,含量分别为4.21%～16.24%和0.97%～10.41%.天然气δ13C1值为-29.0‰～-31.5‰,δ13C2值为-29.4‰～-32.4‰.多参数表明鲕滩气藏天然气是以腐泥型为主的高过成熟天然气.高含H2S的天然气分布区域与含石膏地层分布基本一致,这些H2S为飞仙关组气藏附近的石膏经热化学硫酸盐还原作用(TSR)而生成,CO2是其主要的副产物.在TSR过程中,C2 重烃气体比甲烷更容易与硫酸盐发生反应,也就是C2 重烃气体的消耗速率大于甲烷,从而导致发生TSR反应的天然气C2 含量低、H2S和CO2含量高.天然气δ13C1值与甲烷含量之间具有很好的负相关关系,而与天然气酸性系数[H2S/(H2S CnH2n 2)]具有正相关关系.根据同位素动力学的分馏效应,随着TSR的进行,烃类分子中的12C损耗速率大于13C,残留下来的烃类分子中则更加富集13C,也就是TSR反应使天然气碳同位素变重.     

A protocol for preparing subfossil chironomid head capsules (Diptera: Chironomidae) for stable isotope analysis in paleoclimate reconstruction and considerations of contamination sources

Several techniques are available to examine the isotopic composition of historic lake waters, providing data that can subsequently be used to examine environmental changes. A recently-developed technique is the stable oxygen isotope analysis of subfossil chironomid (Diptera: Chironomidae) head capsules (mostly chitin) preserved in lake sediments. This technique involves a high Temperature Conversion Elemental Analyzer (TC/EA), which has been a relatively recent addition to the suite of online peripherals for analyzing the stable isotopic composition of organic samples. The highly precise and accurate ¹⁸O/¹⁶O and D/H measurements obtainable using the TC/EA with samples in the microgram range make this instrumentation suitable for studying geochemical and biological processes. Preparation of organic samples for isotopic analysis typically requires first weighing each sample into silver/tin capsules. These capsules can introduce oxygen and hydrogen contamination (a “blank effect”), which is especially problematic for analysis of small organic samples (e.g. less than 100 μg). Here we tested tin and silver capsules from two manufacturers and a range of sizes to assess contamination to small organic samples on the TC/EA. We also assessed how a method for cleaning silver capsules affected our analysis of commercial chitin. In general, capsules made of silver have less detectible oxygen than those made of tin, and capsules from the two manufacturers varied in their detectible oxygen. There was no detectable H contamination from silver capsules. In addition to our empirical findings, we present a model demonstrating the influence that contaminant oxygen can have on the δ¹⁸O of small organic samples. Sample mass becomes an important issue for such analyses. In light of our findings, we recommend a minimum sample mass ≥50 μg (approximately 120 whole chironomid head capsules) on a TC/EA-IRMS (Delta^plus XP system). Finally, we present a detailed protocol for preparing and transferring chironomid head capsules into silver capsules that minimizes the influence of contaminant oxygen. This protocol provides the paleo-community with another potential method for reconstructing paleoenvironments.     

宁芜地区铁磷矿床形成机理探索

描述宁芜地区铁磷矿床的成矿机理。探讨了岩浆及热液铁、磷、钛、稀土等的搬运形式及成矿过程。结果表明,氢化物是成矿物质的主要迁移形式,它们迁移至地壳浅部被氧化成矿。     

Primordial hydrogen recombination dynamics with recoil upon scattering in the Ly-<Emphasis Type="Italic">α</Emphasis> line

We show that including the recoil upon scattering in the Ly-α line can lead to a noticeable acceleration of the primordial hydrogen recombination. Thus, for example, for the ΛCDM model, the decrease in the degree of ionization exceeds 1% at redshifts z = 800–1050, reaching ≈1.3% at z = 900. The corresponding corrections to the calculated cosmic microwave background power spectra reach 1.1% and 1.7% for TT and EE spectra, respectively. The radiative transfer in these calculations was treated in the quasi-stationary approximation.We have also obtained numerical solutions (in the diffusion approximation) to the nonstationary problem of radiative transfer in the Ly-α line for a partial frequency redistribution with recoil. We trace the evolution of the local line profile and the relative number of uncompensated transitions from the 2p state to the 1s state. We show that including the nonstationarity of the Ly-α line radiative transfer can lead to an additional acceleration of the primordial hydrogen recombination.     

The highly excited hydrogen b n -factors calculated

Radio recombination line intensities are functions of highly excited atom nonequilibrium populations. These populations are determined by the spontaneous, collision and induced radiation transition rates that arise from the balance equations. The population balance equations are solved in a diffusion approximation which is proved for the departure factors from LTE. Diffusion equation departure coefficients are far from LTE due to the spontaneous transition flow, found as a second-order differential equation general solution. This solution is chosen in an explicit form from a physical situation with the temperature and density determined. The background radiation induced transition rates strongly influence the population flow to the equilibrium distribution. Radio recombination line amplification coefficients are calculated for the different medium temperatures and electron densities; these coefficients permit interpretation of the line intensities in the actual experiments.     

痕量氢气连续观测仪稳定性分析

断裂带氢气浓度连续观测是获取深部构造活动的重要气体地球化学指标之一。由于断裂带岩层氢气浓度背景值较低,因此检验和分析氢气观测仪器的绝对检出限以及仪器稳定性便是选择高效能氢气浓度观测仪器的重要环节。在中条山山前断裂的夏县东郭测点开展了同一取样点相同环境的2套痕量氢气观测仪器对比实验,从记录的资料分析,两条曲线变化趋势、变化形态基本一致,但在细节上稍有差别,通过拟合分析,使用相关系数进行校正后,两条曲线基本重合。结果表明,痕量氢气自动分析仪稳定好,灵敏度高,观测结果一致,且实现了数字化,能够满足地震活动监测工作的需求。