利用测井资料分析成岩作用对储集层的影响

应用测井资料进行压实作用、孔隙演化、裂缝、矿物成分详尽分析基础上 ,结合成岩作用各个阶段对储集层性能影响的研究 ,讨论了应用测井资料分析成岩作用对储集层影响的物理基础 ,进而指出应用测井资料分析成岩作用不同阶段对储集层影响的可行性。方法为 :(1 )成岩作用早期 :应用孔隙度测井和岩性测井资料 ,通过压实曲线分析压实作用区间 ;(2 )成岩作用中期 :首先根据孔隙度测井资料分析声波孔隙度、密度 -中子测井孔隙度 ,分析次生孔隙 ,并应用交会图技术 ,确定矿物成分 ,分析胶结、交代作用形式和强度 ,然后根据泥质指示测井确定泥质含量 ,进一步利用自然伽玛能谱测井 ,尤其是Th、K含量分析粘土矿物 ;(3)成岩作用晚期 :进行次生孔隙、裂缝、颗粒成分与含量、粘土矿物分布规律研究。以上分析方法经吐哈盆地实际资料验证 ,效果良好     

Recommended Values of 239Pu, 240Pu and 239+240Pu Concentrations in Reference Material IAEA-315 (Marine Sediment) Estimated by Thermal Ionisation Mass Spectrometry, Inductively Coupled Plasma-Mass Spectrometry and Alpha Spectrometry

The recommended concentrations of ²³⁹Pu, ²⁴⁰Pu and ^239+240Pu in reference material IAEA‐315 (marine sediment) were estimated by three analytical methods: isotope dilution thermal ionisation mass spectrometry (TIMS), isotope dilution inductively coupled plasma‐mass spectrometry (ICP‐MS) and alpha spectrometry. The determination of ²³⁹Pu and ²⁴⁰Pu (^239+240Pu by alpha spectrometry) was carried out with samples from randomly selected bottles using each method. Plutonium‐238 was also measured by alpha spectrometry. A plutonium‐242 reference material was used as a spike for the quantitative analysis. The influence of ²⁴²Pu in the samples was therefore calculated; however, this contribution was less than the range of uncertainty and did not influence the final results. The obtained data were statistically analysed using variance component analysis and paired comparison. The combined standard uncertainties from “method/measurement”, “bottle” and “sub‐sample” were in the order of 3 to 6%. The main contributions to the uncertainty were from the material heterogeneity and from systematic differences between methods. Based on this study with twenty‐seven analyses using 10–14 g sample mass, concentrations of (38 ± 3) Bq kg^?1, (28 ± 3) Bq kg^?1 and (66 ± 4) Bq kg^?1 are proposed as recommended values for ²³⁹Pu, ²⁴⁰Pu and ^239+240Pu, respectively, and (9.5 ± 0.4) Bq kg^?1 for ²³⁸Pu as an information value in reference material IAEA‐315. In mass concentration units, these amount to (16.4 ± 1.2) ng kg^?1, (3.3 ± 0.4) ng kg^?1 and (0.015 ± 0.003) ng kg^?1 for ²³⁹Pu, ²⁴⁰Pu and ²³⁸Pu, respectively. The certified reference materials NIST 4350B and NIST 4354 were also analysed by TIMS for quality assurance of the method used in this study.     

Sulfur isotope measurement of sulfate and sulfide by high-resolution MC-ICP-MS

We have developed a technique for the accurate and precise determination of ³⁴S/³²S isotope ratios (δ³⁴S) in sulfur-bearing minerals using solution and laser ablation multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). We have examined and determined rigorous corrections for analytical difficulties such as instrumental mass bias, unresolved isobaric interferences, blanks, and laser ablation- and matrix-induced isotopic fractionation. Use of high resolution sector-field mass spectrometry removes major isobaric interferences from O₂⁺. Standard-sample bracketing is used to correct for the instrumental mass bias of unknown samples. Background on sulfur masses arising from memory effects and residual oxygen-tailing are typically minor (< 0.2‰, within analytical error), and are mathematically removed by on-peak zero subtraction and by bracketing of samples with standards determined at the same signal intensity (within 20%). Matrix effects are significant (up to 0.7‰) for matrix compositions relevant to many natural sulfur-bearing minerals. For solution analysis, sulfur isotope compositions are best determined using purified (matrix-clean) sulfur standards and sample solutions using the chemical purification protocol we present. For in situ analysis, where the complex matrix cannot be removed prior to analysis, appropriately matrix-matching standards and samples removes matrix artifacts and yields sulfur isotope ratios consistent with conventional techniques using matrix-clean analytes. Our method enables solid samples to be calibrated against aqueous standards; a consideration that is important when certified, isotopically-homogeneous and appropriately matrix-matched solid standards do not exist. Further, bulk and in situ analyses can be performed interchangeably in a single analytical session because the instrumental setup is identical for both. We validated the robustness of our analytical method through multiple isotope analyses of a range of reference materials and have compared these with isotope ratios determined using independent techniques. Long-term reproducibility of S isotope compositions is typically 0.20‰ and 0.45‰ (2σ) for solution and laser analysis, respectively. Our method affords the opportunity to make accurate and relatively precise S isotope measurement for a wide range of sulfur-bearing materials, and is particularly appropriate for geologic samples with complex matrix and for which high-resolution in situ analysis is critical.     

煤岩显微组分热解气相色谱特征与化学结构剖析

煤结构是目前地球化学研究领域中的一个难点，但却具有极其重要的理论及实际意义，本文采用分步热解气相色谱技术将树皮体，镜质体和丝质体分解为分子量较小的可测定的有机化合物，在此基础上，据不同温度下热解产物的组成特征来还原显微组分的化学结构，实验结果表明，煤显微组分主要由四大类官能团组成，一是热稳定性较低的NOS杂原子官能团；二是脂族（脂链、脂环）结构；三是苯、烷基苯（甲苯、二甲苯）、萘等芳香族化合物，四是热稳定性很高的难以分解的稠环芳烃。上述四类化合物集中于显微组分的不同结构简单中，树皮体和镜质体结构单元外侧主要由热稳定性较低的杂原子化合物以及分子量较小的苯和烷基苯组成，而丝质体结构单元外侧则主要以短链脂族结构为主，三组分结构核部由热稳定性很高的难以分解的稠环芳烃组成。连结核部稠环芳烃与结构单元外侧杂原子等官能团的主要是热稳定性较高的脂链结构，煤显微组分热成烃主要按结构中各官能团键的强弱随热演化程度的加深依次脱除，生成油气，基本上属平行独立依次反应机制，亦“官能团脱除型”，此外，还包括少量的长链脂族结构裂解为短链脂肪烃的“解聚”过程。     

土壤样品中贵金属活动态提取技术

介绍了土壤样品中贵金属铂、钯、金的水提取态、黏土吸附态与可交换态、有机质结合态以及铁锰氧化物结合态等不同相态的提取方法与测定方法。方法检出限为铂0.03 ng/g,钯和金0.01 ng/g。实验了铂、钯、金活动态金属各种提取液介质中痕量贵金属的稳定性、固-液分离方法、提取温度的影响及提取液的处理方法。通过在南非隐伏铂钯矿或矿化区的试验,结果表明所圈定的异常与实际矿(化)体相符,为识别隐伏贵金属铂钯矿床提供了有效信息,对寻找隐伏矿床具有一定的指导意义。     

GGR Biennial Review: Atomic Absorption,Inductively Coupled Plasma-Atomic Emission Spectrometry,Neutron Activation Analysis and X-Ray Fluorescence Spectrometry Review for 2008–2009

This review describes developments major and in trace element determination using atomic absorption spectroscopy (AAS), inductively coupled plasma-atomic emission spectrometry (ICP-AES), instrumental neutron activation analysis (INAA), and X-ray fluorescence (XRF) spectrometry that were reported in 2008 and 2009. Publication levels were comparable to those of previous years, except for XRF which showed an increase in the number of articles published in the past 2 years. In terms of number of publications and impact, the most active field was AAS, while INAA was the least active. As expected for well-established and mature methods, novel developments for all four analytical techniques were relatively sparse. For AAS, the most notable publications concerned developments in sample introduction, particularly focussing on solid samples, increasing analyte sensitivity, and higher sample throughput. For ICP-AES, publication of developments in sample introduction, remediation of matrix effects and calibration continues. Compared with past years, there was a clear focus on sample preconcentration methods, but very few publications reporting new hyphenated speciation methods. For INAA, there were several publications exploring the accuracy and robustness of the method, as well as the requirements for INAA to meet criteria for a primary method of measurement. Two other related techniques, delayed neutron activation analysis, and prompt gamma activation analysis, were also described. Hyphenated XRF techniques showed interesting developments in enabling XRF and XRD analysis on the same spot, and further work characterising and calibrating three-dimensional micro-XRF shows promising results for investigating sample heterogeneity.     

Spatial variability and temporal dynamics of surface water pCO2, ��O2/Ar and dimethylsulfide in the Ross Sea, Antarctica

We report results from two surveys of pCO₂, biological O₂ saturation (??O₂/Ar) and dimethylsulfide (DMS) in surface waters of the Ross Sea polynya. Measurements were made during early spring (November 2006-December 2006) and mid-summer (December 2005-January 2006) using ship-board membrane inlet mass spectrometry (MIMS) for high spatial resolution (i.e. sub-km) analysis. During the early spring survey, the polynya was in the initial stages of development and exhibited a rapid increase in open water area and phytoplankton biomass over the course of our ∼3 week occupation. We observed a rapid transition from a net heterotrophic ice-covered system (supersaturated pCO₂ and undersaturated O₂) to a high productivity regime associated with a Phaeocystis-dominated phytoplankton bloom. The timing of the early spring phytoplankton bloom was closely tied to increasing sea surface temperature across the polynya, as well as reduced wind speeds and ice cover, leading to enhanced vertical stratification. There was a strong correlation between pCO₂, ??O₂/Ar, DMS and chlorophyll a (Chl a) during the spring phytoplankton bloom, indicating a strong biological imprint on gas distributions. Box model calculations suggest that pCO₂ drawdown was largely attributable to net community production, while gas exchange and shoaling mixed layers also exerted a strong control on the re-equilibration of mixed layer ??₂ with the overlying atmosphere. DMS concentrations were closely coupled to Phaeocystis biomass across the early spring polynya, with maximum concentrations exceeding 100 nM.During the summer cruise, we sampled a large net autotrophic polynya, shortly after the seasonal peak in phytoplankton productivity. Both diatoms and Phaeocystis were abundant in the phytoplankton assemblages during this time. Minimum pCO₂ was less than 100 ppm, while ??O₂/Ar exceeded 30% in some regions. Mean DMS concentrations were ∼2-fold lower than during the spring, although the range of concentrations was similar between the two surveys. There was a significant correlation between pCO₂, ??O₂/Ar and Chl a across the summer polynya, but the strength of these correlations and the slope of O₂ vs. CO₂ relationship were significantly lower than during the early spring. Summertime DMS concentrations were not significantly correlated to phytoplankton biomass (Chl a), pCO₂ or ??O₂/Ar. In contrast to the early spring time, there were no clear temporal trends in summertime gas concentrations. Rather, small-scale spatial variability, likely resulting from mixing and localized sea-ice melt, was clearly evident in surface gas distributions across the polynya. Analysis of length-scale dependent variability demonstrated that much of the spatial variance in surface water gases occurred at scales of <20 km, suggesting that high resolution analysis is needed to fully capture biogeochemical heterogeneity in this system.     

Survey of historical New Zealand shellfish samples for accumulation of gymnodimine

In 1994 a major biotoxin event occurred along the east coast of the South Island, New Zealand. Gymnodimine, a unique bioactive spiroimine, was isolated and characterised from Foveaux Strait dredge oysters (Tiostrea chilensis = Ostrea chilensis) collected during this outbreak. This study reports the results of liquid chromatographic‐mass spectrometric analysis for gymnodimine in 217 samples from eight species of shellfish over the years 1993–99. Of these samples 155, covering six species of shellfish, contained detectable gymnodimine with a range in concentration from 14.8 to 23 400 μg/kg. Gymnodimine‐containing shellfish occurred at 37 of the 63 sites sampled from around New Zealand. This study demonstrates that accumulation of gymnodimine is not limited to T. chilensis and can occur in other shellfish species over much of New Zealand. Gymnodimine is a possible cause of the numerous historical biotoxin screen‐positive results.     

大试管回流消解-等离子体发射光谱／质谱法测定植物样品中多元素

采用大试管和红外加热的多孔控温消解炉的简单装置消解植物样品,电感耦合等离子体发射光谱／质谱法测定其中的主量和痕量元素,对消解温度、消解时间、消解溶剂、样品取样量等条件进行考察。用植物国家一级标准物质进行前处理及测定,验证方法的可行性,测定值与标准值基本吻合。方法不仅能同时测定B、Ba、Ca、Cd、Cu、K、Mg、Mn、Na、Ni、P、S、Zn、CoSr、Pb、Cr等元素,还适用于Hg、As挥发性元素的消解测定。方法的精密度（RSD,n=10）≤10％。     

氢化物原子荧光法测定天然水中痕量砷

水样经王水分解,在酸度10％—25％介质中,As(v)用硫脲-抗坏血酸预还原,使As(Ⅱ)与硼氢化钾溶液生成气态氢化物(AsH_3),在原子荧光光度计上测定砷量。方法简便、快速、灵敏。方法检出限为0.08μg/l,相对标准偏差(R.S.D.)为5.05％,回收率为94.3％—105.4％。