Dehydration experiments on natural omphacites: qualitative and quantitative characterization by various spectroscopic methods

A series of natural omphacites from a wide range of P, T occurrences were investigated by electron microprobe (EMP), infrared (IR)-, Mössbauer (MS)- and optical spectroscopy in the UV/VIS spectral range (UV/VIS), secondary ion mass spectrometry (SIMS) and single crystal structure refinement by X-ray diffraction (XRD) to study the influence of hydrogen loss on valence state and site occupancies of iron. In accordance with literature data we found Fe²⁺ at M1 as well as at M2, and in a first approach assigned Fe³⁺ to M1, as indicated by MS and XRD results. Hydrogen content of three of our omphacite samples were measured by SIMS. In combination with IR spectroscopy we determined an absorption coefficient: ε _i,tot = 65,000 ± 3,000 lmol_H2O ^?1 cm^?2. Using this new ε _i,tot value, we obtained water concentrations ranging from 60 to 700 ppm H₂O (by weight). Hydrogen loss was simulated by stepwise heating the most water rich samples in air up to 800°C. After heat treatment the samples were analyzed again by IR, MS, UV/VIS, and XRD. Depending on the type of the OH defect, the grade of dehydration with increasing temperature is significantly different. In samples relatively poor in Fe³⁺ (<0.1 Fe³⁺ pfu), hydrogen associated with vacancies at M2 (OH bands around 3,450 cm^?1) starts to leave the structure at about 550°C and is completely gone at 780°C. Hydrogen associated with Al³⁺ at the tetrahedral site (OH bands around 3,525 cm^?1, Koch-Müller et al., Am Mineral, 89:921–931, 2004) remains completely unaffected by heat treatment up to 700°C. But all hydrogen vanished at about 775°C. However, this is different for a more Fe³⁺-rich sample (0.2 Fe³⁺ pfu). Its IR spectrum is characterized by a very intense OH band at 3,515 cm^?1 plus shoulder at 3,450 cm^?1. We assign this intense high-energy band to vibrations of an OH dipole associated with Fe³⁺ at M1 and a vacancy either at M1 or M2. OH release during heating is positively correlated with decrease in Fe²⁺ and combined with increase in Fe³⁺. That dehydration is correlated with oxidation of Fe²⁺ is indirectly confirmed by annealing of one sample in a gas mixing furnace at 700°C under reducing conditions keeping almost constant OH^? content and giving no indication of Fe²⁺-oxidation. Obtained data indicate that in samples with a relatively high concentration of Fe²⁺ at M2 and low-water concentrations, i.e., at a ratio of Fe^{2+ M2}/H > 10 dehydration occurs by iron oxidation of Fe²⁺ exclusively at the M2 site following the reaction: \( {\left[ {{\text{Fe}}^{{{\text{2 + [ M2]}}}}{\text{OH}}^{ - } } \right]} = {\left[ {{\text{Fe}}^{{{\text{3 + [ M2]}}}} {\text{O}}^{{{\text{2}} - }} } \right]} + {\text{1/2}}\;{\text{H}}_{{\text{2}}} \uparrow . \) In samples having relatively low concentration of Fe²⁺ at M2 but high-water concentrations, i.e., ratio of Fe^{2+ M2}/H < 5.0 dehydration occurs through oxidation of Fe²⁺ at M1.     

高效液相色谱-紫外光谱分析氢醌-双(β-羟乙基)醚

建立了高效液相色谱-紫外光谱法测定聚氨酯扩链剂氢醌-双(β-羟乙基)醚(HQEE)工业品中HQEE主含量和对苯二酚残留的方法。在氰基柱上,以甲醇-水-1%乙酸溶液(体积比10∶50∶40)为流动相,流速1.0 mL/min时,HQEE、对苯二酚及其他相关杂质得到良好分离,紫外光谱285 nm检测。方法简便、快捷,结果准确可靠,在工业生产中可有效地指导HQEE合成过程的质量控制。     

Distribution of phthalate esters in the groundwater of Jianghan plain, Hubei, China

Samples of groundwater were collected from 17 sites in the Jianghan plain in July 2007. Sixteen phthalate esters (PAEs) were detected in samples collected by using solid-phase extraction (SPE)-gas chromatography (GC). The results show that there were one or several PAEs in all the samples, and the concentrations of total PAEs ranged from 80.12 to 1882.18 ng/L. Four PAEs, i.e. di-isobutyl phthalate (DIBP), di-n-butyl phthalate (DBP), bis (2-ethoxyethyl) phthalate (BEEP) and di (2-ethylhexyl) phthalate DEHP) were the dominant species. Among these, DIBP, DBP and DEHP concentrations were closely related to the water supply from the Yangtze River, Hanjiang River and Honghu Lake. However, the distribution of BEEP was irregular, which may be due to the application of some kind of products containing BEEP in the related areas. PAE distribution was irrelevant to the electrical conductivity and sample depth.     

一种适用于沉积有机质族组分分离的微型柱色谱法

硅胶-氧化铝柱色谱是广泛采用的沉积有机质组分分离方法。但在常规柱色谱分离方法中,存在吸附剂、溶剂使用量过大、烷烃/芳烃组分交叉严重等问题。介绍一种微型柱色谱分离法,其分离效果与常规方法的效果基本相同或略有改善,吸附剂用量与样品的比例由100～250降低为25～50,洗脱溶剂与样品的比例由1800～4600降低至250～500。同时,操作程序进一步简化,分析成本和对环境的污染程度大幅度降低。     

离子色谱法测定五氧化二铌和五氧化二钽中痕量氟氯和硫酸根离子的前处理方法

采用马弗炉将样品与NaOH混合进行熔融煅烧，热去离子水提取、离心、稀释后过OnGuard Ⅱ H柱和过滤膜进行前处理，抑制型电导离子色谱法检测，测定了Ta2O5和Nb2O5的氟离子、氯离子和硫酸根离子。该方法对三种被测阴离子的检测限（s／N=3）在0．15～0．70μg／g（以固体样品实际浓度计）或0．136～0．623μg／L（以溶液浓度计），标准曲线线性范围均在两个数量级以上，方法的精密度（RSD，n=7）小于5．46％，回收率为88％～106％，具有灵敏度高、选择性好、重现性佳、对环境友好等特点，用于实际样品的检测，结果令人满意。     

顶空气相色谱法测定地层水中的苯系物

利用极性聚乙二醇弹性石英毛细管柱分离苯系物，在线顶空气相色谱法测定地层水中的苯系物。讨论了色谱柱、载气压力、液相体积、顶空压力、顶空加热温度等因素对测定的影响。该方法实现了地层水中苯、甲苯、乙苯、对二甲苯、间二甲苯、邻二甲苯、异丙苯、苯乙烯等各组分的完全分离，方法的检出限在0．07—0．23μg／L，8次测定相对标准偏差在2．98％-4．91％，加标回收率为95．2％-104％。方法可用于地层水等液体样品中苯系物的测定。     

新疆库米什盆地硝酸盐类矿床成矿离子迁移规律及成矿模型

为了深入认识库米什盆地硝酸盐矿床成矿离子的空间分布特征、表层沉积物中硝酸盐含量较高的原因,以盆地硝酸盐矿床为研究对象,开展研究区内各类补给水样和沉积物样可溶性盐类物质化学组成的定量分析研究;结合野外地质踏勘工作,探讨研究区硝酸盐矿床成矿离子的迁移规律,初步建立盆地硝酸盐矿床沉积成矿作用模型.结果表明,K+、Na+、NO...     

气相色谱法测定地下水中六六六结果的不确定度评定

依照<测量不确定度评定与表示>,对气相色谱法测定地下水中六六六(HCH)四种单体结果进行了不确定度评定.分析了测量过程中引入的不确定度来源,包括提取液体积的量取、样品提取溶液的定容体积、分析仪器的进样量、标准系列溶液的测量以及仪器重复测定等分量引入不确定度及其各参数的采集和计算方法,最后合成标准不确定度,通过乘以95%概率下的扩展因子2,获得测量结果的扩展不确定度.     

High‐Precision,High‐Accuracy Oxygen Isotope Measurements of Zircon Reference Materials with the SHRIMP‐SI

Analytical protocols for SHRIMP‐SI oxygen isotope analysis (δ¹⁸O) of a suite of zircon reference materials (RMs) are presented. Data reduction involved a robust estimate of uncertainties associated with the individual spot as well as for groups where the spot data are combined. The repeatability of δ¹⁸O measurements is dependent on both the analytical conditions and the choice of the primary reference material. Under optimised conditions, repeatability was often better than 0.4‰ (2s) allowing sample uncertainties to be obtained to better than 0.2‰ (at 95% confidence limit). Single spot uncertainty combined the within‐spot precision with the scatter associated with repeated measurements of the primary zircon reference material during a measurement session. The uncertainty for individual spots measured under optimised conditions was between 0.3 and 0.4‰ (at 95% confidence). The analytical protocols described were used to assess a variety of zircon RMs that have been used for geochronology and for which laser fluorination oxygen isotope data are available (Temora 2, FC1, R33, QGNG and Ple?ovice), as well as zircons that have been used as RMs for trace element or other types of determination (Mud Tank, Monastery, 91500, AS57, AS3, KIM‐5, OG1, SL13, CZ3 and several other Sri Lankan zircons). Repeated analyses over nine sessions and seven different mounts show agreement within analytical uncertainty for Temora 2, FC1, R33, QGNG, Ple?ovice and 91500, when normalised to Mud Tank. For existing ion microprobe mounts with these materials, an appropriate δ¹⁸O can be determined. However, care should be taken when using zircons from the Duluth Complex (i.e., FC1, AS57 and AS3) as reference materials as our data indicated an excess scatter on δ¹⁸O values associated with low‐U zircon grains.     

Copper Isotopic Analysis in Geological and Biological Reference Materials by MC‐ICP‐MS

The characterisation of relative copper isotope amount ratios (δ⁶⁵Cu) helps constrain a variety of geochemical processes occurring in the geosphere, biosphere and hydrosphere. The accurate and precise determination of δ⁶⁵Cu in matrix reference materials is crucial in the effort to validate measurement methods. With the goal of expanding the number and variety of available geological and biological materials, we have characterised the δ⁶⁵Cu values of ten reference materials by MC‐ICP‐MS using C‐SSBIN model for mass bias correction. SGR‐1b (Green River shale), DOLT‐5 (dogfish liver), DORM‐4 (fish protein), TORT‐3 (lobster hepatopancreas), MESS‐4 (marine sediment) and PACS‐3 (marine sediment) have for the first time been characterised for δ⁶⁵Cu. Additionally, four reference materials (with published δ⁶⁵Cu values) have been characterised: BHVO‐1 (Hawaiian basalt), BIR‐1 (Icelandic basalt), W‐2a (diabase) and Seronorm? Trace Elements Serum L‐1 (human serum). The reference materials measured in this study possess complex and varied matrices with copper mass fractions ranging from 1.2 µg g^?1 to 497 µg g^?1 and δ⁶⁵Cu values ranging from ?0.20‰ to 0.52‰ with a mean expanded uncertainty of ± 0.07‰ (U, k = 2), covering much of the natural copper isotope variability observed in the environment.