Interaction of copper with fatty acids in Soxhlet extraction and its influence     

Ming Jin  Yanqing Xia  Tianzhu Lei  Junli Qiu  Rui Zhang 《中国地球化学学报》2008,27(2):157-160

Treatment with metallic copper for the removal of elemental sulfur from bitumen extracted from sedimentary rocks or petroleum is the most widely used method. Little attention has been paid, however, to its disadvantages. It was observed that copper can interact with some polar organic substances during conventional sulfur removal, which can strongly influence the quantitative and qualitative determination of bitumen, as has been confirmed by interaction of long-chain fatty acids with copper. The copper soap generated was analyzed by element analysis, inductively coupled plasma optical emission spectrometry （ICP-OES）, thermal analysis （TG-DSC） and Fourier Transform Infrared spectroscopy （FFIR）. Mechanism of the interaction was investigated and elucidated. Our experimental results would necessitate improvement of the present method for sulfur removal and/or a search for a new one.  相似文献   

Laser ablation coupled with ICP-MS applied to U–Pb zircon geochronology: A review of recent advances   总被引：2，自引：2，他引：0  

Alain Cocherie  Michle Robert 《Gondwana Research》2008,14(4):597

Improvements in the technology of laser ablation and ICP-MS instruments make LA-MC-ICPMS a rapid, precise and accurate method for U–Pb zircon geochronology. In this review we describe the main stages of the evolution of this in situ approach from the early 1990s to the present time. Some key points have been progressively improved. The crater size has been reduced to achieve real in situ measurements. The laser wavelength has been reduced as well as the duration of each pulse in order to lower inter-element fractionation. The blank from the gas has to be lowered as far as possible. Double focusing instruments and magnetic field sectors allow flat-topped peaks required for precise isotope ratio measurement to be obtained. The use of a multi-ion counting system significantly improves the sensitivity of the method and the static mode of integration favours the precision of measurement of the transient signal originating from a noisy laser ablated particle beam.Combining the use of a 213 nm UV laser and a MC-ICPMS equipped with a multi-ion counting system operating in static mode, the common precisions achieved for the key ratios ²⁰⁷Pb/²⁰⁶Pb and ²⁰⁶Pb/²³⁸U are better than 1% and 3% (2σ) respectively, including error propagation associated with standard normalization. Until now, the use of a zircon standard has remained necessary to ensure the accuracy of the calculated age. A strategy for common-Pb correction is proposed according to the age of the zircon and according to the Th/U ratio of the grains. After recording sixteen to twenty spot analyses the precision usually achieved on the age is about 1% and even significantly better for Proterozoic samples.In order to show the performance achieved by modern LA-MC-ICPMS geochronology, we tested four zircon samples covering a wide age range from 290 to 2440 Ma. These new age determinations can be compared in term of precision and accuracy since they have already been dated by reference methods (ID-TIMS and SHRIMP). Further developments in the technology of ion counters equipping modern MC-ICPMS and in laser systems will certainly be applied to a large field of geochronology studies in the near future as an alternative to SIMS for in situ age determination.  相似文献   

U-Pb Age Determination for Seven Standard Zircons using Inductively Coupled Plasma–Mass Spectrometry Coupled with Frequency Quintupled Nd-YAG (λ = 213 nm) Laser Ablation System: Comparison with LA-ICP-MS Zircon Analyses with a NIST Glass Reference Material     

Yuji Orihashi    Shun'ichi Nakai  Takafumi Hirata 《Resource Geology》2008,58(2):101-123

This paper evaluates the analytical precision, accuracy and long‐term reliability of the U‐Pb age data obtained using inductively coupled plasma–mass spectrometry (ICP‐MS) with a frequency quintupled Nd‐YAG (λ = 213nm) laser ablation system. The U‐Pb age data for seven standard zircons of various ages, from 28 Ma to 2400 Ma (FCT, SL13, 91500, AS3, FC1, QGNG and PMA7) were obtained with an ablation pit size of 30 μm diameter. For ²⁰⁷Pb/²⁰⁶Pb ratio measurement, the mean isotopic ratio obtained on National Institute of Standards and Technology (NIST) SRM610 over 4 months was 0.9105 ± 0.0014 (n = 280, 95% confidence), which agrees well with the published value of 0.9096. The time‐profile of Pb/U ratios during single spot ablation showed no significant difference in shape from NIST SRM610 and 91500 zircon standards. These results encouraged the use of the glass standard as a calibration standard for the Pb/U ratio determination for zircons with shorter wavelength (λ = 213 nm) laser ablation. But ²⁰⁶Pb/²³⁸U and ²⁰⁷Pb/²³⁵U ages obtained by this method for seven zircon standards are systematically younger than the published U‐Pb ages obtained by both isotope dilution–thermal ionization mass spectrometry (ID‐TIMS) and sensitive high‐resolution ion‐microprobe (SHRIMP). Greater discrepancies (3–4% younger ages) were found for the ²⁰⁶Pb/²³⁸U ages for SL13, AS3 and 91500 zircons. The origin of the differences could be heterogeneity in Pb/U ratio on SRM610 between the different disks, but a matrix effect accuracy either in the ICP ion source or in the ablation‐transport processes of the sample aerosols cannot be neglected. When the ²⁰⁶Pb/²³⁸U (= 0.2302) newly defined in the present study is used, the measured ²⁰⁶Pb/²³⁸U and ²⁰⁷Pb/²³⁵U ages for the seven zircon standards are in good agreement with those from ID‐TIMS and SHRIMP within ±2%. This suggests that SRM610 glass standard is suitable for ICP‐MS with laser ablation sampling (LA‐ICP‐MS) zircon analysis, but it is necessary to determine the correction factor for ²⁰⁶Pb/²³⁸U by measuring several zircon standards in individual laboratories.  相似文献   

Zircon M257 ‐ a Homogeneous Natural Reference Material for the Ion Microprobe U‐Pb Analysis of Zircon     

Lutz Nasdala  Wolfgang Hofmeister  Nicholas Norberg  James M. Martinson  Fernando Corfu  Wolfgang Dörr  Sandra L. Kamo  Allen K. Kennedy  Andreas Kronz  Peter W. Reiners  Dirk Frei  Jan Kosler  Yusheng Wan  Jens Götze  Tobias Häger  Alfred Kröner  John W. Valley 《Geostandards and Geoanalytical Research》2008,32(3):247-265

We introduce and propose zircon M257 as a future reference material for the determination of zircon U‐Pb ages by means of secondary ion mass spectrometry. This light brownish, flawless, cut gemstone specimen from Sri Lanka weighed 5.14 g (25.7 carats). Zircon M257 has TIMS‐determined, mean isotopic ratios (2s uncertainties) of 0.09100 ± 0.00003 for ²⁰⁶pb/²³⁸U and 0.7392 ± 0.0003 for ²⁰⁷pb/²³⁵U. Its ²⁰⁶pb/²³⁸U age is 561.3 ± 0.3 Ma (unweighted mean, uncertainty quoted at the 95% confidence level); the U‐Pb system is concordant within uncertainty of decay constants. Zircon M257 contains ～ 840 μg g^?1 U (Th/U ～ 0.27). The material exhibits remarkably low heterogeneity, with a virtual absence of any internal textures even in cathodoluminescence images. The uniform, moderate degree of radiation damage (estimated from the expansion of unit‐cell parameters, broadening of Raman spectral parameters and density) corresponds well, within the “Sri Lankan trends”, with actinide concentrations, U‐Pb age, and the calculated alpha fluence of 1.66 × 10¹⁸ g^?1. This, and a (U+Th)/He age of 419 ± 9 Ma (2s), enables us to exclude any unusual thermal history or heat treatment, which could potentially have affected the retention of radiogenic Pb. The oxygen isotope ratio of this zircon is 13.9%o VSMOW suggesting a metamorphic genesis in a marble or calc‐silicate skarn.  相似文献   

酸性矿山废水中生物成因次生高铁矿物的形成及环境工程意义   总被引：10，自引：1，他引：9  

周立祥 《地学前缘》2008,15(6)

酸性矿山废水(acid mine drainage,AMD)是一类pH低并含有大量有毒金属元素的废水。AMD及受其影响的环境中次生高铁矿物类型主要包括羟基硫酸高铁矿物(如黄铁矾和施威特曼石等)和一些含水氧化铁矿物(如针铁矿和水铁矿等),而且这些矿物在不同条件下会发生相转变,如施氏矿物向针铁矿或黄铁矾矿物相转化。基于酸性环境中生物成因次生矿物的形成会"自然钝化"或"清除"废水中铁和有毒金属这一现象所获得的启示,提出利用这些矿物作为环境吸附材料去除地下水中砷,不但吸附量大(如施氏矿物对As的吸附可高达120mg/g),而且可直接吸附As(III),还几乎不受地下水中其他元素影响。利用AMD环境中羟基硫酸高铁矿物形成的原理,可将其应用于AMD石灰中和主动处理系统中,构成"强化微生物氧化诱导成矿-石灰中和"的联合主动处理系统,以提高AMD处理效果和降低石灰用量。利用微生物强化氧化与次生矿物晶体不断生长的原理构筑生物渗透性反应墙(PRB)并和石灰石渗透沟渠耦联,形成新型的AMD联合被动处理系统,这将有助于大幅度增加处理系统的寿命和处理效率。此外,文中还探讨了上述生物成因矿物形成在AMD和地下水处理方面应用的优点以及今后需要继续研究的问题。  相似文献   

Rate constants for the reactions of the NO3 radical with HCOOH/HCOO− and CH3COOH/CH3COO− in aqueous solution between 278 and 328 K     

M. Exner  H. Herrmann  R. Zellner 《Journal of Atmospheric Chemistry》1994,18(4):359-378

The kinetics of the aqueous phase reactions of NO₃ radicals with HCOOH/HCOO^– and CH₃COOH/CH₃COO^– have been investigated using a laser photolysis/long-path laser absorption technique. NO₃ was produced via excimer laser photolysis of peroxodisulfate anions (S₂O ₈ ^2– ) at 351 nm followed by the reactions of sulfate radicals (SO ₄ ^– ) with excess nitrate. The time-resolved detection of NO₃ was achieved by long-path laser absorption at 632.8 nm. For the reactions of NO₃ with formic acid (1) and formate (2) rate coefficients ofk ₁=(3.3±1.0)×10⁵ l mol^–1 s^–1 andk ₂=(5.0±0.4)×10⁷ l mol^–1 s^–1 were found atT=298 K andI=0.19 mol/l. The following Arrhenius expressions were derived:k ₁(T)=(3.4±0.3)×10¹⁰ exp[–(3400±600)/T] l mol^–1 s^–1 andk ₂(T)=(8.2±0.8)×10¹⁰ exp[–(2200±700)/T] l mol^–1 s^–1. The rate coefficients for the reactions of NO₃ with acetic acid (3) and acetate (4) atT=298 K andI=0.19 mol/l were determined as:k ₃=(1.3±0.3)×10⁴ l mol^–1 s^–1 andk ₄=(2.3±0.4)×10⁶ l mol^–1 s^–1. The temperature dependences for these reactions are described by:k ₃(T)=(4.9±0.5)×10⁹ exp[–(3800±700)/T] l mol^–1 s^–1 andk ₄(T)=(1.0±0.2)×10¹² exp[–(3800±1200)/T] l mol^–1 s^–1. The differences in reactivity of the anions HCOO^– and CH₃COO^– compared to their corresponding acids HCOOH and CH₃COOH are explained by the higher reactivity of NO₃ in charge transfer processes compared to H atom abstraction. From a comparison of NO₃ reactions with various droplets constituents it is concluded that the reaction of NO₃ with HCOO^– may present a dominant loss reaction of NO₃ in atmospheric droplets.  相似文献   

A preliminary study of the carbon-isotopic content of ambient formic acid and two selected sources: Automobile exhaust and formicine ants   总被引：2，自引：0，他引：2  

Bryan J. Johnson  George A. Dawson 《Journal of Atmospheric Chemistry》1993,17(2):123-140

Relatively large quantities (1 mg) of formic acid have been collected from the atmosphere and subjected to carbon-isotopic analysis, as a means of source discrimination. Ambient formic acid was captured on Ca(OH)₂-treated filters using a high-volume sampler. The collection method was not only efficient (>96%), but also appears to have low artifact production.Most of the samples (36 out of 52) were collected over a two-year period at the summit of Mount Lemmon, Arizona, where a strong seasonality in HCOOH mixing ratio was observed (0.2 ppb during winter months to 1.5 ppb in the summer). Other collection sites included the Oregon coast, Colorado Rockies, urban Tucson, and the North Dakota prairie. The carbon-13 content of atmospheric HCOOH was found to be have little variation (–18 to –25), regardless of location or season. This is consistent with a single dominant source of formic acid. The carbon-14 measurements of 6 Mount Lemmon samples showed high levels of modern carbon (93–113% modern).The emissions from formicine ants and automobile combustion were selected as two other potential sources for isotopic analysis. The HCOOH collected from auto exhaust was much more depleted in¹³C than the atmospheric samples, with a ¹³C of –28.0 and –48.6 from a leaded and unleaded automobile, respectively. Formicine ants, on the other hand, ranged from –17.2 to –20.6.  相似文献   

Kinetics of redox cycling of iron coupled with fulvic acid     

Yiwei Deng  Werner Stumm 《Aquatic Sciences - Research Across Boundaries》1993,55(2):103-111

The kinetics of conversion of iron(III) (hydr)oxides to ferrous iron mediated by fulvic acid have been investigated in order to improve the understanding of the redox cycling of iron at the oxic-anoxic boundary in natural waters. Under the conditions similar to natural waters, fulvic acid is able to reduce the iron(III) (hydr)oxide. The kinetics of the reaction depend on the reactivity of iron(III) (hydr)oxides and the reducing power of the fulvic acid. The rate of reaction is 60 nm/h obtained under following conditions: total concentration of Fe(III) 1.0 × 10^–4 M, pH 7.5, fulvic acid 5 mg/L. The rate is considered as a net result of reduction and oxidation in the > Fe^III-OH/Fe(II) wheel coupled with fulvic acid. In a real natural water system, reductants other than fulvic acid may be of importance. The results obtained in the laboratory, however, provide evidence that the Fe(OH)₃(s)/Fe(II) redox couple is able to act as an electron-transfer mediator for the oxidation of natural organic substances, such as fulvic acid by molecular oxygen either in the absence of microorganisms or as a supplement to microbial activity.  相似文献   

北大别饶拔寨石榴辉石岩P-T-t轨迹及其构造意义     

闫方超  刘庆  马雪盈  何苗 《岩石学报》2021,37(8):2579-2598

P-T-t轨迹作为变质岩的重要研究方法之一，对揭示岩石的构造演化过程具有重要意义。北大别饶拔寨镁铁-超镁铁岩形成的构造环境和就位过程长期以来尚存争议。本文通过岩相学观察、矿物化学研究和温压计计算，揭示出饶拔寨石榴辉石岩经历了四个变质演化阶段：1）超高压变质阶段（M1）：主要根据石榴子石中金红石的出溶，单斜辉石中石英的出溶和磷灰石中不透明矿物的出溶，结合前人研究，认为饶拔寨石榴辉石岩经历过超高压变质阶段（≥2.5GPa）；2）高压麻粒岩相阶段（M2）：矿物组合为石榴子石（变斑晶）和单斜辉石（基质）+斜长石（基质），记录的温压条件为T=648~700℃，P=1.47~1.94GPa；3）中压麻粒岩相阶段（M3）：以石榴子石外围发育的主要由斜方辉石+斜长石组成的内圈"白眼圈"为特征，形成的温压条件为T=781~796℃，P=0.92~0.98GPa；4）角闪岩相阶段（M4）：以石榴子石变斑晶周围发育的外圈"白眼圈"为特征，其矿物组合为角闪石+斜长石的后成合晶，形成的温压条件为T=663~685℃，P=0.50~0.58GPa。石榴辉石岩的锆石SIMS U-Pb定年得到了3组不同的交点年龄，分别为208.1~202.1Ma、227.6Ma和817.7Ma。根据锆石包裹体中角闪石+斜长石的组合，推断208.1~202.1Ma代表了角闪岩相变质年龄的下限，227.6Ma则是高压麻粒岩相的下限年龄，而新元古代年龄（817.7Ma）与区域上的变质岩原岩年龄一致，可能代表了其原岩年龄。结合前人研究，饶拔寨石榴辉石岩记录了顺时针的P-T-t轨迹，揭示了板片俯冲（超高压变质）-碰撞-折返（降压升温过程，~227Ma）-抬升（降压降温过程，208~202Ma）的完整过程。  相似文献   

Acid leaching of ash and coal: Time dependence and trace element occurrences     

Mehtap Paul  Meryem Seferinoğlu  Gul Asiye Ayçık  Åke Sandström  Michael L. Smith  Jan Paul 《International Journal of Mineral Processing》2006

The leaching of coal and coal/asphaltite/wood-ashes in sulfuric acid (pH 1.0, 25 °C, S/L, 1:10) was studied as a function of time; acid consumption and extracted metal concentrations are presented. Whole coals consumed acid rapidly during the first few minutes, followed by slow acid consumption. Wood-, lignite-, and asphaltite-ashes consumed acid in two stages, the rapid phase extending < 30 min and the slow phase extended up to 10 days. The rapid phase was dominated by the dissolution of Ca, K and Mg ions for wood-ash, by Ca, Al and Mg ions for lignite-ash and Ca and Mg ions for asphaltite-ash. The sulfur concentration in solution and the concentrations of Ca, Fe, K, Mg, Na, P, Al and Mn in the aqueous phase verified the neutralizing capacity of the untreated ashes as well as the formation of insoluble sulfates in the residues. The slow phase kinetics differed for different fuels and exhibited leaching of several abundant elements—Fe, Al, K, Na and Mn. Trace elements (Ba, Cd, Co, Cr, Cu, Mo, Ni, Pb, Th, U, V, Zn) sometimes required up to 32 h for maximal extraction from ashes. Suggestions are presented regarding the chemical nature of trace elements in the untreated coals and ashes and suitable residence times for economical industrial processes. We think it possible to combine bacteriological oxidation of sulfidic concentrates of acid leaching from ash of various qualities or even whole coals.  相似文献