On the pH-dependent formation constants of iron(III)-sulfur(IV) transient complexes

An experimental study is described of Fe(III)-S(IV) formation constants measured as a function of pH (1–3), ionic strength (0.2–0.5 M) and [Fe(III)] _T (2.5–5.0×10^–4 M) using a continuous-flow spectrophotometric technique to make observations 160 ms after mixing. Preliminary experiments using pulse-accelerated-flow (PAF) spectrophotometry to measure rate constants on a microsecond timescale are also described. The conditional formation constant at 25 °C can be modeled with the following equation: {ie307-1} where {ie307-2}K ₇ andK ₈ can be interpreted as intrinsic constants for the coordination of HSO ₃ ^– by FeOH²⁺ and Fe³⁺, respectively, but until further evidence is obtained they should be regarded as fitting constants. PAF spectrophotometry showed that the initial reaction of Fe(III) with S(IV) (pH 2.0) is characterized by a second-order rate constant of 4×10⁶ M^–1 s^–1 which is comparable to rate of reaction of FeOH²⁺ with SO ₄ ^2– . However, the PAF results should be regarded as preliminary since unexpected features in the initial data indicate that the reaction may be more complex than expected.     

Carbon, sulfur and O2 across the Permian–Triassic boundary

A model for the carbon and sulfur cycles across the Permian–Triassic boundary has been constructed from carbon and sulfur isotopic data. Results indicate a drop in global organic matter burial, the formation of an anoxic deep ocean, and a large drop in atmospheric oxygen over the time span 270 to 240 Ma. Much of these changes were probably due to a drop in terrestrial productivity and preservation and an increase in global aridity.     

Origin of the Nchanga copper–cobalt deposits of the Zambian Copperbelt

The Zambian Copperbelt forms the southeastern part of the 900-km-long Neoproterozoic Lufilian Arc and contains one of the world’s largest accumulations of sediment-hosted stratiform copper mineralization. The Nchanga deposit is one of the most significant ore systems in the Zambian Copperbelt and contains two major economic concentrations of copper and cobalt, hosted within the Lower Roan Group of the Katangan Supergroup. A Lower Orebody (copper only) and Upper Orebody (copper and cobalt) occur towards the top of arkosic units and within the base of overlying shales. The sulfide mineralogy includes pyrite, bornite, chalcopyrite, and chalcocite, although in the Lower Orebody, sulfide phases are partially or completely replaced by malachite and copper oxides. Carrollite is the major cobalt-bearing phase and is restricted to fault-propagation fold zones within a feldspathic arenite. Hydrothermal alteration minerals include dolomite, phlogophite, sericite, rutile, quartz, tourmaline, and chlorite. Quartz veins from the mine sequence show halite-saturated fluid inclusions, ranging from ~31 to 38 wt% equivalent NaCl, with homogenisation temperatures (Th_TOT) ranging between 140 and 180°C. Diagenetic pyrites in the lower orebody show distinct, relatively low δ ³⁴S, ranging from −1 to −17‰ whereas arenite- and shale-hosted copper and cobalt sulfides reveal distinctly different δ ³⁴S from −1 to +12‰ for the Lower Orebody and +5 to +18‰ for the Upper Orebody. There is also a clear distinction between the δ ³⁴S mean of +12.1±3.3‰ (n=65) for the Upper Orebody compared with +5.2±3.6‰ (n=23) for the Lower Orebody. The δ ¹³C of dolomites from units above the Upper Orebody give δ ¹³C values of +1.4 to +2.5‰ consistent with marine carbon. However, dolomite from the shear-zones and the alteration assemblages within the Upper Orebody show more negative δ ¹³C values: −2.9 to −4.0‰ and −5.6 to −8.3‰, respectively. Similarly, shear zone and Upper Orebody dolomites give a δ ¹⁸O of +11.7 to +16.9‰ compared to Lower Roan Dolomites, which show δ ¹⁸O of +22.4 to +23.0‰_. Two distinct structural regimes are recognized in the Nchanga area: a weakly deformed zone consisting of basement and overlying footwall siliciclastics, and a moderate to tightly folded zone of meta-sediments of the Katangan succession. The fold geometry of the Lower Roan package is controlled by internal thrust fault-propagation folds, which detach at the top of the lowermost arkose or within the base of the overlying stratigraphy and show vergence towards the NE. Faulting and folding are considered to be synchronous, as folding predominantly occurred at the tips of propagating thrust faults, with local thrust breakthrough. The data from Nchanga suggests a strong link between ore formation and the development of structures during basin inversion as part of the Lufilian Orogeny. Sulfides tend to be concentrated within arenites or coarser-grained layers within shale units, suggesting that host-rock porosity and possibly permeability played a role in ore formation. However, sulfides are also commonly orientated along, but not deformed by, a tectonic fabric or hosted within small fractures that suggest a significant role for deformation in the development of the mineralization. The ore mineralogy, hydrothermal alteration, and stable isotope data lend support to models consistent with the thermochemical reduction of a sulfate- (and metal) enriched hydrothermal fluid, at the site of mineralization. There is no evidence at Nchanga for a contribution of bacteriogenic sulfide, produced during sedimentation or early diagenesis, to the ores.Electronic Supplementary Material Supplementary material is available for this article at and is accessible for authorized users.Editorial handling: H. Frimmel     

平湖油气田凝析油回注油藏对开发效果影响机理研究

凝析油回注油藏是平湖油气田开发过程中为应对海底输油管线而采取的一种工程应急措施。凝析油回注油藏会引起油层内流体渗流特征的变化，并进而影响油井恢复生产后的开发指标。从室内物理模拟实验和油藏数值模拟两方面开展凝析油回注油藏的影响效果分析，并根据研究结果提出合理的回注方式，不仅从机理上为解决海上油气田开发工程中所遇类似突发事件的处理提供了依据，而且在物理模拟实验和油藏数值模拟研究相结合对油藏基础研究方面提供一些重要的结论。     

北秦岭古聚会带壳幔再循环

以同构造期代表古洋壳残片的蛇绿岩及产于古岛弧的玄武岩为基础，通过Ｎｄ，Ｐｂ同位素与微量元素示踪及岩浆源区分析，揭示出北秦岭元古宙上地幔以强亏损（εＮｄ（ｔ）＋６．３～＋７．３）和高的Ｙｂ／Ｈｆ，Ｎｂ／Ｌａ和Ｔｈ／Ｌａ比值为特征，北秦岭地壳和上地幔明显具有Ｐｂ同位素比值高的特征．北秦岭丹凤群岛弧火山岩、二郎坪群弧后玄武岩以及松树沟蛇绿岩中变拉斑玄武岩εＮｄ（ｔ）、放射成因Ｐｂ同位素、Ｙ／Ｔｂ和Ｔｉ－ＭｇＯ研究表明，本区玄武岩存在两类性质不同的岩浆源．一类与亏损的北秦岭岩石圈上地幔源区有关；另一类与携带海洋沉积物的洋壳板块俯冲参与有关．由此，论证了北秦岭古聚会带壳幔之间物质再循环     

Transformation of arsenic compounds in modern intertidal sediments of Iriomote Island, Japan

The arsenic accumulation process in intertidal sediments of Iriomote Island, Japan, is analyzed as a naturally balanced arsenic-fixation system. Major and minor element chemistry is analyzed by X-ray fluorescence photometry, mineralogy is investigated by X-ray diffractometry, and four arsenic compounds are characterized by hydrogen-generated atomic absorption photometry. It is found that arsenic is accumulated by iron hydroxides/oxides precipitated following the decomposition of humic acids in the shallower sediment, and is subsequently incorporated into iron sulfide minerals at depth. The arsenic is immobile during incorporation into arsenic-bearing phases, suggesting that arsenic is unlikely to be released into the porewater under natural conditions in early diagenesis. The formation and decomposition of arsenic-bearing organic compounds appear to be associated with the formation and decomposition of arsenic in oxyhydroxides/oxides, suggesting that microbial activity may play an important role in controlling the behavior of arsenic and arsenic-bearing phases in the sediment column.     

Highly Oxidized Magma and Fluid Evolution of Miocene Qulong Giant Porphyry Cu‐Mo Deposit,Southern Tibet,China

The Miocene Qulong porphyry Cu‐Mo deposit, which is located at the Gangdese orogenic belt of Southern Tibet, is the largest porphyry‐type deposit in China, with confirmed Cu ～10 Mt and Mo ～0.5 Mt. It is spatially and temporally associated with multiphase granitic intrusions, which is accompanied by large‐scale hydrothermal alteration and mineralization zones, including abundant hydrothermal anhydrite. In addition to hydrothermal anhydrite, magmatic anhydrite is present as inclusions in plagioclase, interstitial minerals between plagioclase and quartz, and phenocrysts in unaltered granodiorite porphyry, usually in association with clusters of sulfur‐rich apatite in the Qulong deposit. These observations indicate that the Qulong magma‐hydrothermal system was highly oxidized and sulfur‐rich. Three main types of fluid inclusions are observed in the quartz phenocrysts and veins in the porphyry: (i) liquid‐rich; (ii) polyphase high‐salinity; and (iii) vapor‐rich inclusions. Homogenization temperatures and salinities of all type inclusions decrease from the quartz phenocrysts in the porphyry to hydrothermal veins (A, B, D veins). Microthermometric study suggests copper‐bearing sulfides precipitated at about 320–400°C in A and B veins. Fluid boiling is assumed for the early stage of mineralization, and these fluids may have been trapped at about 35–60 Mpa at 460–510°C and 28–42 Mpa at 400–450°C, corresponding to trapping depths of 1.4–2.4 km and 1.1–1.7 km, respectively.     

东胜区污染状况分析

文章利用东胜区主要污染源排放情况以及2005年9月1日-2007年8月31日每日SO2、NO2、PM10浓度监测值和2005-2007年SO2、NO2、PM10平均值,分析了东胜区主要污染类型、污染物来源以及东胜区近3年SO2、NO2、PM10监测值日、月、季、年分布特征和变化规律;提出了消减大气污染物排放的对策。     

兰州市冬季SO2大气环境容量研究

通过数值模拟方法,研究了兰州市冬季SO2的大气环境容量,为大气污染的总量控制方法提供了前提和依据。本文利用RAMs三维非流体静力大气动力模式模拟的气象场驱动中尺度大气扩散模式(HYPACT),模拟出SO2的浓度分布及每个污染单元对于地面浓度的分担率。根据SO2的国家环境空气质量标准(下称质量标准),用线性规划的原理和方法计算了兰州市冬季典型日条件下SO2的大气环境容量。