表生水条件下毒砂溶解作用动力学实验研究

毒砂氧化溶解和释放的砷将对周围水体造成污染.本文用混合流流动反应器研究了毒砂在温度为15、25、35和45℃的FeCl3酸性地表水作用下的氧化溶解过程.结果显示在温度为15～35℃内,毒砂的氧化随FeCl3溶液浓度增加和反应温度升高而加速,而45℃时毒砂的反应速率反而降低;毒砂在与氧化剂FeCl3酸性溶液(浓度小于1×10-4 mol·     

Oxidation Experiment of Natural Megacrystal Clinopyroxene: Implications for Assignment of Mössbauer Spectra

The Mössbauer spectra of natural megacrystal clinopyroxene are usually fitted by 4 sets of symmetric doublets, A‐A', B‐B', C‐C' and D‐D', respectively, in terms of increasing Qs value in literature. But the assignments of those doublets are quite different, except the D‐D' doublet assigned to Fe³⁺at the lattice site M***1 in previous papers. Particularly, the assignment and interpretation of the C‐C' doublet are diverse. The oxidation experiments of natural megacrystal clinopyroxene collected from the Hannuoba basalt, North China, were performed under controlled conditions of temperature at 1000°C and oxygen fugacity of FMQ buffer in 1, 2, ***3 and 5 days respectively. The oxidized samples were then measured by X‐ray diffraction spectrometry and Mössbauer spectrometry. The oxidation of clinopyroxene is characterized by Fe²⁺ → Fe³⁺at M1 under the subsolidus conditions, which is consistent with the increase of the area of the D‐D' doublet when the heating time increases. Accordingly, the area of the A‐A' and B‐B' doublets decreases with the increasing heating time. However, the area of C‐C' keeps almost constant. Therefore, the 4 sets of doublets can be assigned correctly as follows: A‐A' doublet to Fe⁺²at M1, B‐B' Fe²⁺at M1, C‐C' Fe²⁺at M2, and D‐D' Fe³⁺at M1. The M1 site splitting is due to the NNN (Next Nearest Neighbour) effect of the M2 site. The amount of Fe³⁺at the tetrohedral site of megacrystal clinopyroxene is negligible according to this study.     

一个干旱地区毛矾石矿氧化带的矿物组合

在陆相古火山角砾岩筒中由火山热液蚀变产生的含黄铁矿次生石英岩中的硫化物,在特别干旱的条件下生成了以毛矾石及黄钾铁钒为主的13种钒类矿物组成的硫化矿床氧化带,并在其中聚集了毛矾石矿体。毛钒石矿是由反复进行的氧化-渗透淋滤作用而富集形成的。     

论安徽庐枞盆地大鲍庄式喷气沉积-叠加改造型硫铁矿床

庐枞盆地中发育一些大中型硫铁矿床,曾长期被认为是与次火山岩有关的中低温热液成因。本文从矿床层控特点、矿体形态产状、矿石沉积组构、矿物组合及其生成顺序、矿化分带、包裹体及同位素地球化学等诸方面,证明它们具显著的火山喷气沉积成因特征,并受到后期热液叠加改造。提出了大鲍庄式陆相火山喷气沉积-热液叠加改造型硫铁矿的成矿模式。     

Elucidation of the Alum Shale kerogen structure using a multi-disciplinary approach

The significance and validity of integrating data obtained from a variety of analytical techniques to understand, elucidate and model kerogen's complex chemical structure is reported here using degradative (open and closed system pyrolysis, chemical oxidation), non-degradative (¹³C CP/MAS NMR) and optical (incident white light and blue light) methods. Seven Cambrian Alum Shale samples, ranging in maturity from immature to post-mature with respect to petroleum generation, were studied and were chosen for their simple geological history, uniform organic matter type and high organic carbon content. The Alum Shale kerogens, which primarily consist of algal organic matter, liberate low molecular weight gaseous and aromatic compounds on pyrolysis and give mostly branched dicarboxylic acids on chemical oxidation. ¹³C NMR spectroscopy shows that the Alum Shale kerogens are anomalously rich in oxygen-bearing functional groups (such as C = O, ArCO, CHO, CH_xO), most of which apparently remain intact within the kerogen macro-molecule (KMM) through the diagenetic and catagenetic stages. Fragments released by different degradative techniques are quantified and the aromaticity (f_a), O/C and relative proportions of various carbon types estimated by ¹³C NMR. A synthesis of these data has allowed us to better understand the chemistry of the Alum Shale kerogen.     

The behaviour of dissolved arsenic in the estuary of the River Beaulieu

The chemical forms and distribution of dissolved arsenic species in the estuary of the River Beaulieu (Hampshire, U.K.) are reported. ‘Inorganic arsenic (V)’ in both the marine and riverine estuary inputs are in true solution, passing through ultrafiltration membranes having a nominal molecular weight cut-off of 500 daltons. Extensive removal of dissolved ‘inorganic arsenic (V)’ is apparent from the distribution of arsenic in the estuary, with laboratory mixing experiments indicating that removal is favoured in the low salinity region. ‘Inorganic arsenic (III)’ and methylated arsenic species account for up to 41% and 70% of the dissolved arsenic, respectively, but are only found during the warmer months when water temperatures exceed ca. 12°C.     

The Influence of Oxalate on Fe-Catalyzed S(IV) Oxidation by Oxygen in Aqueous Solution

This study demonstrates that oxalate has a strong inhibiting effect onFe-catalyzed S(IV) oxidation by oxygen in aqueous solution. While thepseudo-first order rate constant of S(IV) oxidation was determined to be1.6 × 10³ M^-1 s^-1 in experimentswithout oxalate, the oxidation of S(IV) was totally inhibited at a molarconcentration ratio of iron:oxalate = 1:5 at an oxalate concentration of 4M. Under these conditions, the Fe(II)/Fe(III) ratio remained nearlyconstant during the observed reaction time. The determined rate constants wereindependent of the initial oxidation state of iron. However, with increasingconcentrations of oxalate, a longer induction period is observed forexperiments with iron initially in the Fe(II) oxidation state.     

公婆泉盆地下白垩统新民堡群层序地层和铀成矿特点

本文论述了公婆泉盆地下白垩统新民堡群的层序地层特点———层序分布和时代、界面特征和内部构成、沉积相,以及层间氧化带和铀矿化特点。认为该盆地在公婆泉地段具有一定的找铀矿远景,但北骆驼泉地段铀成矿条件不佳,那林疏怀地段不具备铀成矿远景。     

Product study of the reaction of OH radicals with isoprene in the atmosphere simulation chamber SAPHIR

Atmospheric oxidation of isoprene and its oxidation products methacrolein (MACR) and methyl vinyl ketone (MVK) have an important impact on the photochemical activity in the boundary layer, in particular in forested areas. The oxidation of isoprene by OH radicals was investigated in chamber experiments conducted under tropospheric conditions in the atmosphere simulation chamber SAPHIR at the Research Center Jülich. The aim was to determine the product yield of MVK and MACR in the OH-induced isoprene oxidation and the rate constant of their reaction with OH under real atmospheric conditions. The recently published updated degradation scheme for isoprene from Geiger et al. (2003) was used to determine rate constants and product yields. The fractional yields in the isoprene peroxy radical reaction with NO were found to be 0.41±0.03 for MVK and 0.27±0.03 for MACR. The rate coefficient for MACR with OH was found to be in very good agreement with the recommended value of IUPAC Atkinson (Atkinson et al., 2005). while the rate coefficient for MVK with OH was 27% lower.     

安徽和县香泉独立铊矿床铊的赋存状态研究

分散元素铊成矿作用的相关研究近年来已经取得了重要进展,但矿床中铊的赋存状态研究仍有待深入.香泉独立铊矿床位于长江中下游成矿带北侧的皖东地区,该矿床中铊的赋存状态研究对拓展铊元素成矿研究具有重要意义.本文通过矿相学、微量元素地球化学、电子探针分析和X射线粉晶分析等方法,确定了香泉铊矿床中黄铁矿是铊的主要载体矿物.铊在黄铁矿中主要以类质同象形式替代铁进入黄铁矿晶格,其次以纳米级、次纳米级铊矿物颗粒形式产出.