中国煤中铬的分布、赋存状态及富集因素研究进展

铬是煤中的潜在毒害微量元素,在煤利用过程中铬会发生迁移与转化,并可能释放出造成环境和人体健康的危害。本文分析了中国煤中铬的含量、分布规律、赋存状态及其富集因素等地球化学特征,指出中国煤中铬的含量为0．02～971μg／g,平均为17．18μg／g;煤中铬的赋存状态多样,主要以无机态存在;煤中铬的含量和赋存状态受成煤环境、成煤植物和后生地质作用等因素的影响。     

煤中砷的赋存状态

砷是煤中常见的有害微量元素,由于其丰度较低,定量研究其赋存状态一直很困难。近年来,采用逐级化学提取实验方法对煤中不同赋存状态的砷进行了定量研究,综合分析这些研究可得出以下结论：①煤中砷的赋存状态包括硫化物态砷、有机态砷、砷酸盐态砷、硅酸盐态砷、水溶态和可交换态砷。总体上,硫化物态砷＞有机态砷＞砷酸盐态砷＞硅酸盐态砷＞水溶态和可交换态砷,但在不同的煤样品中,也表现出较大的差异性。②一般而言,煤中大部分砷存在于含砷黄铁矿中,含砷黄铁矿中的砷含量与黄铁矿的成因或类型有关。煤中的砷酸盐态砷主要与铁氧化物和氢氧化物共生;硅酸盐态砷主要进入粘土矿物晶格。③在砷含量较低的煤样品中,有机态砷含量较高,其中在褐煤和低煤级烟煤中,可提取出与腐殖酸和富里酸结合的砷。当前还难以确认有机态砷的化学结构。④贵州特高砷煤中砷的赋存状态较为复杂,在某些样品中与氧结合的有机态砷为主要的赋存状态。     

东林矿煤中砷的含量分布及赋存状态

燃煤引起人砷中毒在我国云贵川地区比较常见,因此有必要研究煤中砷的赋存状态。研究了重庆东林矿4号和6号主采煤层中砷的含量、分布规律及其赋存特征。研究表明:东林矿4号层煤中砷、总硫和灰分的平均含量均大于6号层。东林矿原煤中砷的含量范围为0.20~7.87 μg/g,平均值1.68 μg/g,明显低于重庆及重庆其他矿煤中砷的平均水平,没有明显富集。赋存特征分析表明,东林矿煤中砷具有明显的亲硫性,可能主要赋存于同生黄铁矿中,在硅酸盐矿物相中分布较少。      

贵州中北部燃煤型砷中毒地区煤中砷的赋存状态研究

贵州中北部存在着高砷煤并引起环境和健康问题,对这些地区的煤进行了中子活化分析(INAA)、电子探针(EMPA)、能谱扫描电子显微镜(SEM-EDX)、低温灰化(LTA)、X射线衍射(XRD)、X光吸收精细结构(XAFS)和连续淋滤实验分析,综合研究了这些煤中砷的赋存状态。结果表明不同煤中砷具有不同的赋存状态。在部分样品中砷主要以无机砷的形式存在,而在其它样品中砷主要以有机砷的形式存在。除了黄铁矿和毒砂外,SEM-EDX结合LTA和XRD发现硫酸盐、粘土也不同程度含有砷。XAFS显示煤中的砷主要以As5+的形式存在。连续淋滤实验表明在样品ZJ-1中超过50%的砷不能被淋滤出来,而在另外两个样品(ZJ-8和RH-5B)中绝大部分的砷被淋滤出来。综合分析表明一些煤中以+5价存在的砷主要与有机质结合。煤中如此高的砷及其主要与有机质结合的现象是很罕见。     

中国煤中硫的地球化学研究

燃烧过程中,煤中硫会以硫氧化物等形式释放出来,污染大气以至形成酸雨,对环境造成极大的影响。本文在对中国煤中硫全面分析的基础上．总结并分析了中国煤中硫在不同地区、不同煤层和不同形成环境中的含量与分布规律,阐述煤中硫形成的地质成因和影响因素．以及育机硫、无机硫和元素硫的赋存状态．概述了煤利用过程中硫的转化机理及其对环境的影响．提出了对煤中硫的研究趋势和今后研究方向与热点问题。     

山西沁水煤田首阳山矿15#煤的稀土元素分布规律、赋存状态及其对成煤环境的指示

文章以沁水煤田长治首阳山矿15号煤为研究对象,运用电感耦合等离子体质谱(ICP-MS)和X射线荧光光谱(XRF)等方法对煤中的稀土元素进行测试和分析。探讨了15号煤中稀土元素的富集机理、配分模式、赋存状态以及成煤环境等地球化学特征。结果表明:(1)研究区煤层中的稀土元素含量均值为49.28μg/g,整体含量较低;(2) 15~#煤(除SYS15-2外)和夹矸中稀土元素均为轻稀土富集型(LREY),并且夹矸中轻稀土富集更加明显;(3)稀土元素主要赋存在黏土矿物中;(4)成煤环境整体上以弱还原环境为主,稀土元素物质来源主要为陆源碎屑。     

渭北煤田下峪口矿二叠纪煤中稀土元素地球化学研究

运用电感耦合等离子体质谱（ICP MS）对渭北煤田韩城下峪口矿二叠纪主采煤层及其顶底板中的稀土元素进行了测定。在此基础上,全面分析了稀土元素的含量特征和分布模式,探讨渭北煤田二叠纪煤中稀土元素的主要来源及赋存状态。结果表明：与华北和中国煤均值相比,本区煤层中稀土元素相对不富集,∑REY平均含量为87.70 μg/g;剖面上,2号煤中稀土含量稍高于3号煤,3号煤层中自上而下,稀土元素含量呈降低的趋势,在顶底板中出现富集。研究区煤层中轻稀土元素相对于重稀土元素明显富集,Ce呈微弱正异常,成煤沼泽受海水的影响程度较小。Eu明显负异常,且∑REY含量与CaO含量呈负相关关系,说明当时的成煤环境为酸性还原环境。煤层与其顶底板样品中稀土元素分布模式相似,成煤期间物质来源基本一致,陆源物质供应相对稳定。煤中稀土元素含量与灰分呈不太显著的正相关关系（R=0.216）,表明煤中稀土元素可能以无机态和有机吸附态共存。     

中国煤中的铀、钍和放射性核素

中国煤中的铀平均含量为3mg/kg,在某地富铀煤中检测到的最高值达25660mg/kg,其赋存状态主要是与有机质相结合的方式;钍平均含量6 mg/kg,没有发现异常现象.南方一些地区的石煤中含有较多的放射性核素,并且容易在灰渣中富集,综合利用时应加强监控,以避免产生危害.     

淮南煤田深部A组煤中有害微量元素地球化学特征

以淮南煤田深部A 组煤为研究对象,全层刻槽采集了煤、夹矸和顶底板岩石样品,采用电感耦合等离子质谱仪 （ICP-MS） 测试分析了样品中13 种有害微量元素的含量,对比研究了其分布特征,结合Tessier 五步形态提取法和相关性分 析探讨了煤中有害微量元素的赋存形态。结果表明：（1） 与中国上陆壳中各种微量元素含量均值相比,淮南深部A 组煤中 B,As,Se,Mo,Cd,Pb,Hg 的富集系数均大于1,在A 组煤中表现为富集;A 组煤中B,As,Se,Cd 的含量均高于淮南煤 田上部B 组煤、华北煤以及中国煤中的含量均值;（2） 相关性分析和逐级提取实验结果表明,A 组煤中微量元素主要以残 渣态和铁锰氧化物结合态存在,两者质量分数之和达到55%~98%,其中Ni,Mo,Cd,Hg,Cu,Pb 和Zn 主要赋存于硫化物 矿物中,Mn 主要赋存于碳酸盐矿物中,V,Cr,Se,B 和As 主要赋存于硅铝酸盐等黏土矿物中。（3） B 元素示踪物源及沉 积环境结果显示,淮南煤田深部A 组煤成煤环境为海相咸水沉积环境,稳定的咸水沉积环境以及受海水影响等因素导致A 组煤中微量元素出现不同程度的富集。     

我国煤中砷的含量赋存特征及对环境的影响

在检测了156个煤样中砷含量的基础上,收集了近2000个煤样的资料,分析了我国煤中砷元素的含量和赋存特征及砷富集的地质因素。结果表明,我国多数煤中砷含量处于0.8× 10-6~20×10-6,算术平均值为4× 10-6;砷的赋存方式主要为: a. 类质同象置换硫赋存于黄铁矿中; b. 低变质煤可赋存于有机质中; c. 以粘土矿物和稀有的含砷矿物为载体。煤中砷富集的地质因素,一是后期热液带入煤层;二是由陆源物质带入泥炭沼泽;三是同沉积时期海水的影响。燃用富砷煤是引发环境污染的基本原因,但是燃煤方式也是重要因素。多数煤中砷含量并不高,控制和预防砷的危害还是可以做到的。      

Wavelength-dispersive X-ray fluorescence spectrometric determination of Sc, V, Cr, Co, Ni, Cu, Zn, Rb, Sr, Y, Zr, Nb, Ba, Pb, and Th in komatiites

Komatiites are mantle-derived ultramafic volcanic rocks. Komatiites have been discovered in several States of India, notably in Karnataka. Studies on the distribution of trace-elements in the komatiites of India are very few. This paper proposes a simple, accurate, precise, rapid, and non-destructive wavelength-dispersive x-ray fluorescence (WDXRF) spectrometric technique for determining Sc, V, Cr, Co, Ni, Cu, Zn, Rb, Sr, Y, Zr, Nb, Ba, Pb, and Th in komatiites, and discusses the accuracy, precision, limits of detection, x-ray spectral-line interferences, inter-element effects, speed, advantages, and limitations of the technique. The accuracy of the technique is excellent (within 3%) for Sc, V, Cr, Co, Ni, Cu, Zn, Rb, Sr, Zr, Nb, Ba, Pb, and Th and very good (within 4%) for Y. The precision is also excellent (within 3%) for Sc, V, Cr, Co, Ni, Cu, Zn, Rb, Sr, Y, Zr, Nb, Ba, Pb, and Th. The limits of detection are: 1 ppm for Sc and V; 2 ppm for Cr, Co, and Ni; 3 ppm for Cu, Zn, Rb, and Sr; 4 ppm for Y and Zr; 6 ppm for Nb; 10 ppm for Ba; 13 ppm for Pb; and 14 ppm for Th. The time taken for determining Sc, V, Cr, Co, Ni, Cu, Zn, Rb, Sr, Y, Zr, Nb, Ba, Pb, and Th in a batch of 24 samples of komatiites, for a replication of four analyses per sample, by one operator, using a manual WDXRF spectrometer, is only 60 hours.     

高压微波消解法测定醋酸纤维过滤器采集的微尘粒子中的砷镉钴铬铜铁锰镍铅钒锌

最新的流行病学研究表明,空气中较高浓度的悬浮细颗粒可能对人类的健康有不利的影响。根据该项研究显示,由于心脏病、慢性呼吸问题和肺功能指标恶化而导致死亡率的升高与细尘粒子有关。这些研究结果已经促使欧盟于1999年4月出台了限制空气中二氧化硫、二氧化氮、氧化氮、铅和颗粒物含量的法案(1999/30/EC),对各项指标包括对可吸入PM10颗粒的浓度提出了新的限制性指标。PM10颗粒是指可以通过预分级器分离采集的气体动力学直径小于10μm的细颗粒。目前研究的兴趣重点逐步偏向PM2.5这些更细微颗粒物,PM2.5这种颗粒物对健康有明显的不利影响。在欧盟指令2008/50/EC中,对PM10和PM2.5都提     

硅酸盐类样品中硅、铁、铝、钛、锰、钙、镁、钾、钠和磷的x射线荧光光谱测定

本文拟定了一种以熔融法制备样片,用X射线荧光光谱测定硅酸盐类样品中Si、Fe、Al、Tj、Mn、Ca、Mg、K、Na、P等元素的分析方法。在对不同靶材X光管和分光晶体实验对比的基础上,选择了最佳的测量条件。该法具有快速、准确,测量范围广,检测限低,价格便宜等优点。经过近百个各种类型标样或管理样品的分析对比表明,本法不仅适用于硅酸盐类岩石样品的分析,还适用于铁矿、铝土矿、碳酸盐类岩矿样品以及水泥、耐火材料等样品的分析。     

Isotopic systematics of He,Ar, S,Cu, Ni,Re, Os,Pb, U,Sm, Nd,Rb, Sr,Lu, and Hf in the rocks and ores of the Norilsk deposits

This paper reports the first results of a study of 11 isotope systems (³He/⁴He, ⁴⁰Ar/³⁶Ar, ³⁴S/³²S, ⁶⁵Cu/⁶³Cu, ⁶²Ni/⁶⁰Ni, ⁸⁷Sr/⁸⁶Sr, ¹⁴³Nd/¹⁴⁴Nd, ^206–208Pb/²⁰⁴Pb, Hf–Nd, U–Pb, and Re–Os) in the rocks and ores of the Cu–Ni–PGE deposits of the Norilsk ore district. Almost all the results were obtained at the Center of Isotopic Research of the Karpinskii All-Russia Research Institute of Geology. The use of a number of independent genetic isotopic signatures and comprehensive isotopic knowledge provided a methodic basis for the interpretation of approximately 5000 isotopic analyses of various elements. The presence of materials from two sources, crust and mantle, was detected in the composition of the rocks and ores. The contribution of the crustal source is especially significant in the paleofluids (gas–liquid microinclusions) of the ore-forming medium. Crustal solutions were probably a transport medium during ore formation. Air argon is dominant in the ores, which indicates a connection between the paleofluids and the atmosphere. This suggests intense groundwater circulation during the crystallization of ore minerals. The age of the rocks and ores of the Norilsk deposits was determined. The stage of orebody formation is restricted to a narrow age interval of 250 ± 10 Ma. An isotopic criterion was proposed for the ore-bearing potential of mafic intrusions in the Norilsk–Taimyr region. It includes several interrelated isotopic ratios of various elements: He, Ar, S, and others.     

Viscous, cohesive, non-Newtonian, depositing, radial slurry flow

Mining induced subsidence can significantly affect mining costs where major surface facilities and natural environment need to be protected. Overburden grout injection is a technology used to control coal mine subsidence by injecting the mine waste material extracted from the coal back into the inter-burden rock during longwall mining. The flowing slurry is here categorised as a nonlinear viscous cohesive (Bingham plastic) fluid. During longwall mining the grout slurry is pumped into the separated beds of the rock mass through a central vertical borehole, which is drilled deep into the inter-burden rock strata above the coal seam. However, a blockage can occur in the injection system when the slurry velocity falls below a certain critical threshold velocity, indicating a material phase change from cohesive-viscous to cohesive-frictional. In situ field injection tests through boreholes have been simulated at a smaller scale at the CSIRO laboratory in Brisbane by pumping the slurry through a radial disk (gap = 4 mm) from its centre. Laboratory experiments indicate a general, nonlinear, cohesive, viscous, frictional model for shear behaviour of the slurry, in which the material shear parameters are functions of the disk radial distance. Complete dimensional and dimensionless analytical solutions have been developed based on an approach related to Bingham–Herschel–Bulkley fluid mechanics. The derived formulae include relations for minimum pump pressure, local pressure and pressure gradient, wall shear stress, volume rate, velocity and velocity gradient. The theoretical results match the experimental measurements. The experiments covered slurries with maximum particle sizes of 0.5 to 2 mm with about 50% being larger than 100 µm. The viscosities at the various solids concentrations were measured with a standard torsion viscometer. This study differs from the previous research in several distinct aspects, namely, consideration of the variable shear parameters rather than fixed values, inclusion of total nonlinear behaviour, and implementation of a friction function to mimic behaviour of the deposited and consolidating stiff slurry, which can cause a significant pressure rise as a result of the increased shear resistance.     

硅酸盐中铁、锰、钛、钙、钾、磷、硅、铝、镁、钠、锶、铷、钡的X-射线荧光光谱定量测定

本文介绍样品经四硼酸锂熔融制成玻璃小饼。采用Lachance模式和理论a系数来校正元素间的效应,由3080E型X-射线荧光谱仪和DF-350B数据处理系统完成硅酸盐中十三个项目的测定。     

Bellechester,Minnesota, USA,lagoon collapses

Bellechester, Minnesota, is a small community of approximately 155 residents located on the county line between Goodhue and Wabasha counties in southeast Minnesota's karst region. Bellechester is served by a 21-year-old wastewater treatment facility (WWTF) consisting of three waste-stabilization ponds. On 28 April 1992 six sinkholes were discovered to have drained cell 2 of the WWTF resulting in the loss of approximately 8.7×10⁶ 1 of partially treated effluent and about 600 m³ of soil into previously undetected subsurface voids of unknown dimensions. In the week following the collapse, approximately 200 water wells located within a 5-km radius of the WWTF were sampled in an after-the-fact, emergency sampling program. Twelve samples with elevated fecal coliform levels, 18 samples with nitrate-nitrogen greater than the 10 mg/1 standard, and no samples with elevated chlorides were found. However, the elevated levels could not be unambiguously attributed to the WWTF collapse. This is the third WWTF to fail by sinkhole collapse in southeast Minnesota since 1974. All three collapsed lagoons have been located in similar geomorphic and stratigraphic settings. However, at least two lagoons have collapsed in the adjacent area in northeast Iowa, and these lagoons are located at different stratigraphic positions. Twenty-two WWTFs constructed in southeast Minnesota's karst region in the last 25 years have been identified as subject to potential sinkhole collapse. An unknown but significant number of manure storage lagoons, flood control structures, etc., have also been constructed in the karst region and are at risk. Public agencies are beginning to develop plans to deal with the risk associated with existing and future waste lagoons in this environment. The critical hydrogeologic parameters that can be used to prioritize the risk of collapse at existing facilities include: (1) the lithology of the first bedrock beneath each lagoon, (2) the thickness of surficial materials between the lagoon and the bedrock surface, (3) the presence and construction of liners (seepage rate), and (4) the proximity to existing sinkholes.     

Mercury,arsenic, antimony,and selenium contents of sediment from the Kuskokwim River,Bethel, Alaska,USA

The Kuskokwim River at Bethel, Alaska, drains a major mercury-antimony metallogenic province in its upper reaches and tributaries. Bethel (population 4000) is situated on the Kuskokwim floodplain and also draws its water supply from wells located in river-deposited sediment. A boring through overbank and floodplain sediment has provided material to establish a baseline datum for sediment-hosted heavy metals. Mercury (total), arsenic, antimony, and selenium contents were determined; aluminum was also determined and used as normalizing factor. The contents of the heavy metals were relatively constant with depth and do not reflect any potential enrichment from upstream contaminant sources.     

滇东南花岗岩与锡、银、铜、铅、锌多金属矿床的成因关系

滇东南锡、银、铅、锌多金属矿床主要分布在个旧、白牛厂、都龙3个矿区,而滇东南较大的3个花岗岩体又分别出露在3个矿区或附近.花岗岩体均形成于燕山晚期,岩石化学、矿物成分相似,富含锡、银、铅、锌、钨、铜等成矿元素.矿床主金属元素组合与岩体之间的距离由远而近出现由锡、钨、(铍、铌、钽)→锡、钨、(铁)、铜、铟→锡、铅、锌、银、铟、(锑)有规律的变化.花岗岩浆是成矿物质来源和成矿热源.岩浆侵入初期使上覆地层隆起产生背斜(凹陷部位成向斜);同时使地层产生一系列裂隙、压性断层或层间断裂;岩浆侵入晚期,这些断层再次活动,表现为张性,岩浆产生的含矿热液沿由其活动所造成的断裂迁移、充填、交代、沉淀而形成矿床.     

岩石密度和超高压岩石折返速率

在常温常压条件下对中国大陆科学钻CCSD主孔100-3000米岩心样品进行了密度测量,建立了密度连续剖面,并界定了不同超高压岩石的密度值。通过对比高温高压物性实验资料,岩石密度随着退变程度增强而降低,榴辉岩密度变化序列为3.52g/cm3→3.49g/cm3→3.07g/cm3→2.93g/cm3。超高压长英质岩石密度变化序列为3.00g/cm→2.80g/cm3→2.65g/cm3。上述实验资料是讨论不同折返阶段岩石所受浮力的基础,为研究折返速率大小提供了基本参数。本文通过折返板块运动平衡时,上浮力与粘滞力平衡这一关系式,定量研究了大陆俯冲板块的折返速率,认为密度差产生上浮力从而引起折返,温度对板块折返速率的影响最为显著;密度差大小、折返角度、折返板块大小对折返速率也有直接的影响。定量模拟分析表明,在温度高于850℃时,板块的折返速率可以超过100mm/a;当温度降至700℃时,折返速率则低于1.5mm/a。作者认为在折返早期,温度较高,板块快速折返至60-70km榴辉岩相深度;随着传导散热,温度降低,板块以较慢的速率折返至中下地壳。折返速率的估算表明,浮力是板块折返第一阶段(从>100km深部折返至<40km的中下地壳)的主要驱动力。