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。     

煤中汞的赋存状态研究

对采自贵州省二叠系龙潭组煤层的 32个煤样进行了连续化学浸取实验研究 ,并利用重液分离方法 ,将另外 8个采自同一地区的煤样按密度从 1.4至 2 .8× 10 3kg m3分成 10个密度段。通过测定化学浸取过程主要矿物组成的变化及汞的浸取量 ,对比研究各密度段分样中矿物组成和有机质含量与汞含量间关系 ,得出煤中汞主要赋存于黄铁矿中 ,煤样黄铁矿中汞的分布是不均匀的。研究表明 ,当煤炭被开采堆放到地表后 ,煤中大部分汞可以被酸性矿井水带入环境中 ,这一环境污染问题应予以重视。在洗煤过程中 ,平均 5 1%的汞可以被脱除。因此 ,提高原煤入洗率可以有效地降低煤中汞的含量     

贵州普安矿区20号煤中锂的赋存状态及逐级化学提取实验研究

锂(Li)是一种重要的金属能源,近年来全球锂的需求持续增长。我国煤伴生型锂矿床的发现证明煤矿可能成为锂资源的潜在来源。以贵州普安矿区20号煤为研究对象,采用工业分析、镜下鉴定、X射线荧光光谱(XRF)、电感耦合等离子体质谱(ICP-MS)、激光剥蚀?电感耦合等离子体质谱(LA-ICP-MS)等方法,分析原煤及浮沉实验获得的密度分级试样的基本性质、矿物组成、元素组成及煤中Li的赋存特征。结果表明,原煤中Li含量达134.09 μg/g,在6个密度级样品中,Li含量随煤样密度级的增加而增加(>1.8 g/cm3密度级样品中Li含量最高为212 μg/g),重力分选可使煤中Li得到一定程度的预富集。原煤主要矿物组分包括黏土矿物、黄铁矿、方解石、石英等,基于Li与Al、Si等的相关性以及矿物微区元素含量(LA-ICP-MS)等分析,推测Li可能主要以吸附态赋存于黏土矿物中。逐级化学提取实验结果表明,煤中Li的赋存特征为水溶态(20.96%)、离子交换态(32.90%)、硅酸盐/铝硅酸盐态(22.80%)、碳酸盐/磷酸盐态(10.81%)、二硫化物态(3.92%)和残渣/有机态(2.58%),说明通过离子交换法可以从煤矸石中回收Li。该研究结果为下一步分离提取煤中Li提供了一定理论指导。      

贵州煤中汞的分布,赋存状态及对环境的影响

对贵州省六枝、水城、盘县和贵阳等４大煤田煤中汞的研究表明：煤中汞的平均含量为０．５５２μｇ／ｇ;煤中汞主要赋存于黄铁矿中,硅酸盐矿物相中汞的分布量很少;贵州燃煤引起的汞污染问题非常严重。     

沁水煤田15号煤中氟的赋存状态及其沉积环境分析

氟是煤中有害元素之一,燃煤型氟排放造成的污染已经对人类的健康安全构成威胁。研究煤中氟赋存状态及其沉积环境,对掌握高氟煤分布规律及控制燃煤造成的氟排放具有重要意义。通过对沁水煤田内6座煤矿15号煤样品的分析发现:煤中氟含量与灰分显著相关,与黄铁矿硫、有机硫无相关关系,表明煤中氟主要以无机物形式赋存,且与含硫矿物无关;与钾、镁、硅、铝等元素含量具有显著的相关关系,表明氟有可能的主要赋存形式为金云母、氟金云母等矿物,以及以吸附存在于高岭石、勃姆石、伊蒙混层等黏土矿物中;与钙、磷元素含量无显著相关性,表明氟不以氟磷灰石、含氟羟基磷灰石等矿物大量赋存。此外,通过对沁水煤田15号煤的沉积环境分析发现,弱还原环境、较低盐度、偏酸性、较强的水动力条件有利于该区域煤中氟的富集。     

淮北煤田煤的稀土元素地球化学

采用仪器中子活化分析法（ＩＮＡＡ）测试了淮北煤田６、３煤层１个煤样的稀土元素含量,并探讨了稀土元素地球化学特征,得出以下认识：１１个样吕的平均ΣＲＥＥ为８１．９５３５ｕｇ／ｇ;稀土元素分布模式呈左高右低的、具Ｅｕ负异常的“Ｖ”型曲线。相关分析、聚类分析的结果表明：稀土元素与灰分、陆源碎屑的元素（Ｓｉ、Ａｌ、Ｔｉ、Ｃｒ、Ｃｏ、Ｎｉ、Ｔｈ、Ｔａ、Ｓｃ和Ｒｂ等）的关系密切,而与海相元素（Ｃａ、Ｓｒ等）关     

煤中微量元素的赋存状态

在测定煤中微量元素浓度与灰分产率（Ａｄ），各种形态硫（Ｓｔ，ｄ，Ｓｐ，ｄ，Ｓｓ，ｄＳ０，ｄ）的基础上，运用数理统计方法确定了元素的亲有机／无机性，而且也查明了与粘土矿物，黄铁矿乃至硫酸盐矿物等有关的元素。     

煤中有害微量元素的赋存状态

基于前人资料的分析总结，系统探讨了煤中Ag等26种有害微量元素的赋存状态。研究结果表明：煤中有害元素或多或少都与无机质、有机质有联系，只是联系程度不同。有些在地壳中被认为彼此关系不大的元素，在煤中却密切相关。煤中B、Be、Br等主要以有机相赋存，其它有害元素主要与矿物质有关。     

淮北煤田二叠纪煤中稀土元素地球化学研究

从淮北煤田二叠系10,7,5,4和3煤层中采集34个样品,采用等离子体质谱（ICP-MS）、中子活化（INNA）、等离子体发射光谱（ICP-AES）等方法对样品中主量元素和稀土元素进行了测试,利用X射线衍射等方法对煤中矿物质及其煤质参数进行了测定。在各种测试的基础上,全面分析了稀土元素含量特征、空间分布规律、地球化学参数和分布模式,探讨了淮北煤田二叠纪煤中稀土元素的主要来源及其在煤中的主要赋存方式。研究表明：与华北和国内外其他地区相比,本区煤层中稀土元素相对富集;产于石盒子组煤中的稀土元素含量高于山两组的,在同一煤层中自下而下稀土元素含量有增高趋势,在顶底板中可能出现富集。Ce呈正异常,Eu明显负异常,不同煤层稀土元素的分布模式相似,稀土元素和灰分具有较好的正相关,∑REE与灰分、灰分中的主要元素以及典型陆源灰分中的微量元素正相关,与反映海相的低灰组分相关性较差。结合煤中矿物质的X射线衍射结果,分析获知,淮北煤田二叠纪成煤环境基本不受海水影响,稀土元素主要由陆源供给,而且主要赋存在以高岭石、伊利石为主的粘土矿物中。     

淮北煤田煤中镧系元素和钇的地球化学——“岩浆侵入对淮北花沟西煤中稀土元素分布的影响”的商榷

"岩浆侵入对淮北花沟西煤中稀土元素分布的影响"(高校地质学报,2013,19(4):671-676页)和"岩浆侵入对袁店二井煤矿72煤中稀土元素的影响"(煤炭工程,2014,46(5):119-122页)两文均表明"岩浆侵入致使煤中稀土元素含量增加,使煤中稀土元素发生了二次迁移与富集,且岩浆组分对煤中稀土元素的迁移富集具有一定程度的影响",而经重新整理原作者数据,并对其中镧系元素和钇(REY)的含量特征、上陆壳标准化分配模式的分析后,则得出完全不同的结论:淮北煤田煤中REY平均118mg/kg,天然焦中REY平均128mg/kg,侵入岩中REY平均326mg/kg;煤层侵入岩REY含量高于煤和天然焦,而煤和天然焦中REY含量无显著差别。煤层侵入岩上陆壳标准化的REY分配模式均显著富集LREY,且明显与煤和天然焦的REY分配模式不同,这表明岩浆侵入对煤中镧系元素和钇的影响甚微,且煤中的HREY较LREY和MREY富集。总结得出:对煤中稀土元素地球化学的研究须将钇元素一并分析,且将REY三分(LREY,MREY和HREY)便于更细致的对比;稀土元素分配模式标准化的参考应该尽量选择与煤近似的地质体(如北美页岩、上陆壳、中国煤等),不应均以球粒陨石为标准,方可更准确地解析稀土元素的来源及其在成煤及变质过程中的分异等。     

Geochemistry of Mercury in the Permian Tectonically Deformed Coals from Peigou Mine, Xinmi Coalfield, China

As the mercury emitted from coal combustion can lead to serious environmental issues, researchers pay more attention to the content, distribution and occurrence of mercury in coal. In this paper, the content, distribution, and occurrence of mercury in the Permian tectonically deformed coals from Peigou Mine, Xinmi coalfield, Henan Province were investigated. A total of 18 bench samples were taken from No.2-1 coals seam in Peigou Mine, including 15 coal bench samples, two roofs and one floor. The mercury concentration, mineral composition, and main inorganic element content of 18 samples were determined by DMA-80 direct mercury analyzer, XRD, and XRF respectively. The results show that the mercury content ranges from 0.047 ppm to 0.643 ppm, with an average of 0.244 ppm. Though the coal seam has turned into typical tectonically deformed coal by the strong tectonic destruction and plastic deformation, the vertical distribution of mercury has remarkable heterogeneity in coal seam section. By the analysis of correlation between mercury and the main inorganic elements and the mineral composition in coal, we infer that majority of mercury mainly relates to pyrite or kaolinite.     

卧龙湖煤矿岩浆蚀变煤层中汞的分布与赋存特征

系统采集淮北卧龙湖煤矿岩浆蚀变煤层中岩浆岩、煤及顶底板岩石样品,测试分析了样品中汞、灰分、挥发分、水 分以及各形态硫的含量,探讨了岩浆蚀变煤层中汞的分布与赋存特征。结果表明：（1） 岩浆侵入导致煤中灰分升高,挥发 分降低,煤中硫主要以黄铁矿硫和有机硫存在;（2） 岩浆侵入导致煤中汞的富集,卧龙湖煤矿岩浆蚀变煤层中汞的平均含 量高达0.23×10-6,是华北石炭-二叠纪煤、中国煤以及美国煤中汞的平均含量的1.4 倍,1.2 倍和1.3 倍;（3） 煤中汞的含量 随离岩浆侵入体距离增大有逐渐降低的趋势,但在煤岩接触带附近,汞在岩浆侵入体上方和下方的煤中呈现不同的分布特 征;（4） 煤中的汞主要以无机结合态的形式存在,且大部分赋存在煤中的黄铁矿中,同时亦存在与有机硫结合的汞。岩浆 热液对煤层的侵入,导致煤质以及煤中汞的含量和赋存方式发生了显著变化。     

岩浆侵入煤层中锑的赋存特征——以淮北卧龙湖矿为例

为探讨岩浆蚀变作用对煤层中锑赋存特征的影响,系统采集安徽淮北煤田卧龙湖煤矿岩浆侵入煤层侵入岩和全煤层样品共12个,利用原子荧光光谱法（AFS）测定样品中Sb含量,并对煤质参数进行分析。结果表明：卧龙湖煤矿岩浆侵入区煤表现为超低挥发分,中等灰分,特低硫的特点,煤中的硫主要以有机硫和黄铁矿硫存在。受岩浆热液影响,煤中灰分增加,挥发分减少;岩浆蚀变煤层中锑明显富集,算术平均值达到10.48 mg/kg,且侵入岩上方煤中Sb的平均含量明显增高,煤岩接触带位置Sb的含量达到最高值（13.93 mg/kg）;岩浆蚀变煤中的锑主要以无机结合态形式存在（相关系数r为0.74）,有机硫与煤中Sb呈显著负相关（相关系数r为-0.60）。岩浆侵入作用导致卧龙湖煤矿煤的煤质特征及煤层中锑的赋存方式受到不同程度的影响,研究结果可为特殊地质作用下煤中锑的环境地球化学特征提供参考。     

黔西晴隆矿区晚二叠世煤地球化学变异的地质成因

运用仪器中子活化分析(INAA)、电离耦合等离子体质谱(ICP—MS)、电离耦合等离子体原子发射光谱(ICP—AES)、X射线荧光光谱(XRF)、冷原子吸收光谱(CVAAS)、离子选择性电极法(ISE)、逐级化学提取试验(SCEE)等,结合带能谱仪的扫描电镜(SEMEDX)和MPV—Ⅲ显微镜下观察的煤岩学特征的分析,对贵州晴隆矿区上二叠统含煤岩系8号煤层中微量元素的含量和赋存特征及其影响因素进行了研究。发现该煤层中Cu(263.4μg／g)、Cr(154．2μg／g)、Hg(0．86／μg／g)、Mo(82．47μg／g)、Ni(63．3μg／g)、Pb(200．4／μg／g)、Se(4．25／μg／g)、U(154．8／μg／g)、Zn(214．6／μg／g)和Zr(754．3μg／g)等元素异常富集;而As和F的含量不高,其含量分别为1．58／μg／g和83．4μg／g。逐级化学提取结果显示,该煤层中Hg、Mo、Ni、Pb、Se和Zn元素主要赋存在低温热液成因的黄铁矿脉中;Cr、U和Zr主要存在于粘土矿物中,其中Cr和Zr可能与康滇古陆陆源碎屑供给有关;Cu不仅与粘土矿物有关,而且也和煤中黄铁矿有关。表明低温热液流体和陆源碎屑供给对该煤中主要微量有害元素的含量和赋存特征起了决定作用。     

Modes of Occurrence and Geological Origin of Beryllium in Coals from the Pu'an Coalfield, Guizhou, Southwest China

The concentration, modes of occurrence and geological origin of beryllium in five workable coal beds from the Pu'an Coalfield of Guizhou were studied using the inductively coupled-plasma mass spectrometry (ICP-MS), floating and sinking experiments (FSE) and sequential chemical extraction procedures (SCEP). The results show that the average concentration of beryllium in coals from the Pu'an Coalfield is 1.54μg/g, much lower than that in most Chinese and worldwide coals. Beryllium in the Pu'an coals was not significantly enriched. However, it should be noted that the No. 8 coal bed from the study area has a high concentration of beryllium, 6.89μg/g, three times higher than the background value of beryllium in coal. Beryllium in coal mainly occurs as organic association and has predominantly originated from coal-forming plants when its concentration is relatively low. The concentration of beryllium occurring as organic association is close to that distributed in inorganic matter when beryllium concentration of coal is similar to its background value, and in addition to coal-forming plants, beryllium is mainly derived from detrital materials of terrigenous origin. When beryllium is anomalously enriched in coal, it mainly occurs as organic association and is derived from volcanic tonsteins leached for a long geological time and then adsorbed by organic matter in peat mire.     

Modes of Occurrence and Geological Origin of Beryllium in Coals from the Pu''''an Coalfield, Guizhou, Southwest China

The concentration, modes of occurrence and geological origin of beryllium in five workable coal beds from the Pu'an Coalfield of Guizhou were studied using the inductively coupled-plasma mass spectrometry (ICP-MS), floating and sinking experiments (FSE) and sequential chemical extraction procedures (SCEP). The results show that the average concentration of beryllium in coals from the Pu'an Coalfield is 1.54μg/g, much lower than that in most Chinese and worldwide coals. Beryllium in the Pu'an coals was not significantly enriched. However, it should be noted that the No. 8 coal bed from the study area has a high concentration of beryllium, 6.89μg/g, three times higher than the background value of beryllium in coal. Beryllium in coal mainly occurs as organic association and has predominantly originated from coal-forming plants when its concentration is relatively low. The concentration of beryllium occurring as organic association is close to that distributed in inorganic matter when beryllium concentration of coal is similar to its background value, and in addition to coal-forming plants, beryllium is mainly derived from detrital materials of terrigenous origin. When beryllium is anomalously enriched in coal, it mainly occurs as organic association and is derived from volcanic tonsteins leached for a long geological time and then adsorbed by organic matter in peat mire.     

Modes of Occurrence and Geological Origin of Beryllium in Coals from the Pu''an Coalfield, Guizhou, Southwest China

The concentration, modes of occurrence and geological origin of beryllium in five workable coal beds from the Pu'an Coalfield of Guizhou were studied using the inductively coupled-plasma mass spectrometry (ICP-MS), floating and sinking experiments (FSE) and sequential chemical extraction procedures (SCEP). The results show that the average concentration of beryllium in coals from the Pu'an Coalfield is 1.54μg/g, much lower than that in most Chinese and worldwide coals. Beryllium in the Pu'an coals was not significantly enriched. However, it should be noted that the No. 8 coal bed from the study area has a high concentration of beryllium, 6.89μg/g, three times higher than the background value of beryllium in coal. Beryllium in coal mainly occurs as organic association and has predominantly originated from coal-forming plants when its concentration is relatively low. The concentration of beryllium occurring as organic association is close to that distributed in inorganic matter when beryllium concentration of coal is similar to its background value, and in addition to coal-forming plants, beryllium is mainly derived from detrital materials of terrigenous origin. When beryllium is anomalously enriched in coal, it mainly occurs as organic association and is derived from volcanic tonsteins leached for a long geological time and then adsorbed by organic matter in peat mire.     

贵州普安矿区晚二叠世煤中贵金属元素的赋存状态和地质成因

运用电感耦合等离子体质谱(ICP-MS)和逐级化学提取技术(SCET)对贵州西部普安矿区晚二叠世煤中贵金属元素的含量、赋存状态和成因机理进行了研究.结果表明,贵州普安矿区2号主采煤层的矿物组成主要为低温热液流体成因的黄铁矿和陆源碎屑成因的粘土矿物;与中国煤煤相比,该煤中Rh(38 ng/g)、Pb(640 ng/g)、Ir(9 ng/g)、Pt(98 ng/g)、Au(16 ng/g)和Ag(1620 ng/g)明显富集,其中Pb、Ir、Au的含量分别是中国煤的4.3倍、9倍和5.3倍.逐级化学提取结果表