硫铁矿在中国硫资源中的地位分析

硫铁矿是我国的自有硫资源,几十年来我国硫铁矿产业有了很大发展,但随着我国经济对硫资源需求的大幅增加,各种形式的硫产量的迅速提高、进口硫磺及硫酸的冲击等因素,导致了硫铁矿在硫资源中的地位大幅下降。2015年硫铁矿硫仅占国内硫资源的30%,而硫铁矿制酸更是仅占硫酸总产量的22%左右。为了提高硫铁矿在硫资源中的地位,应该提高制酸技术,降低制酸成本,减少尾气排放,加快产业结构调整,提高硫铁矿产业集约化程度     

广东陆丰硫铁矿首次发现碲铋及多种硫盐矿物

广东陆丰硫铁矿首次发现碲铋及多种硫盐矿物广东陆丰硫铁矿自１９５８年建矿以来，一直作为单独硫铁矿开采。我们在对该矿床物质组分研究过程中，首次发现硫化物、银矿物及少见复杂硫盐矿物十多种。其中ＡＵ，＊ｇ，Ｃｕ，Ｔｅ，Ｂｉ等伴生元素均达到综合利用品位。尤其是...     

我国化工矿产资源现状与地质工作展望

<正> 化工矿产系指用于硫酸工业、化肥工业、纯碱工业和无机盐工业等化学工业有用矿物资源的总称,主要包括硫铁矿(包括黄铁矿、白铁矿、磁黄铁矿),自然硫及酸性天然气中回收硫,磷酸盐(包括磷灰石、磷灰岩、磷块岩)、氯化物(包括食盐、钾盐、钾石盐、光卤石、水     

桂北地区硫铁矿地球化学特征及其意义

通过对桂北地区硫铁矿的铅、硫同位素进行计算和分析,认为该区硫铁矿的物质是多来源,多成因,多阶段演化的结果。推测成矿时代为海西—印支期,以印支期为主;硫源主要来自于同时代沉积的硫酸盐细菌还原作用;同一矿区中,铅、硫同位素组成相似,二者物质来源和成因一致。     

勉-略-阳地区成矿系列新认识

"西北矿产资源潜力评价"项目与"秦岭地质矿产综合研究"项目共同协作研究,对勉县-略阳县-阳平关地区中—新元古代主要地质建造有关成矿系列初步提出如下新认识:1勉-略-阳地区中—新元古代海相火山-沉积变质岩系有关Fe-Cu-Pb-Zn-Co-Au-Ag-硫铁矿成矿系列族a、中—新元古代海相基性火山-沉积变质岩系同生Fe-Cu-Zn-Co-Au-Ag成矿系列(矿床实例:甘肃省筏子坝铜矿、白皂铜矿、阳坝铜矿、杜坝铜矿,陕西省大茅坪铜矿)。b、中—新元古代海相中酸性火山-沉积变质岩系同生Pb-Zn-Cu-Au-Ag-硫铁矿-重晶石成矿系列(矿床实例:陕西省东沟坝铅锌多金属矿,红土石含铜硫铁矿,二里坝含铜硫铁矿)。     

黔北马鬃岭铝土矿床含矿岩系地质特征及形成环境分析

通过对含矿岩系的岩性、岩(矿)石结构构造、化学组成、矿物组成等的研究,认为:含矿岩系的岩性组合规律性强。底部为深色含绿泥石铝质泥岩,之上为浅色铝质泥岩。中部为以一水硬铝石为主的豆鲕-碎屑-蜂窝状-半土状铝土矿,中上部为以勃姆石为主的致密块状铝土矿,顶部为以勃姆石为主的豆状、碎屑状铝土岩(矿)。铝土矿石的形成,是成矿母质经历了风化氧化、剥蚀、搬运、沉积、暴露淋滤,最终形成现在的铝土矿。含矿岩系底部含绿泥石铝质泥岩形成于过渡相的半咸水环境,中部及上部铝土矿(岩)形成于陆相湖泊环境。含矿岩系中的硫铁矿是沉积后的实成岩过程中,流体带入的硫,与岩(矿)石中的氧化铁反应,在孔隙处沉淀而成。     

中化地质矿山总局地质研究院系统内部《硫铁矿石管理样》概况

<正>为了监控硫铁矿石分析质量,提高分析水平,1983年9月,在福州举行的第三次化工地质实验室工作会议上,决定制备含硫量高、中、低的三个硫铁矿石管理样。1984年由原化工部化学矿产地质研究院(简称地研院)第八研究室(现中化地质矿山总局地质研究院分析测试中心)负责研制工作,吉林、辽宁、内蒙古、河北、河南、陕西、四川、湖南、福建和广东等10省的化工地质队实验室参加协作定值,1985年该套硫铁矿石管理样研制成功。     

福建省硫铁矿资源及其综合利用问题

<正> 我省的硫铁矿并非现实优势矿种,但它成矿条件好,类型多,共生有多种有色金属,并伴生有贵金属、分散元素等。从长远看,综合利用、综合回收不仅能促进硫铁矿业的开发,而且可填补省内某些矿种的空白。本文就省内硫铁矿资源的一般概况、利用现状及经济评价要求谈谈其综合利用的迫切性.一、硫铁矿资源的概况及我省的利用现状(一)硫铁矿资源的一般情况硫铁矿是黄铁矿、白铁矿、磁黄铁矿的总称,是硫资源的传统来源。科学技术的发展、选冶工艺的改进为世界硫源开辟了多种途径。西方国家从含硫化氢大于0.1%的酸性天然气     

贵州三岔河硫铁矿矿床中假象黄铁矿的发现及其成因意义

贵州三岔河硫铁矿矿床是西南硫矿带内大型矿床之一。矿床产在二叠系龙潭煤系底部，矿体呈层状，与地层产状一致。在矿床的下部发现一层由假象黄铁矿组成的矿石。柱状假象黄铁矿的特点是：Ａｓ含量高，ＣＯ／Ｎｉ值＞１，Ｓ／Ｓｅ值＜２００００，且交代结构明显。通过假象黄铁矿物性特征、主微量元素、硫同位素的研究，证明它系成岩过程中Ｈ２Ｓ交代火山物质中的辉石或间石类矿物的产物。西南硫矿带煤系硫铁矿的形成与火山作用有关。成矿物质源于峨眉山玄武岩喷发期后气液，经沉积－成岩作用形成黄铁矿床。     

喀斯特小流域石灰土硫同位素组成特征及环境指示意义

用连续提取方法分析了石灰土总硫、SO_4~(2–)、总还原态硫(TRS)和有机硫的硫同位素组成,探讨了石灰土中硫的迁移转化过程及其环境效应。有机硫是石灰土主要的硫形态,随剖面加深总硫和有机硫的δ34S值逐渐增大,其含量降低,这与有机硫持续矿化有关。SO_4~(2–)和TRS的δ34S值随剖面加深平行地增大指示了石灰土中存在SO_4~(2–)异化还原过程,并且TRS是主要产物。高pH值和较低的黏粒含量不利于SO_4~(2–)吸附,生物滞留后剩余的SO_4~(2–)主要通过淋溶迁移出石灰土剖面。当前酸沉降对石灰土的影响并不严重,SO_4~(2–)的淋溶迁移并没有引起石灰土pH值的显著降低。但值得关注的是,有机硫形态是酸沉降输入的SO_4~(2–)在石灰土中主要的硫滞留方式,SO_4~(2–)吸附基本可以忽略,则在硫的年沉降速率显著降低之后,在较长时期内,石灰土中有机硫的矿化可能释放大量的SO_4~(2–)进入地表和地下水体,与之相关的土壤理化性质变化和水体化学组成改变等方面的环境效应值得关注。     

Sulfur geochemistry of Jurassic high-sulfur coals from Egypt

Jurassic high-sulfur coals from the Maghara area in Egypt were analyzed for the abundance and isotopic composition of different forms of sulfur. Analyses indicated that the sulfur occurs in the form of organic, pyrite, and sulfate forms. Pyrite sulfur represents the major fraction, while sulfate sulfur is minor and could be formed during sample preparation for the analyses.The δ³⁴S CDT values of the organic sulfur are positive ranging between 1.0‰ and 13.5‰ with an average of 9.1‰. Pyrite δ³⁴S values are also positive ranging between 1.5‰ and 15.4‰ with an average of 6.6‰. The high δ³⁴S values of the organic sulfur in the Maghara coals suggest a freshwater origin of the organic components of these coals. The lack of correlation between pyrite and organic sulfur isotopes implies different incorporation mechanisms of sulfur. The high-sulfur contents along with the positive and high δ³⁴S values suggest a marine origin of pyrite sulfur and support the geological interpretation of marine invasion after the peat formation that was responsible for the incorporation of the pyrite sulfur.The occurrence of pyrite as euhedral crystals as well as the high and positive δ³⁴S values of the pyrite sulfur indicates the formation of pyrite during diagenesis as a result of marine water invasion of the preexisting peat in a brackish coastal plain environment.     

沁水盆地晚古生代煤中硫的地球化学特征及其对有害微量元素富集的影响

煤中硫是多种有害微量元素的重要载体。基于形态硫分析、电感耦合等离子质谱及X射线衍射等方法分析沁水盆地晚古生代煤中硫和有害微量元素的分布规律,探讨了煤中硫对有害微量元素富集的影响,运用带能谱的扫描电镜和光学显微镜划分煤中硫化物的微观赋存特征。结果表明,沁水盆地煤中硫整体上以有机硫为主,平均占全硫的78%,只有在太原组个别高硫煤中以黄铁矿硫为占优势。显微镜和扫描电镜下可识别出煤中黄铁矿的微观赋存状态包括莓球状、薄膜状、晶粒状、结核状、团窝状黄铁矿和细粒黄铁矿集合体,白铁矿的微观赋存特征包括聚片状、板状和矛头状白铁矿,部分白铁矿与黄铁矿共生。沁水盆地煤中有害微量元素含量整体较低,黄铁矿是有害微量元素As、Se和Hg的重要载体,而有机硫决定了煤中U的富集。研究认为,成煤时期海水对泥炭沼泽的影响导致太原组煤中全硫和黄铁矿硫较高,太原组煤中硫的来源具有多样性,煤中黄铁矿具有多阶段演化的特点。     

沉积过程对自生黄铁矿硫同位素的约束

自生黄铁矿是海洋沉积物中还原态硫的主要赋存形式,其形成过程与有机质矿化相关,影响全球的C-S-Fe生物地球化学循环。自生黄铁矿硫同位素分馏主要受微生物硫酸盐还原的控制,但近期的研究成果表明局部沉积环境的改变也可以影响黄铁矿硫同位素的组成,特别是在浅海环境。在浅海非稳态沉积环境内,物理再改造和生物扰动作用,导致硫酸盐还原带内生成的硫化物被再氧化,进而影响黄铁矿的硫同位素值。浅海沉积过程容易受到古气候和海平面变化的影响,引起沉积速率的剧烈波动,导致有机质和活性铁输入的不稳定,进而影响成岩系统的开放性和硫酸盐还原速率,最终影响黄铁矿的硫同位素值。另外,沉积速率的改变还影响硫酸盐—甲烷转换带的迁移,造成有机质和甲烷厌氧氧化硫酸盐还原的相互转化,产生不同的硫同位素信号。东海内陆架泥质区为研究沉积过程对自生黄铁矿的形成及其硫同位素组成的约束机制提供了很好的研究材料。该区域有很好的沉积学研究基础,自生黄铁矿丰富、并且个别层位有生物气（甲烷为主）存在,是研究边缘海C-S-Fe循环的理想场所。     

冀东峪耳崖金矿床金属矿物特征及其组合意义

峪耳崖金矿床是冀东地区重要的金矿床之一.研究峪耳崖金矿床中金属矿物成分的变化及元素赋存状态,对了解矿床的形成机制及指导找矿具有重要意义.本次工作应用光学显微镜和电子探针(EPMA)对峪耳崖金矿床中的金属矿物进行了研究,并应用氢、氧及硫同位素分析对峪耳崖金矿床的成矿热液来源及硫源进行了探讨.该矿床的载金矿物有石英、黄铁矿、碲铋矿,金矿物为银金矿.其中,黄铁矿的w(S)平均为52.34％,与理论值相比,其普遍亏硫,显示出成矿与热液有关.碲铋矿是本次工作重点研究的载金矿物,与金的产出具关联性.被碲铋矿包裹的银金矿的w(Au)要高于被黄铁矿包裹的银金矿的w(Au).据氢、氧及硫同位素测试结果认为,峪耳崖金矿床的热液来源主要为岩浆水,硫来自深部岩浆源.结合黄铁矿、黄铜矿、闪锌矿、方铅矿、碲铋矿和银金矿等的矿物学特征及组合意义推断,峪耳崖金矿床为中-深成中温岩浆热液矿床,并认为其深部找矿可关注Te、Bi富集异常的区段.     

Occurrence and distribution of sulfur in peat-forming environments of southern Florida

Cores and surface samples of peats from the Everglades—Mangrove region of Southern Florida were analyzed for total sulfur and pyritic sulfur. These values were compared with the petrographic-botanical components of the peats as determined from point-counts of oriented microtome sections. Pyrite occurs as individual euhedral crystals, loosely packed framboids, and lenses or crusts of minute crystals. Framboids and minute crystals are often associated with organic matter and sometimes with bacteria and fungi. Pyrite tends to selectively occur in void spaces in or between peat tissues. In samples containing very small amounts of pyrite, framboidal pyrite is the prevalent form.Marine to brackish peats contain the highest pyrite and total sulfur contents, with brackish peats generally containing more pyrite than marine peats. Pyrite tends to be lower in all peats within 30 cm of the surface, whether marine or brackish.Burial of freshwater peats beneath marine or brackish peats tends to increase the total sulfur and pyritic sulfur in the underlying peats. Burial beneath brackish-water, clay-rich deposits (such as splays) tends to increase total sulfur and pyritic sulfur in the underlying deposits more than burial beneath less clay-rich deposits.     

草莓状黄铁矿的形成机制探讨及其对古氧化-还原环境的反演

【研究目的】草莓状黄铁矿广泛存在于现代沉积物和沉积岩中,其成因机制总体上分为有机成因和无机成因两种,尽管两种机制均有理论与实验的支撑,但尚未建立一种具有普遍意义的形成机制。【研究方法】本文对目前草莓状黄铁矿的形成机理、氧化还原环境的应用及后期环境变化的影响进行了系统的综合研究。【研究结果】不同氧化-还原环境下形成的草莓状黄铁矿在粒径、形态以及硫同位素之间均存在较大的差异,可做为反演古氧化-还原环境的指标。草莓状黄铁矿的微晶尽管与粒径具有一定的正相关性,但是两者在形态演化序列、生长模式、聚集因素等方面与古氧化-还原环境的关系尚不清楚。仅凭草莓状黄铁矿粒径与铬还原法测定的硫同位素反演古氧化-还原环境存在一定的局限性,需要其他指标综合判定,尚需进一步开展草莓状黄铁矿原位硫同位素值与粒径对古氧化-还原环境反演的研究。后期氧化可使草莓状黄铁矿表面化学成分发生变化,但粒径分布依然具有古氧化-还原环境的指示意义。【结论】草莓状黄铁矿的实验模拟、理论体系和多学科交叉的研究中仍存在一些问题,尚需进一步研究。     

Pyrite-hydrocarbon Interaction under Hydrothermal Conditions: an Alternative Origin of H2S and Organic Sulfur Compounds in Sedimentary Environments

Sulfate rocks and organic sulfur from sedimentary organic matter are conventionally assumed as the original sulfur sources for hydrogen sulfide(H_2S) in oil and gas reservoirs. However,a few recent experiments preliminarily indicate that the association of pyrite and hydrocarbons may also have implications for H_2S generation,in which water effects and natural controls on the evolution of pyrite sulfur into OSCs and H_2S have not been evaluated. In this study,laboratory experiments were conducted from 200 to 450° C to investigate chemical interactions between pyrite and hydrocarbons under hydrothermal conditions. Based on the experimental results,preliminary mechanism and geochemical implications were tentatively discussed. Results of the experiments showed that decomposition of pyrite produced H_2S and thiophenes at as low as 330°C in the presence of water and n-pentane. High concentrations of H_2S were generated above 450°C under closed pyrolysis conditions no matter whether there is water in the designed experiments. However,much more organic sulfur compounds(OSCs) were formed in the hydrous pyrolysis than in anhydrous pyrolysis. Generally,most of sulfur liberated from pyrite at elevated temperatures was converted to H_2S. Water was beneficial to breakdown of pyrite and to decomposition of alkanes into olefins but not essential to formation of large amounts of H_2S,given the main hydrogen source derived from hydrocarbons. In addition,cracking of pyrite in the presence of 1-octene under hydrous conditions was found to proceed at 200°C,producing thiols and alkyl sulfides. Unsaturated hydrocarbons would be more reactive intermediates involved in the breakdown of pyrite than alkanes. The geochemistry of OSCs is actually controlled by various geochemical factors such as thermal maturity and the carbon chain length of the alkanes. This study indicates that the scale of H_2S gas generated in deep buried carbonate reservoirs via interactions between pyrite and natural gas should be much smaller than that of thermochemical sulfate reduction(TSR) due to the scarcity of pyrite in carbonate reservoirs and the limited amount of long-chained hydrocarbons in natural gas. Nevertheless,in some cases,OSCs and/or low contents of H_2S found in deep buried reservoirs may be associated with the deposited pyrite-bearing rock and organic matters(hydrocarbons),which still needs further investigation.     

Soft X-ray spectroscopic studies of the reaction of fractured pyrite surfaces with Cr(VI)-containing aqueous solutions

We have used synchrotron-based soft X-ray core-level photoemission and adsorption spectroscopies to study the reaction of aqueous sodium chromate solutions with freshly fractured pyrite surfaces. Pyrite surfaces were reacted with 50 μM sodium chromate solution at pH 7 for reaction times between 1 min and 37 hr. Additional experiments were performed at pH 2 and pH 4 with 50 μM sodium chromate solutions and at pH 7 with 5 mM solutions. At chromate concentrations of 50 μM, all chromium present on the pyrite surface was in the form of Cr(III), while at 5 mM, both Cr(III) and Cr(VI) were present at the pyrite surface. Minor quantities of oxidized sulfur species (sulfate, sulfite, and zero-valent sulfur) were identified as reaction products on the pyrite surface. The amount of oxidized sulfur species observed on the surface was greater when pyrite was reacted with 5 mM Cr(VI) solutions because the rate of chromium deposition exceeded the rate of dissolution of pyrite oxidation products, effectively trapping Cr(VI) and oxidized sulfur species in an overlayer of iron(III)-containing Cr(III)-hydroxide. This work shows that pyrite, an extremely cheap and readily available waste material, may be suitable for the removal of hexavalent chromium from acidic to circumneutral waste streams. The reduced chromium ultimately forms a coating on the pyrite surface, which passivates the pyrite surface towards further oxidation.     

南秦岭柞水—山阳矿集区夏家店金矿床黄铁矿微量元素和氢、氧、硫同位素对矿床成因的制约

为了研究柞水—山阳矿集区夏家店金矿床成因,采用LA-ICP-MS和LA-MC-ICP-MS技术分析夏家店金矿床矿体及围岩样品中黄铁矿原位微量元素及氢、氧、硫同位素组成特征。结果表明,该矿床黄铁矿的Co/Ni 比值为0.11~0.76,说明其与沉积作用有关。矿石中黄铁矿的δ³⁴S值(-9.40‰~7.16‰)与围岩碳质板岩的δ³⁴S值(-8.84‰~10.64‰)接近,黄铁矿的δ³⁴S均值(2.47‰)基本落在岩浆硫的范围内,指示矿石硫可能由地层硫和岩浆硫混合而成。氢、氧同位素测试结果表明,夏家店矿床成矿流体可能主要来自岩浆水,成矿后期有大气降水的加入。综合矿床地质特征、成矿温度、金赋存状态等特征和黄铁矿微量元素、硫同位素组成可知,夏家店金矿床属于卡林型金矿,其成矿流体主要来自岩浆水,成矿后期有大气降水加入;其成矿物质是由深部岩浆与地层混合而成。     

中国硫矿资源预测模型及资源潜力分析

硫是化学工业最重要的基本原料之一,主要用于生产化肥。我国硫矿资源工业开发利用的主要为硫铁矿和伴生硫。2007-2013年,中国地质调查局实施了全国化工矿产资源潜力评价项目,完成了全国硫矿成矿规律及预测研究,编制了相关图件,建设了数据库,取得了阶段性的成果。文章在以往研究和省级硫矿资源潜力评价成果的基础上,总结了全国硫矿时空分布特征,划分了成矿区带和成矿类型,建立了典型矿床和预测工作区的预测模型,最后对全国硫矿资源潜力进行了分类评价汇总。结果表明,全国共有硫矿床、矿点、矿化点共1 437处,其中硫铁矿1 418处,自然硫矿19处。成矿时代跨度为太古宙晚期-新生代,以元古宙硫矿储量最大。全国共划分为46个Ⅲ级硫矿成矿区带和17个矿集区;划分了沉积变质型、沉积型（海相、煤系）、岩浆热液型、海相火山岩型、陆相火山岩型、自然硫型6种预测类型和17个矿床式;梳理了6种预测类型典型硫矿床的预测要素和预测模型。全国共划分沉积变质型硫铁矿预测工作区20个,沉积型硫铁矿58个,岩浆热液型68个,海相火山岩型12个,陆相火山岩型9个,自然硫矿5个。全国共圈定硫矿3级预测区274个,其中硫铁矿268个,自然硫矿6个。全国硫铁矿硫铁矿和自然硫资源总量分别为241.35亿t和5.67亿t,其中预测资源量分别为184.57亿t和2.32亿t。根据成矿地质条件、矿床地质特征、矿石选冶性能、资源量可靠程度,文中遴选出21个硫矿优先勘查区,预测自然硫资源量2 229.3万t(S),硫铁矿50.58亿t(矿石)。该区成矿地质条件好,找矿潜力大,有一定的工作基础,已知矿床深边部等近期可优先安排勘查工作的预测区,远景好时可作为整装勘查基地。