Isotopic evidence for the origin of sulfur in the Herrin (no. 6) coal member of Illinois

The sulfur isotopic composition of the Herrin (No. 6) Coal from several localities in the Illinois Basin was measured. The sediments immediately overlying these coal beds range from marine shales and limestones to non-marine shales. Organic sulfur, disseminated pyrite, and massive pyrite were extracted from hand samples taken in vertical sections.The $\text{δ}{}^{34}\text{S}$ values from low-sulfur coals (< 0.8% organic sulfur) underlying nonmarine shale were +3.4 to +7.3%₀ for organic sulfur, +1.8 to +16.8%₀ for massive pyrite, and +3.9 to +23.8%₀ for disseminated pyrite. In contrast, the $\text{δ}{}^{34}\text{S}\text{values from high-sulfur coals}$ (> 0.8% organic sulfur) underlying marine sediments were more variable: organic sulfur, ?7.7 to +0.5%₀, pyrites, ?17.8 to +28.5%₀. In both types of coal, organic sulfur is typically enriched in ³⁴S relative to pyritic sulfur.In general, δ ³⁴S values increased from the top to the base of the bed. Vertical and lateral variations in δ ³⁴S are small for organic sulfur but are large for pyritic sulfur. The sulfur content is relatively constant throughout the bed, with organic sulfur content greater than disseminated pyrite content. The results indicate that most of the organic sulfur in high-sulfur coals is derived from post-depositional reactions with a ³⁴S-depleted source. This source is probably related to bacterial reduction of dissolved sulfate in Carboniferous seawater during a marine transgression after peat deposition. The data suggest that sulfate reduction occurred in an open system initially, and then continued in a closed system as sea water penetrated the bed.Organic sulfur in the low-sulfur coals appears to reflect the original plant sulfur, although diagenetic changes in content and isotopic composition of this fraction cannot be ruled out. The wide variability of the δ ³⁴S in pyrite fractions suggests a complex origin involving varying extents of microbial H₂S production from sulfate reservoirs of different isotopic compositions. The precipitation of pyrite may have begun soon after deposition and continued throughout the coalification process.     

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。     

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。     

Size and maceral association of pyrite in Illinois coals and their float-sink fractions

The amount of pyrite (FeS₂) removed by physical cleaning varies with differences in the amount of pyrite enclosed within minerals and of free pyrite in feed coals. A microscopic procedure for characterizing the size and maceral association of pyrite grains was developed and evaluate by testing three coals and their washed products. The results yield an index to the cleanability of pyrite. The index is dependent upon particle size and has intermediate values for feed coals, lower values for cleaned fractions, and higher values for refuse fractions; furthermore, it correlates with pyritic sulfur content. In the coals examined, the summed percentage of grain diameters of pyrite enclosed in vitrinite, liptinite, and bi- and trimacerite provides a quantitative measure of the proportion of early diagenetic deposition of pyrite.     

滇东北镇雄煤田晚二叠世煤中硫的可选性

通过对云南省东北部昭通市镇雄干沟乡荣兴煤矿C5煤层原煤筛分浮沉实验的研究,分析了该煤层中全硫及形态硫在不同粒度级和密度级中的分布规律。结果显示,全硫和黄铁矿硫在各粒度级煤中分布较均匀,其含量在各密度级煤中的分布随密度级的增大而增大。该煤层的破碎解离性质较差,但其粒度小于3.0 mm时,可分离出含2.35%全硫的浮煤(浮煤产率达88%)。总体来看,高密度级中,黄铁矿硫>95%;低密度级中,黄铁矿硫<65%,有机硫占30%左右,但其全硫较低。因此,可通过物理方法使浮煤中的硫分降低。     

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.     

Distribution of forms of sulfur in peats from saline environments in the Florida Everglades

Although there is published information on the mechanism of sedimentary pyrite formation resulting from bacterial reduction of sulfate, little is known about the distribution of forms of sulfur, including organic, in peats. In order to increase understanding of the geochemistry of sulfur in coals, we have determined distributions of forms of sulfur in five cores of saline peat and one of brackish peat, all from areas near the Shark River and Whitewater Bay in the coastal swamps of south Florida. All concentrations vary widely with depth. Total sulfur concentrations range up to 6% of dry solids. Minor amounts of sulfur are present as H₂S, S⁰, SO₄²⁻, and acid-soluble sulfide, but the principal forms are usually pyritic and organic. The ratio, organic/pyritic, is highly variable, but at a majority of levels in a profile is considerably greater than unity. It is inferred that topochemical factors are important in determining the distribution of sulfur forms in any element of volume.     

Progressive oxidation of pyrite in five bituminous coal samples: An As XANES and Fe Mössbauer spectroscopic study

Naturally occurring pyrite commonly contains minor substituted metals and metalloids (As, Se, Hg, Cu, Ni, etc.) that can be released to the environment as a result of its weathering. Arsenic, often the most abundant minor constituent in pyrite, is a sensitive monitor of progressive pyrite oxidation in coal. To test the effect of pyrite composition and environmental parameters on the rate and extent of pyrite oxidation in coal, splits of five bituminous coal samples having differing amounts of pyrite and extents of As substitution in the pyrite, were exposed to a range of simulated weathering conditions over a period of 17 months. Samples investigated include a Springfield coal from Indiana (whole coal pyritic S = 2.13 wt.%; As in pyrite = detection limit (d.l.) to 0.06 wt.%), two Pittsburgh coal samples from West Virginia (pyritic S = 1.32–1.58 wt.%; As in pyrite = d.l. to 0.34 wt.%), and two samples from the Warrior Basin, Alabama (pyritic S = 0.26–0.27 wt.%; As in pyrite = d.l. to 2.72 wt.%). Samples were collected from active mine faces, and expected differences in the concentration of As in pyrite were confirmed by electron microprobe analysis. Experimental weathering conditions in test chambers were maintained as follows: (1) dry Ar atmosphere; (2) dry O₂ atmosphere; (3) room atmosphere (relative humidity ∼20–60%); and (4) room atmosphere with samples wetted periodically with double-distilled water. Sample splits were removed after one month, nine months, and 17 months to monitor the extent of As and Fe oxidation using As X-ray absorption near-edge structure (XANES) spectroscopy and ⁵⁷Fe Mössbauer spectroscopy, respectively. Arsenic XANES spectroscopy shows progressive oxidation of pyritic As to arsenate, with wetted samples showing the most rapid oxidation. ⁵⁷Fe Mössbauer spectroscopy also shows a much greater proportion of Fe³⁺ forms (jarosite, Fe³⁺ sulfate, FeOOH) for samples stored under wet conditions, but much less difference among samples stored under dry conditions in different atmospheres. The air-wet experiments show evidence of pyrite re-precipitation from soluble ferric sulfates, with As retention in the jarosite phase. Extents of As and Fe oxidation were similar for samples having differing As substitution in pyrite, suggesting that environmental conditions outweigh the composition and amount of pyrite as factors influencing the oxidation rate of Fe sulfides in coal.     

Progression in sulfur isotopic compositions from coal to fly ash: Examples from single-source combustion in Indiana

Sulfur occurs in multiple mineral forms in coals, and its fate in coal combustion is still not well understood. The sulfur isotopic composition of coal from two coal mines in Indiana and fly ash from two power plants that use these coals were studied using geological and geochemical methods. The two coal beds are Middle Pennsylvanian in age; one seam is the low-sulfur (< 1%) Danville Coal Member of the Dugger Formation and the other is the high-sulfur (> 5%) Springfield Coal Member of the Petersburg Formation. Both seams have ash contents of approximately 11%. Fly-ash samples were collected at various points in the ash-collection system in the two plants. The results show notable difference in δ³⁴S for sulfur species within and between the low-sulfur and high-sulfur coal. The δ³⁴S values for all sulfur species are exclusively positive in the low-sulfur Danville coal, whereas the δ³⁴S values for sulfate, pyritic, and organic sulfur are both positive and negative in the high-sulfur Springfield coal. Each coal exhibits a distinct pattern of stratigraphic variation in sulfur isotopic composition. Overall, the δ³⁴S for sulfur species values increase up the section in the low-sulfur Danville coal, whereas they show a decrease up the vertical section in the high-sulfur Springfield coal. Based on the evolution of δ³⁴S for sulfur species, it is suggested that there was influence of seawater on peat swamp, with two marine incursions occurring during peat accumulation of the high-sulfur Springfield coal. Therefore, bacterial sulfate reduction played a key role in converting sulfate into hydrogen sulfide, sulfide minerals, and elemental sulfur. The differences in δ³⁴S between sulfate sulfur and pyritic sulfur is very small between individual benches of both coals, implying that some oxidation occurred during deposition or postdeposition.The δ³⁴S values for fly ash from the high-sulfur Springfield coal (averaging 9.7‰) are greatly enriched in ³⁴S relative to those in the parent coal (averaging 2.2‰). This indicates a fractionation of sulfur isotopes during high-sulfur coal combustion. By contrast, the δ³⁴S values for fly-ash samples from the low-sulfur Danville coal average 10.2‰, only slightly enriched in ³⁴S relative to those from the parent coal (average 7.5‰). The δ³⁴S values for bulk S determined directly from the fly-ash samples show close correspondence with the δ³⁴S values for SO₄^− 2 leached from the fly ash in the low-sulfur coal, suggesting that the transition from pyrite to sulfate occurred via high-temperature oxidation during coal combustion.     

Geochemistry and Modes of Occurrence of Hazardous Trace Elements in the No. 11 Coal Seam, Antaibao Surface Mine, Shanxi Province

Concentrations of seventeen hazardous trace elements including As, Pb, Hg, Se, Cd, Cr, Co, Mo, Mn, Ni, U, V, Th, Be, Sb, Br and Zn in the No.ll coal seam, Antaibao surface mine, Shanxi Province were determined using Instrumental Neutron Activation Analysis （INAA）, Inductively Coupled Plasma Atomic Emission Spectrometry （ICP-AES）, Cold-Vapor Atomic Absorption Spectrometry （CV-AAS） and Graphite Furnace Atomic Absorption Spectrometry （GF-AAS）. Comparisons with average concentrations of trace elements in Chinese coal show that the concentrations of Hg and Cd in the No. 11 coal seam, Antaibao surface mine are much higher. They may be harmful to the environment in the process of utilization. The variations of the trace elements contents and pyritic suffur in vertical section indicated that： （a） the concentrations of As, Pb, Mn, and pyritic sulfur decrease from roof to floor; （b） the concentrations of Cr, Zn and Mo are higher in roof, floor and lower in coal seam; （c） the concentration of Br, Sb, and Hg are higher in coal seam and lower in roof and floor; （d） the concentrations of Mo, V, Th and AI vary consistently with the ash yield. Cluster analysis of trace elements, pyritic sulfur, ash yield and major elements, such as AI, Fe, P, Ca shows that： （a） pyritic sulfur, Fe, As, Mn, Ni, Be are closely associated and reflect the influence of pyrite; （b） Mo, Se, Pb, Cr, Th, Co, Ca and A! are related to clay mineral, which is the main source of ash; （c） U, Zn, V, Na, P maybe controlled by phosphate or halite; （d） Hg, Br, Sb and Cd may be mainly organic-associated elements which fall outside the three main groups. The concentration distribution characteristics of trace elements in coal seam and the cluster analysis of major and trace elements showed that the contents of trace elements in the No. 11 coal seam, Antaibao surface mine, are mainly controlled by detrital input and migration from roof and floor.     

A simple and inexpensive chromium-reducible sulfur method for acid-sulfate soils

A new chromium-reducible sulfur (CRS) method suitable for the quantification of reduced inorganic S (RIS) in acid-sulfate soils is presented. The new method utilises the reduction of RIS by an acidic Cr(II) solution within a sealed reaction chamber and diffusion of the produced H₂S_(g) into an alkaline Zn solution. It offers rapid sample processing times, without the need for large volumes of high-purity N_2(g) or for specialized, expensive glassware. Examination of pyrite-talc mixtures containing up to 11.8% pyrite, revealed that the method achieves 95–98% recovery of RIS. A comparison between CRS measured by the new diffusion-based method and that measured by a standard purge-and-trap method for 25 pyritic soil samples shows a very strong (r² = 0.996) linear relationship with a slope of 0.995. The ability of the new diffusion-based CRS method to achieve accurate and precise quantification of RIS in acid-sulfate soils is demonstrated.     

The statistical analysis of the sand grain size distribution of Al- Ubay-lah barchan dunes,Northwestern Ar-Rub-Alkhali desert,Saudi Arabia

The paper analyses the statistical parameters of the sand grain size distribution of Al-Ubaylah barchan dunes applying the sieving technique and Folk and Ward, and Trask's equation. The results of the sieving analysis divulged that nearly over 90% of the sand particles fall in the size ranging between 1.50ø and 3.ø. Insignificant amount of sand grains also fall in the size ranging from 0.0ø to 1.50ø and from 3.0ø to 4.0ø respectively. The statistical analysis reveals that the sand is characteristically fine grained, moderately to moderately well sorted with an average diameter of 2.4ø and a standard deviation of 0.64ø. The sand distribution is positively fine skewed and mesokurtic to leptokurtic in nature. No significant variation in the statistical parameters (median, mean, sorting, skewness and kurtosis) of the sand grains samples used in this research is detected. The sand grain size distribution of all the samples can also be considered symmetrical and unimodal in nature. Those abovementioned characteristics are found to be nearly similar to that of other Saudi dune deserts. The miscroscopic investigation undertaken by this researcher displays that quartz represents often more than 99% of the samples. Felsic, mafic and calcium carbonates minerals represent less than 1% of the mineralogical constituents. The sand grains are subrounded to subangular and iron and calcium carbonates coated.     

X射线衍射-扫描电镜等技术研究秘鲁铜硫矿石选矿工艺矿物学特征

秘鲁铜硫矿石的主要回收对象是铜和硫矿物,由于铜矿物嵌布复杂、粒度过细以及与各种脉石矿物或金属矿物交生关系紧密,利用传统工艺矿物学研究方法如化学分析、光学显微镜检测等较难准确定量其工艺矿物学参数。本文采用化学分析、X射线衍射、扫描电镜、偏光显微镜及矿物参数自动分析系统(MLA)等技术手段,研究秘鲁铜硫矿石的化学成分、矿物组成和主要矿物的嵌布特征、粒度分布及单体解离特性等,并对影响选矿指标的主要矿物学因素进行分析。结果表明:矿石中主要元素为Cu(0.65%)和S(9.53%)。矿石中黄铁矿(16.57%)含量较高,形态较为规则,与其他矿物之间的交生关系相对简单,粒度普遍偏粗,其中粒径大于0.30mm的黄铁矿占95.06%。铜矿物主要以不规则粒状、皮壳状、网脉状、纤维状、尘粒状、斑点状分布于脉石中或与黄铁矿、闪锌矿、磁铁矿等金属矿物交生紧密,粒度极不均匀,使得铜矿物解离难度加大,且矿石中云母(12.51%)、绿泥石(3.74%)、滑石(3.34%)、高岭石、蒙脱石(3.59%)等黏土质矿物含量较高,在磨矿过程中易发生泥化从而恶化分选环境。根据该类型矿石的工艺矿物学特性,本文建议采用"粗磨-部分优先浮铜-铜硫混浮-混合精矿再磨再选分离"的工艺流程,可得到质量高的铜、硫精矿。     

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。     

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。     

Sulfur in peat-forming systems of the Okefenokee Swamp and Florida Everglades: origins of sulfur in coal

Six sulfur forms were investigated in profiles of freshwater- and marine-derived peat-forming systems of the Okefenokee Swamp, Georgia and Everglades Swamp, Florida. Total sulfur levels of 0.1–10% were found, thus indicating a major incorporation of sulfur in the very early stages of coal formation. The quantities of hydrogen sulfide and elemental sulfur observed appeared to be indicative of whether marine or freshwater conditions prevailed at the site of deposition. Carbon-bonded sulfur accounted for 70% of the total sulfur in the freshwater peat and 50% of the total sulfur in the marine peat. Over 15% of the total sulfur was in pyritic combination in the marine environment, while levels of pyrite in the freshwater peats were an order of magnitude lower. An ester-sulfate fraction represented 25% of the total sulfur in both freshwater and marine peats. The levels of sulfur forms in the peat profiles are compared to those observed in living plants and to various coals; levels of pyrite and organic sulfur in the peat are similar to those found by other investigators in freshwater-derived and marine-derived coals.     

Sulfur in Coal and Its Environmental Impact from Yanzhou Mining District,China

Sulfur is one of the havardous elements in coal The concentrations of sulfur are relatively high in coal.The major forms of sulfur in coal are pyritic,organic and sulfate.Pyritic and organic sulfur generally account for the bulk of sulfur in coal.Elemental sulfur also occurs in coal,but only in trace to minor amounts.When coals are burned,leached and washed,sulfur will be released in the form of sulfide and H2S,which then reach with O2,water and other substances to change into vitriol,and in some places it may form acid rain.And they will impact water environment,acidify the soil and do great harm to plants and human health.In this paper,on the basis of the data from the Yanzhou mining district,the distribution and concentrations of sulfur are analyzed and the existing forms of sulfur are studied.The variation of sulfur and its impact on the environments also are described when coal is used.     

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。