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.

Distribution, modes of occurrence, and main factors influencing lead enrichment in Chinese coals

Lead is a potentially harmful element that has caused serious environmental pollution during its mining and use along with serious human health problems.This study assessed lead in Chinese coals based on published literature,with a particular focus on data reported since 2004.The analysis included 9447 individual samples from 103 coalfields or mines in 28 provinces in China.The arithmetic mean content of lead in the studied coals was 15.0μg/g.Considering the coal reserves,the weighted-average lead concentration in Chinese coals was calculated to be 19.6μg/g.Lead was significantly enriched in the coals from Henan Province and enriched in the coals from the Tibet Autonomous Region.The coals from Tibet–Western Yunnan and the southern areas of China had elevated lead concentrations.Sulfides are the primary hosts of lead in Chinese coals,although other hosts include silicates,organic matter,carbonates,and other minerals.Source rocks in the sediment-source region and marine environments may be the most significant factors contributing to lead enrichment in Chinese coals.Hydrothermal fluids and peat-forming plants also contribute to lead enrichment in some Chinese coals.

Modes of Occurrence and Cleaning Potential of Trace Elements in Coals from the Northern Ordos Basin and Shanxi Province, China

Based on the analyses of 43 elements in 16 samples of the raw coal and feed coal collected from the northern Ordos basin and Shanxi Province, the modes of occurrence of these elements were studied using the method of cluster analysis and factor analysis, and the cleaning potential of the hazardous elements relatively enriched in the coals was discussed by analyzing six samples of the cleaned coal from the coal-washing plants and coal cleaning simulation experiments. The results shows that the elements Br and Ba show a strong affinity to the organic matter, Cs, Cd, Pb, Zn and Hg partly to the organic matter, and the other trace elements are mainly associated with the mineral matter. Cs, Mo, P, Pb, Zn and S have positive correlations with the two principal factors, reflecting the complexity of their modes of occurrence. Some elements that were thought to show a faint relationship (Be with S and Sb with carbonates) in other rocks are found to have a strong interrelation in the coals. Clay minerals (mainly kaolinite) dominate in the coals, and Ta, Th, Ti, Sc, REE, Hf, U, Se, W, V, Nb, Mo, Al, P, Cr, Pb and Zn are distributed mostly in kaolinite, while K, Rb, Cs, and Na have much to do with illite. Conventional cleaning can reduce the concentrations of most hazardous elements in various degrees. The hazardous elements S, As, Sb, Se, Mo, Pb, Cd and Hg relatively enriched in some coals from the area studied have a relatively high potential of environmental risks. However, by physical coal cleaning processes, more than 60% of As and Hg were removed, showing a high degree of removal, more than 30% of Sb, as well as S, Pb and Cd partly associated with the inorganic matter were removed. Se and Mo showing a relatively low degree of removal could be further removed by deep crushing of the coal during physical cleaning processes, and the concentrations of S, Pb, Cd and Hg with a partial association with the organic matter could be decreased in such ways as the coal blending. Cluster analysis together with factor analysis is a rapid and effective way to deduce the mode of occurrence of an element from bulk samples, and the removability data of most hazardous elements are basically consistent with their modes of occurrence suggested, which indicates that the statistical analysis could predict the cleaning potential of hazardous elements during the physical coal cleaning.

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 1.54 μg/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, 6.89 μg/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.

The distribution and occurrence of mercury in Chinese coals

Mercury is one of the most concerned hazardous elements in coals. 1018 coal samples of different coal-forming periods, coal-accumulating areas and coal ranks all over the country were collected to study the distributions of mercury in Chinese coals. The modes of occurrence of mercury were studied with float-sink experiments of 10 coals from different basins in China and correlation analyses were conducted between concentrations of mercury and maceral and sulfur contents, as well as the ash yield. The theoretic concentrations and affinities of mercury in vitrinite, inertinite, clay and pyrite were then calculated following the methods proposed by Solari. The weighted average concentration of mercury in Chinese coals is 0.154 ~tg/g, which is similar to that in the word coals in general. The mercury concentrations vary largely in the coals of different coal-forming period and coal-accumulating areas as geological settings play key roles in deter- mining the geochemistry of mercury. The concentrations of mercury in coals from south and southwest China and those from North China of C3-P1 are relatively higher while those from North China of Jm-a and Northeast of J3-K1 relatively lower. The general distribution trends of mercury are very similar to that of ash yield, sulfur contents in coals. Pyrite is the dominant carrier of mercury in most coals, especially in some high-sulfur coals with abundant epigenetic pyrite formed during diagenesis and metamorphism. Mercury has higher affinity to vitrinite than to inertinite in most coals, which accords with the geological origin of macerals and geochemistry of mercury.

Distribution and occurrence of trace elements in the No.14 coal from the Huolinhe mine

Optical microscopy, and scanning electron microscopy in conjunction with energy dispersed X-ray spectrometry （SEM-EDX）, have been used to study the minerals and the concentrations of 12 trace elements in the No.14 coal from the Huolinhe mine, Inner Mongolia China. The distribution, affinity and removability of the trace elements were studied by float-sink experiments and petrological methods. A high mineral content, dominated by clay minerals, was found in the No.14 coal from the Huolinhe mine. The concentrations of As, Sb and Hg are relatively high compared to the average values for Chinese coals. As, Cr, Hg, Li, Mn, Pb are mainly associated with the minerals while Cd, Co, Ni, Sb, and Se are evenly distributed between the minerals and the organic matter. Be and Ba are mainly distributed in the minerals with a minor proportion in the organic matter. Most elements have a low organic affinity, although Sb, Se, Co, Cd, Ni are closely integrated with the organic matter. High theoretical removabilities are indicated for most trace elements. So it may be possible to lower the concentrations of trace elements during coal preparation.

Mineralogy and Mode of Occurrence of Gold, Silver and Bismuth of the Caijiaying Lead-Zine-Silver Deposit, Hebei Province

The deposit under study is a hydrothermal filling-metasomatic vein type lead-zinc-silver deposit, in whichgold and silver can be recovered as by-products. These metals mainly occur as microgranular native gold,electrum, stephanite, acanthite, pyraragyrite, freibergite, and native silver. Gold minerals tend to be associatedwith galenobismutite, native bismuth and unnamed Bi_2Te. They are either enclosed in pyrite, marmatite,iron-bearing sphalerite and galens or fill the microfissures of these minerals. Silver minerals usually occur incleavages or fissures of galena, marmatite and pyrite, but are not associated with gold and bismuth minerals.Gold and silver mineralizations occurred later than lead and zinc, while the silver mineralization was precededby that of gold.

Characteristics and geological significance of germanium in Taiyuan coal formation of Huainan Coalfield,Anhui,China

HN-1#is the first fully working coring well of the Taiyuan Formation(Ty)in the Huinan Coalfield and exploration studies are currently underway on the associated resources of the coal-bearing strata.The HN-1#well is located in the Fufeng thrust nappe structural belt in the south of the Huainan Coalfield.Three coal samples from the Ty were collected from HN-1#and inductively-coupled plasma mass spectrometry and inductively-coupled plasma atomic emission spectrometry were used to determine the Ge content of each sample.Based on proximate and ultimate analyses,microscopy data,and analyses of the ash products,some important findings were made.The Ty coal samples had a relatively high total sulfur(Sud)content(4.24%),thus the coal was considered to be a lower ranked coal(high volatility bituminous coal),which also had a low coal ash composition index(k,1.87).Collodetrinite was the main submaceral of the Ty coal.Small amounts of pyrite particles were found in the coal seams of the Ty,while the contents of pyrite and algae in the top and bottom sections of the coal seam were relatively high,which meant that the swampy peat conditions which existed during the formation of the coal seams were affected by seawater;also the degree of mineralization of the coal seam was relatively high,which is consistent with reducing conditions in a coastal environment setting.Atomic force microscopy(AFM)experiments showed that the modes of occurrence of Ge in the Ty coal were mainly those for organic-bound and adsorbed Ge species.The organic carbon isotope values for the Ty coal ranged from-24.1‰to-23.8‰,with an average value of-24.0‰,which is equivalent to the value for terrestrial plants(average value-24.0‰).The Ge content of the Ty coal was 13.57 mg/kg.The Ge content was negatively correlated with volatile matter and the ash yield.

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.

Preliminary study on the mode of occurrence of arsenic in high arsenic coals from southwest Guizhou Province

Coal samples from high arsenic coal areas have been analyzed by electron micropbe analyzer (EMPA), scanning electron microscopy with an energy dispersive X-ray analyzer (SEM-EDX), X-ray diffinction analysis (XRD), low temperature ashing (LTA), transmission electron microscopy (TEM), X-ray absorption fine structure (XAFS), instnunent neutron activation analysis (INAA) and wet chemical analysis. Although some As-bearing minerals such as pyrite, arsenopyrite, realgar (?), As-bearing sulfate, and As-bearing clays are found in the high arsenic coals, their contents do not account for the abundance of arsenic in the some coals. Analysis of the coal indicates that arsenic exists mainly in the form of As 5+ and As 3+, combined with compounds in the organic matrix. The occurrence of such exceptionally high arsenic contents in coal and the fact that the arsenic is dominantly organically associated are unique observations. The modes of occurrence of arsenic in high As-coals are discussed.

Discovery of anomalous gallium enriched in stone coal: Significance, provenance and recommendations

Gallium(Ga)is a critical mineral that plays an irreplaceable role in consumer electronics,clean energy technologies and the aerospace industry.Nowadays competition for gallium resources at the national strategic level has begun to emerge,but gallium resources are unevenly distributed globally,and their presence is not guaranteed.New discoveries revealed an average gallium concentration of thirty-one samples from M_(1),M_(2),M_(3) and M_(4) stone coal-bearing seams of the Cambrian strata on South Qinling Orogenic Belt in central China is 157 mg/kg(9.98–747 mg/kg),which is 27.6-fold higher than the global hard coal average,as well as the existing association of Mo–V–U–Cd–Zn–Ba–Se–Mg–Ni–Cu enrichment.Ga average of these coal seams are 344 mg/kg(M_(3),44.5–747 mg/kg,n=11),270 mg/kg(M_(4),14.3–270 mg/kg,n=5),53.8 mg/kg(M_(2),22.6–75.4 mg/kg,n=8)and 19.8 mg/kg(M_(1),9.98–34.9 mg/kg,n=7)respectively,as well as the thickness of approximately 6,12,8,and 20 m,which be close to or exceed to the boundary grade standard(30 mg/kg)and minimum recoverable thickness(0.7 m)of gal-lium resources exploration.These findings indicate that the Cambrian stone coal deposits,especially in the middle and late Cambrian period,should be considered as promising alternative sources of gallium.The anomalous gallium-enriched sediments originated from a complex combination of hydrothermal flu-ids,original biomass and terrigenous materials.For the M_(1) stone coal-bearing seams,gallium most likely occurred in the mode of GaAs,Ga_(x)In_(1-x)As and GaO(OH),while modes of gallium in the M_(2) to M_(4) seams is interrelated with the organic affinity and clay minerals.The crude reserve estimate of gallium resources in central China is approximately 10.06?104 tons,corresponding to a super-large coal-hosted gallium ore deposit.The unique paleogeographic location and geological structure in central China resulted that this newly discovered deposit is a unique type of gallium-enriched deposit that has been discovered worldwide.These discoveries will provide the critical parameters when developing distinctive benefici-ation processes and appropriate extraction procedures,as well as guidance and effective for future prospecting regions of gallium resources around the globe,involving a combination consider the distri-bution of regional deep–large fault zones and the middle to late Cambrian black rock series deposits.

Geochemistry of rare earth elements and yttrium in Late Permian coals from the Zhongliangshan coalfield, southwestern China

Rare earth elements and yttrium(REY)in coal deposits are considered promising alternative sources for these resources owing to their increasing global demand.This paper reports the geochemical characteristics of REY in the Late Permian coals from an underground K1a seam section of the Zhongliangshan coalfield in Chongqing,southwestern China.The mineralogy,degree of enrichment,distribution patterns,modes of occurrence,and sediment origin of REY were investigated.Compared with the average of world coals,the concentration of REY in the K1a coals were normal,dominated by light REY(LREY),with less medium and heavy REY(MREY,HREY).The fractionation degree of the MREY and HREY are higher than that of LREY in most K1a coal samples,deduced from the mixed enrichment type of REY,mainly including M-H-type,and a few L-M type and H-type.In addition,the combination of anomalies of Ce,Eu,Gd,and Al_(2)O_(3)/TiO_(2) parameters,the terrigenous materials in the K1a coal were derived from the felsic-intermediate rocks at the top of the Emeishan basalt sequence,and the samples were affected by seawater intrusion during early peat accumulation.Although the minerals primarily consist of kaolinite,illite,pyrite,and small amounts of quartz,calcite and anatase,REY are correlated with ash yield,SiO2,and Al_(2)O_(3),revealing that the REY mainly occur in aluminosilicate minerals,especially kaolinite and illite.Meanwhile,REY positively relate to P_(2)O_(5) and Zr,which may exist in phosphate-containing minerals or zircon.Furthermore,most samples in the K1a coal or ash do not reach the cut-off grade for the beneficial recovery of REY.With the exception of central Guizhou,southwestern Chongqing,and the junction of western Guizhou and northeastern Yunnan,the REY content in coals from southwestern China are high,and its by-products are suitable as potential REY sources.