Geochemistry of sulfur and hazardous trace elements in coals and its bearing on human health

Hazardous air pollutants, including compounds of sulfur and toxic trace elements, are emitted during coal combustion. Geochemical studies of these constituents in coals provide information about their species, regional distribution and origins. The data are useful in understanding the cause and scope of human health problems related to these hazardous elements and in designing preventive or remedial measures. Sulfur in coal is a problem because sulfur dioxide emitted during coal combustion is a main source of acid rain. The sulfur isotopic evidence shows that sulfur in low-sulfur coal is derived primarily from parent plant materials. Sulfur enrichment in medium- and high-sulfur coals is caused by the sulfate in seawater that flooded the peat swamp during coal formation. The sulfur content of a coal is controlled primarily by the depositional environment of coal seams. Only pyritic sulfur can be removed by physical coal cleaning processes （coal preparation）. Sulfur dioxide emission can be reduced using clean coal technologies, such as flue-gas desulfurization, fluidized-bed combustion, and integrated gasification and combined cycle.     

Sulfur Isotopic Characteristics of Coal in China and Sulfur Isotopic Fractionation during Coal—burning Process

The determined results of the sulfur contents and isotopic composition of coal samples from major coal mines in 15 provinces and regions of China show that the coal mined in the north of China is characterized by higher ^34S and lower sulfur content, but that in the south of China has lower ^34S and higher sulfur content.During the coal-burning process in both indrstrial and daily use of coal as fuel the released sulfur dioxide is always enriched in lighter sulfur isotope relative to the corresponding coal;the particles are always enriched in heavier sulfur isotope.The discussion on the environmental geochemical significance of the above-mentioned results also has been made.     

Hydrochemistry and H-O-C-S Isotopic Geochemistry Characteristics of Geothermal Water in Nyemo-Nagqu, Tibet

Nyemo-Nagqu, Tibet, is rich in high-temperature geothermal resources. The geothermal fields in Yangbajain and Yangyi as well as 11 unexplored geothermal fields along the geothermal belt from Nyemo to Nagqu were systematically investigated and the hydrochemistry data were collected from the whole field. Meanwhile, H-O-C-S isotope data were obtained for the new fields, and H-O isotope data for the Yangbajain and Yangyi fields. A comparison of the Nyemo-Nagqu geothermal fields with those in the Yangbajain area shows that the types of high-temperature geothermal water are dominated by Cl-Na and Cl·HCO_3-Na, while the types of medium-high-temperature geothermal water are dominated by HCO_3-Na. The concentrations of Li, F, SiO_2, and HBO_2 in the geothermal water are positively correlated with Cl content, indicating possible mixing with magma water. The reservoir temperatures range from 90 to 270°C by geothermometers. Slight drifting of ~(18)O was recorded at the Dongweng and Nyingzhong high-temperature geothermal fields, while more significant drifting was recorded at Gulu. The geothermal water is mainly replenished by atmospheric precipitation. The low tritium contents(1 TU) of the geothermal water from Nyingzhong, Gulu, and Luoma indicate that it is mainly replenished by sub-modern(prior to 1952) water, while the high tritium content(8.4 TU) in Yuela implies modern water replenishment. Other geothermal fields are replenished by a mix of sub-modern fresher water. The isotopic data in this study show that the carbon and sulfur in the geothermal water originates mainly from sediment leaching, with some of the carbon and sulfur having a deep origin.     

Speciation of sulfate components in size-fractionated aerosol particles using sulfur K-edge X-ray absorption near-edge structure （XANES）

Sulfates are a main constituent of aerosols, which sulfate aerosols, it is necessary to determine what can cause various environmental problems sulfate ions are contained in these aerosols In the evaluation of the influence of In this study, sulfur K-edge XANES was used to determine sulfate species present in size-fractionated aerosol particles based on the post-edge structure after the main absorption peak in the XANES region. Aerosol samples were collected as part of the Japan-China joint project, ＂Asian Dust Experiment on Climate Impact＂ using a low-volume Andersen-type air sampler. XANES was measured at Beamline BL-9A at Photon Factory, Japan. A comparison of the XANES spectra of reference sulfate materials and aerosol samples collected in Tsukuba in Japan clearly showed that （NH4）2SO4 was the main sulfur species in particles with a smaller diameter and gypsum was the main sulfur species in particles with a larger diameter. A simulation of the XANES spectra by reference materials allows us to obtain the quantitative mixing ratios of the different sulfate species present in the aerosol samples. The presence of minor sulfur species other than （NH4）2SO4 and gypsum at the surface of mineral aerosols is suggested in our simulations and by a surface-sensitive conversion electron/He-ion yield XANES. In the absence of a contribution from a large dust event, the mole concentration of gypsum in the mineral aerosol fraction determined by XANES is similar to that of Ca which is determined independently using ion chromatography. This shows that the Ca and sulfate in the mineral aerosols are present only as gypsum. Considering that calcite is the main Ca mineral in the original material arising from an arid and semi-arid area in China, it is strongly suggested that gypsum is formed in aerosol during its long-range transportation by a reaction between calcite and sulfate ions.     

Sulfur isotopic composition of the Tianqiao Pb-Zn ore deposit,Northwest Guizhou Province,China：Implications for the source of sulfur in the ore-forming fluids

The Tianqiao Pb-Zn ore deposit of Guizhou Province, China, is located in the mid-east of the Si-chuan-Yunnan-Guizhou Pb-Zn-Ag multi-metallic mineralization area, which is representative of the Pb-Zn ore de-posits in this area. It consists of three main orebodies, whose Pb+Zn reserves are more than 0.2 million ton. This paper analyzes the sulfur isotopic composition of these orebodies. The data show that the ore minerals (galena, sphalerite, pyrite) in these orebodies are enriched in heavy sulfur, with δ34SV-CDT values varying between 8.35‰ and 14.44‰, i.e. the δ34SV-CDT values of pyrite are between 12.81‰ and 14.44‰, the mean value is 13.40‰; the δ34SV-CDT values of sphalerite are range from 10.87‰ to 14.00‰, the mean value is 12.53‰; the δ34SV-CDT values of galena are range from 8.35‰ to 9.83‰, the mean value is 8.84‰, and they have the feature of δ34Spyrite>δ34Ssphalerite>δ34Sgalena, which indicates the sulfur isotope in ore-forming fluids has attained equilibrium. The δ34S V-CDT values of the deposit are close to those of sulfates from carbonate strata of different ages in the ore-field (15‰), which suggests that the sulfur in the ore-forming fluids should be derived from the thermo-chemical sulfate reduction of sulfates from the sedimentary strata.     

用高温石墨管原子吸收分光光度法测定土壤和污泥中的镉、铅、铜、镍、钴

Some soft and mud samples have been determined for eadmiun, lead, copper,nickel and cobalt by atomic absorption speetrophotometry with a high-temperature graphite tube, after their extraction with sodium diethylthiocarbonate into methy lisolutyl ketone. The tests of the effects of acidity on extraction and interference have been also carried out and the optimum conditions have been obtained. In addition, experiments on recoveries by this procedure have been performed for the elements in ppb amount. The recovery of the metals added to soil samples is made in the same manner and the precision values are given in this paper. This method is considered as to be applicable to the determination of soil and mud samples for the above-mentioned elements, of which the concentration is higher than 1 ppb.     

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.     

Nitrogen Contents and Isotopic Characteristics of Mesozoic and Cenozoic Granites in Northeastern China

The method of determining the nitrogen isotopic composition of granites in the northeastern part of China is described.The content and isotopic values of nitrogen released from granite samples by stepwise heating were determined as well.The results showed that the diferent areas of northeastern China hae a great difference in nitrogen content and isotopic composition.Nitrogen released from the granites is 1.64-6.23μL/g ,with the maximum at about 600℃,from rhyolite and granophyre is 108.98-755.96μL/g,with the maximum at about 900℃,It is proved that fluid is characterized by heterogeneity in the deep crust of the different areas in northeastern China.The nitrogen isotopic compositions in different ranges of temperautes are wweighted.And the nitrogen isotopic compositions in different anges of temperatures are weighted.And the nitrogen isotopic values are 9.2‰ to 17.0‰,with a variation range of 7.8‰,The nitrogen isotopic ratios may have been fractionated during degassing and the fluid released from granites is the residual component.     

Geochemical Characterization and Origin of High-Sulfur, Heavy Oils in Jiyang Sub-Basin, East China

High-sulfur, heavy petroleum is widely occurring in the Tertiary lacustrine Jiyang sub-basin, Bohai Bay Basin. They are differentiated into two families based on the bulk properties and biomarker compositions. Family 1 is characterized by high resins (40%–71%) and sulfur (2%–4%), and low wax (1%–6%), with n-alkanes removed by biodegradation, whereas family 2 is characterized by extremely abundant sulfur (3%–10%), and high asphaltenes (7%–31%) and wax (2%–19%), with no evidence of microbial attack. The oils of family 1 are distributed in the reservoir, lower than 1500 m throughout the sub-basin. Biomarker assemblages, such as low pristane/phytane ratios (<1 Pr/Ph) and a high abundance of carotane, gammacerane, and dinosterane, suggest that they are derived from the calcareous mudstones and shales among the stratified, saline Es4u unit, in addition to the in situ biodegradation-concentrated sulfur content. However, the oils of family 2 are identified only in the western Zhanhua and eastern Chezhen depressions, with a depth deeper than 1700 m. Physical properties, together with biomarker ratios, including even-numbered n-alkanes, <1 Pr/Ph, trace diasteranes, higher C35 homohopanes, and abundant dibenzothiophene series, with >1 dibenzothiophene/phenanthrene, indicate an origin from carbonate source rocks. The X-ray diffraction analysis showed that the carbonate source rock is limited in the Es4u unit of the Bonan sag, which is different from most other source rocks in the same horizon. It is suggested that the high-sulfur, heavy oils are generated at the early stage of the oil window. Bacterial sulfate reduction might be responsible for the occurrence of sulfur species in the high-sulfur, heavy oils, while heavy biodegradation will enhance sulfur concentrations.     

Ge（Li）γ谱仪测量^135U的丰度

In this paper a technique for determining ^235U abundance is described. After chemical separation, uranium-rich ore (a compound of uranium with chemical and radioactive pure)is made into U3O8 by burning at 850℃, and then the U3O8 is prepared as the radioactive measuring source with a definite weight and shape. The measurement is carried out of the net area of 185.7 keV γ -ray peak of ^235U by Ge (Li) γ -ray spectrometer, with the mixture of a number of primary uranium ores as normal abundance standard. Parallel analysis and counting are performed on the standard and samples with the same method. The abundance of ^235U will be known by comparing their net areas of 185.7 keV γ ray peaks of ^235U both in the samples and the standard. Two samples of uranium ore from China which are suspected to be anomalous in U abundance and one sample from Oklo natural reactor have been determined. The precision of the method is better than 1%.     

Extreme Enrichment of Tellurium in Deep-Sea Sediments

Tellurium is a sort of scattered rare element on the earth. Its concentration is very low in earth＇s crust, only 1.0 ng/g. However, it has extremely high abundance in Co-rich crusts, marine polymetallic nodules, deep-sea sediments and aerolites. To find out the origin of tellurium enrichment in deep-sea sediments, we analyzed and compared tellurium concentrations and helium isotope compositions in the magnetic parts and those in the bulk parts of deep-sea sediments. The result indicates that the helium content, 3He/4He ratio and tellurium concentration are obviously higher in the magnetic parts than those in the bulk parts. The 3He abundance varies synchronously with the tellurium concentration. 3He and Te have a distinct positive correlation with each other. It is the first time that the paper brings forward that the extreme enrichment of tellurium in deep-sea sediments, like helium isotope anomalies, probably results from the input of interplanetary dust particles （IDPs）. Similarly, the extreme enrichment of tellurium in marine polymetallic nodules and Co-rich crusts is possibly related to IDPs.     

Geology and geochemical evaluation of Taftan Volcano, Sistan and Baluchestan Province, southeast of Iran

At a glance of its stratighraphy, the Taftan Volcano can be classified as three groups： pre-, syn- and post-volcanic deposits. The pre-volcanic deposits consist mostly of flysch facies and colored mélange complex. The syn-volcanic deposits are mainly the product of the Taftan Volcano which is mostly composed of pyroclastic and lava flows from the main body of this volcano. The post-volcanic deposits are mostly epiclastic and reworked materials from the Taftan Volcano due to its erosion and weathering. Major and trace elements, and Sr/Rb isotopic compositions determined on whole-rock samples from the Taftan Volcano showed that the volcano was formed at the continental margin. The whole-rock isotopic composition of the Taftan Volcano showed a feature of strong enrichment with ^87Sr/^86Sr=0.705326-0.705921. Geochronological samples of the Tartan Volcano determined by the ^40K/^40Ar method gave an age range of 6.95±0.72 to 0.71±0.03 Ma. The rare-earth element patterns are characterized by high LREE and nearly strongly linear patterns for MREE to HREE, suggesting that distinctive minerals such as olivine and pyroxene crystallized in the early magmatic stage and then were involved in reaction between the lower crust and residual magma. The integrated isotope and trace element systematics and tectonic structure beneath the Taftan Volcano suggested the lower-crust assimilation by the primary magma. The primary magma had generated from a heterogeneous mantle source and a secondary petrogenetical process. This magma could have been affected by the subduction of the Oman Sea undemeath the continental Eurasia plate.     

An Interesting Element Association of Au—Sb—As—W and Its Geochemical Interpretation—A Review

The occurrences and characteristics of the association of Au-Sb-As-W are summarized.An interpretation of the association is given according to the fact that the content of reduced sulfur in the ore-forming solution is much high relative to Cl in this kind of ore deposits especially for the Au-Sb-As with W,using the data on their complexes and solubility,The high dfineness of gold and the separation of gold from the base metals Cu,Pb,Zn,and sometimes from Ag in this kind of ore deposits are also interpreted.     

Experimental Study on Treatment of High-concentrated Sulfur Wastewater by Process of Depositing Natrojarosite and Its Environmental Significance

High-concentrated sulfur wastewater with sodium and COD （chemical oxygen demand） up to 26000 mg/L from a chemical plant, Jiangsu Province of China has been treated by deposition of natrojarosite in lab. The results indicated that the COD of the wastewater was decreased sharply from 26000 mg/L to 1001 mg/L, with removal rate of COD up to 96% by twice precipitations of natrojarosite and twice oxidation of H202. The treated sulfur wastewater reached the requirement of subsequent biochemical treatment to water quality. The optimal operational parameters should be controlled on pH value between 2.50 and 3.20 and 50 g FeCly6H2O solid added in per liter wastewater. The study provided an experimental basis for pretreatment of high-concentrated sulfur wastewater and proposed a new mineralogical method on treatment of other wastewaters. Depositing process of jarosite and its analogs should be able to be used to treat wastewater from mine and other industries to remove S, Fe and other toxic and harmful elements, such as As, Cr, Hg, Pb, etc. in the water.     

超基性岩矿物化学特征与成矿关系讨论

The most productive chromite ore deposits are formed by crystallizing from chromite-ore magmas under definite physico-chemical conditions. The formation of chromite ore is controlled mainly by the degree of differentiation of ultrabasic magma. How to diagnose uitrabasic magmatie differentiation is key to the understanding of the mechanism of formation of chromite ore. It is considered that chromite ore is derived from ulttabasic rocks. The rock-forming minerals include olivine, pyroxene and spinel. The minerals are well homomorphous minerals. The contents of major chemical elements in these minerals show little variation. On the contrary in those ultrubasie rocks which show no association with chromite ore deposits the contents of the elements vary over a wide range. Abundant data available.indicate that chromite ore deposits arc derived from chrore.ire-ore magmas resulting from the transport and accumulation of chromic elements. Since the transport and accumulation of chromic elements follows the statistical law,we must study the mechanism of formation of ehromite ore from the statistical point of view. If chromite ore is formed from spinel under the action of gravitation o.r other dynamic actions, we must elucidate the mechanism of formation of chromite ore from the dynamic viewpoint.     

Stabilities of heavy metals in soils treated with red mud

This paper discussed the stabilities of heavy metals in soils treated with red mud. Soil has been polluted by heavy metals more and more seriously during recent several decades, and they are harmful to mankind and animals. The current tendency is to develop in-situ technique by using industrial processing waste as additives to stabilized heavy metals to minimize the disturbance of contaminated soils. Soil samples were collected from the Niujiaotang mining area, Guizhou Province, southwestern China. They were farmed soils polluted weakly by fly ash （QBT） and polluted badly by waste water （BXT） from smelter, respectively. One of the red mud samples （BRM） was collected from Bayer process and the other （CRM） from confederate process in the Alumina Plant of Guizhou. Free metal ion concentrations were analyzed with Donnan Membrane Technique and predicted with ECOSAT. The concentrations of free heavy metal ions in QBT increased after appending CRM, but decreased when adding BRM. The more the red mud was added, the higher the concentration would be, and the free concentrations of nickel and cadmium ions would vary more greatly than those of copper and zinc ions. When appending red muds into BXT, the free concentrations of copper and zinc ions varied little. While those of free nickel and cadmium decreased obviously at the ratio of 2.00%. The variation of the concentration was still biggish after appending BRM at the ratio of 0.50%, but smaller than that of 2.00%. The concentrations of free cadmium ions increased after adding CRM at the ratio of 0.50%. All experimental processes were modeled through ECOSAT. The predicted and measured results were consistent, except for zinc. Contributions of soil sorbents to the heavy metal adsorptions were also modeled through ECOSAT. The sorbents in soil included soil organic matter, iron hydroxides, clay and the Donnan gel of soil organic matter. Compared to the soils without red muds, no matter what kind of red mud and how much was added in soil, the contributions changed slightly.     

Metallogenic Mechanism of the Tianbaoshan Pb—Zn Deposit,Sichuan

The Tianbaoshan Pb-Zn deposit in Sichuan Province,exhibiting open-space-filling and /or replacement textures,occurs as being of vine style in the Sinian(Late Proterozoic) carbonate rocks,and is simple in ore composition.A systematic study of lead isotope and rareearth elements reveals that the ore-forming materials were derived from multiple sources.The ultimate source of the sulfur in all stages in seawater sulfate but the reducing mechanisms are different,The carbon was derved from marine carbonate and organic matter,The ore-forming fluid,meteoric in origin,belongs to a Ca^2 -Mg^2 -Cl^--Hco3^- type of weak acidic to alkalic solutions with a salinity of about 5wt% NaCl.The ore was formed at the depth of about 1 km from 150 to 250℃ during the main stage of ore deposition.The heated meteoric water,after extracting ore materials from wall rocks,evolved into ore-forming solution with a low salinity, in which metals were trasported as chloride complexes such as PbCl,ZnCl and ZnCl.The metal-bearing solution moved upward along deep faults to low-pressure zones,where the metal ions reacted with reduced sulfur and were precipitated as sulfied minerals.The textures of the minerals were controlled by the rate at which the reduced sulfur was supplied.     

Geochemical features of heavy metals in core sediments of northwestern Taihu Lake, China

Sequential core sediments from northwestern Taihu Lake in China were analyzed for grain size, organic carbon and heavy metal content. The sediments are composed of organic-poor clayey-fine silts. The chemical speciations of Cu, Fe, Mn, Ni, Pb, and Zn were also analyzed using the BCR sequential extraction procedure. Cu, Fe, Ni, and Zn are mainly associated with the residue fraction; Mn is concentrated mainly in exchangeable/carbonate fraction and residue fraction; and Pb mainly in Fe/Mn oxide fraction and organic/sulfide fraction. The exchangeable/carbonate fractions of Cu, Fe, Ni, Zn and Pb are lower. The fractions of Ni, Pb and Zn bound to the Fe/Mn oxide have significant correlations with reducible Mn; the organic/sulfide fractions of Cu, Mn, Ni, Pb, and Zn have significant correlations with TOC. The extractable fractions of Cu, Mn, Ni, Pb, and Zn are high at the top 4 cm of the core sediments as compared to those in the deeper layers, showing the anthropogenic input of heavy metals is due to rapid industrial development. The heavy metal pollution history of the sediments has been recorded since the late 1970s, determined by the result of ^137Cs dating.     

Petrography,chronology and Hf isotope constraints on origin of the ore-bearing granodiorite in Zhibula copper deposit,TibetEI北大核心CSCD

The Zhibula skarn-type copper polymetallic deposit is a large copper deposit. It is located 2-3 km south of the Qulong porphyry copper deposit, in the middle section of the Gandise metallogenic belt in Tibet. The ores are commonly bedded, stratoid and vein-like hosted in the interformational detachment zone between tuff and marble and in the fracture zone. The granodiorite was discovered lately in the drill holes. The contact zone between granodiorite and tuff or marble is skarnized. The skarn-type ore deposit is closely related to the granodiorite as was demonstrated by the gradual change from the tuff, hornfels, and skarn, to the skarnized granodiorite. LA-ICP-MS zircon U-Pb dating yields a weight average 206Pb/238U age of 16.0±0.4 Ma, which is close to the Re-Os isochron age (16.9±0.6 Ma) of molybdenites from the ores. The granodiorite has εHf(t) values in range of 3.2-12 and single-stage model ages between 209-563 Ma, which are similar to those of the Miocene intrusives in the Qulong areas. The zircon Hf isotopic compositions of the granodiorite indicate that the magma is likely resulted from partial melting of the juvenile lower crust. The granodiorites are determined as the ore-forming intrusive of the Zhibula skarn-type deposit, and they are derived from the same magma system with those associate with Qulong deposits. Both of them are are of hydrothermal origin. ©, 2015, Science Press. All right reserved.     

吉林陨石的不透明矿物

Opaque minerals in the Jilin meteorite inelude kamacite, taenite troilite, chromite, ilmenite, schreibersite, pyrite, pyrrhotite, chalcopyrite, sphalerite and graphite.Five of the above-mentioned minerals have been discussed in more detail in terms of optical and physical properties, chemical composition, coexisting relationship, and the order of crystallization. It is indicated from this study that, with the exception of a small amount of Ni-Fe cbondrules, silicate minerals are the first to erystallize followed by chromite, ilmenite at the early stage of nebula condensation, while Ni-Fe phase in the matrix is considered to be of a more later erigin. At the late stage of nebula condensation troilite resulted from the reaction of Ni-Fe metal with residual H2S vapor. As indicated by the occurrence of coarse grained Ni-Fe metal, the recrystallization of troilite and the apparent Neumann lines in kamaeite, it is expected that opaque minerals in the Jilin metevrite have undergone different degrees of thermal and impact metamorphisms.