Studies of distribution, release and environmental influences of Fushun oil shale and its self-combustion

Three dumping sites have been formed at the northern region of Fushun City, Liaoning Province, for a large number of gangues including much oil shale that had been piled onto ground as gangue during long-term coal exploitation at West Fushun Open-pit Mine. Under appropriate conditions, self-combustion occurs after long-term exposure of oil shale and consequently such phenomena could be found almost everywhere at the three dumping sites. Much polycyclic aromatic hydrocarbons （PAHs） must be generated through oil shale self-combustion, a kind of incomplete combustion. In this paper, in order to make clear the PAHs distribution in oil shale and its self-combustion and their potential effects on surrounding environment, coal, low-grade oil shale, high-grade oil shale, burning oil shale, burnt oil shale and shaly soil collected from West Fushun Open-Pit Mine and West Dumping Site were analyzed quantitatively in 16 US EPA priority PAHs for the first time. Results showed that 16 PAHs in all samples were less than those in some bitumites and carbonaceous coals and were as much as those in lignites and anthracites from some Chinese mining areas. Coal and low-grade oil shale were abundant in lower molecular-weighted PAHs in contrast to high-grade oil shale with rich higher molecular-weighted PAHs. They had more benzo[a] pyrene than the highest background value in soils in Liaoning Province. So PAHs in these crude oil shales could cause potential effects on environment. There were at least 5121.40 p.g/kg PAils generated and at least 3976.70 μg/kg PAHs released into environment in the period from combustion beginning to sampling on the basis of calculation. Furthermore, the concentrations of 3-4 ring PAHs among them were very high. Therefore it could be said that oil shale self-combustion aggravated the environmental impacts of PAHs in oil shale. The low concentrations of PAHs in shaly soil showed that much PAHs had been released through recultivation and biodegradation.     

Geochemistry of soils derived from black shale, central Hunan, China

The black shale formed under anoxic conditions usually contains high concentrations of many metals. Weathering of such black shale might cause the emission of many metals. Moreover, soils derived from black shale （SBS） are believed to be affected by black shale weathering. In recent years, many studies such as Lee et al. （2002）, Woo et al. （2002）, Fang et al. （2002）, Pasava et al. （2003）, and Peng et al. （2004） have approached the heavy metal contaminations of SBS, but systematical geochemical study is rare. Presently, the SBS and its corresponding black shales （CBS） were both sampled from central Hunan （China）, and analyzed for a large number of elements, using an Elan6000 ICP-MS/AES machine at Guangzhou Institute of Geochemistry, CAS. In this paper, some preliminary results are reported. The analytical results show that the SBS in central Hunan contains very high concentrations of heavy metals such as Co, Cu, Hg, Mo, Pb, Zn, U, Th, Sb, T1, Cd, Cr, Sc, V, Sn, As, Se, and Ni.     

The petrologic characteristics of carbonaceous shale and its significance of shale (las. Lucaogou formation,southern junggar basin北大核心CSCD

In the margin of southern Junggar basin, there is a potential of shale gas with the upper Permian l.uoaogou Formation. For a detailed understanding and evaluation with the shale gas geological characteristics of l.uoaogou Formation, the petrologic characteristics of the carbonaceous shale was researched, and the results show that: ( 1 ) in l.ucaogou Formation, the mean value of the brittle mineral percentages of the upper member, the middle member and the lower member are all more than 50%, but it is the highest in the middle member, and it is second in the lower member. At the same time, in the lower member, the mean value of the brittle mineral percentages is significantly lower than the upper and middle members; (2)the main brittle mineral in each member are quartz+feldspar, and there is a same change rule between the quartz+feldspar content and the total brittle mineral, that is; The quartz + feldspar content is the highest in the middle member, followed with the lower member, and it is obviously low in the upper member; (3 )from the lower member to the upper member, the content of carbonate in the carbonaceous shale are gradually reduced; (4) the clay mineral content of the carbonaceous shale of the upper member is far higher than the lower and middle members. And the clay mineral in each member are mainly constituted with illite and illite/Mongolia inter layer; ( 5 ) in the northern margin of the western part of the Bogda Mountain, south Junggar Basin, the brittle mineral content of the carbonaceous shale generally present as a decreasing trend from west to east to Fu Rang.     

Seismically induced shale diapirism: the Mine d’Or section,Vilaine estuary,Southern Brittany

The Pénestin section (southern Brittany) presents large regular undulations, commonly interpreted as evidence of periglacial pingos. It is an upper Neogene palaeoestuary of the Vilaine River reactivated during the middle Quaternary (middle terrace). It is incised into a thick kaolinitic saprolite and deformed by saprolite diapirs. This paper presents the arguments leading to a mechanistic interpretation of the deformations at Pénestin. Neither recent transpressive tectonics nor diagnostic evidence of periglacial pingo have been found despite evidence for a late paleo-permafrost. The major deformational process is shale diapirism, initially triggered by co-seismic water supply, with further loading and lateral spreading on an already deformed and deeply weathered basement, which allowed the shale diapirism to develop. Deformations are favoured by the liquefaction of the saprolite and a seaward mass movement and recorded, rather distant, effects of an earthquake (c. 280 ka B.P.) resulting from the progressive subsidence of the southern Armorican margin. These deformations triggered by an earthquake are similar to those induced by classical shale diapirism. They are probably common in tectonically active continental environments with shallow water table.     

What controls selenium release during shale weathering?

This study demonstrates that only a combination of a chromous chloride reduction with dual sequential extraction schemes can clearly separate the proportions of Se present in the sulphide versus the organic pools in shales. The data reveals that even small amounts of pyrite outcompete the organic matter for the available Se and pyrite oxidation will control the release of selenium during shale weathering.     

Re–Os age of non-mineralized black shale from the Kupferschiefer, Poland, and implications for metal enrichment

Six samples of non-mineralized black shale from a Kupferschiefer section in the northern part of the Polish Zechstein Basin (Zdrada IG-8 drill hole: 1026.16–1026.90 m) were studied for Re–Os isotopes and selected major and trace elements. These black shales, averaging 5.82 wt.% C_org and 1.69 wt.% S_tot, display very low base metal values (up to 106 ppb Cu, 792 ppb Pb, and 144 ppb Zn) and have abundances of 64–1376 ppb Re and 0.37–1.25 ppb Os, with a ¹⁸⁷Os/¹⁸⁸Os ratio of 6.95–22.5. The regression of all Re–Os data yields an age of 247 ± 20 Ma, which is within the range of uncertainties of previous Rb–Sr and K–Ar geochronological studies. The scatter in the Re–Os data can be explained in terms of fluctuations in sedimentary conditions, i.e., restricted basin with terrestrial influence.     

Biomarker signatures from Neoproterozoic–Early Cambrian oil,western India

The Neoproterozoic–Early Cambrian time is the cradle of multicellular, eukaryotic life and thereafter metazoan life started populating the planet. Biomarkers, which record the chronicles of biotic events on Earth, have been investigated using gas chromatography–mass spectrometry from a suite of nine oil samples extracted from oil stained sediments and a crude oil of Neoproterozoic–Early Cambrian age from Bikaner-Nagaur Basin, western India. The biomarker distribution is characterized by high concentration of both tricyclic terpanes and pentacyclic hopanes. The predominance of C₂₉ regular sterane over C₂₇ and C₂₈ steranes indicates green algal contribution and may imply the prominence and diversification of the same algal group. The low pristane/phytane ratio and occurrence of substantial quantity of gammacerane, monomethyl 2-methyl-2-(2,4,8-trimethyltridecyl) chroman and 1,1,7,8-tetramethyl-1,2,3,4 tetrahydrophenanthrene are indicative of stratified water column as well as anoxic and enhanced salinity condition of the environment of deposition. This paper reports for the first time the presence of methyltrimethyltridecyl chromans (MTTCs) from Neoproterozoic–Early Cambrian time. Putative C₁₉ norsteranes, probably indicative of sponge input, are recorded in the studied samples and also reported from other infracambrian oils and sediments. Normal alkanes (n-C₁₇ and n-C₁₈) and isoprenoids (pristane and phytane) are highly depleted in δ¹³C. The overall biomarker distribution and carbon isotope data of oils from Bikaner-Nagaur Basin show similarities with those of other infracambrian oils like Huqf oils from Oman and Baykit High oils from eastern Siberia.     

Methane adsorption in the low–middle-matured Neoproterozoic Xiamaling marine shale in Zhangjiakou,Hebei

The adsorption capacity of high–over-matured shale has been widely investigated, but the adsorption capacity and the main factors influencing low–middle-matured, type II kerogen-containing, and organic-rich marine shale have been rarely explored. This research conducts organic geochemistry, mineralogical composition, adsorption isotherm tests to reveal the adsorption and main influencing factors of the different geochemistry characteristics, mineralogical compositions, temperature and pressure conditions of the low–middle-matured Neoproterozoic Xiamaling marine shale in Zhangjiakou, Hebei. The investigated shale is in a low–middle maturity stage, contains type II kerogen and is rich in organic matter. The results show that the total organic carbon (TOC) content of the Xiamaling shale is positively correlated with the methane adsorption capacity, which is the most important influencing factor on the adsorptive property of shale. The methane adsorption capacity first decreases to the minimum value as the temperature reaches 360°C equivalent Ro (EqRo = 1.0%), then increases and reaches the maximum value at 620°C (EqRo = 3.28%) and finally decreases again as the temperature rises at the last simulation stage. The mineral components exhibit an insignificant influence on the methane absorbability because of organic-matter coatings. The TOC-normalised methane adsorption capacity is positively correlated with the illite–smectite and clay-mineral contents but shows no significant correlation with brittle minerals, such as quartz. Soluble organic matter and kerogen caused the methane dissolution and adsorbtion, respectively. The strong dissolution property of the soluble organic matter is the most important cause of the larger adsorption capacity of the original shale compared with that of the residual samples. Moreover, the methane adsorption capacity of the Xiamaling shale decreases with increasing temperature, and increases with pressure below the critical pressure but decreases exceeding the critical pressure.     

Lithological features,reconstruction of redox setting,and composition of the provenances of the Upper Triassic Kular–Nera shale belt

Comprehensive lithogeochemical analysis is carried out for Norian sediments from the central part of the Kular–Nera shale belt. The sediments are represented by alternation of sandstones and siltstones. Petrochemical typification shows that the sandstones are subdivided into graywacke, arkose, and subarenite, while the siltstones belong to shale. The Norian sediments were mainly deposited in an oxidizing environment of a well-aerated basin in the distal parts of the Verkhoyansk passive continental margin. They are characterized by a high sorting of sedimentary material. The correlation between the rock-forming elements and the wide range of (La/Yb) _n ratios indicate that the sedimentation basin contained the disintegration products of both acid [(La/Yb) _n = 10.52–27.26] and mafic [(La/Yb] _n = 6.22–8.96)] rocks. The high values of the La/Sc and Th/Co ratios are typical of acid rocks. The low K₂O/Al₂O₃ values (0.16 ± 0.02) and high Zr/Sc ratio (10.1 ± 2.74) are typical of redeposited material. It is established that several provenances were involved in the formation of the Norian sediments in the central part of the Kular–Nera shale belt. Multicomponent clastics and well-sorted recycled material were supplied into the sedimentation basin.     

Selenium enrichment in Carboniferous Shales,Britain and Ireland: Problem or opportunity for shale gas extraction?

The Carboniferous Bowland Shale in England, and its correlatives in Ireland, contain anomalously high concentrations of trace elements, including selenium (Se), molybdenum (Mo) and arsenic (As). High levels of these elements reflect high sulphur contents as these elements occur as trace constituents of pyrite. Anomalous Se in particular may have a volcanic provenance, from contemporary volcanic activity and/or drainage from Ordovician volcanogenic sulphide deposits. Following concern over the release of Se and As into groundwater during shale gas extraction in the US, the potential fate of Se and As during any future shale gas extraction from the Bowland Shale merits attention. It is at least an environmental issue that must be managed, but at best it could be an opportunity for extraction of Se in an environmentally sensitive manner.     

Oil-source correlation of Lower-Triassic oil seepages in Ni’erguan village,Southern Guizhou Depression,China

There are abundant bitumens and oil seepages stored in vugs in a Lower-Triassic Daye formation (T₁d) marlite in Ni’erguan village in the Southern Guizhou Depression. However, the source of those oil seepages has not been determined to date. Multiple suites of source rocks of different ages exist in the depression. Both the oil seepages and potential source rocks have undergone complicated secondary alterations, which have added to the difficulty of an oil-source correlation. For example, the main source rock, a Lower-Cambrian Niutitang Formation (?₁n) mudstone, is over mature, and other potential source rocks, both from the Permian and the Triassic, are still in the oil window. In addition, the T₁d oil seepages underwent a large amount of biodegradation. To minimize the influence of biodegradation and thermal maturation, special methods were employed in this oil-source correlation study. These methods included catalytic hydropyrolysis, to release covalently bound biomarkers from the over mature kerogen of ?₁n mudstone, sequential extraction, to obtain chloroform bitumen A and chloroform bitumen C from the T₁d marlite, and anhydrous pyrolysis, to release pyrolysates from the kerogen of T₁d marlite. Using the methods above, the biomarkers and n-alkanes released from the oil samples and source rocks were analysed by GC–MS and GC-C-IRMS. The oil-source correlation indicated that the T₁d oil seepage primarily originated from the ?₁n mudstone and was partially mixed with oil generated from the T₁d marlite. Furthermore, the seepage also demonstrated that the above methods were effective for the complicated oil-source correlation in the Southern Guizhou Depression.     

Pyrite characteristics and shale gas significance of the Niutitang Formation in Cengong area,Guizhou ProvinceSCIEI北大核心CSCD

黄铁矿特征研究可为页岩沉积环境恢复与页岩气富集保存规律预测提供依据。以贵州岑巩地区岑页1井牛蹄塘组为研究对象,基于岩心、薄片、扫描电镜及微量元素、硫同位素地球化学,确定牛蹄塘组页岩沉积环境及页岩气富集地质条件。研究表明,牛蹄塘组页岩黄铁矿发育为草莓状、自形-半自形及他形(主要为胶状他形)三种形态,不同形态的黄铁矿形成于不同沉积环境,草莓状黄铁矿形成于缺氧还原环境,自形-半自形黄铁矿形成于贫氧环境,胶状他形黄铁矿指示沉积过程有热液活动的参与。测试井牛蹄塘组整体处于较开放的沉积水体,上段为含氧-贫氧环境,硫同位素整体变轻且发生负漂;中段为较缺氧环境,硫同位素跨度大且发生正漂;下段为还原性更强的沉积环境,硫同位素小幅度负漂。黄铁矿含量与有机质富集密切相关,与黄铁矿有关的孔隙为页岩气吸附、保存及运移提供载体,且草莓状黄铁矿指示的缺氧硫化环境更利于有机质保存。研究工作系统梳理了黄铁矿对牛蹄塘组页岩沉积环境及储层页岩气富集的指示作用,为页岩气勘探提供指示。     

Degradation of petroleum contaminants in oil

The treatment of diesel-contaminated soil with hydrogen peroxide oxidation is investigated in this paper. The factors influencing reactions such as initial oil content, H2O2 dosage, pH-value, catalyst and so on are studied. The results indicate that it is feasible to remediate diesel-contaminated soil by adding oxidant directly at room temperature because of higher absolute removal content although the degradation efficiency is low for the contaminated soil of 1%, 2% and 5% initial oil content. The more the H2O2 dosage, the better the degradation efficiency; it is economical and efficient to add 4 mL H2O2 to 10 g diesel-contaminated soil （2% or so） directly in-situ chemical oxidation （ICO）. For the contaminated soil of 5% initial oil content, when pH-value is 5-8 and H202 dosage is 20 mL, the removal efficiency reaches more than 96%; when pH-value is 1-3 and volume ratios of H2O2 to Fe^2＋ are 1 ： 1, 2：2, the degradation efficiencies are all very high （i.e., 86%-88% or so）. It can be concluded that the degradation efficiencies are comparative when adding 1 mL or 2 mL H2O2 of Fenton Reagent or adding 4 mL of H2O2 only to 10 g diesel-contaminated soil.     

Microwave remediation of oil contaminated soils

The contamination of soil has been the result of commercial, industrial and military activities. Among the variety of the available technologies of organic contaminated soils, thermal methods ensure the greatest efficiency of the above 99%. Thermal techno…     

Paleomagnetism of the Cu�CZn�CPb-bearing Kupferschiefer black shale (Upper Permian) at Sangerhausen, Germany

Syngenetic, diagenetic and epigenetic models have been proposed for the Cu?CZn?CPb Kupferschiefer mineralization at Sangerhausen, Germany. Paleomagnetic and rock magnetic measurements have been made on 205 specimens from mine workings on the margin of the Sangerhausen Syncline. The mineralization is richest in the ??0.5-m-thick Upper Permian (258?±?2?Ma) Kupferschiefer black marly shale (nine sites) and dies out over ??0.2?m in the underlying Weisliegend sandstones (three sites) and overlying Zechstein carbonates (two sites). Except for one site of fault zone gypsum, characteristic remanent magnetization directions were isolated for all 14 sites using alternating field and thermal step demagnetization. These directions provide a negative fold test, indicating that the remanence postdates Jurassic fault block tilting. Rock magnetic measurements show that the Kupferschiefer shale marks a redox front between the oxidized Weissliegend sandstones and non-oxidized Zechstein carbonates. The 14 site directions give a Late Jurassic paleopole at 149?±?3?Ma. It is significantly different from the paleopole reported by E.C. Jowett and others for primary or early diagenetic Rote F?ule alteration that gives an age of 254?±?6?Ma on the current apparent polar wander path and is associated with Kupferschiefer mineralization. We suggest that the Late Jurassic extensional tectonic event that formed the nearby North German Basin also reactivated Variscan basement faults and extended them up through the overlying strata, thereby allowing hydrothermal basement fluids to ascend and epigenetically mineralize the Kupferschiefer shale. The possibility of a 53?±?3?Ma mineralization age is also considered.     

A possible shale gas prospect? First results of the organic composition and thermal maturity of the Carboniferous Namoi Formation,northern NSW,Australia

The Namoi Formation in the Werrie Syncline, north and west of Tamworth, is part of the well-preserved Devonian–Carboniferous fore arc in the New England Fold Belt. The formation is between 640–914 m thick and consists of dominant olive-green mudstones with lenses of sandstone and oolitic limestone. To assess shale gas prospectivity, we analysed five outcrop samples from the Namoi Formation in the Keepit area. Well-preserved aliphatic and aromatic hydrocarbon fractions do not show evidence of weathering or biodegradation. n-Alkanes in all samples have a unimodal distribution maximising at C₂₆ to C₂₈. Little odd-to-even n-alkane carbon number predominance and relatively low Pr/n-C₁₇ and Ph/n-C₁₈ ratios are consistent with a high thermal maturity. Based on the distribution of alkylnaphthalenes and alkylphenanthrenes, the Namoi Formation is in the gas window. Calibration of the methylphenanthrene index and ratio with vitrinite reflectance suggests a calculated reflectance around 2.1%, which given a normal geothermal gradient is equivalent to a maximum temperature of 205°C for the deepest burial of the formation. There is a dominance of parent polycyclic aromatic hydrocarbons (PAH) over alkylated PAHs, supporting a high thermal maturity. Some samples contain biomarkers suggestive of a marine depositional environment, including the C₃₀ sterane index and the C₃₁/C₃₀ hopane ratio. The Namoi Formation is a prospective shale-gas source, as it has been buried sufficiently to be well within the gas window. Where it is exposed at the surface gas will have been lost, but elsewhere it will be buried beneath other sediments and may still retain gas. Key exploration uncertainties include information on organic richness, lateral variation in thermal maturity, mineralogy, and porosity–permeability relationships.     

Islands and oil — locality and structure

This paper analyses the meeting between the international petroleum industry and two local communities. The building of an oil terminal in a local community is both a major event, and a generator of processes on the local level. Three different angles is used to enlighten these processes; categorised as as place, people and mind. The place analysis consentrates on the effects on population and workforce development, the people analysis look at the institutional and planning processes, and the mind analysis the effects on the feeling of local identification. The paper demonstrates that local factors are of crucial importance even for the international petroleum industry.     

“Source-Diagenesis-Accumulation” enrichment and accumulation regularity of marine shale gas in southern China

After the breakthrough of shale gas exploration and development in the Ordovician Wufeng Formation (Fm.) and Silurian Longmaxi Fm. of Chongqing Jiaoshiba area, Changning-Weiyuan area, etc. in Sichuan basin, a series of discovery and breakthrough were obtained by China Geological Survey in the Cambrian Niutitang Fm. and Sinian Doushantuo Fm. shale of the areas with complicated structure outside Sichuan basin. Based on the understanding of the law of shale gas enrichment in Longmaxi Fm. in the basin, this paper puts forward three elements of the formation and enrichment of shale gas, which are the “Source”, the “Diagenesis” and the “Accumulation”, after deeply studying the law shale gas enrichment and accumulation in Sinian-Cambrian reservoir of the complex structure area outside the basin. The “Source” means the sedimentary environment and petrological characteristics of organic shale. The “Diagenesis” means the basin tectonic subsidence and hydrocarbon generation and expulsion process of organic matter. The “Accumulation” means the tectonic uplift and shale gas preservation. It is proposed that the Sinian-Cambrian and Ordovician-Silurian black shale series in the middle and upper Yangtze region of southern China were both formed in the deep-water shelf environment of rift trough and foreland basin respectively. The dessert intervals were formed in the strong reduction environment under transgressive system tract. The shale lithology belongs to calcium-siliceous and charcoal-siliceous respectively. Based on the summary of structural evolution in Yangtze area, the correlation of structural burial depth with shale diagenesis and the coupling evolution of organic matter with pore structure are discussed. Combining with structural styles, the preservation conditions of shale gas are discussed. Five types of shale gas reservoir control models are further described. Two types of future exploration directions, which are reverse fault syncline and paleo-uplift margin in complex structural area outside the basin, are proposed.     

A three-scale micro-mechanical model for elastic–plastic damage modeling of shale rocks

Acta Geotechnica - This paper is devoted to study the elastic–plastic damage behavior of heterogeneous shale rocks. The representative microstructure of this kind of rocks is first studied in...