Distribution and geochemical significance of trace elements in shale rocks and their residual kerogens

There is a dearth of information about the distribution of trace elements in kerogen from shale rocks despite several reports on trace element composition in many shale samples. In this study, trace elements in shale rocks and their residual kerogens were determined by inductively coupled plasma–mass spectrometry. The results from this study show redox-sensitive elements relatively concentrated in the kerogens as compared to the shales. This may be primarily due to the adsorption and complexation ability of kerogen, which enables enrichment in Ni, Co, Cu, and Zn. For the rare earth elements (REEs), distinct distribution characteristics were observed for shales dominated by terrigenous minerals and their kerogen counterparts. However, shales with less input of terrigenous minerals showed similar REE distribution patterns to their residual kerogen. It is speculated that the distribution patterns of the REEs in shales and kerogens may be source-related.     

The morphological characteristics of gully systems and watersheds in Dry-Hot Valley,SW China

Gully systems and watersheds are geomorphic units with clear boundaries that are relatively independent of basin landscapes and play an important role in natural geography. In order to explore the morphological characteristics of gully systems and watersheds in the Dry-Hot Valley [South West (SW) China], gullies are interpreted from online Google images with high resolution and watersheds are extracted from digital elevation model at a scale of 1:50,000. The results show that: (1) There are 17,382 gullies (with a total area of 1141.66 km²) and 42 watersheds in the study area. (2) The average gully density of the study area (D) is 4.29 km/km², gully frequency (F) is 14.39 gullies/km², the branching ratio (B) is 5.13, the length ratio (L) is 3.12, and the coefficient of the main and tributary gullies (M) is 0.06. The degree of gully erosion is strong to extremely strong, the main development intensity of gully erosion ranges from intense to moderate, and the type of gully system is tributary. (3) The watershed areas (A) are between 0.39 and 96.43 km², the relief ratio (R) is from 0.10 to 0.19, the circularity ratio (C) is from 0.30 to 0.83, the texture ratio (T) is from 0.82 to 39.35, and the dominant geomorphological texture type is fine. (4) There is a quantitative relationship between F and D:F?=?0.624D² (R?=0.84) and T is closely related to D, F, M (R²?>?0.7). A, R and C are related to M (R²?>?0.5). The development of gully systems is the result of coupling effects between multiple factors. In this area, the degree of erosion and the condition of the main and tributary gullies can be controlled by the degree of topographic breakage in the watershed, which provides some theoretical basis for the evaluation of gully erosion by the latter. In addition, the scale, relief, and shape have a significant impact on the locations of the main and tributary gullies. For tributary gullies, attention should be paid to the interception and control of runoff and sediment in the small confluence branches in order to prevent gully expansion and head advance. These features can inform the development of targeted measures for the control of soil erosion.     

Constraints of molybdenite Re–Os and scheelite Sm–Nd ages on mineralization time of the Kukaazi Pb–Zn–Cu–W deposit,Western Kunlun,NW China

The Kukaazi Pb–Zn–Cu–W polymetallic deposit, located in the Western Kunlun orogenic belt, is a newly discovered skarn-type deposit. Ore bodies mainly occur in the forms of lenses and veins along beddings of the Mesoproterozoic metamorphic rocks. Three ore blocks, KI, KII, and KIII, have been outlined in different parts of the Kukaazi deposit in terms of mineral assemblages. The KI ore block is mainly composed of chalcopyrite, scheelite, pyrrhotite, sphalerite, galena and minor pyrite, arsenopyrite, and molybdenite, whereas the other two ore blocks are made up of galena, sphalerite, magnetite and minor arsenopyrite and pyrite. In this study, we obtained a molybdenite isochron Re–Os age of 450.5 ± 6.4 Ma (2σ, MSWD = 0.057) and a scheelite Sm–Nd isochron age of 426 ± 59 Ma (2σ, MSWD = 0.49) for the KI ore block. They are broadly comparable to the ages of granitoid in the region. Scheelite grains from the KI ore block contain high abundances of rare earth elements (REE, 42.0–95.7 ppm) and are enriched in light REE compared to heavy REE, with negative Eu anomalies (δEu = 0.13–0.55). They display similar REE patterns and Sm/Nd ratios to those of the coeval granitoids in the region. Moreover, they also have similar Sr and Nd isotopes [⁸⁷Sr/⁸⁶Sr = 0.7107–0.7118; ε_Nd(t) = ?4.1 to ?4.0] to those of such granitoids, implying that the tungsten-bearing fluids in the Kukaazi deposit probably originate from the granitic magmas. Our results first defined that the Early Paleozoic granitoids could lead to economic Mo–W–(Cu) mineralization at some favorable districts in the Western Kunlun orogenic belt and could be prospecting exploration targets.     

Constraints on sedimentary ages of the Chuanlinggou Formation in the Ming Tombs,Beijing, North China Craton: LA-ICP-MS and SHRIMP U–Pb dating of detrital zircons

Detrital zircons in five sedimentary samples, MC1 to MC5, from the bottom of the Chuanlinggou Formation in the Ming Tombs District, Beijing, were dated with the LA-ICP-MS and SHRIMP U–Pb methods. Age spectra of the five samples show a major peak at 2500 Ma and a secondary peak at 2000 Ma, suggesting their provenances were mainly from the crystalline basement of the North China Craton and the Trans-North China Orogen. The youngest zircon has an age of 1673 ± 44 Ma, indicating that the Chuanlinggou Formation was deposited after this age. From sample MC4 to MC5, lithology changed from a clastic rock (fine-grained sandstone) to a carbonate rock (fine-grained dolomite), suggesting that the depositional basin became progressively deeper. The age spectrum of sample MC5 shows a major peak at 2500 Ma and a secondary peak at 2000 Ma. Sample MC4, which is stratigraphically lower than sample MC5, only had one peak at 2500 Ma. We conclude that there was a transgressive event when sediments represented by MC5 was deposited, and seawater carried ca. 2000 Ma clastic materials to the basin where the Chuanlinggou Formation was deposited, leading to the addition of ca. 2000 Ma detritus. Our research indicates that the source area for the sediments became more extensive with time. We conclude that the Chuanlinggou Formation in the Ming Tombs District was deposited in a low-energy mud flat sedimentary environment in the inter-supra tidal zone because it is mainly composed of silty mudstone and fine-grained sandstone with relatively simple sedimentary structures.     

Geochemical and Petrological Studies on the Early Carboniferous Sidingheishan Mafic–Ultramafic Iintrusion in the Southern Margin of the Central Asian Orogenic Belt, NW China

The Sidingheishan mafic-ultramafic intrusion is located in the eastern part of the Northern Tianshan Mountain, along the southern margin of the Central Asian Orogenic Belt in northern Xinjiang autonomous region of China. The Sidingheishan intrusion is mainly composed of wehrlite, olivine websterite, olivine gabbro, gabbro and hornblende gabbro. At least two pulses of magma were involved in the formation of the intrusion. The first pulse of magma produced an olivine-free unit and the second pulse produced an olivine-bearing unit. The magmas intruded the Devonian granites and granodiorites.An age of 351.4±5.8 Ma(Early Carboniferous) for the Sidingheishan intrusion has been determined by U-Pb SHRIMP analysis of zircon grains separated from the olivine gabbro unit. A U-Pb age of 359.2±6.4 Ma from the gabbro unit has been obtained by LA-ICP-MS. Olivine of the Sidingheishan intrusion reaches 82.52 mole% Fo and 1414 ppm Ni. On the basis of olivine-liquid equilibria, it has been calculated that the MgO and FeO included in the parental magma of a wehrlite sample were approximately10.43 wt% and 13.14 wt%, respectively. The Sidingheishan intrusive rocks are characterized by moderate enrichments in Th and Sm, slight enrichments in light REE, and depletions in Nb, Ta, Zr and Hf. The ε_(Nd)(t) values in the rock units vary from +6.70 to +9.64, and initial ~(87)Sr/~(86)Sr ratios range between 0.7035 and0.7042. Initial ~(206)Pb/~(204)Pb, ~(207)Pb/~(204)Pb and ~(208)Pb/~(204)Pb values fall in the ranges of 17.23-17.91,15.45-15.54 and 37.54-38.09 respectively. These characteristics are collectively similar to the Heishan intrusion and the Early Carboniferous subduction related volcanic rocks in the Santanghu Basin, North Tianshan and Beishan area. The low(La/Gd)_(PM) values between 0.26 and 1.77 indicate that the magma of the Sidingheishan intrusion was most likely derived from a depleted spinel-peridotite mantle.(Th/Nb)_(PM)ratios from 0.59 to 20.25 indicate contamination of the parental magma in the upper crust.Crystallization modeling methods suggest that the parental magma of the Sidingheishan intrusion was generated by flush melting of the asthenosphere and subsequently there was about 10 vol%contamination from a granitic melt. This was followed by about 5 vol% assimilation of upper crustal rocks. Thus, the high-Mg basaltic parental magma of Sidingheishan intrusion is interpreted to have formed from partial melting of the asthenosphere during the break-off of a subducted slab.     

Elemental characteristics of lacustrine oil shale and its controlling factors of palaeo-sedimentary environment on oil yield: a case from Chang 7 oil layer of Triassic Yanchang Formation in southern Ordos Basin

As an important unconventional resource, oil shale has received widespread attention. The oil shale of the Chang 7 oil layer from Triassic Yanchang Formation in Ordos Basin represents the typical lacustrine oil shale in China. Based on analyzing trace elements and oil yield from boreholes samples, characteristics and paleo-sedimentary environments of oil shale and relationship between paleo-sedimentary environment and oil yield were studied. With favorable quality, oil yield of oil shale varies from 1.4% to 9.1%. Geochemical data indicate that the paleo-redox condition of oil shale’s reducing condition from analyses of V/Cr, V/(V + Ni), U/Th, δU, and authigenic uranium. Equivalent Boron, Sp, and Sr/Ba illustrate that paleosalinity of oil shale is dominated by fresh water. The paleoclimate of oil shale is warm and humid by calculating the chemical index of alteration and Sr/Cu. Fe/Ti and (Fe + Mn)/Ti all explain that there were hot water activities during the sedimentary period of oil shale. In terms of Zr/Rb, paleohydrodynamics of oil shale is weak. By means of Co abundance and U/Th, paleo-water-depth of oil shale is from 17.30 to 157.26 m, reflecting sedimentary environment which is mainly in semi deep–deep lake facies. Correlation analyses between oil yield and six paleoenvironmental factors show that the oil yield of oil shale is mainly controlled by paleo-redox conditions, paleoclimate, hot water activities, and depth of water. Paleosalinity and paleohydrodynamics have an inconspicuous influence on oil yield.