Distinctive volcanic ash-rich lacustrine shale deposition related to chemical weathering intensity during the Late Triassic: Evidence from lithium contents and isotopes.

The Late Triassic Carnian Pluvial Episode (CPE) witnessed enormous climate change closely associated with volcanic activity. However, the coupling relationship between volcanic activity and climate change, which may be linked to chemical weathering, has not yet been fully uncovered. We used lithium contents and isotopes of volcanic ash (VA)-bearing lacustrine shale to constrain their deposition pathways and response to climate changes, i.e., weathering intensity, during the Late Triassic era. Elevated δ7Li (i.e., >2.5‰) and low Li contents (i.e., <65 microgram per gram) in shale likely document the direct depositing of volcanic lithium from airborne VA, which mainly inherited Earth's interior δ7Li signal. By contrast, shale yields markedly high lithium contents (i.e., >135 microgram per gram), alongside relatively low δ7Li (i.e., <0‰), likely implying waterborne VA dominated by intensified weathering under a super humidity climate. Hence, this study provides evidence for the differential VA-rich shale deposition model related to chemical weathering states synchronous with climate changes during the CPE period.

Shift in the Mode of Carbon Cycling Recorded by Biomarkers and Carbon Isotopic Compositions in the Yanchang Formation, Ordos Basin: Autotrophy vs Heterotrophy.

Organic-rich shales and mudstones have long been investigated regarding the control of source, environment, climate, etc. on the enrichment of organic carbon. However, little is documented about how autotrophy and heterotrophy influence organic carbon cycling/export. Here, we show molecular and carbon isotopic compositional changes of the shale or mudstone source rocks from the Chang 3 to 7 members of the Yanchang Formation. The Chang 7 member source rocks have higher quality (480-500 mg/g) and total organic carbon (TOC) (15.3% on average) than other member source rocks; the sterane/hopane ratio and the δ13C of organic carbon and kerogen decrease from the Chang 3 to 7 members, but Δδ ([average δ13C of n-C17 + n-C18] - [average δ13C of pristane + phytane]) increases, and no aryl isoprenoids and C40 aromatic carotenoids (e.g., isorenieratane) were observed. These low maturity biomarker features suggest that there were no water stratification, photic zone euxinia (PZE), and no obvious change in the organic matter source, and the water column is generally anoxic. A comparison of the δ13C of Pr and Ph with the δ13C of the n-C17 and n-C18 alkanes reveals a shift in the mode of carbon cycling/export (autotrophy versus heterotrophy) in the Yanchang Formation and that there was dominant heterotrophic bacterial activity or bacterial biomass in the Chang 7 member. The TOC spike in the Chang 7 member may result from boosted carbon cycling/export that improves organic carbon preservation than other members. Possible external forcings on the shift are abundant hydrothermal- or volcanic-derived metal salts as electron acceptors in the palaeowater, which is a reasonable explanation for enhanced heterotrophic bacterial activity. This finding improves our understanding of heterotrophic bacterial activity control on organic matter (OM) preservation and may be a significant supplement for understanding the ecological or environmental forcings in the Yanchang Formation, Ordos Basin.

Fractionation of carbon and hydrogen isotopes of TSR-altered gas products under closed system pyrolysis.

Thermochemical sulfate reduction (TSR) is common in marine carbonate gas reservoirs, leading to complicated isotope characteristics of TSR-altered gas. This study aims to better understand how TSR affects the geochemical and isotopic compositions of alkanes in pyrolysis products. Pyrolysis of TSR were conducted with crude oil, nonane (C9) and methylnaphthalene (MN) in the presence of MgSO4 solution at temperatures of 350 °C, 360 °C, and 370 °C for different durations of 4-219 h in a closed system. Results show that carbon and hydrogen isotope compositions of alkane gas resulting from TSR (pyrolysis with crude oil and MgSO4) became heavier with increasing carbon number, i.e., δ13C1 < δ13C2 < δ13C3 and δ2H-C1 < δ2H-C2 < δ2H-C3. Compared with the δ13C1, δ13C2 and δ13C3 increased in a much wider range as heating continued. Carbon and hydrogen isotopes of alkane gas produced by TSR became heavier with increasing gas souring index. Values for δ13C1-δ13C2 and δ2H-C1- δ2H-C2 typically decreased as oil and C9 underwent thermal cracking. Comparative experiments using C9 in the presence of MgSO4 produced partially reversed carbon isotope series (δ13C1 > δ13C2), which, for the first time, confirmed the ability of TSR to cause isotopic reversal from pyrolysis. The residual heavy alkanes gradually became 13C-enriched during TSR, which increased δ13C2 values and changed the partially reversed isotope sequence to a positive sequence (δ13C1 < δ13C2). The discovery of a partial reversal of the carbon isotope series of alkane gases through pyrolysis will further deepen the understanding of TSR-altered natural gas.

[Effects of land use type on soil nutrient distribution in northern agro-pasture ecotone].

Soil samples under five land use types were collected from Duolun County in the northern agro-pasture ecotone. Chemical analysis showed that soil nutrient content was the lowest in farmland, medium in grassland, and the highest in woodland, indicating that reclamation accelerated the decomposition of soil organic matter and the further loss of soil nutrients. To investigate the effects of land use type on soil organic matter, available phosphors, available nitrogen and total nitrogen, soils from four different land use types in the catchments with slopes steeper than 15 degrees were sampled and analyzed. Vertically, the content of soil nutrients from slope bottom to its top was two times higher in land use type cropland-grassland-woodland than in grassland-woodland-cropland. Such a difference indicated the positive effects of the former land use type on soil nutrient retention. Therefore, selecting this optimal land use type in studied area could improve local eco-environment and economic benefits.