Toxic interactions at the physiological and biochemical levels of green algae under stress of mixtures of three azole fungicides.

Assessing the interactions between environmental pollutants and these mixtures is of paramount significance in understanding their negative effects on aquatic ecosystems. However, existing research often lacks comprehensive investigations into the physiological and biochemical mechanisms underlying these interactions. This study aimed to reveal the toxic mechanisms of cyproconazole (CYP), imazalil (IMA), and prochloraz (PRO) and corresponding these mixtures on Auxenochlorella pyrenoidosa by analyzing the interactions at physiological and biochemical levels. Higher concentrations of CYP, IMA, and PRO and these mixtures resulted in a reduction in chlorophyll (Chl) content and increased total protein (TP) suppression, and malondialdehyde (MDA) content exhibited a negative correlation with algal growth. The activity of catalase (CAT) and superoxide dismutase (SOD) decreased with increasing azole fungicides and their mixture concentrations, correlating positively with growth inhibition. Azole fungicides induced dose-dependent apoptosis in A. pyrenoidosa, with higher apoptosis rates indicative of greater pollutant toxicity. The results revealed concentration-dependent toxicity effects, with antagonistic interactions at low concentrations and synergistic effects at high concentrations within the CYP-IMA mixtures. These interactions were closely linked to the interactions observed in Chl-a, carotenoid (Car), CAT, and cellular apoptosis. The antagonistic effects of CYP-PRO mixtures on A. pyrenoidosa growth inhibition can be attributed to the antagonism observed in Chl-a, Chl-b, Car, TP, CAT, SOD, and cellular apoptosis. This study emphasized the importance of gaining a comprehensive understanding of the physiological and biochemical interactions within algal cells, which may help understand the potential mechanism of toxic interaction.

Lithofacies Types and Physical Characteristics of Organic-Rich Shale in the Wufeng-Longmaxi Formation, Xichang Basin, China.

The shale of the Upper Ordovician Wufeng Formation and the Lower Silurian Longmaxi Formation in the Xichang Basin is the main replacement horizon for the shale gas exploration being conducted in the Sichuan Province, except for the Sichuan Basin. The fine identification and classification of the types of shale facies are important for shale gas exploration and development evaluation. However, the lack of systematic experimental studies on rock physical characteristics and micro-pore structures leads to a lack of physical evidence for the comprehensive prediction of shale sweet spots. Therefore, the present study used different means, such as core observation, total organic carbon content (TOC), helium porosity measurement, X-ray diffraction analysis, and mechanical properties analysis, in combination with the analysis of the whole rock mineral composition and characteristics of shale, for the identification and classification of the lithofacies of the shale layer, the systematic petrology and hardness measurement of the shale samples with different lithofacies, and discussion of the dynamic and static elastic properties of the shale samples and the control factors. It was revealed that nine types of lithofacies existed in the Wufeng Formation- the Long11 sub-member in the Xichang Basin, among which moderate organic carbon content-siliceous shale facies, moderate organic carbon content-mixed shale facies, and high-organic carbon content-siliceous shale facies were the best lithofacies with the optimum reservoir conditions, providing sufficient space for shale gas accumulation. The siliceous shale facies mainly developed organic pores and fractures, and the pore texture was excellent overall. The mixed shale facies mainly developed intergranular pores and mold pores, with a preference toward pore texture. The argillaceous shale facies mainly developed dissolution pores and interlayer fractures, and the pore texture was relatively poor. The geochemical characteristics of the organic-rich shale samples with TOC > 3.5% revealed that the sample was composed of microcrystalline quartz grains as the rock support framework, while the intergranular pores were located between the rigid quartz grains, which exhibited hard pores in the analysis of their mechanical properties. In the relatively organic-poor shale samples with TOC < 3.5%, the quartz source was mainly terrigenous clastic quartz, and the sample was composed of plastic clay minerals as the rock support skeleton, while the intergranular pores were located between argillaceous particles, which exhibited soft pores in the analysis of their mechanical properties. The difference in the rock fabric of the shale samples resulted in an ″initial increase followed by a decrease″ trend of velocity with quartz content, with the organic-rich shale samples exhibiting low velocity-porosity and velocity-organic matter content change rate, and the two kinds of rocks were easier to distinguish in the correlation diagram of the combined elastic parameters such as the P-wave impedance-Poisson ratio and the elastic modulus-Poisson ratio. The samples dominated by biogenic quartz exhibited greater hardness and brittleness, while the samples dominated by terrigenous clastic quartz exhibited lower hardness and brittleness. These results could serve as a basis for logging interpretation and seismic ″sweet spot″ prediction of high-quality shale gas reservoirs in Wufeng Formation-Member 1 of the Longmaxi Formation.