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The eco-risk of roxarsone (ROX) was evaluated using multiple responses of earthworm biomarkers under different ROX concentrations for 28 d. With the increasing total arsenic accumulation (TAs-E), biological responses in earthworm generally showed a two-stage changes of homeostasis dysregulation and dose-dependent alterations. At the early periods, ROX stress increased the reactive oxygen species (ROS) and lipid peroxidation (LPO) in a similar manner, and apparently disrupted mitochondrial calcium ([Ca2+]m). But earthworms regulated their mitochondrial and redox homeostasis through stable mitochondrial membrane potential (MMP) and increase of ATP level, superoxide dismutase (SOD) and catalase (CAT). After 14 d, the positively correlated mitochondrial effects of ROS, [Ca2+]m, MMP and ATP were related to the behavioral inhibition of burrow length, depth and reuse rate as well as antioxidant up-regulation of Nrf2, HO-1, sod1 and cat. These results contributed possible biomarkers from the dose-dependent relationship between mitochondrial, antioxidant and behavioral responses. Multiple biological detection in earthworms can better reflect the sub-chronic ecotoxicity of phenylarsenic pollutants in soil.

Arsenate (As-V) is a ubiquitous contaminant in soil as a result of excessive use of veterinary drugs and pesticides, causing enormous environmental risks. Multiple biomarkers have been used to assess the ecotoxicity of arsenic, however, the mechanisms of toxicity remain unclear. This paper describes the exposure of the earthworm (Eisenia fetida) to natural soil with different As-V concentrations for 28 days, then biomarkers from oxidative stress and burrowing behavior were quantified to evaluate As-V stress. Dynamic changes in reactive oxygen species (ROS), lipid peroxidation (MDA), adenosine triphosphate (ATP) content and antioxidant enzymes activity (Gpx, SOD, CAT) implied two stages of intensified stress responses and physiological adaptability. The transcriptional expression and regulation of antioxidant enzymes showed different responses. The mRNA expression of sod1 was up-regulated, while that of cat showed no significant change. The related regulators, nuclear factor erythroid 2-related factor 2 (Nrf2) and heme oxygenase-1 (HO-1), showed dose-dependent activation, suggesting antioxidant defense induced by Nrf2 signaling. The burrowing behavior after 14-day exposure indicated that As-V inhibited burrowing activity, especially the burrow length and maximum burrow depth. These multiple biomarkers were integrated using a biomarker response index (BRI) model, which showed significant dose-effect relationship especially on day 28, and suggested that ATP was a sensitive and representative biomarker. This study provided evidence that burrowing activity, Nrf2 and HO-1 were useful biomarkers warranting inclusion into the BRI model. Arsenic toxicity was comprehensively understood through redox homeostasis regulation, biochemical and behavioral changes, and these results suggested new strategies for soil pollutants diagnosis.

The kinetic compensation effect between the activation energy and the pre-exponential factor has extensively existed in the thermochemical conversion processes of lignocellulosic biomass. The research on the kinetic compensation effect in lignocellulosic biomass torrefaction has been insufficient yet. The torrefaction of the pinewood sample was experimentally investigated by thermogravimetric analysis (TGA) at five isothermal temperatures of 220, 250, 265, 280 and 295 °C. The reaction order model was used to analyze the isothermal torrefaction kinetics of lignocellulosic biomass, and the results showed that many sets of activation energy and pre-exponential factor could describe the experimental data at each temperature equally well and they excellently satisfied the kinetic compensation effect relationship. The linear regression lines of the kinetic compensation effect points at different temperatures intersected at one point, whose values corresponded to the obtained optimal kinetic parameters. A kinetic-compensation-effect-based method was developed and verified to determine the kinetic parameters of isothermal biomass torrefaction. Based on the optimal kinetic parameters, the thermodynamic parameters (including Gibbs free energy, enthalpy, and entropy) of biomass torrefaction processes at various temperatures were calculated and analyzed.

The exponential temperature change in nonisothermal kinetic analysis is usually used in the experimental investigation of biomass pyrolysis kinetics. In this paper, the applying of exponential temperature change for nonisothermal kinetics of thermally stimulated processes is discussed. Two approximations for the temperature integral occurring in nonisothermal kinetics with exponential temperature program are proposed. These approximations are more accurate in the evaluation of the integral than Gorbachev approximation. Based on the newly proposed approximations, the corresponding integral methods for nonisothermal kinetics with exponential temperature change have been developed. A systematic analysis of the relative errors involved in the kinetic parameters determined from these integral methods has been carried out, the results indicate that the proposed integral methods are more accurate than Gorbachev integral method. It is expected that the results will be helpful for the kinetic analysis of biomass pyrolysis with exponential temperature program.

Torrefaction aroused as a promising pretreatment technique that can improve the fuel properties and thermochemical conversion performance of biomass. The kinetics of biomass torrefaction is fundamental for the investigation of torrefaction reaction mechanisms, and the simulation and optimization of torrefaction processes. The commonly used empirical reaction model has some theoretical drawbacks in describing the kinetics of biomass torrefaction. In this study, the torrefaction kinetics of beech wood was studied using thermogravimetric analysis (TGA) at isothermal temperatures of 493, 523 and 553 K. The nth-order kinetic model was presented to analyze the kinetic experimental data at all torrefaction temperatures simultaneously. The pattern search method was used to optimize the kinetic parameters of the nth-order model for biomass torrefaction. Predicted results from the nth-order model with the optimal kinetic parameters were compared with the experimental data and indicated that the nth-order model satisfactorily predicted the experimental data of beech wood torrefaction at different torrefaction temperatures.