The application of biochar in remediation and recovery of heavy metals and/or organic contaminants in water and soil is increasing. However, the adverse effect of biochar to aquatic organisms has not received enough attention. In this study, we conducted a study on the biotoxicity of biochar pyrolyzed from pine needle under oxygen-limited conditions. The toxicity of biochar was expressed with the following endpoints: cell growth, chlorophyll-a (Chl-a), reactive oxygen species (ROS), superoxide dismutase (SOD) content of Scenedesmus obliquus (S. obliquus) and the luminescence of Photobacterium phosphoreum (P. phosphoreum). Here, the effect of free radicals (FRs) contained in biochar was stressed. Our results show that the toxicity of biochar is significantly correlated with the concentration of FRs in biochar particles. Meanwhile, we found the FRs-containing biochar could induce the production of acellular ROS (such as ·OH) in water, which would also induce the production of interior cellular ROS in aquatic organisms. Our findings provide a new insight into the mechanism of toxicity aroused by biochar applications and aid in understanding its potential ecological risk.

Aryl phosphorus-containing flame retardants (aryl-PFRs) have been frequently detected with increasingly used worldwide as one of alternatives for brominated flame retardants. However, information on their adverse effects on human health and ecosystem is insufficient, with limited study on their molecular mode of action in vitro. In this study, the cytotoxicity, DNA damage, mitochondrial impairment and the involved molecular mechanisms of certain frequently detectable aryl-PFRs, including 2-ethylhexyldiphenyl phosphate (EHDPP), methyl diphenyl phosphate (MDPP), bisphenol-A bis (diphenyl phosphate) (BDP), isodecyl diphenyl phosphate (IDPP), cresyl diphenyl phosphate (CDP) and the structurally similar and widely used organophosphorus pesticide chlorpyrifos (CPF), were evaluated in A549 cells using high-content screening (HCS) system. Aryl-PFRs showed different lethal concentration 50 (LC50) values ranging from 97.94 to 546.85 μM in A549 cells using CCK-8 assay. EHDPP, IDPP, CDP, MDPP and CPF demonstrated an ability to induce DNA damage, evidenced by increased DNA content and S phase-reducing cell cycle arrest effect using fluorophore dye cocktail assay. Additionally, the selected aryl-PFRs induced mitochondrial impairment by the increasing mitochondrial mass and decreasing mitochondrial membrane potential. Moreover, BDP, MDPP, and CDP, which contain short alkyl chains showed their potential oxidative stress with intracellular ROS and mitochondrial superoxide overproduction from an initially relatively low concentration. Additionally, based on the promotion of firefly luminescence in p53-transfected A549 cells, p53 activation was found to be involved in aryl-PFRs-induced DNA damage. Further real-time PCR results showed that all selected aryl-PFRs triggered p53/p21/gadd45β-, and p53/p21/mdm2-mediated cell cycle pathways, and the p53/bax mediated apoptosis pathway to induce DNA damage and cytotoxic effects. These results suggest that aryl-PFRs (e.g., BDP, MDPP, CDP) cause oxidative stress-mediated DNA damage and mitochondrial impairment, and p53-dependent pathway was involved in the aryl-PFRs-induced DNA damage and cell cycle arrest. In conclusion, this study improves the understanding of PFRs-induced adverse outcomes and the involved molecular mechanism.

As non-biological molecules, molecular imprinted polymers (MIPs) can be made as antibody mimics for the development of luminescence sensors for various targets. The combination of MIPs with nanomaterials is further recognized as a useful option to improve the sensitivity of luminescence sensors. In this work, the recent progresses made in the fabrication of fluorescence, phosphorescence, chemiluminescence, and electrochemiluminescence sensors based on such combination have been reviewed with emphasis on the detection of pesticides/herbicides. Accordingly, the materials that are most feasible for the detection of such targets are recommended based on the MIP technologies.

The conductive polyurethane/polypyrrole/graphene (CPU/PPy/Gr) particle electrode was prepared by an in-situ oxidative polymerization method and used as particle electrodes to degrade levofloxacin (LEV) in a three-dimensional electrode reactor. The prepared CPU/PPy/Gr electrode was characterized systematically and the effects of initial pH, initial LEV concentration, aeration volume, voltage, and electrolyte concentration on the degradation efficiency were investigated. Results showed that more than 90% LEV was degraded and the energy consumption was 20.12 kWh/g LEV under conditions of pH 7, 6 V voltage, 2.0 L/min aeration volume, 20 mg/L initial LEV concentration, and 7 mM concentration of electrolyte (Na₂SO₄). A possible electrochemical oxidation pathway of LEV by the CPU/PPy/Gr electrode was proposed. In addition, the biotoxicity of LEV and its oxidation products was calculated using ECOSAR (Ecological Structure Activity Relationships) program in EPISuite. Toxicity evaluation using luminescent bacteria showed that the toxicities of some intermediates were higher than the parent compound. But the toxicity of degradation processes for LEV was effective decreasing. A possible reactive mechanism in the three-dimensional reactor was also recommended. In brief, the prepared CPU/PPy/Gr particle electrode constitutes an insight into the promising practical application in the wastewater treatment.

The humic-like substances were the main organic components in most wastewater (e.g. domestic sewage, toilet wastewater and landfill leachate). Two types of actual humic-like substances (fulvic acid (FA) and biologically treated landfill leachate (BTLL)) were selected to describe the changes in the properties of humic-like substances (complexation ability, aromaticity and mobility) during electrochemical oxidation. Meanwhile, the acute cytotoxicity of FA and BTLL was also tested by acute toxicological test of luminescent bacteria. The results showed that the consumption of coordinating groups such as phenolic groups and hydrogen bonds reduced the complexation ability of FA and BTLL. The functional groups were degraded with the removal order of quinone group, phenolic group and aromatic group, and finally realized the molecular saturation and aromaticity decrease for humic-like substances. The mobility of FA and BTLL was decreased because of the enhancement of hydrophobicity during electrolysis process. Furthermore, the available chlorine produced during electrochemical oxidation was the main acute cytotoxicity substance, therefore, it is necessary to remove it before discharge in order to reduce ecological risks. This study provides a basis for understanding and evaluating the electrochemical degradation process of humic-like substances in detail.

The aim of this study was to determine the effect of biochar aging on the content of polycyclic aromatic hydrocarbons (PAHs) (the total content – Ctot, and the freely dissolved – Cfree) in biochar and its ecotoxicity. Two biochars (BCS and BCM) with varying properties were aged for 420 days at different temperatures (−20 °C, 4 °C, 20 °C, 70 °C), at a variable temperature (−20/20 °C), in the presence of nutrients, and in the presence of inoculum and nutrients. After the aging process, Ctot and Cfree PAHs were determined in samples obtained and an ecotoxicological analysis was performed, which involved tests with bacteria (Vibrio fischeri), invertebrates (Folsomia candida) and plants (Lepidium sativum). Aging significantly affected all the parameters tested. The range of changes in the studied parameters depended on the type of biochar and ageing conditions. In the case of most of the aging methods, PAH content (Ctot, Cfree) and toxicity were found to decrease. Aging in the presence of microorganisms and nutrients and in the presence of nutrients alone caused the greatest reduction in Ctot PAH content (a reduction from 30 to 100% relative to non-aged biochar), Cfree PAH content (a reduction from 12 to 100%), root growth inhibition (a reduction from 73 to 90%), and luminescence inhibition (a reduction from 24 to 100%). In the case of Cfree PAHs and toxicity to F. candida, some aging methods caused their increase. The study also found a significant relationship between the changes in Ctot PAH content during aging and inhibition of root growth (BCS, BCM) and inhibition of V. fischerii luminescence (BCM). In no case was a significant correlation (P ≥ 0.05) between Cfree PAHs and the investigated toxicity parameters found.

Biochar has potential for application for in situ metal-contaminated sediment remediation, mainly because of its cost-effectiveness. In this study, the effectiveness of Phyllostachys pubescens (PP) biochar for immobilization of cadmium (Cd) chromium (Cr), copper (Cu), nickel (Ni), lead (Pb) and zinc (Zn) by decreasing the bioavailable fraction was investigated using a series of laboratory sediment remediation microcosms. The results demonstrated that biochar could significantly reduce the bioavailable fraction of metals (except for Cr) by diffusive gradients in thin film (DGT) measurement in porewater. Additionally, amended sediment treated with 15% w/w biochar resulted in 79.71%, 73.20%, 54.86%, 49.75%, 31.16% and 0.99% reductions in the acid-soluble fraction for Cu, Pb, Ni, Zn, Cd, and Cr, respectively. Similarly, bioaccumulation of metals (except for Cr) by Limnodrilus hoffmeisteri was reduced by 18.45%–59.15% in biochar amended sediment. PP biochar at 15% could also reduce the inhibition or lethality rate by 37.5%, 18.1% and 36.3% for Chlorella vulgaris, Daphnia magna and luminescent bacteria Vibrio qinghaiensis, respectively. Overall, these results demonstrate the potential for biochar application for in situ sediment remediation.

A previous study has revealed that the parameter k∙ECₓ, characterizing the shape of concentration-response curves (CRCs), could predict the combined toxicity of binary mixtures. This study further explored the predictability of multi-component mixtures. Eleven component mixtures were designed using the uniform design ray, and the acute toxicity of the eleven environmental pollutants and their mixtures to Vibrio fischeri was determined using microplate toxicity analysis. We used independent action (IA) and the effect residual ratio (ERRₓ) models to evaluate the combined toxicity of multi-component mixtures and ascertain the functional relationship between σ²₍ₖ∙ECₓ₎, a parameter characterizing the CRC morphological difference of multi-component mixtures, and combined toxicity. The variance σ²₍ₖ∙ECₓ₎ of each component characteristic parameter of multi-component mixtures gradually increased in the concentration range, and the relationship between σ²₍ₖ∙ECₓ₎ and ERRₓ was consistent with the exponential function. The literature verification showed that this rule is generally applicable to the acute toxicity of multi-component mixtures to luminescent bacteria. The exponential function showed the variation rule of the joint action of multi-component mixtures. In the present study, the joint toxicity of multi-component mixtures can be predicted from single toxicity and small amount of multiple toxicity, circumventing complex multi-component toxicity experiments.

Co-pyrolysis of sewage sludge (SL) with plant biomass gains attention as a way to minimize SL-derived biochar drawbacks, such as high amount of toxic substances, low specific surface area and carbon content. The toxicity of soil amended with SL- (BCSL) or SL/biomass (BCSLW)-derived biochar was evaluated in long-term pot experiment (180 days). The results were compared to SL-amended soil. Biochars produced at 500, 600, or 700 °C were added to the soil (podzolic loamy sand) at a 2% (w/w) dose. Samples were collected at four different time points (at the beginning, after 30, 90 and 180 days) to assess the potential toxicity of SL-, BCSL- or BCSLW-amended soil. The bacteria Aliivibrio fischeri (luminescence inhibition – Microtox), the plant Lepidium sativum (root growth and germination inhibition test – Phytotoxkit F), and the invertebrate Folsomia candida (mortality and reproduction inhibition test – Collembolan test) were used as the test organisms. Depending on the organism tested and the sample collection time point variable results were observed. In general, SL-amended soil was more toxic than soil with biochars. The leachates from BCSLW-amended soil were more toxic to A. fischeri than leachate from BCSL-amended soil. A different tendency was observed in the case of phytotoxicity. Leachate from BCSL-amended soil was more toxic to L. sativum compared to BCSLW-amended soil. The effect of biochars on F. candida was very diversified, which did not allow a clear trend to be observed. The toxic effect of SL-, BCSL- or BCSW-amended soil to particular organisms was observed in different time, point's periods, which may suggest the different factors affecting this toxicity.

The study aimed to evaluate the ecotoxicity of soil (S) amended with biochars (BCKN) produced by the thermal conversion of sewage sludge (SSL) at temperatures of 500 °C, 600 °C, or 700 °C and SSL itself. The ecotoxicological tests were carried out on organisms representing various trophic levels (Lepidium sativum in plant, Folsomia candida in invertebrates, and Aliivibrio fischeri in bacteria). Moreover, the study evaluated the effects of three plants (Lolium perenne, Trifolium repens, and Arabidopsis thaliana) growing on BCKN700-amended soil on its ecotoxicological properties. The experiment was carried out for six months. In most tests, the conversion of sewage sludge into biochar caused a significant decrease in toxicity by adding it to the soil. The pyrolysis temperature directly determined this effect. The soil amended with the biochars produced at higher temperatures (600 °C and 700 °C) generally exhibited lower toxicity to the test organisms than the SSL. Because of aging, all the biochars lost their inhibition properties against the tested organisms in the solid-phase tests and had a stimulating influence on the reproductive ability of F. candida. With time, the fertilizing effect of the BCKN700 amended soil also increased. The aged biochars also did not have an inhibitory effect on A. fischeri luminescence in the leachate tests. The study has also demonstrated that the cultivation of an appropriate plant species may additionally reduce the toxicity of soil fertilized with biochar. The obtained results show that the conversion of sewage sludge to biochar carried out at an appropriate temperature can become a useful method in reducing the toxicity of the waste and while being safe for agricultural purposes.