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Biochars are used globally in agricultural crop production and environmental remediation. However, environmentally persistent free radicals (EPFRs), which are stable emerging pollutants, are generated as a characteristic feature during biomass pyrolysis. EPFRs can induce the formation of reactive oxygen species, which poses huge agro-environmental and human health risks. Their half-lives and persistence in both biochar residues and in the atmosphere may lead to potentially adverse risks in the environment. This review highlights the comprehensive research into these bioreactive radicals, as well as the bottlenecks of biochar production leading up to the formation and persistence of EPFRs. Additionally, a way forward has been proposed, based on two main recommendations. A global joint initiative to create an all-encompassing regulations policy document that will improve both the technological and the quality control aspects of biochars to reduce EPFR generation at the production level. Furthermore, environmental impact and risk assessment studies should be conducted in the extensive applications of biochars in order to protect the environmental and human health. The highlighted key research directions proposed herein will shape the production, research, and adoption aspects of biochars, which will mitigate the considerable concerns raised on EPFRs. Keywords: Biochar, Environmentally persistent free radicals, Reactive oxygen species, Environmental fate, Risk

Soil amendment with biochars is currently being studied worldwide as a sustainable agricultural practice to improve soil and water quality, increase crop productivity, and augment soil carbon storage. However, the formation of polyaromatic hydrocarbons (PAHs) during biochar production is inevitable. Therefore, it is crucial to assess the risks in food safety and human health of crops grown in biochar-amended soils. This paper performed a synthesis study of PAH concentrations in biochars and estimated the risks of soils amended with biochars, based on refereed articles published between 2012 and 2018. The PAH concentrations in biochars ranged greatly, with the dominant proportion being 2–3 ringed PAHs (40%–71%). Biochar application increased the PAH levels in soils at drastically varying extents (0.02–3574 μg/kg), which led to a broad range of PAH concentrations in food crops grown in biochar-amended soils. A five-step method was then introduced to assess the toxicity of biochar-borne PAHs to human health. The total mean incremental lifetime cancer risk for adults was estimated to range between 2.0 × 10−6–1.9 × 10−5 via direct contact with and ingestion (inhalation) of contaminated soils or consumption of tainted crops. These results indicated that biochar amendment in soils might pose potential risks to food safety and human health, but the overall cancer risks through exposure to biochar-borne PAHs in soils and food crops were low. Higher application rates (e.g. ≥20 t/ha) of biochars with high PAH contents can be avoided to minimize human cancer risks. Although biochar application in arable farmlands has many environmental and agronomic benefits, holistic and systematic approaches are required to fully assess the benefits and risks before their large-scale adoption. PAHs in biochar may be reduced by improving the biochar production process and developing a cost-effective post-manufacturing treatment. Keywords: Biochar, Polyaromatic hydrocarbon, Soil, Crop, Human health, Contamination risk

Biochars are added to soil to improve agronomic yield. This greenhouse- and field-scale study evaluated poly cyclic aromatic hydrocarbon (PAH) contamination in 35 commercial and laboratory-produced biochars, and assessed the effects of biochar amendment of soils on PAH accumulation in vegetables and the risk for cancer. The total and bioavailable PAH concentrations in biochars varied from 638 to 12,347 mu g/kg and from below the detection limit (BDL) to 2792 mu g/kg, respectively. PAH formation in biochars decreased with increasing production temperature (350-650 degrees C). Root exudates enhanced PAH release from biochars. The total PAH concentrations in eight edible vegetables growing in biochar-amended soil varied according to biochar and vegetables type from BDL to 565 mu g/kg. A health risk assessment framework was integrated with the benzo [a] pyrene toxic equivalency quotient and the incremental lifetime cancer risk (ILCR) to estimate the exposure risk for human beings via ingestion of PAH-contaminated vegetables. The total ILCR for adults was above 10(-6), which suggests a risk to human health from direct exposure to PAHs in vegetables grown in biochar-amended soil. These results demonstrate that biochar application may lead to contamination of plants with PAHs, which represents a risk to human health. The PAH levels in biochars produced using different conditions and/or feed-stocks need to be evaluated and biochars should be pretreated to remove PAHs before their large-scale agronomic application. Jiangsu Provincial Key Research and Development Plan, China [BE2017718, BE2015682]; Jiangsu Environmental Monitoring Research Fund, China [1706]; National Natural Science Foundation of China [41771523, 41877125, 31770549]; Special Fund for Agro-scientific Research in Public Interest, China [201503107] This work was supported by the Jiangsu Provincial Key Research and Development Plan, China (BE2017718, BE2015682), the Jiangsu Environmental Monitoring Research Fund, China (1706), the National Natural Science Foundation of China (41771523, 41877125, 31770549), and the Special Fund for Agro-scientific Research in Public Interest, China (201503107).