Aging is an important natural process affecting the physiochemical properties of biochar, while mechanistic understanding of its effect on the adsorbed heavy metals is still lacking. After adsorption of Cd²⁺ and Pb²⁺, biochars produced from wheat straw (WS) and maize straw (MS) at 300 and 500 °C (denoted as WS300, WS500, MS300, and MS500, respectively) were subjected to 60 cycles of wet–dry or freeze–thaw aging. The results showed that simulated aging treatment transformed the Cd²⁺ and Pb²⁺ adsorbed on the low-temperature biochars from the readily and potentially bioavailable fractions into the non-bioavailable one, while the fractionation of Cd²⁺ and Pb²⁺ adsorbed on WS500 and Pb²⁺ on MS500 barely changed. Spectroscopic characterization revealed that simulated aging enhanced the complexation of Cd²⁺ and precipitation of Pb²⁺ on the biochars. These findings suggest that heavy metals could be effectively immobilized on low-temperature biochars amended to contaminated soils in the long term.

The release of fine particles from biochar materials applied in the environment may have important environmental implications, such as mobilization of environmental contaminants. In natural environments biochar fine particles can undergo various transformation processes, which may change their surface chemistry and consequently, the mobility of the particles. Here, we show that sulfide reduction can significantly alter the transport of wheat-straw- and pine-wood-derived biochar fine particles in saturated porous media. Counterintuitively, the sulfide-reduced biochar particles exhibited greater mobility in artificial groundwater than their non-reduced counterparts, even though reduction led to decrease of surface charge negativity and increase of hydrophobicity (from the removal of surface O-functional groups), both should favor particle deposition, as predicted based on extended Derjaguin–Landau–Verwey–Overbeek (XDLVO) theory. Using transport experiments conducted in single-cation background solutions containing K⁺, Mg²⁺ or Ca²⁺ under different pH conditions, we show that the surprisingly greater mobility of sulfide-reduced biochar particles was attributable to the removal of surface carboxyl groups during reduction, as this markedly alleviated particle deposition through cation bridging, wherein Ca²⁺ acted as the bridging agent in linking the surface O-functional groups of biochar particles and quartz sand. These findings show the critical roles of surface properties in dictating the mobility of biochar fine particles and call for further understanding of their transport properties, which apparently cannot be simply extrapolated based on the findings of other (engineered) carbonaceous nanomaterials.

Straw-return methods that neither negatively impact yield nor bring environmental risk are ideal patterns. To attain this goal, it is necessary to conduct field observation to evaluate the environmental influence of different straw-return methods. Therefore, we conducted a 2-year field study in 2015–2017 to investigate the emissions of methane (CH₄) and nitrous oxide (N₂O) and the changes in topsoil (0–20 cm) organic carbon (SOC) density in a typical Chinese rice-wheat rotation in the Eastern China. These measurements allowed a complete greenhouse gas accounting (net GWP and GHGI) of five treatments including: FP (no straw, plus fertilizer), FS (wheat straw plus fertilizer), FB (straw-derived biochar plus fertilizer), FSDI (wheat straw with straw-decomposing microbial inoculants plus fertilizer) and CK (control: no straw, no fertilizer). Average annual SOC sequestration rates were estimated to be 0.20, 0.97, 1.97 and 1.87 t C ha⁻¹ yr⁻¹ (0–20 cm) for the FP, FS, FB and FSDI treatments respectively. Relative to the FP treatment, the FS and FSDI treatments increased CH₄ emissions by 12.4 and 17.9% respectively, but decreased N₂O emissions by 19.1 and 26.6%. Conversely, the FB treatment decreased CH₄ emission by 7.2% and increased N₂O emission by 10.9% compared to FP. FB increased grain yield, but FS and FSDI did not. Compared to the net GWP (11.6 t CO₂-eq ha⁻¹ yr⁻¹) and GHGI (1.20 kg CO₂-eq kg⁻¹ grain) of FP, the FS, FB and FSDI treatments reduced net GWP by 12.6, 59.9 and 34.6% and GHGI by 10.5, 65.8 and 37.7% respectively. In rice-wheat systems of eastern China, the environmentally beneficial effects of returning wheat straw can be greatly enhanced by application of straw-decomposing microbial inoculants or by applying straw-derived biochar.

Livestock manure is a reservoir of antibiotic resistance genes (ARGs), posing a potential risk to environment and human health. However, there has been no optimization study about the comprehensive composting treatment for livestock manure ARGs based on multiple operation factors. In this study, anaerobic composting of swine manure in light was conducted under different combined conditions of composting time, temperature, water content, pH, heavy metal passivators and wheat straw. The diversity and relative abundance of ARGs in the compost were detected using high throughput quantitative real-time PCR, and the concentrations of antibiotics and heavy metals were determined. The results showed that under the optimized conditions (composting time, 30 d; temperature, 50 °C; water content, 50%; pH 9.0; heavy metal passivators and wheat straw), compared with the control, the detected number of ARGs and mobile genetic elements in the compost was reduced by 45% and 27.3%, and their relative abundance decreased by 33.9% and 36.9%, respectively. Moreover, the exchangeable heavy metal content of the compost declined by 34.7–57.1%, and the antibiotic level decreased by 28.8–77.8%. This study proposes that synergistic effects of key parameters can effectively mitigate the combined contamination of ARGs, antibiotics, and heavy metals in swine manure.Optimized parameters (anaerobic composting time 30 d, temperature 50 °C, water content 50%, pH 9.0) effectively mitigated the combined pollution of ARGs, antibiotics, and heavy metals in swine manure.

Proper management of waste crop residues has been an environmental concern for years. Yellow mealworms (larvae of Tenebrio molitor Linnaeus, 1758) are major insect protein source. In comparison with normal feed wheat bran (WB), we tested five common lignocellulose-rich crop residues as feedstock to rear mealworms, including wheat straw (WS), rice straw (RS), rice bran (RB), rice husk (RH), and corn straw (CS). We then used egested frass for the production of biochar in order to achieve clean production. Except for WS and RH, the crop residues supported mealworms’ life activity and growth with consumption of the residues by 90% or higher and degraded lignin, hemicellulose and cellulose over 32 day period. The sequence of degradability of the feedstocks is RS > RB > CS > WS > RH. Egested frass was converted to biochar which was tested for metal removal including Pb(II), Cd(II), Cu(II), Zn(II), and Cr(VI). Biochar via pyrolysis at 600 °C from RS fed frass (FRSBC) showed the best adsorption performance. The adsorption isotherm fits the Langmuir model, and kinetic analysis fits the Pseudo-Second Order Reaction. The heavy metal adsorption process was well-described using the Intra-Particle Diffusion model. Complexation, cation exchange, precipitation, reduction, deposition, and chelation dominated the adsorption of the metals onto FRSBC. The results indicated that crop residues (WS, RS, RB, and CS) can be utilized as supplementary feedstock along with biochar generated from egested frass to rear mealworms and achieve clean production while generating high-quality bioadsorbent for environment remediation and soil conditioning.

Biomass derived biochar is a stable carbon-rich product with potential for soil amendment. Introduced into the natural environment, biochar will naturally experience ‘ageing’ processes that are liable to change its physicochemical properties and the mobility of sorbed pollutants over the longer term. To elucidate the reciprocal effects of biochar ageing and heavy metal adsorption on the affinity of biochar for organic pollutants, we systematically assessed the adsorption of diethyl phthalate (DEP), representative of phthalic acid esters (PAEs), to fresh and aged biochars with and without coexistence of Cd²⁺. Long-term oxidative ageing was simulated using 5% H₂O₂ and applied to biochar samples made from corn cob, maize straw and wheat straw made by pyrolysis at both 450 °C and 650 °C. Our results showed that biochar made at lower temperature (450 °C) and from straw exhibited the higher adsorption capacity, owing to their greater polarity and abundance of O-containing functional groups. The adsorption of DEP onto fresh biochars was found to be driven by van der Waals force and H-bonding. Biochar made at the higher temperature (650 °C) displayed higher carbon stability than that produced at lower pyrolysis temperature. Oxidized biochar showed lower adsorption capacity than fresh biochar owing to the formation of three-dimensional water clusters on biochar surface, which blocked accessible sites and decreased the H-bonding effect between DEP and biochars. The coexistence of Cd²⁺ suppressed the sorption of DEP, via competition for the same electron-rich sites. This indicates that cation/π-π EDA interactions are the primary mechanism for PAE and Cd²⁺ stabilization on biochar. Our study sheds light on the mechanism of organic pollutant sorption by biochar, as well as the potential susceptibilities of this sorption to ageing effects in the natural environment.

Nitrated phenols are among the major constituents of brown carbon and affect both climates and ecosystems. However, emissions from biomass burning, which comprise one of the most important primary sources of atmospheric nitrated phenols, are not well understood. In this study, the concentrations and proportions of 10 nitrated phenols, including nitrophenols, nitrocatechols, nitrosalicylic acids, and dinitrophenol, in fine particles from biomass smoke were determined under three different burning conditions (flaming, weakly flaming, and smoldering) with five common types of biomass (leaves, branches, corncob, corn stalk, and wheat straw). The total abundances of fine nitrated phenols produced by biomass burning ranged from 2.0 to 99.5 μg m−3. The compositions of nitrated phenols varied with biomass types and burning conditions. 4-nitrocatechol and methyl nitrocatechols were generally most abundant, accounting for up to 88–95% of total nitrated phenols in flaming burning condition. The emission ratios of nitrated phenols to PM2.5 increased with the completeness of combustion and ranged from 7 to 45 ppmm and from 239 to 1081 ppmm for smoldering and flaming burning, respectively. The ratios of fine nitrated phenols to organic matter in biomass burning aerosols were comparable to or lower than those in ambient aerosols affected by biomass burning, indicating that secondary formation contributed to ambient levels of fine nitrated phenols. The emission factors of fine nitrated phenols from flaming biomass burning were estimated based on the measured mass fractions and the PM2.5 emission factors from literatures and were approximately 0.75–11.1 mg kg−1. According to calculations based on corn and wheat production in 31 Chinese provinces in 2013, the total estimated emission of fine nitrated phenols from the burning of corncobs, corn stalks, and wheat straw was 670 t. This work highlights the apparent emission of methyl nitrocatechols from biomass burning and provides basic data for modeling studies.

Biochar plays an important role in the behaviors of organic pollutants in the soil environment. The role of humic acid (HA) and metal cations on the adsorption affinity of polychlorinated biphenyls (PCBs) to the biochars in an aqueous medium and an extracted solution from a PCBs-contaminated soil was studied using batch experiments. Biochars were produced with pine needles and wheat straw at 350 °C and 550 °C under anaerobic condition. The results showed that the biochars had high adsorption affinity for PCBs. Pine needle chars adsorbed less nonplanar PCBs than planar ones due to dispersive interactions and separation. Coexistence of HA and metal cations increased PCBs sorption on the biochars accounted for HA adsorption and cation complexation. The results will aid in a better understanding of biochar sorption mechanism of contaminants in the environment.

To characterize the emissions of polycyclic aromatic hydrocarbons (PAHs) from residential biomass burning and coal combustion in field environments, smoke samples were collected from the combustion of six types of biomass in heated kangs and four types of coal in traditional stoves and semi-gasifier stoves. The emission factors (EFs) of the total PAH were in the range of 84.5–344 mg/kg for biomass burning, with lower EFs for biomass with higher densities, and in the range of 38.0–206 mg/kg for coal combustion, with lower EFs for coals with higher maturity. Moreover, EFs were lower from high-density biomass fuels (wood trunk, 84.5 ± 11.3 mg/kg) than low-maturity coals (bituminous coal, 206 ± 16.5 mg/kg). Parent, oxygenated, alkylated, and nitrated PAHs accounted for 81.1%, 12.6%, 6.2%, and 0.1%, respectively, of the total-PAH EFs from biomass burning, and 84.7%, 13.8%, 1.4%, and 0.1%, respectively, of the total-PAH EFs from coal combustion. PAH source profiles differed negligibly between biomass fuels but differed significantly between bituminous coal and anthracite coal fuels. The characteristic species of sources were phenanthrene, 9-fluorenone, and 2-nitrobiphenyl for biomass burning, and were phenanthrene, benzo[ghi]perylene, 1,4-naphthoquinone, and 2-nitrobiphenyl for coal combustion. The ratios of benzo[b]fluoranthene/(benzo[b]fluoranthene + benzo[k]fluoranthene) were 0.40–0.45 for biomass burning and 0.89–0.91 for coal combustion, and these significantly different values constitute unique markers for distinguishing these fuels in source apportionment. Benzo[a]pyrene-equivalent factor emissions were 2.79–11.3 mg/kg for biomass and 7.49–41.9 mg/kg for coal, where parent PAHs contributed 92.0%–95.1% from biomass burning and 98.6%–98.8% from coal combustion. Total-PAH emissions from residential heating were 1552 t across Shaanxi province, to which wheat straw (445 t) in biomass burning and bituminous coal (438 t) in coal combustion were the highest contributors. Results from this study provide crucial knowledge for the source identification of PAHs as well as for the design of abatement strategies against pollutant emissions.

Natural aging alters the surface physicochemical properties of biochars, which can affect the retention of heavy metals. This work investigated the effect of biochar aging on stabilization of heavy metals (Cd and Ni) and soil enzyme activities simulated with laboratory wet–dry (WD) and freeze–thaw (FT) cycling. A wheat straw (WS) biochar and a corn straw (CS) biochar were subjected to 30 WD or FT cycles, and Cd- and Ni-contaminated alkaline soils amended with the two fresh biochars (at 5% w/w) were subjected to 30-day constant moisture incubation and 30 WD or FT cycles. WD and FT aging caused slight reduction in the pH of the biochars, significant increases in their O contents and surface areas, and formation of new carbonate minerals. WS biochar was more effective than CS biochar at reducing the phytoavailable Cd in the soil, with reduction of 12.1%, 14.6%, and 12.9% under constant moisture incubation, WD aging, and FT aging, respectively. Reduction in phytoavailability of Ni by the addition of biochars was observed only under WD aging, by 17.0% and 18.5% in the presence of WS and CS biochars, respectively. Biochar amendment also reduced the distribution of Cd in the acid soluble and reducible fractions in all aging regimes. The addition of biochars decreased catalase activity in almost all aging regimes and invertase activity under FT aging, but increased urease activity under FT aging. Comparison of the enzyme activities in the soils amended with biochars under constant moisture and accelerated aging conditions indicates WD aging significantly decreased the activities of catalase, invertase, and urease in all treatments, while FT aging significantly increased urease activity in all treatments. These findings suggest that biochars can stabilize Cd in alkaline soils under changing environmental conditions, although the activities of some soil enzymes could be negatively impacted.