Pyrolysis is a promising thermochemical conversion process that transforms biomass into biochar, a carbon-rich solid material, in an oxygen-limited environment. This study focuses on the utilization of rice byproducts, namely rice straw and rice husk as feedstock for biochar production through low-temperature pyrolysis. The aim is to explore the potential of these biochars as cost-effective adsorbents for removing metal contaminants from aqueous solutions, with a particular emphasis on Pb(II) removal. Physicochemical properties of the biochars produced at a low temperature of 300 °C were thoroughly investigated, including surface morphology and their adsorption capacity for Pb(II). Remarkably, the rice straw biochar (RSB) produced at 300 °C exhibited exceptional Pb(II) adsorption capacity, with a value of 390.10±0.30 mg/g, and demonstrated a high Pb(II) removal efficiency of 96.10±0.30% when modified with 30% w/w H2O2. A crucial aspect of this study lies in the evaluation of the cost-effectiveness of the biochar production process, particularly when compared to commercially available adsorbents. By demonstrating the potential of rice byproduct-derived biochar as an efficient Pb(II) biosorbent in aqueous environments, this work not only provides new insights into the preparation of biochar using low-temperature pyrolysis but also offers a viable and economical solution for metal-contaminated water treatment. The findings of this research contribute to the field of sustainable waste utilization and highlight the significant potential of rice byproduct-based biochar as an environmentally friendly adsorbent for heavy metal removal.

Metal oxide-modified biochar showed excellent adsorption performance in wastewater treatment. Iron nitrate and potassium permanganate were oxidative modifiers through which oxygen-containing groups and iron–manganese oxides could be introduced into biochar. In this study, iron–manganese (Fe–Mn) oxide-modified biochar (BC-FM) was synthesized using rice straw biochar, and the adsorption process, removal effect, and the mechanism of cadmium (Cd) adsorption on BC-FM in wastewater treatment were explored through batch adsorption experiments and characterization (SEM, BET, FTIR, XRD, and XPS). Adsorption kinetics showed that the maximum adsorption capacity of BC-FM for Cd(II) was 120.77 mg/g at 298 K, which was approximately 1.5–10 times the amount of adsorption capacity for Cd(II) by potassium-modified or manganese-modified biochar as mentioned in the literature. The Cd(II) adsorption of BC-FM was well fit by the pseudo-second-order adsorption and Langmuir models, and it was a spontaneous and endothermic process. Adsorption was mainly controlled via a chemical adsorption mechanism. Moreover, BC-FM could maintain a Cd removal rate of approximately 50% even when reused three times. Cd(II) capture by BC-FM was facilitated by coprecipitation, surface complexation, electrostatic attraction, and cation-π interaction. Additionally, the loaded Fe–Mn oxides also played an important role in the removal of Cd(II) by redox reaction and ion exchange in BC-FM. The results suggested that BC-FM could be used as an efficient adsorbent for treating Cd-contaminated wastewater.

The effectiveness of biochar as a sorptive material to remove contaminants, particularly heavy metals, from water is dependent on biomass type and pyrolysis condition. Biochars were produced from pulp mill sludge (PMS) and rice straw (RS) with nitrogen (N₂) or carbon dioxide (CO₂) as the purging gas. The sorptive capacity of the biochars for cadmium(II), copper(II), nickel(II) and lead(II) was studied. The heavy metal adsorption capacity was mainly affected by biomass type, with biochars adsorption capacities higher for lead(II) (109.9–256.4 mg g⁻¹) than for nickel(II) (40.2–64.1 mg g⁻¹), cadmium(II) (29.5–42.7 mg g⁻¹) and copper(II) (18.5–39.4 mg g⁻¹) based on the Langmuir adsorption model. The highest lead(II) adsorption capacities for PMS and RS biochars were 256.4 and 133.3 mg g⁻¹, respectively, when generated using N₂ as the purging gas. The corresponding lead(II) adsorption capacities were 250.0 and 109.9 mg g⁻¹, respectively, when generated using CO₂ as the purging gas. According to the intraparticle diffusion model, 30–62% of heavy metal adsorption was achieved in 1 h; film diffusion was the rate-dominating step, whereas pore diffusion was a rate-limiting step. Ion exchange and complexation between heavy metals and biochar surface functional groups such as carbonyl and hydroxyl groups were effective mechanisms for heavy metal sorption from the aqueous solution. We conclude that proper selection of both the feedstock type and the purging gas is important in designing biochars for the effective removal of potentially toxic metals from wastewater.

Low concentrations of vanadium (V) are essential for various plant species but it becomes toxic to plants, animals, and humans at high levels. A significant amount of V is currently being emitted into the atmosphere due to intensified industrial processing. Therefore, this study aimed at evaluating the effect of raw (BC) and HNO₃-modified biochar (OBC) derived from rice straw on growth, photosynthetic assimilation, relative chlorophyll content, SPAD index, ion leakage, enzyme activities, hydrogen peroxide (H₂O₂), bioavailability and V uptake by rice in a laboratory-scale experiment. Characterization of OBC and BC by FTIR (Fourier transform infrared spectroscopy), SEM (scan electron microscopy), BET (Brunauer–Emmett–Teller), elemental analysis, and z-potential revealed a substantial difference between both of them. The V-stress significantly reduced the rice plant growth, biomass yield, chlorophyll parameters, root length and surface area. Under V-stress conditions, root accumulated more V than shoots and OBC significantly improved the above-mentioned parameters, while, decreasing hydrogen peroxide (H₂O₂) and malondialdehyde (MDA) levels in plants. The antioxidant function and gene expression levels induced by V-stress and OBC application further increased the expression profile of three genes (SOD, POD, and CAT) encoding antioxidant enzymes and one metal-tolerant conferring gene (OsFSD1). In summary, these results demonstrated the critical role of OBC in mitigating the detrimental effects of high V-stress on rice growth and enhancing plant defence against V-stress.

Magnetic biochars were prepared by chemical co-precipitation of Fe³⁺/Fe²⁺ onto rice straw (M-RSB) and sewage sludge (M-SSB), followed by pyrolysis treatment, which was also used to prepare the corresponding nonmagnetic biochars (RSB and SSB). The comparison of adsorption characteristics between magnetic and nonmagnetic biochars was investigated as a function of pH, contact time, and initial Cd²⁺ concentration. The adsorption of nonmagnetic biochars was better described by pseudo-second-order kinetic model, and the adsorption of RSB and SSB was better described by Langmuir and Freundlich models, respectively. Magnetization of the biochars did not change the applicability of their respective adsorption models, but reduced their adsorption capabilities. The maximum capacities were 42.48 and 4.64 mg/g for M-RSB and M-SSB, respectively, underperforming their nonmagnetic counterparts of 58.65 and 7.22 mg/g for RSB and SSB. Such a reduction was fundamentally caused by the decreases in the importance of cation-exchange and Cπ-coordination after magnetization, but the Fe-oxides contributed to the precipitation-dependent adsorption capacity for Cd²⁺ on magnetic biochars. The qualitative and quantitative characterization of adsorption mechanisms were further analyzed, in which the contribution proportions of cation-exchange after magnetization were reduced by 31.9% and 12.1% for M-RSB and M-SSB, respectively, whereas that of Cπ-coordination were reduced by 3.4% and 31.1% for M-RSB and M-SSB, respectively. These reductions suggest that for adsorbing Cd²⁺ the choice of conventional biochar was more relevant than whether the biochar was magnetized. However, magnetic biochars are easily separated from treated solutions, depending largely on initial pH. Their easy of separation suggests that magnetic biochars hold promise as more sustainable alternatives for the remediation of moderately Cd-contaminated environments, such as surface water and agriculture soil, and that magnetic biochars should be studied further.

Pyrogenic char (biochar) with a high sorption capacity (B-HSC) can sequester hazardous chemicals (e.g., phenanthrene). However, when sorption inhibits bioavailability of some functional chemicals (e.g., the herbicidal efficacy of diuron in soil), biochar with a low sorption capacity (B-LSC) is required to prevent sorption effects. The pyrolytic B-HSC generation has been reported, but information on B-LSC formation is scarce. How fast B-HSC and B-LSC could be generated is unknown until now. Here, biochars were rapidly prepared (the shortest heating time reached 5 min and the cooling time reached < 30 min) by a direct-pyrolysis method by directly exposing packaged rice straw and pine wood to 350 °C, 500 °C and 700 °C and out-of-furnace cooling at room temperature. The sorption of diuron, phenanthrene, and twelve other chemicals was investigated. B–HSCs were obtained within 30 min of rice straw pyrolysis, and the biochar Kd values quickly increased to 7-730-fold that of the raw biomass as –OH and C–O–C in (hemi)cellulose of rice straw rapidly degraded, increasing hydrophobic interactions between the char and chemicals (solubility ≤ 82.8 g/L). In contrast, B-LSCs were generated within 30 min of PW pyrolysis, and the Kd values of the biochars were 0.2–3.0-fold that of the raw biomass, as the surface area development and hydrophobicity-driven sorption were probably delayed by the late degradation of lignin aromatic C–O and phenolic –OH. Biochar amendment revealed an enhancement effect of B-HSC but not of B-LSC on soil sorption. The fast formation of B-LSC and B-HSC provides a guide to develop time- and cost-effective technique in pyrolytically producing weakly or strongly sorbing biochars for organic chemical management.

Decision-making related to nitrogen (N) fertilization is a crucial step in agronomic practices because of its direct interactions with agronomic productivity and environmental risk. Here, we hypothesized that soil apparent N balance could be used as an indicator to determine the thresholds of N input through analyzing the responses of the yield and N loss to N balance. Based on the observations from 951 field experiments conducted in rice (Oryza sativa L.) cropping systems of China, we established the relationships between N balance and ammonia (NH₃) volatilization, yield increase ratio, and N application rate, respectively. Dramatical increase of NH₃ volatilizations and stagnant increase of the rice yields were observed when the N surplus exceeded certain levels. Using a piecewise regression method, the seasonal upper limits of N surplus were determined as 44.3 and 90.9 kg N ha⁻¹ under straw-return and straw-removal scenarios, respectively, derived from the responses of NH₃ volatilization, and were determined as 53.0–74.9 and 97.9–112.0 kg N ha⁻¹ under straw-return and straw-removal scenarios, respectively, derived from the maximum-yield consideration. Based on the upper limits of N surplus, the thresholds of N application rate suggested to be applied in single, middle-MLYR, middle-SW, early, and late rice types ranged 179.0–214.9 kg N ha⁻¹ in order to restrict the NH₃ volatilization, and ranged 193.3–249.8 kg N ha⁻¹ in order to achieve the maximum yields. If rice straw was returned to fields, on average, the thresholds of N application rate could be theoretically decreased by 17.5 kg N ha⁻¹. This study provides a robust reference for restricting the N surplus and the synthetic fertilizer N input in rice fields, which will guide yield goals and environmental protection.

We quantified the transport and transformation of Cd in historically contaminated soil (OS) and artificially contaminated soil (NS), treated with 3% (w/w) rice straw biochar prepared at 400 °C (BC400) and 700 °C (BC700) under combined dry-wet and freeze-thaw cycles for 72 days simulating the natural aging process of 8 years. An improved three-layer mesh experiment was developed to simulate the natural situation in field. The result showed that the total Cd concentration increased in the biochar but decreased in the soil, suggesting that Cd was transported from the soil into the biochar during the aging process. The total Cd concentration in BC400 treated with both soils was higher than that in BC700 treated with both soils, however, BC700 displayed stronger ability on immobilizing Cd than BC400 because the Tessier exchangeable Cd fraction in BC700 treated both soils was lower than that in BC400 treated with both soils. The average Tessier exchangeable Cd fraction in the soil and biochar decreased in all treatments during the aging process, indicating that Cd tended to be more stable in the soil for a long term. The result also showed that biochar could immobilizate Cd by decreasing the Tessier exchangeable Cd fraction of soil and biochar, and the quantitative contributions of biochar and soil to Cd immobilization were different in OS and NS treated with BC400 and BC700. The biochar contribution to the reduction in Tessier exchangeable Cd fraction accounted for 40–85% in NS treated with BC400 and 54–82% in NS treated with BC700. However, in OS treated with biochar, the biochar contribution accounted for nearly 100%, and soil had almost no contribution. In summary, OS did not contribute to Cd immobilization, while NS contributed nearly 50% to Cd immobilization, and BC700 was more effective in immobilizing Cd than BC400.

Knowledge of adsorption behavior of organic contaminants on high heat temperature treated biochars is essential for application of biochars as adsorbents in wastewater treatment and soil remediation. In this study, isotherms of 25 aromatic compounds adsorption on biochars pyrolyzed at 700 °C from biomass including wood chips, rice straw, bamboo chips, cellulose, lignin and chitin were investigated to establish correlations between adsorption behavior and physicochemical properties of biochars. Isotherms were well fitted by Polanyi theory-based Dubinin-Ashtakhov (DA) model with three parameters, i.e., adsorption capacity (Q⁰) and adsorption affinity (E and b). Besides the negative correlation of Q⁰ with molecular maximum cross-sectional areas (σ) of organic compounds, positive correlations of Q⁰ with total pore volume (Vₜₒₜₐₗ) and average diameter of micropore (D) of biochars were observed, indicating that adsorption by biochars is captured by the pore-filling mechanism with molecular sieving effect in biochar pores. Linear solvation energy relationships (LSERs) of adsorption affinity (E) with solvatochromic parameters of organic compounds (i. e., αₘ and π∗) were established, suggesting that hydrophobic effect, π-π interaction and hydrogen-bonding interaction are the main forces responsible for adsorption. The regression coefficient (π₁) and intercept (C) of obtained LSERs are correlated with biochar H/C and Rₘᵢcᵣₒ, respectively, implying that biochars with higher aromaticity and more micropores have stronger π-π bonding potential and hydrophobic effect potential with aromatic molecule, respectively. However, hydrogen-bonding potential of biochars for organic molecules is not changed significantly with properties of biochars. A negative correlation of b with biochar H/C is also obtained. These correlations could be used to predict the adsorption behavior of organic compounds on high heat temperature treated biochars from various biomass for the application of biochars as sorbents and for the estimating of environmental risks of organic compounds in the present of biochars.

The research was conducted to investigate the accumulation, distribution and availability of Cd in paddy soil and their relation to Cd in rice plants under 30-year fertilization regimes. Six treatments were involved in the study: control without fertilization (CK), chemical fertilizer (NPK), high nitrogen chemical fertilizer (HN), rice straw incorporation (ST), low and high dosage of manure fertilizer (LM and HM). Total and DTPA extractable concentration of Cd (T-Cd and DTPA-Cd) in bulk soils (20 cm topsoil), profiles (0–60 cm) and aggregates (>2, 1–2, 0.5–1, 0.25–0.5, 0.053–0.25 and < 0.053 mm) were investigated. The Cd concentration in relevant rice plant (roots, stems, leaves, husks and grains) were also analyzed. Manure fertilizers caused T-Cd accumulation in bulk soil with a significant increase of 36.2% in LM and 81.2% in HM. Similar impacts of manure fertilizers were observed in DTPA-Cd in the bulk soil. Further, the HM generated a further accumulation in deeper soil layers, presenting a remarkable increase of T-Cd (28.3%–225%) in 10–40 cm and DTPA-Cd (116%–158%) in 10–30 cm profiles. Moreover, the continuous application of manure fertilizers enhanced the availability of Cd in all aggregate size classes with an increase of 17.3%–87.8% in DTPA-Cd. Organic fertilizers (LM, HM and ST) heightened the content of Cd (38.0%–152%) in all parts of rice plant. The accumulation of Cd in rice plants was directly affected by fertilization regimes and Cd availability in the 10–20 cm soil layers and 0.25–0.5 mm aggregates. In conclusion, long-term application of manures resulted in increasing availability of Cd in aggregates and in topsoil and subsoil layers, which accordingly enhanced the accumulation of Cd in rice plants.