The stability of mercury (Hg) contamination in soil environments can change over time. This has implications for agricultural sites under long-term management after in situ treatment involving soil amendments. In this study, rice husk biochar (RHB) and sulfur modified rice husk biochar (SRHB) were synthesized and applied (dosage = 5% dry wt.) to a Hg polluted agricultural soil collected from Guizhou province, Southern China (soil total Hg content = 28.3 mg/kg; C = 2%; and, S = 0.1%). The long-term stabilization effectiveness of the soil treatments was evaluated by a combined approach involving: (i) accelerated aging for 104 simulated years; (ii) soil extraction as a proxy for plant uptake; and, (iii) sequential extraction to identify Hg fractions. The SRHB amendment raised the soil’s total S content by approximately an order of magnitude (to 0.9%), which remained at a generally constant level throughout the simulation. The initial pH levels for the untreated and treated soils were alkaline and remained between 7.0 and 7.5 for the first 50 years of simulated aging, before decreasing as the simulation time increased further. The pH of the SRHB treated soils did not drop below that of untreated soils during the simulation. Soil extraction tests with 0.1 M HCl solution indicated that RHB and SRHB treatments could effectively immobilize the Hg in soil for at least 50 and 75 simulated years, respectively. At simulated year 50, the amount of Hg extracted from RHB and SRHB treated soils was <200 ng/L and <100 ng/L, respectively. Thus, showing SRHB to be a particularly promising remedial option. The soil Hg was mostly associated with the stable sequential extraction fractions (F3-5). By the end of the simulation, the F5 fraction for SRHB and RHB treated soils reduced by 44.6%, and 42.0%, respectively, whereas the F4 fraction increased by >400% in both cases. In summary, SRHB may provide long-lasting Hg stabilization at contaminated sites. Therefore, further research toward the development of this stabilization technology is warranted.

Magnetic biochar (MBC) has been used to remove hexavalent chromium (Cr(VI)) from water, but the roles of Fe₃O₄ and persistent free radicals (PFRs) in MBC in Cr(VI) removal are still less investigated. In this work, the MBC synthesized by microwave co-pyrolysis of solid-state FeSO₄ and rice husk was employed to remove Cr(VI) from water. In comparison to the rice husk biochar (BC), the MBC exhibits the 3.2- and 11.7-fold higher adsorption and reduction efficiency of Cr(VI), resulting in the higher Cr(VI) removal efficiency (84.3%) and equilibrium adsorption capacity of MBC (8.35 mg g⁻¹) than that (26.5% and 2.63 mg g⁻¹) of BC. Multiple characterization results revealed that the high Cr(VI) removal performance of MBC was mainly attributed to the presence of active Fe₃O₄ and carbon-centered PFRs in the porous and graphitic MBC. The Fe₃O₄ not only provided active chemisorption/reduction sites for Cr(VI) via its Fe(II)ₒcₜ and Fe(III)ₒcₜ coordination, but also facilitated the generation of more active electron donating carbon-centered PFRs than carbon-centered PFRs with an oxygen atom in the graphitic structure to reduce Cr(VI). The presence of Fe₃O₄ also elevated 36.7 m² g⁻¹ of BET-surface area and 0.043 cm² g⁻¹ of pore volume of MBC, promoting the Cr(VI) removal. The Fe₃O₄ and carbon-centered PFRs contributed to ∼81.8% and ∼18.2% of total Cr(III) generation, respectively. In addition, the initial solution pH was responsible for determining the relative significance of Cr(VI) adsorption and reduction. This study provides new insights into the mechanisms of Cr(VI) removal from water by the MBC.

Bioremediation of real-time petroleum refining industry oily waste (PRIOW) is a major challenge due to the poor emulsification potential and oil sludge disintegration efficiency of conventional bioamphiphile molecules. The present study was focused on the design of a covalently engineered supramolecular bioamphiphile complex (SUBC) rich in hydrophobic amino acids for proficient emulsification of hydrocarbons followed by the concomitant degradation of total petroleum hydrocarbons (TPH) in PRIOW using the hydrocarbonoclastic microbial bio-formulation system. The synthesis of SUBC was carried out by pH regulated microbial biosynthesis process and the yield was obtained to be 450.8 mg/g of petroleum oil sludge. The FT-IR and XPS analyses of SUBC revealed the anchoring of hydrophilic moieties of monomeric bioamphiphilic molecules, resulting in the formation of SUBC via covalent interaction. The SUBC was found to be lipoprotein in nature. The maximum loading capacity of SUBC onto surface modified rice hull (SMRH) was achieved to be 45.25 mg/g SMRH at the optimized conditions using RSM-CCD design. The SUBC anchored SMRH was confirmed using SEM, FT-IR, XRD and TGA analyses. The adsorption isotherm models of SUBC onto SMRH were performed. The integrated approach of SUBC-SMRH and hydrocarbonoclastic microbial bio-formulation system, emulsified oil from PRIOW by 92.86 ± 2.26% within 24 h and degraded TPH by 89.25 ± 1.75% within 4 days at the optimum dosage ratio of SUBC-SMRH (0.25 g): PRIOW (1 g): mass of microbial-assisted biocarrier material (0.05 g). The TPH degradation was confirmed by SARA fractional analysis, FT-IR, ¹H NMR and GC-MS analyses. The study suggested that the application of covalently engineered SUBC has resulted in the accelerated degradation of real-time PRIOW in a very short duration without any secondary sludge generation. Thus, the SUBC integrated approach can be considered to effectively manage the hydrocarbon contaminants from petroleum refining industries under optimal conditions.

Arsenic contamination of ground water is a worldwide issue, causing a number of ailments in humans. As an engineered and integrated solution, a hybrid vertical subsurface flow constructed wetland (VSSF-CW) amended with BCXZM composite (Bacillus XZM immobilized on rice husk biochar), was found effective for the bioremediation of arsenic contaminated water. Biological filter was prepared by amending top 3 cm of VSSF-CW bed with BCXZM. This filter scavenged ∼64% of total arsenic and removal efficiency of ∼95% was achieved by amended and planted (As + P + B) VSSF-CW, while non-amended (As + P) VSSF-CW showed a removal efficiency of ∼55%. The unplanted and amended (As + B) VSSF-CW showed a removal efficiency of ∼70%. The symbiotic association of Bacillus XZM, confirmed by SEM micrographs, significantly (p ≤ 0.05) reduced reactive oxygen species (ROS) and malondialdehyde (MDA) accumulation in Typha latifolia, hence, increasing the plant growth (2 folds). An increase in the indole acetic acid (IAA) and arsenic accumulation in plant was also observed in As + P + B system. The removal efficiency of the system was compromised after 4th consecutive cycle and 48 h was observed as optimum retention time. The FTIR-spectra showed the involvement of -N-H bond, carboxylic acids, –CH₂ stretching of –CH₂ and –CH₃, carbonyl groups, -C-H, C–O–P and C–O–C, sulphur/thiol and phosphate functional groups in the bio-sorption of arsenic by BCXZM filter. Our study is a first reported on the simultaneous phytoextraction and biosorption of arsenic in a hybrid VSSF-CW. It is proposed that BCXZM can be applied effectively in CWs for the bioremediation of arsenic contaminated water on large scale.

Supplemental activated biochar pellet fertilizers (ABPFs) were evaluated as a method to sequester carbon and reduce greenhouse gas (GHG) emissions, and improve rice production. The evaluated treatments were a control (standard cultivation method, no additives applied), activated rice hull biochar pellets with 40% of N (ARHBP-40%), and activated palm biochar pellets with 40% of N (APBP-40%). The N supplied by the ARHBP-40% and APBP-40% treatments reduced the need for supplemental inorganic nitrogen (N) fertilizer by 60 percent. The ARHBP-40% treatment sequestered as much as 1.23 tonne ha⁻¹ compared to 0.89 tonne ha⁻¹ in the control during the rice-growing season. In terms of greenhouse gas (GHG) emissions, CH₄ emissions were not significantly different (p > 0.05) between the control and the ARHBP-40%, while the lowest N₂O emissions (0.002 kg ha⁻¹) were observed in the ARHBP-40% during the crop season. Additionally, GHG (CO₂-equiv.) emissions from the ARHBP-40% application were reduced by 10 kg ha⁻¹ compared to the control. Plant height in the control was relatively high compared to others, but grain yield was not significantly different among the treatments. The application of the ARHBP-40% can mitigate greenhouse gas emissions and enhance carbon sequestration in crop fields, and ABPFs can increase N use efficiency and contribute to sustainable agriculture.

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.

Arsenic (As) pollution remains a major threat to the quality of global soils and drinking water. The health effects of As pollution are often severe and have been largely reported across Asia and South America. This study investigated the possibility of using unmodified biochar derived from rice husk (RB) and aspen wood (WB) at 400 °C and 700 °C to enhance the precipitation of calcium/arsenic compounds for the removal of As(III) from solution. The approach was based on utilizing calcium to precipitate arsenic in solution and adding unmodified biochar to enhance the process. Using this approach, As(III) concentration in aqueous solution decreased by 58.1% when biochar was added, compared to 25.4% in the absence of biochar. Varying the pH from acidic to alkaline enabled an investigation into the pH dependent dynamics of the approach. Results indicated that significant precipitation was only possible at near neutral pH (i.e. pH = 6.5) where calcium arsenites (i.e. Ca(AsO₂)₂, and CaAsO₂OH•½H₂O) and arsenates (i.e. Ca₅(AsO₄)₃OH) were precipitated and deposited as aggregates in the pores of biochars. Arsenite was only slightly precipitated under acidic conditions (pH = 4.5) while no arsenite was precipitated under alkaline conditions (pH = 9.5). Arsenite desorption from wood biochar was lowest at pH 6.5 indicating that wood biochar was able to retain a large quantity of the precipitates formed at pH 6.5 compared to pH 4.5 and pH 9.5. Given that the removal of As(III) from solution is often challenging and that biochar modification invites additional cost, the study demonstrated that low cost unmodified biochar can be effective in enhancing the removal of As(III) from the environment through Ca–As precipitation.

In general, the remediation performance of heavy metals can be further improved by metal-oxide modified biochar. This work used MgO-modified rice husk biochar (MgO-5%@RHB-450 and MgO-5%@RHB-600) with high surface activity for simultaneous remediation and removal of heavy metals in soil and wastewater. The adsorption of MgO-5%@RHB-450/MgO-5%@RHB-600 for Cd(II), Cu(II), Zn(II) and Cr(VI) followed the pseudo-second order, with the adsorption capacities reaching 91.13/104.68, 166.68/173.22, 80.12/104.38 and 38.88/47.02 mg g⁻¹, respectively. The addition of 1.0% MgO-5%@RHB-450 and MgO-5%@RHB-600 could effectively decrease the CaCl₂-extractable Cd concentration (CaCl₂–Cd) by 66.2% and 70.0%, respectively. Moreover, MgO-5%@RHB-450 and MgO-5%@RHB-600 facilitated the transformation of exchangeable fractions to carbonate-bound and residual fractions, and reduced the exchangeable fractions by 8.1% and 9.6%, respectively. The mechanisms for the removal of heavy metals from wastewater by MgO-5%@RHB-450 and MgO-5%@RHB-600 mainly included complexation, ion exchange and precipitation, and the immobilization mechanisms in soil may be precipitation, complexation and pore filling. In general, this study provides high-efficiency functional materials for the remediation of heavy metal pollution.

Batch sorption of metformin hydrochloride (MET) onto a specially designed biochar mix consisting of both macro (MAC) and micro (MIC) algae, rice husk and pine sawdust was conducted. Pyrolysis of both MAC and MIC algae mixture was done followed by chemical activation with hydrogen-peroxide. Additionally, sorption of MET under the influence of pH was separately investigated. Batch studies of isotherms were well described by Freundlich model with high non-linearity and Freundlich exponent values ranged anywhere from 0.12 to 1.54. Heterogeneity of MET adsorption to the bonding sites was attributed to the surface functional groups of the modified biochar. Amongst the four biochars, the activated macroalgae biochar (MACAC) and microalgae biochar (MICAC) depicted favourable adsorption of MET with maximum adsorption at pH 7. Up to 76% of MET removal from the environment was obatained using the MACAC biochar. Scanning electron micrographs coupled with energy dispersive X-ray, as well as elemental analyses confirmed formation of oxygen containing surface functional groups due to activation strengthening chemisorption as the main sorption mechanism. Further, Fourier transform infra-red spectroscopy and other surface functional group analyses along with Zeta potential measurements reinforced our proposed sorption mechanism. Lowest zeta potential observed at pH 7 enhanced the electrostatic force of attraction for both the biochars. Negative zeta potential value of the biochars under different pH indicated potential of the biochars to adsorb other positively charged contaminants. From a techno-economic perspective, capital expenditure cost is not readily available, however, it is envisaged that production of pyrolyzed biochar from algal biomass could make the process economically attractive especially when the biochar could be utilised for high-end applications.