Impact of iron-modified biochars on soil nitrous oxide emissions: Variations with iron salts and soil fertility.

Nitrous oxide (N2O) emissions from soils are a significant environmental concern due to their contribution to greenhouse gas emissions. Biochar has been considered as a promising soil amendment for its potential to influence soil processes. Iron modification of biochar has been extensively discussed for its ability to enhance adsorption of pollutants, yet its impact on mitigating soil N2O emissions remains poorly understood. In the present study, corn straw (CB) and wood (WB) biochars were treated with FeSO4/FeCl3 (SCB and SWB) and Fe(NO3)3 (NCB and NWB). The effects of these biochars on soil N2O emissions were investigated using soils with varying fertility levels over a 35-day incubation period at 20 °C. Results revealed significant variations in biochar surface chemistry depending on biochar feedstock and iron salts. Compared to pristine biochars, NWB and NCB exhibited higher pH, total N content, and dissolved NO3-N concentrations (246 ± 17 and 298 ± 35 mg kg-1, respectively), but lower bulk and surface C content. In contrast, SWB and SCB demonstrated acidic pH and elevated dissolved NH4-N concentrations (5.38 ± 0.43 and 4.19 ± 0.22 mg kg-1, respectively). In forest soils, NWB and NCB increased cumulative N2O emission by 28.5% and 67.0%, respectively, likely due to the introduction of mineral nitrogen evidenced by significant positive correlation with NO3-N or NH4-N. Conversely, SWB and SCB reduced emissions in the same soil by 28.5% and 6.9%, respectively. In agricultural soil, most biochars, except SWB, enhanced N2O emissions, possibly through the release of labile organic carbon facilitating denitrification. These findings underscore the significance of changes in biochar surface chemistry and the associated potential risk in triggering soil N2O emissions. This study highlights the need for a balanced design of biochar that considers both engineering benefits and climate change mitigation.

Formation mechanisms and degradation methods of polycyclic aromatic hydrocarbons in biochar: A review.

Biochar has been widely used in soil amendment and environmental remediation. Polycyclic aromatic hydrocarbons (PAHs) could be produced in preparation of biochar, which may pose potential risks to the environment and human health. At present, most studies focus on the ecotoxicity potential of biochar, while there are few systematic reviews on the formation mechanisms and mitigation strategies of PAHs in biochar. Therefore, a systematical understanding of the distribution, formation mechanisms, risk assessment, and degradation approaches of PAHs in biochar is highly needed. In this paper, the distribution and content of the total and bioavailable PAHs in biochar are reviewed. Then the formation mechanisms, influencing factors, and potential risk assessment of PAHs in biochar are systematically explored. After that, the effective strategies to alleviate PAHs in biochar are summarized. Finally, suggestions and perspectives for future studies are proposed. This review provides a guide for reducing the formation of biochar-associated PAHs and their toxicity, which is beneficial for the development and large-scale safe use of environmentally friendly biochar.

One-step preparation of a novel graphitic biochar/Cu0/Fe3O4 composite using CO2-ambiance pyrolysis to activate peroxydisulfate for dye degradation.

Herein, a one-step co-pyrolysis protocol was adopted for the first time to prepare a novel pyrogenic carbon-Cu0/Fe3O4 heteroatoms (FCBC) in CO2 ambiance to discern the roles of each component in PDS activation. During co-pyrolysis, CO2 catalyzed formation of reducing gases by biomass which facilitated reductive transformation of Fe3+ and Cu2+ to Cu0 and Fe3O4, respectively. According to the analysis, the resulting metal (oxide) catalyzed graphitization of biocharand decomposition of volatile substances resulting in an unprecedented surface area (1240 m2/g). The resulting FCBC showed greater structural defects and less electrical impedance. Batch experiments indicated that Rhodamine B (RhB) degradation by FCBC (100%) was superior to Fe3O4 (50%) and Cu0/Fe3O4 (76.4%) in persulfate (PDS) system, which maintained reasonable efficiency (75.6%-63.6%) within three cycles. The reactive oxygen species (ROS) associated with RhB degradation was identified by an electron paramagnetic resonance and confirmed by scavenging experiments. RhB degradation invoked both (sulfate and dominantly hydroxyl) radical and non-radical (singlet oxygen, 1O2) pathways. Regarding FCBC, Cu0 can continuously react with Fe3+ in Fe3O4 to generate larger quantities of Fe2+, and both Cu0 and Fe2+ activated PDS to yield sulfate radicals which was quickly converted to hydroxyl radical. Besides, Cu0/Cu2+ could complex with PDS to form a metastable complex, which particularly contributed to 1O2 generation. These cascade reactions by FCBC were reinforced by carbonyl group of biochar and favorable electron transfer ability. This work highlighted a new approach to prepare a magnetic and environment-benign heterogonous catalyst to remove organic pollutants in water.

Enhanced removal of sulfonamide antibiotics from water by phosphogypsum modified biochar composite.

Antibiotic pollution has become a global eco-environmental issue. To reduce sulfonamide antibiotics in water and improve resource utilization of solid wastes, phosphogypsum modified biochar composite (PMBC) was prepared via facile one-step from distillers grains, wood chips, and phosphogypsum. The physicochemical properties of PMBC were characterized by scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FTIR), Zeta potential, X-ray diffraction (XRD), etc. The influencing factors, adsorption behaviors, and mechanisms of sulfadiazine (SD) and sulfamethazine (SMT) onto PMBC were studied by batch and fixed bed column adsorption experiments. The results showed that the removal rates of SD and SMT increased with the increase of phosphogypsum proportion, while decreased with the increase of solution pH. The maximum adsorption capacities of modified distillers grain and wood chips biochars for SD were 2.98 and 4.18 mg/g, and for SMT were 4.40 and 8.91 mg/g, respectively, which was 9.0-22.3 times that of pristine biochar. Fixed bed column results demonstrated that PMBC had good adsorption capacities for SD and SMT. When the solution flow rate was 2.0 mL/min and the dosage of PMBC was 5.0 g, the removal rates of SD and SMT by modified wood chips biochar were both higher than 50% in 4 hr. The main mechanisms of SD and SMT removal by PMBC are hydrogen bonding, π-π donor-acceptor, electrostatic interaction, and hydrophobic interaction. This study provides an effective method for the removal of antibiotics in water and the resource utilization of phosphogypsum.

Biochar as a potential strategy for remediation of contaminated mining soils: Mechanisms, applications, and future perspectives.

Soil heavy metal contamination caused by mining activities is a global issue. These heavy metals can be enriched in plants and animals through the food chain, and eventually transferred to the human system and threatening public health. Biochar, as an environmentally friendly soil remediation agent, can effectively immobilize heavy metals in soil. However, most researchers concern more about the remediation effect and mechanism of biochar for industrial and agricultural contaminated soil, while related reviews focusing on mining soil remediation are limited. Furthermore, the remediation effect of soil in mining areas is affected by many factors, such as physicochemical properties of biochar, pyrolysis conditions, soil conditions, mining environment and application method, which can lead to great differences in the remediation effect of biochar in diverse mining areas. Therefore, it is necessary to systematically unravel the relevant knowledge of biochar remediation, which can also provide a guide for future studies on biochar remediation of contaminated soils in mining areas. The present paper first reviews the negative effects of mining activities on soil and the advantages of biochar relative to other remediation methods, followed by the mechanism and influencing factors of biochar on reducing heavy metal migration and bioavailability in mining soil were systematically summarized. Finally, the main research directions and development trends in the future are pointed out, and suggestions for future development are proposed.

Mechanism analysis of MnFe2O4/FeSX for removal of Cr(VI) from aqueous phase.

By using Na2S as a sulfur source, sulfur-doped MnFe2O4 was prepared using one-step solvent thermal method and utilized to remove hexavalent chromium. The materials were characterized through scanning electron microscopy, transmission electron microscopy, high-resolution TEM, X-ray diffraction, Fourier-transform infrared spectroscopy, Brunauer-Emmett-Teller method, zeta potential test, vibrating sample magnetometry, and X-ray photoelectron spectroscopy. When the pH was 3, the adsorption capacity of MnFe2O4/FeSX-0.5 to Cr(VI) was 43.36 mg/g, which was roughly five times that of MnFe2O4 (8.90 mg/g). MnFe2O4/FeSX-0.5 and MnFe2O4 fitted the Freundlich and pseudo-second-order kinetic models well. The electrochemical test analysis results showed that MnFe2O4/FeSX had a faster MnFe2O4 electron transfer rate and higher electron transfer capacity than MnFe2O4, and thus promoted the reduction of Cr(VI) to Cr(III). This finding could be attributed to the lower electronegativity of the sulfur element than the oxygen element. In addition, the formation of additional FeSX through sulfur doping improved the Cr(VI) removal ability of the prepared materials. The XPS and desorption results showed that more than 80% of the adsorbed Cr(VI) were reduced to Cr(III), which indicated that reduction was an important mechanism for Cr(VI) removal. This study verified that sulfur-doped manganese ferrite can be utilized in the high-efficiency removal of Cr(VI).

Pinewood outperformed bamboo as feedstock to prepare biochar-supported zero-valent iron for Cr6+ reduction.

In this work, pinewood and bamboo were pyrolyzed at 600 °C to prepare PBC and BBC-supported zerovalent iron (ZVI), respectively. Raman spectra suggested PBC was more intensively carbonized than BBC as indicated by higher ID/IG ratio. XRD and TEM confirmed nanoscaled ZVI was well dispersed in PBC but soldered in chain-structure in BBC. Maximal chromate (Cr(VI)) sorption capacity followed the order of PBC/ZVI (5.93 g kg-1)>BBC/ZVI (3.61 g kg-1)>BBC (3.55 g kg-1)>PBC (2.59 g kg-1). Desorption and XPS of four Cr-spent sorbents suggested reduction accounted for 79-88% of overall Cr(VI) detoxification. Greater Cr(VI) reduction of BBC than PBC indicated greater tendency of BBC to donate electrons. However, Cr(VI) reduction by PBC/ZVI was 1.7 times greater than BBC/ZVI, corresponding to greater electron transfer of PBC/ZVI (2.5 µA e-) than BBC/ZVI (0.5 µA e-). Thus, PBC is more conducible to transfer electrons as evidenced by Tafel and Amperometric analyses. Demineralization of pristine BC enhanced the difference between PBC/ZVI and BBC/ZVI regarding Cr(VI) reduction, suggesting the dominant role of biopolymers in biomass in terms of electron transfer capacity. Three model biopolymers were compared which indicated lignin-BC had lower electron transfer rates than cellulose-BC and hemicellulose-BC. BC prepared by lignin extracted from pinewood exhibited higher corrosion rate and lower electrical resistance than that from bamboo. Thus, unfavorable lignin in bamboo compromised electron transfer of BBC and Cr(VI) reduction by BBC/ZVI.

Remediation of neonicotinoid-contaminated soils using peanut shell biochar and composted chicken manure: Transformation mechanisms of geochemical fractions.

Soil remediation techniques are promising approaches to relieve the adverse environmental impacts in soils caused by neonicotinoids application. This study systematically investigated the remediation mechanisms for peanut shell biochar (PSB) and composted chicken manure (CCM) on neonicotinoid-contaminated soils from the perspective of transformation of geochemical fractions by combining a 3-step sequential extraction procedure and non-steady state model. The neonicotinoid geochemical fractions were divided into labile, moderate-adsorbed, stable-adsorbed, bound, and degradable fractions. The PSB and CCM addition stimulated the neonicotinoid transformation in soils from labile fraction to moderate-adsorbed and stable-adsorbed fractions. Compared with unamended soils, the labile fractions decreased from 47.6% ± 11.8% of the initial concentrations to 12.1 ± 9.3% in PSB-amended soils, and 7.1 ± 4.9% in PSB and CCM-amended soils, while the proportions of moderate-adsorbed and stable-adsorbed fractions correspondingly increased by 1.8-2.4 times and 2.3-4.8 times, respectively. A small proportion (<4.8%) in bound fractions suggested there were rather limited bound-residues after 48 days incubation. The PSB stimulated the -NO2-containing neonicotinoid-degraders, which promoted the degradable fractions of corresponding neonicotinoids by 8.2 ± 6.3%. Degradable fraction of neonicotinoids was the dominant fate in soils, which accounted for 58.3 ± 16.7%. The findings made beneficial theoretical supplements and provided valuable empirical evidence for the remediation of neonicotinoid-contaminated soils.

Biochar supported nanoscale zerovalent iron-calcium alginate composite for simultaneous removal of Mn(II) and Cr(VI) from wastewater: Sorption performance and mechanisms.

Heavy metal pollution in water caused by industrial activities has become a global environmental issue. Among them, manganese mining and smelting activities have caused the combined pollution of Cr(VI) and Mn(II) in water, posing a serious ecotoxicological risk to ecological environments and human health. To efficiently remove Cr(VI) and Mn(II) from wastewater, a novel biochar supported nanoscale zerovalent iron-calcium alginate composite (CA/nZVI/RSBC) was synthesized by liquid-phase reduction and calcium alginate embedding methods. The adsorption performance and mechanisms of Cr(VI) and Mn(II) by CA/nZVI/RSBC were investigated. The maximum adsorption capacities of Cr(VI) and Mn(II) onto CA/nZVI/RSBC fitted by the Langmuir model were 5.38 and 39.78 mg/g, respectively, which were much higher than the pristine biochar. The iron release from CA/nZVI/RSBC was comparatively lower than that of nZVI/RSBC. Mn(II) presence enhanced the reduction of Cr(VI) by CA/nZVI/RSBC. The results of XRD, XPS, and site energy distribution analysis indicated that redox was the predominant mechanism of Cr(VI) adsorption, while electrostatic attraction dominated Mn(II) adsorption. This study provides a novel alternative way for the simultaneous removal of Cr(VI) and Mn(II) in wastewater.

Highly Durable PtNi Alloy on Sb-Doped SnO2 for Oxygen Reduction Reaction with Strong Metal-Support Interaction.

Carbon-supported Pt is currently used as catalyst for oxygen reduction reaction (ORR) in fuel cells but is handicapped by carbon corrosion at high potential. Herein, a stable PtNi/SnO2 interface structure has been designed and achieved by a two-step solvothermal method. The robust and conductive Sb-doped SnO2 supports provide sufficient surfaces to confine PtNi alloy. Moreover, PtNi/Sb0.11 SnO2 presents a more strongly coupled Pt-SnO2 interface with lattice overlap of Pt (111) and SnO2 (110), together with enhanced electron transfer from SnO2 to Pt. Therefore, PtNi/Sb0.11 SnO2 exhibits a high catalytic activity for ORR with a half-wave potential of 0.860 V versus reversible hydrogen electrode (RHE) and a mass activity of 166.2 mA mgPt -1 @0.9 V in 0.1 M HClO4 electrolyte. Importantly, accelerated degradation testing (ADT) further identify the inhibition of support corrosion and agglomeration of Pt-based active nanoparticles in PtNi/Sb0.11 SnO2 . This work highlights the significant importance of modulating metal-support interactions for improving the catalytic activity and durability of electrocatalysts.

Effects of biochar on the phytotoxicity of polyvinyl chloride microplastics.

Polyvinyl chloride microplastics (PVC-MPs) are toxic to crops, resulting in economic losses during agricultural production. Owing to its strong adsorption capacity, biochar can effectively remove MPs from water. It is presumed that biochar can alleviate the phytotoxicity of PVC-MPs. To verify this hypothesis, the effects of different concentrations of corncob biochar (CCBC) on the phytotoxicity of PVC-MPs were investigated using hydroponic experiments. The results showed that PVC-MPs attached to lettuce roots substantially inhibited the growth and quality of lettuce. The tested CCBC adsorbed the PVC-MPs. At appropriate concentrations, CCBC alleviated the inhibitory effect of PVC-MPs on lettuce yield; however, it decreased some quality indicators. The single PVC-MPs induced oxidative damage to lettuce, as demonstrated by the increased hydrogen peroxide (H2O2) and malondialdehyde (MDA) content. Addition of CCBC considerably decreased the contents of H2O2 and MDA in the lettuce shoots but increased the H2O2 content in the roots. These findings indicate that CCBC may alleviate the adverse effects caused by PVC-MPs to the lettuce shoots but aggravate the toxic effects on the lettuce roots. This study provides a basis for understanding the removal of the phytotoxicity of MPs.

Adsorption and photocatalytic degradation of quinolone antibiotics from wastewater using functionalized biochar.

Quinolone antibiotics are emerging environmental contaminants, which cause serious harm to the ecological environment and human health. How to effectively remove these emerging pollutants from water remains a major challenge worldwide. In this study, a novel Fe/Ti biochar composite (Fe/Ti-MBC) was prepared by facile one-step co-pyrolysis of wood chips with hematite and titanium dioxide (TiO2) for adsorption and photocatalytic degradation of ciprofloxacin (CIP) and norfloxacin (NOR) in water. The results showed that the degradation efficiencies of Fe/Ti-MBC to CIP and NOR were 88.4% and 88.0%, respectively. The π-π interactions and polar interactions are the main adsorption mechanisms for CIP and NOR. In the photocatalytic process, h+ and ·OH are the main active substances for the oxidative degradation of CIP and NOR. This study shows that Fe/Ti-MBC is an effective and recyclable composite, providing a novel alternative way for antibiotics degradation.

Degradation of organic pollutants from water by biochar-assisted advanced oxidation processes: Mechanisms and applications.

Biochar has shown large potential in environmental remediation because of its low cost, large specific surface area, porosity, and high conductivity. Biochar-assisted advanced oxidation processes (BC-AOPs) have recently attracted increasing attention to the remediation of organic pollutants from water. However, the effects of biochar properties on catalytic performance need to be further explored. There are still controversial and knowledge gaps in the reaction mechanisms of BC-AOPs, and regeneration methods of biochar catalysts are lacking. Therefore, it is necessary to systematically review the latest research progress of BC-AOPs in the treatment of organic pollutants in water. In this review, first of all, the effects of biochar properties on catalytic activity are summarized. The biochar properties can be optimized by changing the feedstocks, preparation conditions, and modification methods. Secondly, the catalytic active sites and degradation mechanisms are explored in different BC-AOPs. Different influencing factors on the degradation process are analyzed. Then, the applications of BC-AOPs in environmental remediation and regeneration methods of different biochar catalysts are summarized. Finally, the development prospects and challenges of biochar catalysts in environmental remediation are put forward, and some suggestions for future development are proposed.

Engineered biochar effects on soil physicochemical properties and biota communities: A critical review.

Biochar can be effectively used in soil amendment, environmental remediation as well as carbon sequestration. However, some inherent characteristics of pristine biochars (PBCs) may limit their environmental applications. To improve the physicochemical properties of PBCs and their effects on soil amendment and pollution remediation, appropriate modification methods are needed. Engineered biochars (EBCs) inevitably have a series of effects on soil physicochemical properties and soil biota after being applied to the soil. Currently, most studies focus on the effects of PBCs on soil physicochemical properties and their amendment and remediation effects, while relatively limited studies are available on the impacts of EBCs on soil properties and biota communities. Due to the differences of biochars modified by various methods on soil physicochemical properties and biota communities, the impact mechanisms are different. For a better understanding of the recent advances in the effects of EBCs on soil physicochemical properties and biota communities, a systematic review is highly needed. In this review, the development of EBCs is firstly introduced, and the effects of EBCs on soil physicochemical properties and biota communities are then systematically explored. Finally, the suggestions and perspectives for future research on EBCs are put forward.

Calcium alginate-nZVI-biochar for removal of Pb/Zn/Cd in water: Insights into governing mechanisms and performance.

Heavy metals pollution in water caused by the intensification of industrial processes and human activities has attracted worldwide attention. Finding an environmental-friendly and efficient remediation method is in need. In this study, the calcium alginate entrapment and liquid-phase reduction method were used to prepare calcium alginate-nZVI-biochar composite (CANRC), which was firstly used to remove Pb2+, Zn2+, and Cd2+ in water. The effects of pyrolysis temperature, solution pH, and coexisting ions, etc. during adsorption processes were explored. Scanning electron microscope-Energy dispersive spectrometer (SEM-EDS), X-ray diffraction spectroscopy (XRD), and X-ray photoelectron spectroscopy (XPS) were used to characterize the physicochemical properties of CANRC before and after adsorption. Different adsorption models and site energy analysis were used to analyze the possible mechanisms. The results showed that CANRC prepared at 300 °C and a 5 wt% Fe loading ratio had the maximum adsorption capacities with a dosage of 2.5 g/L and pH = 5.0- 6.0. The adsorption process was more in line with the Langmuir isotherm model dominated by monolayer adsorption. The maximum adsorption capacities of Pb2+, Zn2+, and Cd2+ were 247.99, 71.77, and 47.27 mg/g, respectively. Site energy analysis combined with XRD and XPS analysis indicated that surface complexation and precipitation were the main adsorption mechanisms. This study provides an alternative way for the removal of heavy metals from water.

Immobilization of zinc and cadmium by biochar-based sulfidated nanoscale zero-valent iron in a co-contaminated soil: Performance, mechanism, and microbial response.

Mining and smelting of mineral resources causes excessive accumulation of potentially toxic metals (PTMs) in surrounding soils. Here, biochar-based sulfidated nanoscale zero-valent iron (SNZVI/BC) was designed via a one-step liquid phase reduction method to immobilize cadmium (Cd) and zinc (Zn) in a copolluted arable soil. A 60 d soil incubation experiment revealed that Cd and Zn immobilization efficiency by 6 % SNZVI/BC (25.2-26.2 %) was higher than those by individual SNZVI (13.9-18.0 %) or biochar (14.0-19.3 %) based on the changes in diethylene triamine pentaacetic acid (DTPA)-extractable PTM concentrations in soils, exhibiting a synergistic effect. Cd2+ or Zn2+ replaced isomorphously Fe2+ in amorphous ferrous sulfide, as revealed by XRD, XPS, and high-resolution TEM-EDS, forming metal sulfide precipitates and thus immobilizing PTMs. PTM immobilization was further enhanced by adsorption by biochar and oxidation products (Fe2O3 and Fe3O4) of SNZVI via precipitation and surface complexation. SNZVI/BC also increased the concentration of dissolved organic carbon and soil pH, thus stimulating the abundances of beneficial bacteria, i.e., Bacilli, Clostridia, and Desulfuromonadia. These functional bacteria further facilitated microbial Fe(III) reduction, production of ammonium and available potassium, and immobilization of PTMs in soils. The predicted function of the soil microbial community was improved after supplementation with SNZVI/BC. Overall, SNZVI/BC could be a promising functional material that not only immobilized PTMs but also enhanced available nutrients in cocontaminated soils.

Remediation of lead and cadmium co-contaminated mining soil by phosphate-functionalized biochar: Performance, mechanism, and microbial response.

The remediation of heavy metals contaminated soils is of great significance for reducing their risk to human health. Here, pristine pinewood sawdust biochar (BC) and phosphate-functionalized biochar (PBC) were conducted to investigate their immobilization performance towards lead (Pb) and cadmium (Cd) in arable soils severely polluted by Pb (9240.5 mg kg-1) and Cd (10.71 mg kg-1) and microbial response in soils. Compared to pristine BC (2.6-12.1%), PBC was more effective in immobilizing Pb and Cd with an immobilization effectiveness of 45.2-96.2% after incubation of 60 days. Moreover, the labile Pb and Cd in soils were transformed to more stable species after addition of PBC, reducing their bioavailability. The immobilization mechanisms of Pb and Cd by PBC were mainly to facilitate the formation of stable phosphate precipitates e.g., Cd3(PO4)2, Cd5(PO4)3OH, Cd5H2(PO4)4‧4H2O, and pyromorphite-type minerals. Further, PBC increased pH, organic matter, cation exchange capacity, and available nutrients (phosphorus and potassium) in soils. High-throughput sequencing analysis of 16 S rRNA genes indicated that the diversity and composition of bacterial community responded to PBC addition due to PBC-induced changes in soil physicochemical properties, increasing the relative abundance of beneficial bacteria (e.g., Brevundimonas, Bacillus, and norank_f__chitinophagaceae) in the treated soils. What's more, these beneficial bacteria could not only facilitate Pb and Cd immobilization but also alter nutrient biogeochemical transformation (nitrogen and iron) in co-contaminated soils. Overall, PBC could be a promising material for immobilization of Pb and Cd and the simultaneous enhancement of soil quality and available nutrients in co-contaminated mining soils.

Biogeochemical behaviour and toxicology of chromium in the soil-water-human nexus: A review.

Chromium (Cr) affects human health if it accumulates in organs to elevated concentrations. The toxicity risk of Cr in the ecosphere depends upon the dominant Cr species and their bioavailability in the lithosphere, hydrosphere, and biosphere. However, the soil-water-human nexus that controls the biogeochemical behaviour of Cr and its potential toxicity is not fully understood. This paper synthesizes information on different dimensions of Cr ecotoxicological hazards in the soil and water and their subsequent effects on human health. The various routes of environmental exposure of Cr to humans and other organisms are also discussed. Human exposure to Cr(VI) causes both carcinogenic and non-carcinogenic health effects via complicated reactions that include oxidative stress, chromosomal and DNA damage, and mutagenesis. Chromium(VI) inhalation can cause lung cancer; however, incidences of other types of cancer following Cr(VI) exposure are low but probable. The non-carcinogenic health consequences of Cr(VI) exposure are primarily respiratory and cutaneous. Research on the biogeochemical behaviour of Cr and its toxicological hazards on human and other biological routes is therefore urgently needed to develop a holistic approach to understanding the soil-water-human nexus that controls the toxicological hazards of Cr and its detoxification.

Iron-modified phosphorus- and silicon-based biochars exhibited various influences on arsenic, cadmium, and lead accumulation in rice and enzyme activities in a paddy soil.

Contamination of paddy soils with potentially toxic elements (PTEs) has become a severe environmental issue. Application of functionalized biochar for rice cultivation has been proposed as an effective means to reduce environmental risks of these PTEs in paddy soils. This work was undertaken to seek the positive effects of a rice husk-derived silicon (Si)-rich biochar (Si-BC) and a pig carcass-derived phosphorus (P)-rich biochar (P-BC), as well as their Fe-modified biochars (Fe-Si-BC and Fe-P-BC) on the enzyme activity and PTE availability in an As-Cd-Pb-contaminated soil. A rice cultivation pot trial was conducted using these functionalized biochars as soil amendments for the alleviation of PTE accumulation in rice plants. Results showed that Si-BC decreased the concentrations of As in rice grain and straw by 59.4 % and 61.4 %, respectively, while Fe-Si-BC significantly (P < 0.05) enhanced plant growth, increasing grain yield (by 38.6 %). Fe-Si-BC significantly (P < 0.05) elevated Cd and Pb accumulation in rice plants. P-BC enhanced the activities of dehydrogenase, catalase, and urease, and reduced grain-Pb and straw-Pb by 49.3 % and 43.2 %, respectively. However, Fe-P-BC reduced plant-As in rice grain and straw by 12.2 % and 51.2 %, respectively, but increased plant-Cd and plant-Pb. Thus, Fe-modified Si- and P-rich biochars could remediate paddy soils contaminated with As, and enhance the yield and quality of rice. Application of pristine P-rich biochar could also be a promising strategy to remediate the Pb-contaminated paddy soils and limit Pb accumulation in rice.

Biochar inhibited hydrogen radical-induced Cd bioavailability in a paddy soil.

Herein, hydrogen (H·) radical was observed as a new pathway to produce hydroxyl (OH·) radicals that promoted cadmium sulfide (CdS) dissolution and thus Cd solubility in paddy soils. In soil incubation experiments, the bioavailable Cd concentrations in flooded paddy soils were increased by 8.44 % as the soil was aerated for 3d. For the first time, the H· radical was observed in aerated soil sludge. The association of CdS dissolution with free radicals was thereafter confirmed in an electrolysis experiment. Both H· and OH· radicals in electrolyzed water were confirmed by the electron paramagnetic resonance analysis. In the system with CdS, water electrolysis increased soluble Cd2+ concentration by 60.92 times, which was compromised by 43.2 % when the radical scavenger was introduced. This confirmed the free radicals can lead to oxidative dissolution of CdS. The H· radical was generated in systems with fulvic acid or catechol irradiated by ultraviolet lights, indicating soil organic carbon could be an important precursor for H· and OH· radicals. Biochar application decreased soil DTPA-Cd by 22-56 % invoking mechanisms besides adsorption. First, biochar quenched radicals and reduced CdS dissolution by 23.6 % in electrolyzed water in which -C-OH of biochar was oxidized to CO. Second, biochar boosted Fe/S-reducing bacteria and thus compromised CdS dissolution, as affirmed by a reversal correlation between soil available Fe2+ and DTPA-Cd concentrations. A similar phenomenon occurred in Shewanella oneidensis MR-1-inoculated soils. This study provided new insights into the bioavailability of Cd and offered feasible measures to remediate Cd-contaminated paddy soils with biochars.