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To reveal the respective evolution of soil and biochar on competitive heavy metal adsorption mechanisms after natural ageing, three soils and two biochars were tested in this study. The soil-biochar interlayer samples were buried in the field for 0.5, 1, and 2 years, for which competitive adsorption characteristics and mechanisms of soils and biochars in four systems (Cd, Cd+Ni, Cd+Cu, and Cd+Ni+Cu) were investigated. Results showed that physicochemical properties, adsorption capacity and mechanisms of soils and biochars all changed the most in the first 0.5 years. The properties and adsorption capacity of biochars gradually weakened with the ageing time, meanwhile, those of soils gradually enhanced. After co-ageing with acidic soil for 0.5 years, the Cd(II) adsorption capacity of modified biochar decreased by 86.59% in the ternary system; meanwhile, that of acidic soil increased by 65.52%. The contributions of mineral mechanisms decreased significantly, while non-mineral mechanisms were slightly affected by ageing. This study highlighted that when using biochar to remediate heavy metal-contaminated soils, biochar should be applied at least half a year in advance before planting crops so that biochar can fully contact and react with the soil.

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This study investigated the effects of soil water content on Cd immobilization and uptake by leek with the combined application of biochar and organic fertilizer using mechanism experiment and pot experiment. Mechanism experiment was conducted with the three-layer mesh method, which can reveal the individual mechanisms and contributions of biochar and soil to Cd immobilization. The results of mechanism experiment showed that the Cd adsorption amount by biochar was very little at low soil water content (θw = 20%, w/w), and both of Cd adsorption amount and rate significantly increased at higher θw (40% and 60%). The Cd immobilization by biochar at higher θw (40% and 60%) was significantly better than that at low θw (20%) in soils because F1 (percentages of exchangeable Cd) decreased with increasing moisture. For example, the F1 percentages were 58.27%, 40.67%, and 38.46% in the soil at 4.40 mg·kg-1 under M20, M40, and M60 (θw = 20%, 40%, 60%) at day 120, respectively. The results of pot experiment showed that the Cd in leek leaves and roots continuously accumulated with planting time in each batch, and biochar and organic fertilizer treatments significantly reduced the Cd enrichment in leek. Combined treatment of biochar and organic fertilizer (BO) is superior to biochar treatments (BC) and CK for Cd immobilization in soil. For example, the percentages of F1 under the treatments of CK, BC, and BO were 64.43%, 49.13%, and 43.67% at 75% field water capacity treatment, respectively. For the same treatment, with increasing water contents, the better the Cd was immobilized in the soil and the greater the leek biomass. However, the total uptake of Cd by leek were increased by promoting crop growth under water content conditions.

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In this study, the effects of coexistence with microplastics and co-ageing with the soil on adsorption behaviors and mechanisms of biochar for heavy metals were investigated. Adsorption experiments of Cd, Ni, and Cu by microplastics, biochar, and their combination were conducted in single, binary, and ternary systems. The results indicated that the heavy metal adsorption by microplastics was ranked as Ni > Cd > Cu, which increased with decreasing particle size, and the adsorption capacity of microplastics was enhanced after dry-wet and freeze-thaw ageing. Biochar preferentially adsorbed Cd in the single system, while the maximum adsorption of Cu was observed in the binary and ternary systems due to the minimizing impact of competition on the Cu adsorption by biochar. The heavy metal adsorption by the combination of microplastics and biochar was less than that by single biochar, and the smaller the particle size of microplastics, the greater the negative effects on heavy metal adsorption. Coexistence with microplastics reduced Cd adsorption of biochar by 0.72 %-50.35 %, Ni adsorption by 1.17 %-30.43 %, and Cu adsorption by 5.78 %-47.88 %, respectively. Moreover, coexistence with microplastics exacerbated the adverse impacts of competition on biochar adsorption for heavy metals. The contribution percentages of biochar mineral mechanisms for heavy metal adsorption were ranked as Cu > Cd > Ni. When coexisting with microplastics or after ageing, the mineral mechanisms of heavy metal adsorption by biochar significantly decreased. This study investigated the competitive adsorption behaviors and mechanisms of heavy metals by biochar when coexisting with microplastics, which highlighted that the application of biochar for the remediation of heavy metal pollution should be concerned with the impacts of microplastics.

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This study investigated the competitive adsorption and immobilization of cadmium (Cd), nickel (Ni), and copper (Cu) by biochar in unsaturated soils under single-, binary-, and ternary-metal systems. The results showed that the immobilization effects by the soil itself were in the order of Cu > Ni > Cd, and the adsorption capacities of freshly contaminated heavy metals by biochar were in the order of Cd > Ni > Cu in unsaturated soils. The adsorption and immobilization of Cd by biochars in soils was weakened by competition more in the ternary-metal system than that in the binary-metal system; the competition with Cu caused a more significant weakening effect than that with Ni. For Cd and Ni, nonmineral mechanisms preferentially adsorbed and immobilized Cd and Ni compared to mineral mechanisms, but the contributions of the mineral mechanisms to the adsorption gradually increased and became dominant with increasing concentrations (at average percentages of 62.59%-83.30% and 41.38%-74.29%, respectively). However, for Cu, the contributions of the nonmineral mechanisms to Cu adsorption were always dominant (average percentages of 60.92%-74.87%) and gradually increased with increasing concentrations. This study highlighted that the types of heavy metals and coexistence should be focused when remediating heavy metal contamination in soils.

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In this study, cadmium (Cd) transport and immobilization on passivators (biochar, organic fertilizer) and soils under saturated-unsaturated conditions were independently analyzed. The results showed that the Cd adsorption capacities of biochar and organic fertilizer were comparable in acidic soils. But in alkaline soils, the Cd adsorption capacity of organic fertilizer was significantly larger than that of biochar. In acidic soils, passivators effectively immobilized Cd, and the total net effects were in the order: combination (44.05-58.13%) > 3% biochar (31.96-46.88%) > 3% organic fertilizer (28.78-41.82%). In alkaline soils, all treatments had negative effects on Cd immobilization. For acidic soils, the immobilization of Cd was mainly attributed to the passivators, and the positive contribution percentages of relatively stable Cd increase by passivators were 81.05-100%, while those by soils were 0-18.95%. For alkaline soils, after the treatments of passivators, although a considerable amount of Cd was immobilized inside the passivator, Cd was activated more inside the soil. Therefore, it is noteworthy that soil conditions must be fully considered when applying biochar and organic fertilizers for Cd remediation.

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In this study, original and two KMnO4-modified rice straw biochars (pre- and postmodification) were prepared, which were all pyrolysed at 400 °C. Premodified biochar had the largest Cd adsorption capacity, strongest acid and solute buffering capacity, which benefited from the increase of carbonate content, specific surface area, and the emergence of Mn(II) and MnOx through modification. Original and premodified biochars were then conducted four types of aging process by an improved three-layer mesh method, namely, aging without soil and co-aging with acid (pH = 5.00), neutral (pH = 7.00), and alkaline (pH = 8.30) soils. The adsorption capacities of modified biochar were always larger than those of original biochar after aging processes. After four aging processes, Cd(II) adsorption capacities were basically in the order of aged biochar without soil > biochar co-aged with alkaline soil > biochar co-aged with neutral soil > biochar co-aged with acid soil, and KMnO4-modified biochar was always better than original biochar after co-aging with soils. The dominant adsorption mechanism of original and premodified biochars (fresh and aged) for Cd(II) was all the precipitation and adsorption with minerals (accounted for 58.55 ~ 85.55%). In this study, we highlighted that biochar remediation for Cd should be evaluated by co-aging with soil instead of aging without soil participation.

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Instead of traditional batch and column experiments with large water-soil ratios, this study investigated the behaviors and mechanisms of Cd adsorption and immobilization by biochar in unsaturated soils, in which the soil moisture conditions were closer to those in the actual field. The transport, transformation, and immobilization of cadmium (Cd) by pristine and KMnO4-modified biochars in unsaturated soils were investigated during a 48-week mild aging process. Biochar acidified with HCl solution was employed to quantify the contributions of mineral and non-mineral components in biochar to Cd adsorption and immobilization in unsaturated soils with a three-layer mesh method. The behaviors and mechanisms of Cd adsorption by biochar in unsaturated soils significantly differed from those in aqueous solutions. The equilibrium times of Cd adsorption by biochar in unsaturated soils (weeks) were much longer than those in aqueous solutions (hours). The percentages of the Cd adsorbed by pristine and modified biochar remained relatively constant relative to the total Cd in unsaturated soils, which accounted for 39.50-49.39 % and 57.35-68.94 %, respectively. The contribution of mineral components to Cd adsorption dominated in both unsaturated soils (45.00-94.09 %) and aqueous solutions (70.73-95.51 %). The process of Cd immobilization in unsaturated soils was that biochar firstly adsorbed the exchangeable Cd from the soil, and then converted it to relatively stable Cd. After aging for 48 weeks, the contributions of non-mineral components to Cd immobilization dominated in unsaturated soil with a low concentration (1.23 mg·kg-1), and the contributions of mineral components to Cd immobilization dominated in unsaturated soil with medium-high concentrations (4.08-51.26 mg·kg-1).

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This study investigated saturated-unsaturated soils, which were closer to the actual field conditions than traditional batch and column experiments with large water-soil ratios. The competitive adsorption, immobilization, and desorption of Cd, Ni, and Cu in soils treated with original and KMnO4-modified biochars were investigated under combined aging. Moreover, the employment of a three-layer mesh method enabled the independent analysis of heavy metals on biochar and soil during aging. The results showed that the order of biochar adsorption capacities was Cd > Cu > Ni in tested soils, and competing with Ni and Cu enhanced the Cd adsorption on biochars. Cd desorbed most with the CaCl2 solution while Ni and Cu desorbed most with citric acid. Modified biochar had improved immobilization effects compared to original biochar, and maintained the most stable remediation effects. The maximum variations in the stable Cd fraction during aging were 7.21%, 13.26%, and 14.71% for modified biochar, original biochar, and CK, respectively. However, for Ni and Cu, the biochar application reduced the residual fraction and increased desorption by citric acid. However, the stable fractions of Ni and Cu remained dominant, accounting for 83.28-97.85% and 86.31-98.96%, respectively.

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Cd long-term immobilization by biochar and potential risk in soils with different pH were quantified under a combined artificial aging, which simulated five years of aging in the field based on local climate. Two biochars (original and KMnO4-modified) and five soils with different pH were tested, and an improved three-layer mesh method was employed in this study. Five aging cycles were carried out (Cycle 1-Cycle 5), and each aging cycle quantitatively simulated 1 year of natural aging. As the aging time increased, Cd leaching loss in all soils gradually increased from Cycle 1 to Cycle 5; for relatively stable Cd fraction, it decreased firstly and then stabilized in acidic and neutral soils (S1-S4), while it decreased firstly and then increased in alkaline soil (S5). Biochars significantly promoted Cd immobilization in strongly acidic soil (S1) by increasing relatively stable fractions and decreasing leaching loss. For weakly acidic and neutral soils (S2-S4), although biochars still had positive effects, the immobilization effects were weakened to certain extents compared with S1. The percentage of Cd leaching loss decreased by 19.12% in strongly acidic soil (S1) and by 1.12-11.35% in weakly acidic and neutral soils (S2-S4) after modified biochar treatment. For alkaline soil (S5), the application of biochars had negative effects on Cd immobilization by decreasing relatively stable fractions and increasing leaching loss, and posed risks to the environment. For strongly acidic soil (S1) and weakly acidic and neutral soils (S2-S4), the percentages of relatively stable fractions increased from 6.09-19.93% to 24.98-36.70% after modified biochar treatment. However, for alkaline soil, the percentage of relatively stable fractions decreased from 55.27% to 53.93% after biochar treatment. The more acidic the soil, the more effective the Cd immobilization by biochar. Biochars with high pH level are not suitable for the remediation of alkaline Cd contaminated soil.

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To investigate the effects of competitive adsorption with Ni(II) and Cu(II) on the adsorption of Cd(II) by modified biochar co-aged with acidic soil, four biochars were employed in this study, namely original biochar, KMnO4-modified biochar and two aged biochars which co-aged with an acidic soil using above biochars under freeze-thaw cycling and dry-wet cycling for 54 days simulating 6 years of natural aging. The results showed that biochar adsorption capacities of three heavy metal ions were in the order of Cd(II) > Cu(II) > Ni(II) in the single system while Cu(II) > Cd(II) > Ni(II) in binary and ternary systems. Modification improved biochar adsorption capacity of Cd(II), but competitive adsorption with Ni(II) and Cu(II) weakened the improvement of modification on adsorption performance of modified biochar in binary and ternary systems. The QMBC/QBC of Cd(II) (QMBC and QBC are the adsorption capacities of heavy metals by modified and original biochars) decreased from 231.57% (single system) to 216.67%∼219.41% (binary system) and further decreased to 207.74% (ternary system). Co-aging with soil weakened the adsorption capacities of biochars for Cd(II), even worse, competition aggravated this negative effect of co-aging. The QAMBC/QMBC of Cd(II) (QAMBC is the adsorption capacities of heavy metals by aged modified biochar) decreased from 65.41% (single system) to 14.43%∼19.46% (binary and ternary systems). Therefore, the impact of competition should be fully considered when evaluating Cd long-term remediation effects of modified biochar in Cd polluted soils accompanied with other heavy metals.

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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.

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In this study, competitive adsorption behaviour and mechanisms of Cd2+, Ni2+ and NH4+ by fresh and artificially ageing biochars produced from rice straw at 400 and 700 °C (RB400, RB700, HRB400 and HRB700) were investigated. Cd2+ competed with Ni2+ and NH4+ for the overlapped adsorption sites on the biochars. For Cd2+ and Ni2+ adsorption, cation exchange (Qci) and mineral co-precipitation (Qcp) were the primary mechanisms for the low-temperature and high-temperature biochars, respectively. However, the other potential mechanisms (Qco) made the greatest contributions to NH4+ adsorption (>60%). Cd2+ and Ni2+ competition increased the proportions of mineral co-precipitation (Qcp) and other potential mechanisms (Qco) but decreased that of cation exchange (Qci) mechanism. Biochar ageing increased the contribution of surface complexation (Qcf) mechanism, especially for the low-temperature biochars. This study indicated that biochar aging and types and states of adsorbates should be considered when biochars were applied to remove contaminants.

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Adsorption mechanisms and competition between Cd2+ and Ni2+ for adsorption by rice straw biochars prepared at 400 °C (RB400) and 700 °C (RB700) were investigated in this study. Based on the Langmuir model, the maximum adsorption capacities (mg g-1) of Cd2+ and Ni2+ on RB400 and RB700 were in the order of Cd2+ (37.24 and 65.40) > Ni2+ (27.31 and 54.60) in the single-metal adsorption isotherms and Ni2+ (25.20 and 32.28) > Cd2+ (24.22 and 26.78) in the binary-metal adsorption isotherms. Cd2+ competed with Ni2+ for binding sites at initial metal concentrations >10 mg L-1 for RB400 and > 20 mg L-1 for RB700. The adsorption sites for Cd2+ and Ni2+ on the biochars largely overlapped, and the binding of Cd2+ and Ni2+ to these sites was affected by the occupation sequence of these metals. For Cd2+ and Ni2+ adsorption in the binary system, cation exchange and precipitation were the dominant adsorption mechanisms on RB400 and RB700, respectively, accounting for approximately 36% and 60% of the adsorption capacity. Competition decreased the contribution of cation exchange but increased that of precipitation and other potential mechanisms. Results from this study suggest that types and concentrations of metal ions should be taken into account when removing metal contaminants from water or soil using biochars.

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