Effects of BC on metal uptake by crops (availability) and the vertical migration behavior in soil: A 3-year field experiments of crop rotation.

Biochar (BC) has been substantiated to effectively reduce the available content of heavy metals (HMs) in soil-plant system; however, the risk of biochar (BC)derived dissolved organic matter (DOM) induced metal vertical migration has not been well documented, especially in the long-term field conditions. Therefore, this study investigated HM vertical migration ecological risks and the long-term effectiveness of the amendment of biochar in the three successive years of field trials during the rotation system. The results revealed that biochar application could increase soil pH and DOM with a decrease in soil CaCl2 extractable pool for Pb, Cu, and Cd. Furthermore, the results indicated a significant decrease in acid phosphatase activities and an increase in urease and catalase activities in the soil. Cucumber was shown to be safe during a three-year rotation system in the field. These results suggest that BC has the potential to enhance soil environment and crop yields. BC derived DOM-specific substances were identified using parallel factor analysis of excitation-emission matrix in deep soil (0-60 cm). The study incorporated HM concentration fluctuations in deep soils, providing an additional interpretation of DOM and co-migration of HMs.The environmental risk associated with the increase in DOM hydrophobicity should not be ignored by employing BC for soil HM remediation applications. The study enhances understanding of biochar-derived DOM's migration and stabilization mechanisms on heavy metals, providing guidelines for its use as a soil amendment.

Three-year field experiments revealed the immobilization effect of natural aging biochar on typical heavy metals (Pb, Cu, Cd).

Biochar has been widely used for the remediation of heavy metal contaminated soil, while the long-term field aging on its properties and the performance in the ability of metal immobilization must not be overlooked. In this study, the stability of immobilized heavy metals (Cd, Cu, Pb) on biochar during a 3-year remediation for soil in the field was investigated through desorption experiments. The results indicated that the application of biochar and its aging in the field both remarkably increased the immobilization of the 3 metal ions in the field under 3-year remediation. The cumulative desorption of the 3 metals decreased with biochar aging, and the desorption rate of Pb2+, Cu2+ and Cd2+ in T3 (Application of 30 t·hm-2 of biochar) for the third year was 0.08 %, 0.20 % and 13.15 %. Meanwhile, both the desorption rates and extents exhibited significant difference with the order of Pb2+ < Cu2+ < Cd2+. The increased soil pH, the enhancement of O/C ratio (Increase from 0.30 for fresh BC to 0.61 for aged BC(S3)) and oxygen-containing functional groups in biochar, and the accretion of organo-mineral micro-agglomerates on biochar surfaces and in pores during field aging process jointly contributed the immobilization of metals in soils mainly through co-precipitation and complexation. Our results provide new insights into the practical application of biochar in soils contaminated with multiple heavy metals from the perspective of long-term effects, which suggests that the potential release risk of metals become slighter over time.

The adsorption affinity of N-doped biochar plays a crucial role in peroxydisulfate activation and bisphenol A oxidative degradation.

Metal-free biochar to activate persulfate and degrade organic contaminants has attracted great attention in advanced oxidation processes, while the role of biochar adsorption in the activation and oxidative decomposition process still needed to be further clarified. In this study, nitrogen-doped porous biochar derived from a waste litchi branch was prepared as a peroxydisulfate (PDS) activator for bisphenol A (BPA) degradation, in which the regulation behavior of biochar adsorption was evaluated on the basis of phase distribution and PDS activation mechanism. N-doped biochar obtained at 800 °C with urea and sodium bicarbonate added presented a high specific surface area (821 m2/g), abundant nanopores, and a graphitic structure, and showed the best adsorption capacity and catalytic activity toward BPA. At a dosage of 0.15 g/L NBC-800, 95% BPA can be completely degraded within 60 min with an apparent rate constant (kobs) of 0.0483 min-1. The identified active sites and reactive oxygen species as well as electrochemical tests suggested that both free radicals O2•- and •OH and nonradical pathways including 1O2 originated from C = O and surface electron-transfer mechanisms were involved in BPA decomposition. The experiments and activation mechanisms all confirmed that BPA adsorption on the NBC-800 surface was an extremely crucial step for BPA oxidative degradation.

Field-scale fluorescence fingerprints of biochar-derived dissolved organic matter (DOM) provide an effective way to trace biochar migration and the downward co-migration of Pb, Cu and As in soil.

Although the benefits of biochar amendment for heavy metal(loid) immobilization in soil have been widely recognized, its migration in soil and the resultant effects on the risk of downward migration of metal(loid)s are still poorly understood. In this study, based on biochar derived dissolved organic matter (DOM), excitation-emission matrix coupled with parallel factor analysis (EEM-PARAFAC) technique was employed to trace biochar migration within one year in 0-100 cm soil profiles in the field. The vertical co-migration of Pb, Cu and As was also analyzed. With biochar amended, DOM, humification index (HIX) and biological index (BIX) in 0-60 cm soil profiles increased significantly, while pH only increased in the topsoil. The identified water-extracted DOM components showed that biochar could enhance the content of fulvic acids and humic acids in soil DOM and biochar might migrate downward to 60 cm soil profiles. Furthermore, toluene/methanol-extracted DOM also confirmed the migration extent of biochar, which was more suitable to trace biochar migration because of its high resistance to the long-term ageing in the field. Moreover, we found that biochar reduced the content of Cu in 0-60 cm soil profiles, but increased the available Pb and As in the 20-40 cm soil layers. The Pearson's correlation study confirmed a strong correlation (0.568**≤R ≤ 0.803**) between the content of heavy metal(loid)s and humic-like components of soil DOM, which suggested that biochar co-migrated with Pb, Cu and As, and the potential environmental risks of biochar should be fully evaluated while it was applied for soil metal(loid) remediation.

An assessment of integrated amendments of biochar and soil replacement on the phytotoxicity of metal(loid)s in rotated radish-soya bean-amaranth in a mining acidy soil.

Knowledge is insufficient on feasible remediation techniques to agricultural soils contaminated by multiple heavy metal(loid)s with elevated concentrations and extreme acidy from acid mine drainages (AMD). We aimed to elucidate the effect of integrated biochar (BC) and soil replacement on improving the mining soil properties and then alleviating the phytotoxicity of As, Pb, Cd, Cu, and Zn on radish (Raphanus sativus L.)-soya bean (Glycine max Merr.) -amaranth (Amaranthus tricolor L.) rotation and the potential risk of crops to human health. Biochar and soil replacement showed outstanding effects on improving soil properties by increasing soil pH values, reducing available metal(loid)s, and enhancing the activity of catalase, urease and acid phosphatase. Also, the integrated technique regulated the physiological disorders of crops caused by metal(loid)s, specifically increasing chlorophyll content and reducing malondialdehyde (MDA) in the three crops, and reducing the content of metal(loid)s in edible parts of plants. The combination of biochar and soil replacement exhibited better remediation effect than the single application of biochar or soil replacement, which played different roles in remediating mining farmland. Biochar exhibited efficacy in soil pH amelioration, metal stabilization and soil enzyme activity enhancement, while soil replacement alleviated metal(loid)s stress through the dilution effect. Among the 8 treatments, only biochar combined with 35% (S35BC) and 50% (S50BC) of replaced soil could achieve the safe production of the three crops under the three-season crop rotation.

Biochar and exogenous calcium assisted alleviation of Pb phytotoxicity in water spinach (Ipomoea aquatica Forsk) cultivated in Pb-spiked soil.

The consumption of vegetables grown in Pb-polluted soils causes serious threats to human health around the globe. In this study, we evaluated the Pb toxicity alleviation in water spinach grown of pot experiments in Pb-spiked soil treated with biochar and exogenous calcium. The results showed that both biochar and exogenous calcium alleviated Pb stress in water spinach, which was mainly manifested on its improved soil health and increased growth and decreased Pb uptake. Incorporation of 3% biochar significantly reduced CaCl2 extracted Pb by 53.6% and decreased Pb accumulation in roots (67.1%) and shoots (80.8%). Our also findings indicated that Pb detoxification mechanism of biochar and exogenous calcium was totally different, while they can induce a synergistic impact on water spinach Pb stress alleviation. The combination of biochar and exogenous calcium in Pb-contaminated soil remediation may complement each other and reduce Pb entry into the human body through vegetables.

Immobilization of heavy metal(loid)s in acid paddy soil by soil replacement-biochar amendment technology under normal wet condition.

The remediation of agricultural soil contaminated by acid mine drainages (AMD) with extreme acidity and elevated concentrations of metal(loid)s still remains to be solved. In the present study, the combination of soil replacement-biochar (BC) amendment was adopted in 270-day incubation experiments to evaluate the effect on the metal(loids) (As, Pb, Cu, Cd, and Zn) immobilization and soil properties (pH, dissolved organic carbon (DOC), redox potential (Eh), and soil water holding capacity (SWC)). The incubation study showed that soil replacement-biochar amendment improved soil health by changing soil properties, which in turn exhibited significant effects on CaCl2-extracted metal(loid)s. The combination of soil replacement and biochar amendment exhibited positive effect on the immobilization of Pb, Cu, Cd, and Zn, while, the risk of As and Cd mobility induced by biochar in the ageing process should be paid attention. Further laboratory seed germination study suggested that soil replacement-biochar amendment could effectively alleviate the stress of metal(loid)s, with the treatment of S50BC achieving the best remediation results. The results of this study suggested that soil replacement-biochar amendment was a promising remediation technology for agricultural soil contaminated by AMD. Graphical abstract.

Assessing biochar application to immobilize Cd and Pb in a contaminated soil: a field experiment under a cucumber-sweet potato-rape rotation.

Cd and Pb are common toxic contaminants prevailing in agricultural soils contaminated by mining activities. In this study, biochar was used to stabilize Cd and Pb contaminated soil for safe with three crops rotation condition within one year. Field experiments were carried out to investigate the effect of Litchi branch biochar (BC), pyrolyzed at 600 °C and applied at 4 rates [(0 t ha-1 (T0), 10 t ha-1 (T1), 20 t ha-1 (T2) and 30 t ha-1 (T3)]) on remediation of Cd and Pb in agricultural soil near Dabaoshan Mine in South China under a cucumber-sweet potato-rape rotation. The results showed that the application of BC can significantly increase the pH, cation exchange capacity and soil organic matter. After cultivation of crops, the pH values decrease gradually, with the biggest drop of 0.45 pH units in T3 treatment after rape cultivation. BC application increased the yield of three crops up to onefold to twofold in T3 treatment as compared to the control. The uptake of Cd and Pb in all three crops decreases with the increase in BC doses, which is mainly related to the decrease in bioavailable metals in their respective soil treatments. Under 1-year crops rotation, the remediation ability of BC still remains, while Cd and Pb can exhibit different risk to different crops. The data of this study can provide scientific suggestions for the selection of suitable crops and proper BC amount in remediation of heavy metal contaminated soil.

Effect of ageing process on bisphenol A sorption and retention in agricultural soils amended with biochar.

The ageing of biochar and organic pollutant itself in soils can both influence the retention of organic pollutant in field soils. In this study, column experiments were adopted to determine the effect of ageing process on bisphenol A (BPA) sorption and retention in two typical Chinese agricultural soils with lychee branch biochar added. The effect of biochar ageing on soil organic matter (SOM) was specially investigated. Experimental results showed that the addition of biochar significantly increased the condensation and rigid of SOM, which could further increase with biochar ageing in soils. As a result, the addition of biochar significantly increased BPA sorption capacity (5.86 times and 3.30 times) and retention rate (13.60 times and 4.47 times) in fluvo-aquic soil and phaeozem respectively, while BPA sorption capacity and retention rate decreased obviously after biochar ageing in the two soils for 2 months as compared with the freshly incorporated biochar treatments, which may be attributed to the surface coverage and/or pore blockage of some sorption sites owning to DOC. With biochar incorporated, 2 months of BPA ageing increased BPA retention rate by about 4.50 times in both soils as compared with BPA newly spiked treatments. The results of this study could provide important parameters for prediction and control of organic pollutants such as BPA in soils.

Fractionation and release of Cd, Cu, Pb, Mn, and Zn from historically contaminated river sediment in Southern China: Effect of time and pH.

The release of in situ heavy metals (cadmium [Cd], copper [Cu], lead [Pb], manganese [Mn], and zinc [Zn]) from contaminated river sediment near a Cu-iron mine in South China was experimentally studied. The effects of pH values and the kinetics of heavy metal release were investigated. In addition, species of the 5 metals in the sediment were determined as a function of pH and time. Rates and extents of metal desorption were studied over 30 d, and a 3-parameter, 2-compartment model was used to analyze the desorption kinetics. The rate constants (ks ) for the slowly desorbing fraction of heavy metals were found to be 5 to 6 orders of magnitude lower than the corresponding rate constants (kr ) for the rapidly desorbing fraction, suggesting that slow desorption is the rate-limiting step. The partition coefficients (Kd ) varied significantly among metals, on the order Pb > Cu >Zn > Cd > Mn, indicating that the sediment had a much higher retention capability for strongly hydrolyzed metals than for weakly hydrolyzed ones. The amount of metals released from the sediment decreased dramatically at the final pH of 2 to 4 and leveled off in the pH range of 5 to 8. Release time and pH exhibited a varied influence on the fractionation of metals, and had a more remarkable influence on more mobile fractions and hardly any effect on the residual fraction during the desorption process. The fractionation of strongly adsorbing metals like Pb was not as dependent on release time and pH as it was for the weakly bonded metals like Mn and Cd. The results indicate that in situ heavy metals may exhibit a sustainable potential for release and may increase health risks when the pH of the river is lowered. Environ Toxicol Chem 2019;38:464-473. © 2018 SETAC.

Enhanced reactivity of nZVI embedded into supermacroporous cryogels for highly efficient Cr(VI) and total Cr removal from aqueous solution.

Novel supermacroporous PSA-nZVI composites with nanoscale zero-valent iron particles (nZVI) embedded into poly (sodium acrylate) (PSA) cryogels were synthesized through ion exchange followed by in-situ reduction. The magnetic composites were evaluated for material characterizations and their efficiency for Cr(VI) and total Cr removal from aqueous medium in batch experiments. PSA-nZVI composites with high nZVI loading capacity up to 128.70 mg Fe/g PSA were obtained, and the interconnected macroporous structure of PSA cryogel remained unaltered with nZVI uniformly distributed on PSA cryogel as determined by TGA, SEM, TEM, XRD and XPS analyses. PSA-nZVI composites showed faster reaction rate than free nZVI both for Cr(VI) and total Cr removal, suggesting no mass transfer resistance and the enhanced reactivity of nZVI in PSA carrier. PSA-nZVI composites exhibited much more remarkable performance for Cr(VI) and total Cr removal than free nZVI particles in high removal capacity and broad pH application range (pH 4-10). The reaction mechanisms were also elucidated with XPS analyses before and after Cr(VI) reduction reactions. These results demonstrate that PSA cryogel acts as an excellent carrier and shows multiple functions in nZVI particle dispersion, pH buffering and oxidation resistance in addition to immobilizing nZVI particles from release.

Removal of sulfuric acid mist from lead-acid battery plants by coal fly ash-based sorbents.

Sorbents from coal fly ash (CFA) activated by NaOH, CaO and H2O were prepared for H2SO4 mist removal from lead-acid battery plants. The effects of parameters including temperature, time, the ratios of CFA/activator and water/solid during sorbent preparation were investigated. It is found that the synthesized sorbents exhibit much higher removal capacity for H2SO4 mist when compared with that of raw coal fly ash and CaO except for H2O activated sorbent and this sorbent was hence excluded from the study because of its low capacity. The H2SO4 mist removal efficiency increases with the increasing of preparation time length and temperature. In addition, the ratios of CFA/activator and water/solid also impact the removal efficiency, and the optimum preparation conditions are identified as: a water/solid ratio of 10:1 at 120 °C for 10h, a CFA:CaO weight ratio of 10:1, and a NaOH solution concentration of 3 mol/L. The formation of rough surface structure and an increased surface area after NaOH/CaO activation favor the sorption of H2SO4 mist and possible sorption mechanisms might be electrostatic attractions and chemical precipitation between the surface of sorbents and H2SO4 mist.

Application of Mn/MCM-41 as an adsorbent to remove methyl blue from aqueous solution.

In this study, the application of Mn loaded MCM-41 (Mn/MCM-41) was reported as a novel adsorbent for methyl blue (MB) from aqueous solution. The mesoporous structure of Mn/MCM-41 was confirmed by XRD technique. Surface area, pore size and wall thickness were calculated from BET equation and BJH method using nitrogen sorption technique. FT-IR studies showed that Mn were loaded on the hexagonal mesoporous structures of MCM-41. It is found that the MCM-41 structure retained after loading of Mn but its surface area and pore diameter decreased due to pore blockage. Adsorption of MB from aqueous solution was investigated by Mn/MCM-41 with changing Mn content, adsorbent dosage, initial MB concentration, contact time, pH and the temperature. Under the chosen condition (25°C, 0.02 g adsorbent dosage, 6.32 pH, 50 mg L(-1) MB, 1 wt.% Mn), a high MB adsorption capacity (45.38 mg g(-1)) was achieved by Mn/MCM-41 process at 120 min, 8.6 times higher than MCM-41. The electrostatic interaction was considered to be the main mechanism for the dye adsorption. The experimental data fitted well to Freundlich and Dubinin-Radushkevich isotherms. The adsorption of MB on Mn/MCM-41 followed pseudo-second-order kinetics. Thermodynamic parameters suggested that the adsorption process is endothermic and spontaneous.

Competitive sorption between 1,2,4-trichlorobenzene/tetrachloroethene and 1,2,4,5-tetrachlorobenzene by soils/sediments from South China.

1,2,4-Trichlorobenzene (1,2,4-TCB) and tetrachloroethene (PCE) were chosen to study their competitive effect on 1,2,4,5-tetrachlorobenzene (1,2,4,5-TeCB) sorption by three soils/sediments from South China with different fractions of natural organic matter (NOM) employing a batch technique. Results showed that cosolutes 1,2,4-trichlorobenzene and tetrachloroethene exhibited apparent competition against 1,2,4,5-tetrachlorobenzene in all of the three sediments. 1,2,4-Trichlorobenzene was more effective competitor than tetrachloroethene because the structure of 1,2,4-TCB is very close to that of 1,2,4,5-TeCB. Furthermore, the extent of competition depended on the rigidity of sediment NOM matrixes. The more reduced and condensed the matrixes are, the larger extent of competitive effect would the corresponding sediment show at a given sorbed volume of competitor.

Equilibrium, kinetics and thermodynamic studies for sorption of chlorobenzenes on CTMAB modified bentonite and kaolinite.

The sorption of chlorobenzenes (CBs) by cetyltrimethylammonium bromide (CTMAB) modified bentonite and kaolinite was investigated. The sorption isotherms for CBs were nearly linear, suggesting that sorption could be described by a distribution process. The distribution coefficient (K(d)) was primarily affected by the amount of sorbed surfactant. The organic carbon normalized sorption coefficient (K(oc)), however, was particularly dependent on arrangement of the surfactant cations. The K(d) of CBs was larger for CTMAB-bentonites than that for CTMAB-kaolinites, while the case for K(oc) was opposite. Thus, the clay mineral structure and morphology had a considerable influence on the surfactant arrangement, which was responsible for the partitioning of CBs. The sorption of CBs onto both CTMAB-bentonites and CTMAB-kaolinites followed pseudo-second-order kinetics. The intra-particle diffusion model for sorption was also investigated and compared to identify sorption mechanism. The sorption of CBs both on CTMAB-bentonites and CTMAB-kaolinites was exothermic in nature and accompanied by an increase in entropy and a decrease in Gibbs energy in the temperature range of 15-35 degrees C. The results indicated that CBs strongly interacted with CTMAB modified bentonite and kaolinite.

[Desorption kinetics of 1,2,4,5-tetrachlorobenzene in sediments].

Sediment desorption batch technique experiments were conducted to study the influence of different types of natural organic matter (NOM) of sediment, initial solid-phase solute loading levels and temperatures on the desorption rates of 1,2,4,5-tetrachlorobenzene. A 4-parameter biphasic first-order kinetic model described the desorption of 1,2,4,5-tetrachlorobenzene from the sediments. The results indicate that the rate constants k(s) for the slowly desorbing fraction of each sample is up to 2 orders of magnitude lower than the corresponding rate constants k(r), for the rapidly desorbing fraction, suggesting that the slow desorption is the rate-limiting step. Desorption rate constants for the slowly desorbing fraction are found to range from 1.19 x 10(-3) h(-1) to 2.88 x 10(-3) h(-1) for sediments that contain different types of NOM, respectively; rates and extents of 1,2,4,5-tetrachlorobenzene on several sediments increases with lower degree of sediment NOM condensation. When the sorbed initial solid-phase 1,2,4,5-tetrachlorobenzene concentration increases from 13.3 microg x g(-1) to 25.3 microg x g(-1), the constant k(s) increases from 1.26 x 10(-3) h(-1) to 2.52 x 10(-3) h(-1). Moreover, the rate constants for desorption increase strongly with increasing temperature, and the activation enthalpies for slow desorption appears to be 9.45-21.43 kJ x mol(-1), which can provide information on the feasibility of bioremediation of aged contaminants.

[Nonlinear sorption behaviors of chlorobenzenes on sediments].

Sorption isotherms of chlorobenzene, 1,4-dichlorobenzene, 1,2,4-trichlorobenzene and 1,2,4,5-tetrachlorobenzene on 5 sediments were examined to understand its sorption behavior. All systems examined exhibits nonlinear sorption. All sorption isotherms are nonlinear as evidenced by the Freundlich n values of 5 sediments being between 0.858 to 0.956. Sorption nonlinearity is found to be a function of the polarity index of sediments natural organic matter (NOM) with a high correlative coefficient of 0.9947, suggesting that the degree of condensation of NOM, characterized by its polarity index, is correlated with the sorption behavior of 1,2,4-trichlorobenzene. In addition, the sorption affinity (Koc) of the sediments for 1,2,4-trichlorobenzene increases with decreasing of NOM polar, indicating that a higher sorption affinity in the sediments is associated with a higher degree of condensation of NOM. The Freundlich n values of chlorobenzene, 1,4-dichlorobenzene, 1,2,4-trichlorobenzene and 1,2,4,5-tetrachlorobenzene are 0.755, 0.788, 0.858, 0.949 respectively, indicating that the smaller CBs molecule may result in more significant sorption nonlinearity.