Removal of potentially toxic elements from contaminated soil and water using bone char compared to plant- and bone-derived biochars: A review.

Conversion of hazardous waste materials to value-added products is of great interest from both agro-environmental and economic points of view. Bone char (BC) has been used for the removal of potentially toxic elements (PTEs) from contaminated water, however, its potential BC for the immobilization of PTEs in contaminated water and soil compared to bone (BBC)- and plant (PBC)-derived biochars has not been reviewed yet. This review presents an elaboration for the potentials of BC for the remediation of PTEs-contaminated water and soil in comparison with PBC and BBC. This work critically reviews the preparation and characterization of BC, BBC, and PBC and their PTEs removal efficiency from water and soils. The mechanisms of PTE removal by BC, BBC, and PBC are also discussed in relation to their physicochemical characteristics. The review demonstrates the key opportunities for using bone waste as feedstock for producing BC and BBC as promising low-cost and effective materials for the remediation of PTEs-contaminated water and soils and also elucidates the possible combinations of BC and BBC aiming to effectively immobilize PTEs in water and soils.

Microscopic mechanism about the selective adsorption of Cr(VI) from salt solution on O-rich and N-rich biochars.

The adsorption of Cr(VI) on biochars can be suppressed by coexisting anions, but the roles of O-containing functional groups and in particular N-containing functional groups are unclear. In this study, we combined spectroscopic and molecular simulation approaches to investigate the selective adsorption of Cr(VI) on the O-rich (PB, UB1) and N-rich (UB3, UB5) biochars under strong competition of anions. The elemental analysis and pyrolysis-gas chromatography/mass spectrometry indicated that the structures of PB and UB1 were similar, and so were the UB3 and UB5. Quantification of functional groups showed that for UB1, 75.3% of Cr(VI) removal was attributed to O-containing groups, while 53.3-72.7% of that was mediated by N-containing groups in UB3 and UB5. X-ray photoelectron spectra and density functional theory calculations confirmed that for O-rich biochars, surface complexation and strong H-bonds between carboxyl/hydroxyl and HCrO4- improved Cr(VI) removal in the presence of anions, while for N-rich biochars, Cr(VI) adsorption was depressed by coexisting anions in the order of Cl->NO3- >SO42- because of the weaker H-bond between protonated amino groups and HCrO4-. This study presents a novel approach for quantitative, molecular-level evaluation of the roles of biochar functional groups in the Cr(VI) removal from complex environmental systems.

Engineered biochars from catalytic microwave pyrolysis for reducing heavy metals phytotoxicity and increasing plant growth.

Pb, Ni, and Co are among the most toxic heavy metals that pose direct risks to humans and biota. There are no published studies on biochars produced at low temperatures (i.e., 300 °C), which possess high sorption capacity for heavy metal remediation and reclamation of contaminated sandy soils. This research studied the effect of catalytic microwave pyrolysis of switchgrass (SG) using bentonite and K3PO4 to produce biochar at low temperature (300 °C) with high sorption capacity for reducing the phytotoxicity of heavy metals, and investigated the synergistic effects of catalyst mixture on biochar sorption capacity. The quality of the biochars was examined in terms of their impacts on plant growth, reducing phytotoxicity and uptake of heavy metals in sandy soil spiked with Pb, Ni, and Co. All catalysts increased the micropore surface area and cation-exchange capacity of biochars, and resulted in biochars rich in plant nutrients, which not only decreased heavy metal phytotoxicity, but also boosted plant growth in the spiked soil by up to 140% compared to the sample without biochar. By mixing bentonite and K3PO4 with SG during microwave pyrolysis, the efficacy of biochar in reducing phytotoxicity and heavy metals uptake was further enhanced because of the highest micropore surface area (402 m2/g), moderate contents of Ca, Mg, K, and Fe for ion-exchange and moderate concentration of phosphorus for the formation of insoluble heavy metal compounds. Generally, the biochar created at 300 °C (300-30KP) showed similar performance to the biochar created at 400 °C (400-30KP) in terms of reducing heavy metal bioavailability.

The role of tailored biochar in increasing plant growth, and reducing bioavailability, phytotoxicity, and uptake of heavy metals in contaminated soil.

Microwave-assisted catalytic pyrolysis was investigated using K3PO4 and clinoptilolite to enhance biochar sorption affinity for heavy metals. The performance of resulting biochar samples was characterized through their effects on plant growth, bioavailability, phytotoxicity, and uptake of heavy metals in a sandy soil contaminated with Pb, Ni, and Co. The produced biochars have high cation-exchange capacity (CEC) and surface area, and rich in plant nutrients, which not only reduced heavy metals (Pb, Ni, and Co), bioavailability and phytotoxicity, but also increased plant growth rate by up to 145%. The effectiveness of biochar in terms of reduced phytotoxicity and plant uptake of heavy metals was further improved by mixing K3PO4 and clinoptilolite with biomass through microwave pyrolysis. This may be due to the predominance of different mechanisms as 10KP/10Clino biochar has the highest micropore surface area (405 m2/g), high concentrations of K (206 g/kg), Ca (26.5 g/kg), Mg (6.2 g/kg) and Fe (11.9 g/kg) for ion-exchange and high phosphorus content (79.8 g/kg) for forming insoluble compounds with heavy metals. The largest wheat shoot length (143 mm) and lowest extracted amounts of Pb (107 mg/kg), Ni (2.4 mg/kg) and Co (63.9 mg/kg) were also obtained by using 10KP/10Clino biochar at 2 wt% load; while the smallest shoot length (68 mm) and highest extracted amounts of heavy metals (Pb 408 mg/kg, Ni 15 mg/kg and Co 148 mg/kg) for the samples treated with biochars were observed for soils mixed with 1 wt% 10Clino biochar. Strong negative correlations were also observed between biochar micropore surface area, CEC and the extracted amounts of heavy metals. Microwave-assisted catalytic pyrolysis of biomass has a great potential for producing biochar with high sorption affinity for heavy metals and rich nutrient contents using properly selected catalysts/additives that can increase microwave heating rate and improve biochar and bio-oil properties.

Engineered biochar from microwave-assisted catalytic pyrolysis of switchgrass for increasing water-holding capacity and fertility of sandy soil.

Engineered biochars produced from microwave-assisted catalytic pyrolysis of switchgrass have been evaluated in terms of their ability on improving water holding capacity (WHC), cation exchange capacity (CEC) and fertility of loamy sand soil. The addition of K3PO4, clinoptilolite and/or bentonite as catalysts during the pyrolysis process increased biochar surface area and plant nutrient contents. Adding biochar produced with 10wt.% K3PO4+10 wt.% clinoptilolite as catalysts to the soil at 2wt% load increased soil WHC by 98% and 57% compared to the treatments without biochar (control) and with 10wt.% clinoptilolite, respectively. Synergistic effects on increased soil WHC were manifested for biochars produced from combinations of two additives compared to single additive, which may be the result of increased biochar microporosity due to increased microwave heating rate. Biochar produced from microwave catalytic pyrolysis was more efficient in increasing the soil WHC due to its high porosity in comparison with the biochar produced from conventional pyrolysis at the same conditions. The increases in soil CEC varied widely compared to the control soil, ranging from 17 to 220% for the treatments with biochars produced with 10wt% clinoptilolite at 400°C, and 30wt% K3PO4 at 300°C, respectively. Strong positive correlations also exist among soil WHC with CEC and biochar micropore area. Biochar from microwave-assisted catalytic pyrolysis appears to be a novel approach for producing biochar with high sorption affinity and high CEC. These catalysts remaining in the biochar product would provide essential nutrients for the growth of bioenergy and food crops.