Mingliang Zhang

In this study, Mg-modified sludge biochar (MB) and Mg-Fe double oxides/sludge biochar composites (MFB) were synthesized for enhanced removal of phosphate from aqueous solution. The phosphate adsorption followed the Langmuir-Freundlich isotherm model, and the maximum capacity was 142.31 mg P/g and 35.41 mg P/g for MB and MFB, respectively. MB exhibited the higher adsorption capacity at pH 8–9 and performed well under the influences of coexisting anions and temperature (4–45 °C). Adsorption kinetics was well described by the pseudo-second-order kinetic model, indicating the chemical bonding between phosphate and adsorption sites. The adsorption capacity of phosphate decreased by < 15% after three successive recycles. Based on FTIR, XRD, and XPS analysis, the main mechanisms for phosphate removal by MB included electrostatic attraction, surface complexation, and precipitation. Hydroxides/oxides particles of Mg on the surface of MB with positive charge could adsorb HPO₄²⁻ and PO₄³⁻ to form surface complex and convert to MgHPO₄ and Mg₃(PO₄)₂. The released amounts of Fe, Cd, Cr, Pb, Cu, Zn, Sb, and As from MB and MFB were low and acceptable. However, the released amount of Mg was as high as 4.9 wt% for MB and 8.7 wt% for MFB at the pH corresponding maximum adsorption capacity, posing a risk of salt increase. The grass (Lolium perenne L.) germination and early growth with the addition of P-laden biochars as fertilizer are seriously inhibited due to the high alkalinity, particularly for MB. The environmental risk of P-laden biochars (with high alkalinity and salt content) as fertilizer should be emphasized in practical application.

Maize straw biochar-supported nanoscale zero-valent iron composite (MSB-nZVI) was prepared for efficient chromium (Cr) removal through alleviating the aggregation of zero-valent iron particles. The removal mechanism of MSB-nZVI was investigated by scanning electron microscopy with energy dispersive X-ray (SEM-EDX), X-ray diffractometry (XRD), and X-ray photoelectron spectroscopy (XPS). Cr(VI) removal from aqueous solution by MSB-nZVI was greatly affected by pH and initial concentration. The removal efficiency of Cr(VI) decreased with increasing pH, and the removal kinetics followed the pseudo-second-order model. XRD patterns of MSB-nZVI before and after reaction showed that reduction and precipitation/co-precipitation (FeCr₂O₄, Fe₃O₄, Fe₂O₃) occurred with the conversion of Cr(VI) to Cr(III) and Fe(0) to Fe(II)/Fe(III). The produced precipitation/co-precipitation could be deposited on the MSB surface rather than being only coated on the surface of nZVI particles, which can alleviate passivation of nZVI. For remediation of Cr(VI)-contaminated saline–alkali soil (pH 8.6–9.0, Cr 341 mg/kg), the released amount of Cr(VI) was 70.7 mg/kg, while it sharply decreased to 0.6–1.7 mg/kg at pH 4.0–8.0, indicating that the saline–alkali environment inhibited the remediation efficiency. These results show that MSB-nZVI can be used as an effective material for Cr(VI) removal from aqueous solution and contaminated soil.

The removal efficiency and mechanism of Cr(VI) removal from aqueous solution on semi-decomposed maize straw biochars pyrolyzed at 300 to 600 °C were investigated. The removal of Cr(VI) by the biochars decreased with pyrolysis temperature increasing from 300 to 600 °C, and the maximum removal capacity of Cr(VI) for maize straw biochar pyrolyzed at 300 °C was 91 mg/g at pH 2.0. The percentage removal of Cr(VI) rapidly decreased with pH increasing from 2.0 to 8.0, with the maximum (>99.9%) at pH 2.0. The variation of Cr(VI) and Cr(III) concentrations in the solution after reaction showed that Cr(VI) concentration decreased while Cr(III) increased and the equilibrium was reached after 48 h, while the redox potential after reaction decreased due to Cr(VI) reduction. X-ray photoelectron spectroscopy (XPS) semi-quantitative analysis showed that Cr(III) accounted for 75.7% of the total Cr bound to maize straw biochar, which indicated reductive adsorption was responsible for Cr(VI) removal by the biochars. Cr(VI) was firstly adsorbed onto the positively charged biochar surface and reduced to Cr(III) by electrons provided by oxygen-containing functional groups (e.g., C=O), and subsequently part of the converted Cr(III) remained on the biochar surface and the rest released into solution. Fourier transform infrared (FTIR) data indicated the participation of C=O, Si–O, –CH₂ and –CH₃ groups in Cr(VI) removal by the biochars. This study showed that maize straw biochar pyrolyzed at 300 °C for 2 h was one low-cost and efficient adsorbent for Cr(VI) removal from aqueous solution.

The influence of pyrolysis temperature on cadmium (Cd) removal capacity and mechanisms by maize straw biochars (MSB) and Platanus leaves biochars (PLB) pyrolyzed at 300, 400, 500 and 600 °C was investigated. The results showed that the biochars pyrolyzed at 500 °C had the highest adsorption capacity for Cd, and the maximum adsorption at pH 5.0 was 35.46 mg/g and 25.45 mg/g for MSB and PLB, respectively. The increase in adsorption efficiency with increasing temperature indicated that the adsorption of Cd onto the biochars was endothermic. Based on the balance analysis between cations (Ca²⁺ and Mg²⁺) released and Cd adsorbed onto biochar in combination with SEM-EDX, FTIR, and XRD analysis, it was concluded that cation exchange, complexation with surface functional groups, precipitation with minerals (CdCO₃), and coordination with π electrons were the dominant mechanisms responsible for Cd adsorption by MSB. With the pyrolysis temperature increasing from 300 to 600 °C, the contribution of cation exchange (Ca²⁺ and Mg²⁺) on Cd removal by MSB decreased from 37.4% to 11.7%, while the contribution of precipitation with Otavite (CdCO₃) and Cd²⁺-π electrons interaction increased. For PLB, the insoluble Cd minerals were not detected by XRD, and the contribution of cation exchange had no significant difference for PLB pyrolyzed at 300, 400, 500 and 600 °C.

The adsorption properties of synthetic zeolite from coal bottom ash (CBA) were investigated for Cd and Ni removal from simulated acidic wastewater. The results showed that alkaline fusion synthetic zeolite significantly increased the specific surface area, pore volume, and cation exchange capacity (CEC) compared with CBA. The effects of various experimental parameters such as coexisting ion competition, pH, contact time, and temperature on the adsorption capacity and adsorption mechanism were investigated. Compared with single-metal ion adsorption, the adsorption capacity for Cd or Ni decreased in multiple-metal ions adsorption due to the competition effect of coexisting ion. Adsorption efficiency increased with increasing pH and the equilibrium was achieved at around 5.5 (>pH_pzc 4.5). The adsorption equilibrium was achieved within 4 h and followed the pseudo-second-order kinetic model. The result concluded that ion exchange was the primary adsorption mechanism. Moreover, zeolite exhibited strong neutralizing capacity, which could be attractive for acidic wastewater treatment.