CaAl-Layered Double Hydroxides-Modified Biochar Composites Mitigate the Toxic Effects of Cu and Pb in Soil on Pea Seedlings.

Compound contamination of soil with heavy metals copper (Cu) and lead (Pb) triggered by mining development has become a serious problem. To solve this problem, in this paper, corncob kernel, which is widely available and inexpensive, was used as the raw material of biochar and modified by loading CaAl-layered double hydroxides to synthesize biochar-loaded CaAl-layered double hydroxide composites (CaAl-LDH/BC). After soil remediation experiments, either BC or CaAl-LDH/BC can increase soil pH, and the available phosphorus content and available potassium content in soil. Compared with BC, CaAl-LDH/BC significantly reduced the available content of Cu and Pb in the active state (diethylenetriaminepentaacetic acid extractable state) in the soil, and the passivation rate of Cu and Pb by a 2% dosage of CaAl-LDH/BC reached 47.85% and 37.9%, respectively. CaAl-LDH/BC can significantly enhance the relative abundance of beneficial microorganisms such as Actinobacteriota, Gemmatimonadota, and Luteimonas in the soil, which can help to enhance the tolerance and reduce the enrichment ability of plants to heavy metals. In addition, it was demonstrated by pea seedling (Pisum sativum L.) growing experiments that CaAl-LDH/BC increased plant fresh weight, root length, plant height, catalase (CAT) activity, and protein content, which promoted the growth of the plant. Compared with BC, CaAl-LDH/BC significantly reduced the Cu and Pb contents in pea seedlings, in which the Cu and Pb contents in pea seedlings were reduced from 31.97 mg/kg and 74.40 mg/kg to 2.92 mg/kg and 6.67 mg/kg, respectively, after a 2% dosage of CaAl-LDH/BC, which was a reduction of 90.84% and 91.03%, respectively. In conclusion, compared with BC, CaAl-LDH/BC improved soil fertility and thus the plant growth environment, and also more effectively reduced the mobility of heavy metals Cu and Pb in the soil to reduce the enrichment of Cu and Pb by plants.

[Mn/Al-layered Double Oxide-loaded Biochar Reduced the Toxic Effects of Heavy Metals on Ryegrass in Soil].

The combined pollution of heavy metal Cu and Cd in soil induced by the e-waste dismantling process has become a severe problem. To deal with this issue, crab shell biochar (BC) and Mn/Al-layered double oxide-loaded crab shell biochar (LDO/BC) were prepared using coprecipitation and co-pyrolysis of discarded crab shells and manganese aluminum salt. The experimental results showed that not only were the soil pH, available phosphorus, available potassium, and soil enzymatic activity enhanced, but the contents of DTPA-Cu and DTPA-Cd in the soil were also reduced after remediation by BC and LDO/BC. Microbial community analysis indicated that BC-1% could promote the relative abundance of Gemmatimonadota and Acidobacteriota; meanwhile, LDO/BC-1% could promote the relative abundance of Proteobacteria, which could reduce the accumulation of Cd in plants. Ryegrass was planted for further investigating the toxic effect of heavy metals in soil after remediation. The results demonstrated that after remediating with BC-5% and LDO/BC-1%, ryegrass grew more vigorously and with a lower content of the heavy metals Cu and Cd in the plants than that of CK, and the germination rate increased by 29% and 60%, respectively. Further, LDO/BC-1% had a more excellent remediation performance than that of the other groups, and the Mn in LDO/BC could reduce the content of heavy metal Cd adsorbed by ryegrass in soil.

Remediation of Cu and As contaminated water and soil utilizing biochar supported layered double hydroxide: Mechanisms and soil environment altering.

Preparing materials for simultaneous remediation of anionic and cationic heavy metals contamination has always been the focus of research. Herein a biochar supported FeMnMg layered double hydroxide (LDH) composites (LB) for simultaneous remediation of copper and arsenic contamination in water and soil has been assembled by a facile co-precipitation approach. Both adsorption isotherm and kinetics studies of heavy metals removal by LB were applied to look into the adsorption performance of adsorbents in water. Moreover, the adsorption mechanisms of Cu and As by LB were investigated, showing that Cu in aqueous solution was removed by the isomorphic substitution, precipitation and electrostatic adsorption while As was removed by complexation. In addition, the availability of Cu and As in the soil incubation experiments was reduced by 35.54%-63.00% and 8.39%-29.04%, respectively by using LB. Meanwhile, the addition of LB increased the activities of urease and sucrase by 93.78%-374.35% and 84.35%-520.04%, respectively, of which 1% of the dosage was the best. A phenomenon was found that the richness and structure of microbial community became vigorous within 1% dosage of LB, which indirectly enhanced the passivation and stabilization of heavy metals. These results indicated that the soil environment was significantly improved by LB. This research demonstrates that LB would be an imaginably forceful material for the remediation of anionic and cationic heavy metals in contaminated water and soil.

Regulating the exposed crystal facets of α-Fe2O3 to promote Fe2O3-modified biochar performance in heavy metals adsorption.

α-Fe2O3 modified biochar (Fe2O3/BC) was prepared to remove Cu(II), Pb(II) and As(V). By adjusting the calcination temperature, the morphology and exposed crystal facets of α-Fe2O3 on the biochar were changed which further affected the adsorption performance. The kinetics and isotherms were investigated systematically to reveal adsorption effect of the adsorbent on Cu(II), Pb(II) and As(V). The results indicated that chemisorption process was the dominant adsorption mechanism. Fe2O3/BC-350 exhibited superior adsorption capacity for Cu(II) (258.22 mg/g) and Pb(II) (390.60 mg/g), and Fe2O3/BC-250 showed relatively good adsorption capacity for As(V) (5.78 mg/g). By adsorption mechanism analysis, electrostatic adsorption, ion exchange, precipitation and complexation were coexisted in the process of removing metal ions by Fe2O3/BC. The repeatability test and the effect of ion strength exhibited the strong stability of Fe2O3/BC. Meanwhile, density functional theory (DFT) calculations manifested that the (202) facet of α-Fe2O3 on Fe2O3/BC-350 possessed the lowest adsorption energies of Cu(II) and Pb(II). While for As(V), it was the (104) facet of α-Fe2O3 on Fe2O3/BC-250 that exhibited the lowest adsorption energy. DFT results revealed that different Fe2O3/BC had different adsorption affinities to various heavy metals. In general, this work not only prepared a promising adsorbent via a simple procedure, but also served as a reference for researchers in designing absorbents with specific active facet for efficient heavy metals remediation.

Mobilization or immobilization? The effect of HDTMA-modified biochar on As mobility and bioavailability in soil.

Biochar plays an essential role in soil remediation, but its effect on the arsenic remediation has been controversial. In this study, hexadecyl trimethyl ammonium bromide (HDTMA-Br) modified or unmodified biochar on As mobility and bioavailability in soil were studied. The sequential extraction experiment showed that As in the original soil mainly existed in the occluded form (78.24%), followed by Fe‒As (20.72%) and Al‒As (0.88%) forms. With the addition of the modified and unmodified biochars, the contents of Ca‒As and Fe‒As increased by 0.36 - 0.95% and 2.06 - 3.36%, respectively, suggesting the increased potential toxicity of As. The NaH2PO4 extraction result showed that the unmodified biochar increased the As availability by 3.23 - 22.76%, whereas the HDTMA-modified biochar reduced the As availability by 4.80 - 13.41%. Pot experiment showed that the unmodified and modified biochar increased the biomass of Brassica pekinensis, and the modified biochar (HB5) decreased the uptake of As by plants by 80.77% compared to the unmodified biochar. In particular, the plant achieved better growth in the modified biochar treatment (average height 8.31 cm) than in the unmodified biochar treatment (average height 6.97 cm). Therefore, both biochars facilitated phase transformation of As from the stable to the mobile states in the soil. Nevertheless, the HDTMA-modified biochar had an effect on alleviating As bioavailability and toxicity.

Simultaneous immobilization of As and Cd in a mining site soil using HDTMA-modified zeolite.

Arsenic (As) and cadmium (Cd) co-contamination has been a typical problem in Chinese agricultural land adjacent to historical metal mining and smelting activities. Remediation of As and Cd in soil has encountered many difficulties owing to the distinct nature of the two metal(loid)s. In this study, we developed a remediation scheme by adding a hexadecyltrimethylammonium (HDTMA)-modified zeolite to a mining site soil and evaluated the immobilization effect. The result of the increased surface zeta potential indicates that the HDTMA modification conferred the zeolite with adsorbability towards As through the cationic surfactant head. The addition of the highest dosage of HDTMA-modified zeolite (10%) to the contaminated soil greatly improved soil organic matter by 1.4 times, partly due to the elevated C loading on the zeolite from HDTMA. Sequential extraction results show that the addition of HDTMA-modified zeolite not only increased the residual fraction of As (by 2.7-5.9%) but also reduced the toxicity-related fraction (by 2.3-2.7%) when compared to the unmodified zeolite and blank treatments. The oxidizable fractions of Cd in the modified zeolite treatment were significantly higher than that in the blank soil. Besides, the exchangeable fractions of Cd were all significantly reduced in the zeolite treatments. Enzyme activity assays show that the HDTMA-modified zeolite treatment could greatly improve soil microbial environment. The physiologically based extraction test (PBET) also proved that the bioavailability of As and Cd was reduced after the modified zeolite treatment.