Uncovering nano-bonechar for attenuating fluoride in naturally contaminated soil.

Fluoride ion (F-) is one of the major geogenic contaminants in water and soil. Excessive consumption of these geogenic contaminants poses serious health impacts on humans and plants. In this study, a novel carbonaceous material, nano-bonechar, was synthesized from cow bones and applied as a soil amendment at rates of 0, 0.5, 1, and 2% to remediate and revitalize naturally F--contaminated soil. The results revealed that the nano-bonechar significantly reduced the mobility and bioavailability of F- by 90% in the contaminated soil, and improved the soil quality by increasing the soil water holding capacity, soil organic matter, and the bioavailable contents of PO43-, Ca2+, and Na+. Subsequently, the pot experiment results showed a significant reduction in the uptake of F- by 93% in Zea mays plants. Moreover, the nano-bonechar application improved the plant's growth, as indicated by the higher fresh and dry weights, root and shoot lengths, and total content of PO43-, Ca2+, and K+ than those of un-amended soil. The F-immobilization in soil was mainly due to the presence of the hydroxyapatite [Ca10(PO4)6(OH)2] mineral in the nano-bonechar. Ion exchange between OH- (of nano-bonechar) and F- (of soil), and the formation of insoluble fluorite (CaF2) contributed to the attenuation of F- mobility in the soil. It is concluded that nano-bonechar, due to its size and enrichment in hydroxyapatite, could successfully be utilized for the rapid remediation and revitalization of F--contaminated agricultural soil.

Adsorption and immobilization performance of pine-cone pristine and engineered biochars for antimony in aqueous solution and military shooting range soil: An integrated novel approach.

Antimony (Sb-V), a carcinogenic metalloid, is becoming prevalent in water and soil due to anthropogenic activities. Biochar could be an effective remedy for Sb(V)-contaminated water and soil. In this study, we used pristine and engineered pinecone-derived biochar as an innovative approach for treating Sb(V)-contaminated water and shooting range soil. Biochar was produced from pine-cone waste (pristine biochar) and enriched with Fe and Al salts via saturation (engineered biochar). Adsorption tests in water revealed that iron-modified biochar showed higher adsorption capacity (8.68 mg g-1) than that of the pristine biochar (2.49 mg g-1) and aluminum-modified biochar (3.40 mg g-1). Isotherm and kinetic modeling of the adsorption data suggested that the adsorption process varied from monolayer to multilayer, with chemisorption as the dominant interaction mechanism between Sb(V) and the biochars. The post-adsorption study of iron-modified biochar by Fourier Transform Infrared (FTIR) and X-ray diffraction (XRD) further supported the chemical bonding and outer-sphere complexation of Sb(V) with Fe, N-H, O-H, C-O and CC components. The pristine and iron-modified biochars also successfully immobilized Sb(V) in a shooting range soil, more so in the latter. Subsequent sequential extractions and post-analysis by scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), and elemental dot mapping revealed that Sb in the treated soil transformed to a more stable form. It was concluded that iron-modified biochar could act as an efficient material for the adsorption and immobilization of Sb(V) in water and soil, respectively.

Soil acidification and the liming potential of biochar.

Soil acidification in managed ecosystems such as agricultural lands principally results from the increased releasing of protons (H+) from the transformation reactions of carbon (C), nitrogen (N) and sulphur (S) containing compounds. The incorporation of liming materials can neutralize the protons released, hence reducing soil acidity and its adverse impacts to the soil environment, food security, and human health. Biochar derived from organic residues is becoming a source of carbon input to soil and provides multifunctional values. Biochar can be alkaline in nature, with the level of alkalinity dependent upon the feedstock and processing conditions. This review covers the fundamental aspects of soil acidification and of the use of biochar to address constraints related to acidic soil. Biochar is increasingly considered as an effective soil amendment for reducing soil acidity owing to its liming potential, thereby enhancing soil fertility and productivity in acid soils. The ameliorant effect on acid soils is mainly because of the dissolution of carbonates, (hydro)-oxides of the ash fraction of biochar and potential use by microorganisms.

Effectiveness of the engineered pinecone-derived biochar for the removal of fluoride from water.

Drinking fluoride (F-)-contaminated water (>1.5 mg L-1) causes severe dental and skeletal disorders. In the central province of Pakistan, ∼20 times higher levels of F- in the drinking groundwater (compared with the 1.5 mg L-1 permissible limit of the World Health Organization) are triggering bone abnormalities in teenagers. In this study, we demonstrated the potential of pinecone-derived biochar (pristine) impregnated with Fe- and Al-salts (engineered) to defluoridate water. Batch mode adsorption experiments were carried out under variable conditions of solution pH, F- initial concentration, adsorbent dose, and contact time. The engineered biochars resulted in greater adsorption than that of pristine biochar. Specifically, the AlCl3-modified biochar exhibited a maximum adsorption capacity of 14.07 mg g-1 in spiked water and 13.07 mg g-1 in in-situ groundwater. The equilibrium isothermal and kinetic models predicted monolayer, cooperative, and chemisorption types of the adsorption process. The chemical interaction and outer-sphere complexation of F- with Al, Na, and H elements were further confirmed by the post-adsorption analysis of the AlCl3-modified biochar by FTIR and XRD. The AlCl3-modified biochar resulted in 87.13% removal of F- from the in-situ F--contaminated groundwater, even in the presence of naturally occurring competing ions (such as Cl-, HCO3-, SO42-, and NO3-). We conclude that the AlCl3-modified biochar derived from pinecone could be a promising cost-effective adsorbent for the defluoridation of water.