Mahtab Ahmad

Biochar as a sorbent for contaminant management in soil and water: A review

Biochar is a stable carbon-rich by-product synthesized through pyrolysis/carbonization of plant- and animal-based biomass. An increasing interest in the beneficial application of biochar has opened up multidisciplinary areas for science and engineering. The potential biochar applications include carbon sequestration, soil fertility improvement, pollution remediation, and agricultural by-product/waste recycling. The key parameters controlling its properties include pyrolysis temperature, residence time, heat transfer rate, and feedstock type. The efficacy of biochar in contaminant management depends on its surface area, pore size distribution and ion-exchange capacity. Physical architecture and molecular composition of biochar could be critical for practical application to soil and water. Relatively high pyrolysis temperatures generally produce biochars that are effective in the sorption of organic contaminants by increasing surface area, microporosity, and hydrophobicity; whereas the biochars obtained at low temperatures are more suitable for removing inorganic/polar organic contaminants by oxygen-containing functional groups, electrostatic attraction, and precipitation. However, due to complexity of soil-water system in nature, the effectiveness of biochars on remediation of various organic/inorganic contaminants is still uncertain. In this review, a succinct overview of current biochar use as a sorbent for contaminant management in soil and water is summarized and discussed.

Effects of pyrolysis temperature on soybean stover- and peanut shell-derived biochar properties and TCE adsorption in water

Conversion of crop residues into biochars (BCs) via pyrolysis is beneficial to environment compared to their direct combustion in agricultural field. Biochars developed from soybean stover at 300 and 700 °C (S-BC300 and S-BC700, respectively) and peanut shells at 300 and 700 °C (P-BC300 and P-BC700, respectively) were used for the removal of trichloroethylene (TCE) from water. Batch adsorption experiments showed that the TCE adsorption was strongly dependent on the BCs properties. Linear relationships were obtained between sorption parameters (K(M) and S(M)) and molar elemental ratios as well as surface area of the BCs. The high adsorption capacity of BCs produced at 700 °C was attributed to their high aromaticity and low polarity. The efficacy of S-BC700 and P-BC700 for removing TCE from water was comparable to that of activated carbon (AC). Pyrolysis temperature influencing the BC properties was a critical factor to assess the removal efficiency of TCE from water.

Trichloroethylene adsorption by pine needle biochars produced at various pyrolysis temperatures.

In this study, pine needles were converted to biochar (BC) at different pyrolysis temperatures of 300, 500, and 700 °C to sorb trichloroethylene (TCE), and the changes in BC properties with each temperature were evaluated. Pyrolysis temperature showed a pronounced effect on BC properties. Decreases in molar H/C and O/C ratios resulted from removing O- and H-containing functional groups with increasing temperature, and produced high aromaticity and low polarity BCs. BCs produced at higher temperature showed greater TCE removal efficiency from water due to their high surface area, micro-porosity, and carbonized extent. The performance of various BCs for TCE removal was assessed by the Freundlich, Langmuir, Temkin, and Dubinin-Radushkevich adsorption models, among which the Temkin and Dubinin-Radushkevich models best described TCE adsorption onto various BCs, indicating prevailing sorption mechanism as pore-filling.

Effects of soil dilution and amendments (mussel shell, cow bone, and biochar) on Pb availability and phytotoxicity in military shooting range soil.

Bioavailability and bioaccessibility determine the level of metal toxicity in the soils. Inorganic soil amendments may decrease metal bioavailability and enhance soil quality. This study used mussel shell, cow bone, and biochar to reduce lead (Pb) toxicity in the highly contaminated military shooting range soil in Korea. Water-soluble and 1-M ammonium nitrate extractions, and a modified physiologically based extraction test (PBET) were performed to determine Pb bioavailability and bioaccessibility in the soil, respectively. Active C in the soil was also measured to evaluate the effects of the amendments on biological soil quality. The Pb contaminated soil was diluted in serial with uncontaminated soil for the bioassays. Seed germination and root elongation tests using lettuce (Lactuca sativa) showed increases in germination percentage and root length in soil treated with the amendments. Biochar was most effective and increased seed germination by 360% and root length by 189% compared to the unamended soil. Up to 20% soil dilution resulted in more than 50% seed germination. Bioavailability and bioaccessibility of Pb in the soils were decreased by 92.5% and 48.5% with mussel shell, by 84.8% and 34.5% with cow bone, and by 75.8% and 12.5% with biochar, respectively, compared to the unamended soil. We found that the Pb availability in the military shooting range soil can be reduced effectively by the tested amendments or soil dilution alternately, thereby decreasing the risk of ecotoxicity. Furthermore, the increasing active C from the amendments revitalized the soil contaminated with Pb.

Speciation and phytoavailability of lead and antimony in a small arms range soil amended with mussel shell, cow bone and biochar: EXAFS spectroscopy and chemical extractions.

Mussel shell (MS), cow bone (CB) and biochar (BC) were selected to immobilize metals in an army firing range soil. Amendments were applied at 5% (wt) and their efficacies were determined after 175 d. For metal phytoavailability test, maize (Zea mays L.) plants were cultivated for 3weeks. Results showed that all amendments decreased the exchangeable Pb by up to 99% in planted/unplanted soils. Contrarily, exchangeable Sb were increased in the MS- and CB-amended soils. The rise in soil pH (~1 unit) by the amendments affected Pb and Sb mobility in soils. Bioavailability of Pb to maize was reduced by up to 71% in the amended soils. The Sb uptake to maize was decreased by up to 53.44% in the BC-amended soil. Sequential chemical extractions showed the transformation of easily available Pb to stable residual form with the amendment treatments. Scanning electron microscopic elemental dot mapping revealed the Pb association with Al and Si in the MS-amended soil and that with P in the CB- and BC-amended soils. Additionally, the extended X-ray absorption fine structure spectroscopic analysis indicated the transformation of organic bound Pb in unamended control soil to relatively more stable Pb-hydroxide (Ksp=10(-17.1)), chloropyromorphite (Ksp=10(-84.4)) and Pb-phosphate (Ksp=10(-23.8)) in soils amended with MS, CB and BC, respectively. Application of BC was the best in decreasing the phytoavailability of Pb and Sb in the studied army firing range soil.

Immobilization of lead in a Korean military shooting range soil using eggshell waste: an integrated mechanistic approach.

This study evaluated the effectiveness of eggshell and calcined eggshell on lead (Pb) immobilization in a shooting range soil. Destructive and non-destructive analytical techniques were employed to determine the mechanism of Pb immobilization. The 5% additions of eggshell and calcined eggshell significantly decreased the TCLP-Pb concentration by 68.8% due mainly to increasing soil pH. Eggshell and calcined-eggshell amendments decreased the exchangeable Pb fraction to ≈ 1% of the total Pb in the soil, while the carbonate-associated Pb fraction was increased to 40.0-47.1% at >15% application rates. The thermodynamic modeling on Pb speciation in the soil solution predicted the precipitation of Pb-hydroxide [Pb(OH)(2)] in soils amended with eggshell and calcined eggshell. The SEM-EDS, XAFS and elemental dot mapping revealed that Pb in soil amended with calcined eggshell was associated with Si and Ca, and may be immobilized by entrapping into calcium-silicate-hydrate. Comparatively, in the soil amended with eggshell, Pb was immobilized via formation of Pb-hydroxide or lanarkite [Pb(2)O(SO(4))]. Applications of amendments increased activities of alkaline phosphatase up to 3.7 times greater than in the control soil. The use of eggshell amendments may have potential as an integrated remediation strategy that enables Pb immobilization and soil biological restoration in shooting range soils.

Pyrolysis condition affected sulfamethazine sorption by tea waste biochars

Sulfamethazine (SMT) as a veterinary drug has been detected frequently in the environment. In this study, six biochars produced from tea waste (TW) at 300 and 700 °C with or without N2 and steam activation were characterized and evaluated for SMT sorption in water. The sorption of SMT was interpreted as a function of biochar production condition, SMT concentration, pH and physicochemical characteristics of biochar. Distribution coefficient data showed high sorption of SMT at low pH (∼3) and the highest sorption density of 33.81 mg g(-1) was achieved by the steam activated biochar produced at 700 °C. The steam activation process increased the adsorption capacity by increasing the surface area of the biochar. The π-π electron donor-acceptor interaction, cation-π interaction and cation exchange at low pH were the primary mechanisms governing SMT retention by biochars. Overall, steam activated tea waste biochar could be a promising remedy of SMT removal from water.

Enhanced sulfamethazine removal by steam-activated invasive plant-derived biochar.

Recent investigations have shown frequent detection of pharmaceuticals in soils and waters posing potential risks to human and ecological health. Here, we report the enhanced removal of sulfamethazine (SMT) from water by physically activated biochar. Specifically, we investigated the effects of steam-activated biochars synthesized from an invasive plant (Sicyos angulatus L.) on the sorption of SMT in water. The properties and sorption capacities of steam-activated biochars were compared with those of conventional non-activated slow pyrolyzed biochars. Sorption exhibited pronounced pH dependence, which was consistent with SMT speciation and biochar charge properties. A linear relationship was observed between sorption parameters and biochar properties such as molar elemental ratios, surface area, and pore volumes. The isotherms data were well described by the Freundlich and Temkin models suggesting favorable chemisorption processes and electrostatic interactions between SMT and biochar. The steam-activated biochar produced at 700 °C showed the highest sorption capacity (37.7 mg g(-1)) at pH 3, with a 55% increase in sorption capacity compared to that of non-activated biochar produced at the same temperature. Therefore, steam activation could potentially enhance the sorption capacities of biochars compared to conventional pyrolysis.

An assessment of the utilization of waste resources for the immobilization of Pb and Cu in the soil from a Korean military shooting range

Military shooting range soils contaminated by heavy metals have been subjected to remediation efforts to alleviate the detrimental effects of exposure on humans and the surrounding environment. Waste materials can be used as cost-effective soil amendments to immobilize heavy metals in contaminated soils. In this study, naturally occurring lime-based waste materials including egg shells, oyster shells, and mussel shells were assessed for their effectiveness toward heavy metal immobilization in military shooting range soil in Korea. Soil was treated in batch leaching experiments with 0, 2.5, 5, 10, and 15% of each lime-based waste material. The results showed that the lime-based waste materials effectively reduced water-soluble Pb at an application rate of 2.5% by weight of the soil. Increase in soil pH from 6.6 to 8.0 was considered to be the main chemistry of Pb immobilization, which was supported by the formation of insoluble Pb species at high pH values as confirmed by the visual MINTEQ thermodynamic model. In contrary, water-soluble Cu was increased in the lime-based waste material-treated soils when compared to the untreated soil. This was likely attributed to the formation of soluble Cu–DOC (dissolved organic carbon) complexes as all lime-based waste materials applied increased DOC contents in the soil. Therefore, care must be taken in selecting the appropriate amendment for immobilizing metals in shooting range soils.

Toxicity of synthetic chelators and metal availability in poultry manure amended Cd, Pb and As contaminated agricultural soil.

Chelating agents added to contaminated soils may increase solubility and phytoextraction efficiency of soil metals. However, they can create negative effects on soil biological quality. A 90-day incubation experiment was conducted to evaluate mixed effects of chelating agents and poultry manure on changes in available Cd, Pb and As, CO2-C efflux, microbial biomass C, dissolved organic C (DOC), and N mineralization in metal-polluted agricultural soil. Application of poultry manure resulted in a considerable increase in soil pH, DOC, CO2-C efflux, net N mineralization, net N nitrification, and microbial biomass C compared to those in unmanured soil. Availability of arsenic increased twice in manure amended soil due to changes in pH and DOC. However, adding poultry manure did not affect the concentrations of available Pb and Cd compared to those in control soil. Chelating agents increased CO2-C efflux, DOC, and metal availability but decreased microbial biomass C and net N mineralization. Maximum decrease in microbial biomass C, net N mineralization, and net N nitrification, was observed in EDTA applied soil possibly due to high metal availability to soil microorganisms. Overall results revealed that the application of synthetic chelators in combination with poultry manure enhances available As and demonstrates better environment for soil biota.