Anushka Upamali Rajapaksha

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.

Engineered/designer biochar for contaminant removal/immobilization from soil and water: Potential and implication of biochar modification

The use of biochar has been suggested as a means of remediating contaminated soil and water. The practical applications of conventional biochar for contaminant immobilization and removal however need further improvements. Hence, recent attention has focused on modification of biochar with novel structures and surface properties in order to improve its remediation efficacy and environmental benefits. Engineered/designer biochars are commonly used terms to indicate application-oriented, outcome-based biochar modification or synthesis. In recent years, biochar modifications involving various methods such as, acid treatment, base treatment, amination, surfactant modification, impregnation of mineral sorbents, steam activation and magnetic modification have been widely studied. This review summarizes and evaluates biochar modification methods, corresponding mechanisms, and their benefits for contaminant management in soil and water. Applicability and performance of modification methods depend on the type of contaminants (i.e., inorganic/organic, anionic/cationic, hydrophilic/hydrophobic, polar/non-polar), environmental conditions, remediation goals, and land use purpose. In general, modification to produce engineered/designer biochar is likely to enhance the sorption capacity of biochar and its potential applications for environmental remediation.

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.

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.

Surface complexation modeling and spectroscopic evidence of antimony adsorption on iron-oxide-rich red earth soils.

Few studies have investigated surface complexation of antimony (Sb) on natural sorbents. In addition, intrinsic acidic constants, speciation, and spectroscopic data are scarce for Sb sorption in soil. Only simple sorption models have been proposed to describe the sorption of Sb(V) on specific mineral surfaces. This study therefore assessed the mechanisms of Sb(III) and Sb(V) adsorption on natural red earth (NRE), a naturally occurring iron coated sand, at various pHs and Sb loadings. The Sb(V) adsorption followed typical anion adsorption curve with adsorption reaching maximum around pH 4-5, while no pH dependence was observed for Sb(III) sorption. The FT-IR spectra revealed that shifts in absorbance of the hydroxyl groups in iron-oxide were related to the Fe-O-Sb bonds and provided evidence for inner sphere bond formation. Direct evidence on the strong interaction of Sb(III) and Sb(V) with ≡Fe-O and ≡Al-O was observed from the decrease in Fe-2p, Al-2p, and Si-2p peaks of the X-ray photoelectron spectroscopy (XPS) data before and after Sb(V) and Sb(III) adsorption on NRE. Successful data modeling using the 2-pK diffuse double layer model (DDLM) with the FITEQL revealed that sorption occurs through the formation of bidentate mononuclear and binuclear complexes. Model simulations showed a high affinity to the ≡FeOH sites at high Sb loadings, whereas at low loadings, both≡ FeOH and ≡AlOH sites showed similar affinities to Sb. In the case of Sb(V), multilayer formation was also revealed in addition to surface complexation by the isotherm data fitted with the Freundlich model and two sites Langmuir equations, which indicated heterogeneous multilayer adsorption of Sb(V) on NRE.

Invasive plant-derived biochar inhibits sulfamethazine uptake by lettuce in soil.

Veterinary antibiotics are frequently detected in soils posing potential contamination of food crops. Sulfamethazine (SMT) uptake was investigated by lettuce (Lactuca sativa L.) grown in the soils treated with/without biochar derived from an invasive plant, burcucumber (Sicyos angulatus L.) (BBC700). Soils were contaminated with SMT at 5 and 50mgkg(-1), and treated with/without 5% BBC700 (ww(-1)). The lettuces were harvested after 5weeks of cultivation and were analyzed for SMT by a high performance liquid chromatography-tandem mass spectrometry after solid-phase extraction. With 5% BBC700, the uptake of SMT was reduced by 86% in the soil spiked with 5mgkg(-1) SMT compared to the control whereas a 63% reduction was observed in the soil spiked with 50mgkg(-1) SMT. Application of BBC700, into soils effectively reduced the SMT uptake by lettuce.

Cr(VI) Formation related to Cr(III)-muscovite and birnessite interactions in ultramafic environments.

Chromium is abundantly and primarily present as Cr(III) in ultramafic rocks and serpentine soils. Chromium(III) oxidation involving chromite (FeCr2O4) via interactions with birnessite has been shown to be a major pathway of Cr(VI) production in serpentine soils. Alternatively, Cr(III)-bearing silicates with less Cr(III) may provide higher Cr(VI) production rates compared to relatively insoluble chromite. Of the potential Cr(III)-bearing silicates, Cr(III)-muscovite (i.e., fuchsite) commonly occurs in metamorphosed ultramafic rocks and dissolution rates may be comparable to other common Cr(III)-bearing phyllosilicates and clays. Here, we examine the formation of Cr(VI) related to Cr(III)-muscovite and birnessite (i.e., acid birnessite) interactions with and without humic matter (HM) via batch experiments. Experimentally, the fastest rate of Cr(VI) production involving Cr(III)-muscovite was 3.8 × 10(-1) μM h(-1) (pH 3 without HM). Kinetically, Cr(III)-muscovite provides a major pathway for Cr(VI) formation and Cr(VI) production rates may exceed those involving chromite depending on pH, available mineral surface areas in solution, and the abundance of Cr(III) present. However, when HM is introduced to the system, Cr(VI) production rates decrease by as much as 80%. This highlights that HM strongly decreases but may not completely suppress the formation and mobilization of Cr(VI). A Sri Lankan serpentine soil was utilized to provide context with regards to the experimental results. Despite Cr(VI) in the soil solids and Cr(VI) formation being favorable from Cr(III)-bearing minerals, no detectable Cr(VI) was released into soil solutions potentially due to the abundance of HM. Overall, the dynamic interactions of Cr(III)-bearing silicates and birnessite provide a kinetically favorable route of Cr(VI) formation which is tempered by humic matter.

Mechanisms of antimony adsorption onto soybean stover-derived biochar in aqueous solutions

Limited mechanistic knowledge is available on the interaction of biochar with trace elements (Sb and As) that exist predominantly as oxoanions. Soybean stover biochars were produced at 300 °C (SBC300) and 700 °C (SBC700), and characterized by BET, Boehm titration, FT-IR, NMR and Raman spectroscopy. Bound protons were quantified by potentiometric titration, and two acidic sites were used to model biochar by the surface complexation modeling based on Boehm titration and NMR observations. The zero point of charge was observed at pH 7.20 and 7.75 for SBC300 and SBC700, respectively. Neither antimonate (Sb(V)) nor antimonite (Sb(III)) showed ionic strength dependency (0.1, 0.01 and 0.001 M NaNO3), indicating inner sphere complexation. Greater adsorption of Sb(III) and Sb(V) was observed for SBC300 having higher -OH content than SBC700. Sb(III) removal (85%) was greater than Sb(V) removal (68%). Maximum adsorption density for Sb(III) was calculated as 1.88 × 10(-6) mol m(-2). The Triple Layer Model (TLM) successfully described surface complexation of Sb onto soybean stover-derived biochar at pH 4-9, and suggested the formation of monodentate mononuclear and binuclear complexes. Spectroscopic investigations by Raman, FT-IR and XPS further confirmed strong chemisorptive binding of Sb to biochar surfaces.

Natural and synthesised iron-rich amendments for As and Pb immobilisation in agricultural soil

The immobilisation of heavy metals in contaminated soils is a promising alternative to conventional remediation techniques. Very few studies have focused on the use of iron-rich nanomaterials and natural materials for the adsorption of toxic metals in soils. Synthesised iron-rich nanomaterials (Fe and Zr–Fe oxides) and natural iron-rich materials (natural red earth; NRE) were used to immobilise As and Pb in contaminated agricultural soil. Total concentrations of As and Pb in the initial soil (as control) were 170.76 and 1945.11 mg kg−1, respectively. Amendments were applied into the soil at 1, 2.5 and 5% (w/w) in triplicate and incubated for 150 days. Except for the NRE-amended soil, soil pH decreased from 5.6 to 4.9 with increasing application rates of Fe and Zr–Fe oxides. With addition of Fe and Zr–Fe oxides at 5%, the ammonium acetate (NHO4Ac)-extractable Pb was greatly decreased by 83 and 65% compared with NRE addition (43%). All subjected amendments also led to a decrease in NHO4Ac-extractable As in the soils, indicating the high capacity of As immobilisation. Soil amended with NRE showed a lower ratio of cy19:0 to 18:1ω7c, indicating decreased microbial stress. The toxicity characteristic leaching procedure produced results similar to the NHO4Ac extraction for As and Pb. The NRE addition is recommended for immobilising heavy metals and maintaining biological soil properties.