Impact of Pyrolysis Temperature and Feedstock on Surface Charge and Functional Group Chemistry of Biochars.

The capacity of biochars to adsorb ionic contaminants is strongly influenced by biochar surface chemistry. We studied the effects of biomass feedstock type, pyrolysis temperature, reaction media pH, and AlCl pre-pyrolysis feedstock treatments on biochar anion exchange capacity (AEC), cation exchange capacity (CEC), point of zero net charge (PZNC), and point of zero salt effect (PZSE). We used the relationship between PZNC and PZSE to probe biochar surfaces for the presence of unstable (hydrolyzable) surface charge functional groups. The results indicate that biochars produced at ≤500°C have high CECs and low AEC, PZSE, and PZNC values due to the dominance of negative surface charge arising from carboxylate and phenolate functional groups. Biochars produced at ≥700°C have low CEC and high AEC, PZSE, and PZNC values, consistent with a dominance of positive surface charge arising from nonhydrolyzable bridging oxonium (oxygen heterocycles) groups. However, biochars produced at moderate temperatures (500-700°C) have high PZSE and low PZNC values, indicating the presence of nonbridging oxonium groups, which are rapidly degraded under alkaline conditions by OH attack on the oxonium α-C. Biochars treated with AlCl have high AEC, PZSE, and PZNC values due to variably charged aluminol groups on biochar surfaces. The results provide support for the presence of both hydrolyzable and nonhydrolyzable oxonium groups on biochar surfaces. They also demonstrate that biochars produced at high pyrolysis temperatures (>700°C) or those receiving pre-pyrolysis treatments with AlCl are optimized for anionic contaminant adsorption, whereas biochars produced at low pyrolysis temperatures (400°C) are optimized for cationic contaminant adsorption.

Comparison of the Physical and Chemical Properties of Laboratory and Field-Aged Biochars.

The long-term impact of biochar on soil properties and agronomic outcomes is influenced by changes in the physical and chemical properties of biochars that occur with time (aging) in soil environments. Fresh biochars, however, are often used in studies because aged biochars are generally unavailable. Therefore, a need exists to develop a method for rapid aging of biochars in the laboratory. The objectives of this study were to compare the physicochemical properties of fresh, laboratory-aged (LA), and field-aged (FA) (≥3 yr) biochars and to assess the appropriateness of a laboratory aging procedure that combines acidification, oxidation, and incubations as a mimic to field aging in neutral or acidic soil environments. Twenty-two biochars produced by fast and slow pyrolysis, and gasification techniques from five different biomass feedstocks (hardwood, corn stover, soybean stover, macadamia nut shells, and switchgrass) were studied. In general, both laboratory and field aging caused similar increases in ash-free volatile matter (% w/w), cation and anion exchange capacities, specific surface area, and modifications in oxygen-containing surface functional groups of the biochars. However, ash content increased for FA (18-195%) and decreased for LA (22-74%) biochars, and pH decreased to a greater extent for LA (2.8-6.7 units) than for FA (1.6-3.8 units) biochars. The results demonstrate that the proposed laboratory aging procedure is effective for predicting the direction of changes in biochar properties on field aging. However, in the future we recommend using a less aggressive acid treatment.

Biochar amendment affects leaching potential of copper and nutrient release behavior in contaminated sandy soils.

Copper (Cu) contamination to soil and water is a worldwide concern. Biochar has been suggested to remediate degraded soils. In this study, column leaching and chemical characterization were conducted to assess effects of biochar amendment on Cu immobilization and subsequent nutrient release in Cu-contaminated Alfisol and Spodosol. The results indicate that biochar is effective in binding Cu (30 and 41%, respectively, for Alfisol with and without spiked Cu; 36 and 43% for Spodosol) and reducing Cu leaching loss (from ∼47 to 10% for the Cu-spiked Alfisol and from 48 to 9% for the Cu-spiked Spodosol). Copper was likely retained on biochar surfaces through complexation, as suggested by Fourier-transform infrared spectra. Biochar amendment converts a portion of Cu from available pool to more stable forms, thus resulting in decreased activities of free Cu and increased activity of organic Cu complexes in leachate. Reduction of >0.45-µm solids and nanoparticles concentrations in leachate was also observed. In addition, biochar application rate was correlated negatively with P, Ca, Mg, Zn, Mn, and NH-N concentration ( < 0.05) but positively with K and Na concentration ( < 0.05) in leachates. These results documented the potential of biochar as an effective amendment for Cu immobilization and mitigation of leaching risk for some nutrients.

Impact of biochar-based slow-release N-fertilizers on maize growth and nitrogen recovery efficiency.

Biochar has been used to address several environmental problems and may be efficacious as a carrier of N-fertilizer in slow-release N-fertilizer (SRF) formulations. Our objective was to compare the efficacy of SRF pellets formulated with different mass ratios of biochar and urea with traditional N-fertilizers for improving N use efficiency by maize (Zea mays L.) grown under greenhouse conditions. Two different soil types, four SRF formulations with different biochar-to-urea (BCN) ratios (1:2 BCN, 1:3 BCN, 1:4 BCN, and 1:6 BCN), three traditional N-fertilizers (urea, urea ammonium nitrate, and S-coated urea), and unfertilized controls for each soil were tested. The accelerated urea release test showed significantly less loss of urea for the SRF over time than the traditional N-fertilizers. The biochar-based SRF formulations significantly (p < 0.05) decreased nitrate leaching loss for both soils relative to the traditional fertilizers. All the SRF formulations increased maize shoot (1%-34%) and root (0%-23%) biomass, N-recovery efficiency (17%-50%), and soil potential mineralizable-N relative to urea and S-coated urea. The results also indicate that the BCN ratio in the SRF formulation can be used to influence the timing of N release and plant N uptake. The results of the greenhouse study suggest that biochar-based SRFs have potential agronomic and environmental benefits; however, more research is needed to assess their agronomic value under field conditions.

Estimating the organic oxygen content of biochar.

The organic O content of biochar is useful for assessing biochar stability and reactivity. However, accurately determining the organic O content of biochar is difficult. Biochar contains both organic and inorganic forms of O, and some of the organic O is converted to inorganic O (e.g., newly formed carbonates) when samples are ashed. Here, we compare estimates of the O content for biochars produced from pure compounds (little or no ash), acid-washed biomass (little ash), and unwashed biomass (range of ash content). Novelty of this study includes a new method to predict organic O content of biochar using three easily measured biochar parameters- pyrolysis temperature, H/C molar ratio, and %biochar yield, and evidence indicating that the conventional difference method may substantially underestimate the organic O in biochar and adversely impact the accuracy of O:C ratios and van Krevelen plots. We also present evidence that acid washing removed 17% of the structural O from biochars and significantly changes O/C ratios. Environmental modelers are encouraged to use biochar H:C ratios.

Modification of pyrogenic carbons for phosphate sorption through binding of a cationic polymer.

This study reports on the development of modified pyrogenic carbonaceous materials (PCMs) for recovering orthophosphate (PO4-P). The PCMs include softwood and hardwood biochars and a commercial granular activated carbon (GAC) that were modified by irreversible adsorption of the quaternary ammonium polymer, poly(diallyldimethylammonium) chloride (pDADMAC), which reverses electrokinetic charge and increases PO4-P sorption. MgO-doped biochars were prepared by a literature method for comparison. Imaging and spectroscopic analyses characterize pDADMAC coverage, MgO doping, and binding of PO4-P. At environmentally relevant concentrations, PO4-P sorption by the pDADMAC-treated biochars was ~100 times greater than that of the corresponding unmodified biochars, and was comparable to that of the corresponding MgO-doped biochars on a coating content basis. The pDADMAC-coated carbons bind PO4-P by ion exchange, while the MgO-doped biochars bind PO4-P principally by forming an amorphous Mg phosphate species. Susceptibility to competition from other relevant anions (Cl-, NO3-, HCO3-/CO32-, SO42-) and poultry and dairy manure extracts was moderate and comparable for the two types of modified softwood biochars. Sorption to the pDADMAC-treated biochars appears to be more reversible than to the MgO-doped biochars using stepwise water extraction. Greater reversibility may be advantageous for trapping and recycling phosphate.

Quantification and characterization of chemically-and thermally-labile and recalcitrant biochar fractions.

The C:N ratios of biochar labile fractions is important for assessing biochar stability and N cycling in soil. Here we compare chemically and thermally labile fractions for nine biochars produced from five biomass feedstocks using four production techniques. Biochar fractionation methods included proximate analysis, hot water extraction, acid and base extractions (0.05 M, 0.5 M, 1 M, 2 M, 3 M, and 6 M of either H2SO4 or NaOH), and oxidation with 15% H2O2 and 0.33 M KMnO4 (pH 7.2). Results show chemical addition reactions cause underestimation of mass of the labile fraction for chemical extraction and oxidation procedures but not the thermal procedure. Estimates of C and N in labile and recalcitrant fractions were not adversely affected by addition reactions, because solvents were independent of C or N. Results indicate that herbaceous biochars may be a source of N fertility while hardwood biochars may immobilize N during the first few years after biochar application to soils.

Arsenic sorption on zero-valent iron-biochar complexes.

Arsenic (As) is toxic to human and is often found in drinking water in India and Bangladesh, due to the natural abundance of arsenides ores. Different removal procedures such as precipitation, sorption, ion exchange and membrane separation have been employed for removal of As from contaminated drinking water (CDW), however, there is a critical need for low-cost economically viable biochar modification methods which can enhance As sorption. Here we studied the effectiveness of zero-valent iron (ZVI)-biochar complexes produced by high temperature pyrolysis of biomass and magnetite for removing As5+ from CDW. Batch equilibration and column leaching studies show that ZVI-biochar complexes are effective for removing As5+ from CDW for the studied pH range (pH ∼7-7.5) and in the presence of competing ions. XPS As 3d analysis of ZVI-biochar complexes exposed to As5+ in the batch and column studies show primarily As3+, indicating simultaneous oxidation of Fe° to Fe3+ and reduction of As5+ to As3+. SEM-EDS and XRD analyses show isomorphous substitution of As3+ for Fe3+ in neo-formed α/γ-FeOOH on biochar surfaces, which is attribute to co-precipitation. This study also demonstrates the efficacy of pyrolyzing biomass with low-cost iron ores at 900 °C to rapidly produce ZVI-biochar complexes, which have potential to be used for treatment of As CDW.

Particulate copper in soils and surface runoff from contaminated sandy soils under citrus production.

Soil contamination by copper (Cu) is a worldwide concern. Laboratory incubation and soil Cu characterization were conducted to examine the effects of external Cu loading and liming on Cu speciation in both bulk soil and particulates of an Alfisol and Spodosol under citrus production. Also, drainage water from the sites was evaluated for dissolved and particulate forms of Cu. Soil available Cu estimated by CaCl2, NH4OAc, or Mehlich-3 extraction significantly increased with external Cu loads and decreased with soil pH. Most increases in soil Cu occurred in the exchangeable and oxide-bound fractions. Organically bound Cu was the dominant fraction in both bulk soil and particulates, but more in particulates than bulk soil (P ≤ 0.001). Organically bound Cu was highly correlated with total recoverable Cu (P ≤ 0.01), increased significantly with external Cu loads (P ≤ 0.001), and decreased with soil pH (P ≤ 0.05). Lime addition converted part of Cu from available pools to more stable forms. Organically bound Cu complexes were found to dominate in soil solution or surface runoff. These results indicate that most Cu accumulated in the contaminated soils is highly mobile, and thus may impact citrus production and the environment.