Evaluation of a pH- and time-dependent model for the sorption of heavy metal cations by poultry litter-derived biochar.

Common isotherm and kinetic models cannot describe the pH-dependent sorption of heavy metal cations by biochar. In this paper, we evaluated a pH-dependent, equilibrium/kinetic model for describing the sorption of cadmium (Cd), copper (Cu), nickel (Ni), lead (Pb), and zinc (Zn) by poultry litter-derived biochar (PLB). We performed sorption experiments across a range of solution pH, initial metal concentration, and reaction time. The sorption of all five metals increased with increasing pH. For Cd, Cu, and Pb, kinetics experiments demonstrated that sorption rates were greater at pH 6.5 than at pH 4.5. For each metal, all sorption data were described using single set of four adjustable parameters. Sorption edge and isotherm data were well described with R2 > 0.93 in all cases. Time-dependent sorption was well described (R2 ≥ 0.90) for all metals except Pb (R2 = 0.77). We then used the best-fit model parameters to calculate linear distribution coefficients (KD) and equilibration times as a function of pH and initial solution concentration. These calculations provide a more robust way of characterizing biochar affinity for metal cations than Freundlich distribution coefficients or Langmuir sorption capacity. Because this model can characterize metal cation sorption by biochar across a wider range of reaction conditions than traditional isotherm or kinetic models, it is better suited for estimating metal cation/biochar interactions in engineered or natural systems.

Designing amendments to improve plant performance for mine tailings revegetation.

To provide recommendations for establishment of plants on low-pH Formosa Mine tailings, two greenhouse experiments were conducted to evaluate the use of remedial amendments to improve the survival and growth of Douglas fir (Pseudotsuga menziesii) seedlings. A preliminary experiment indicated that 1% lime (by weight) raised tailings pH, permitting seedling survival. However, high rates of biosolid application (BS; 2% by weight) added to supply nutrients were phytotoxic when added with lime. A gasified conifer biochar (BC) added to tailings at 1%, 2.5%, or 5% (by weight), along with lime and BS, caused an additional increase in pH, decreased electrical conductivity (EC), and tended to increase the survival of Douglas fir. The addition of a locally sourced microbial inoculum (LSM) did not affect survival. A subsequent experiment expanded our experimental design by testing multiple levels of amendments that included lime (0.5% and 1% by weight), three application rates (0.2%, 0.5%, and 2%) of two nutrient sources (BS or mineral fertilizer), BC (0% and 2.5%), and with or without LSM. There were many interactions among amendments. In general, Douglas fir survival was enhanced when lime and BC were added. These experiments suggest that amending with lime, a nutrient source, and BC would enhance revegetation on low-pH, metal-contaminated mine tailings.

Magnesium activation affects the properties and phosphate sorption capacity of poultry litter biochar.

Biochars with a high affinity for phosphorus (P) are promising soil amendments for reducing P in agricultural run-off. Poultry litter (PL) is an abundant biochar feedstock. However, PL-derived biochars are typically high in soluble P and therefore require chemical modification to become effective P sorbents. This study investigated the effect of magnesium (Mg) activation on extractable P (EP) and P sorption capacities of PL-derived biochars. Biochar was produced at 500-900 °C from PL activated with 0-1 M Mg. Three differentially aged PL feedstocks were evaluated (1-, 3-5-, and 7-9-year-old). Increased Mg activation level and pyrolysis temperature both resulted in EP reductions from the biochars. Specifically, biochars produced at temperatures ≥ 700 °C from PL activated with ≥ 0.25 M Mg had negligible EP. X-ray diffractograms indicated that increased Mg loading favored the formation of stable Mg3(PO4)2 phases while increasing temperature favored the formation of both Mg3(PO4)2 and Ca5(PO4)3OH. Maximum P sorption capacities (Pmax) of the biochars were estimated by fitting Langmuir isotherms to batch sorption data and ranged from 0.66-10.35 mg g-1. Average Pmax values were not affected by PL age or pyrolysis temperature; however, biochars produced from 1 M Mg-activated PL did have significantly higher average Pmax values (p < 0.05), likely due to a greater abundance of MgO. Overall, the results demonstrated that Mg activation is an effective strategy for producing PL-derived biochars with the potential ability to reduce P loading into environmentally sensitive ecosystems.

Phytostabilization of acidic mine tailings with biochar, biosolids, lime, and locally-effective microbes: Do amendment mixtures influence plant growth, tailing chemistry, and microbial composition?

Abandoned mine lands present persistent environmental challenges to ecosystems and economies; reclamation an important step for overcoming these challenges. Phytostabilization is an elegant and cost-effective reclamation strategy, however, establishing plants on severely degraded soils is problematic, often requiring soil amendment additions. We evaluated whether amendment mixtures composed of lime, biochar, biosolids, and locally effective microbes (LEM) could alleviate the constraints that hinder phytostabilization success. We hypothesized that 1) plants grown in tailings amended with lime, biochar, and biosolids (LBB) would establish faster and grow larger than plants grown in tailings amended with lime only, and 2) the LEM source would influence microbial community function and structure in amended mine tailings. We conducted a greenhouse study that simulated in situ conditions to measure the influence of LBB-LEM amendment blends on plant growth, plant nutrients, metal concentrations, microbial function, and microbial community structure. Blue wildrye [Elymus glaucus Buckley ssp. Jepsonii (Burtt Davy) Gould] was grown in tailings collected from the Formosa mine site amended with various combinations of LBB-LEM. The above and below ground biomass of plants grown in mine tailings amended with LBB was 3 to 4 times larger than the biomass of plants grown in tailings amended only with lime. Although the LEM addition did not influence immediate plant growth, it did affect nutrient content and altered the rhizosphere community membership. As such, it is not yet clear if LEM-driven alterations in microbial membership will advance mine reclamation strategies by improving long-term growth.

Microbial response to designer biochar and compost treatments for mining impacted soils.

The Oronogo-Duenweg mining belt is a designated United States Environmental Protection Agency Superfund site due to lead-contaminated soil and groundwater by former mining and smelting operations. Sites that have undergone remediation - in which the O, A, and B horizons have been removed alongside the lead contamination - have an exposed C horizon and are incalcitrant to revegetation efforts. Soils also continue to contain quantifiable Cd and Zn concentrations. In order to improve soil conditions and encourage successful site revegetation, our study employed three biochars, sourced from different feedstocks (poultry litter, beef lot manure, and lodge pole pine), at two rates of application (2.5%, and 5%), coupled with compost (0%, 2.5% and 5% application rates). Two plant species - switchgrass (Panicum virgatum) and buffalograss (Bouteloua dactyloides) - were grown in the amended soils. Amendment of soils with poultry litter biochar applied at 5% resulted in the greatest reduction of soil bioavailable Cd and Zn. Above ground biomass yields were greatest with beef lot manure biochar applied at 2.5% with 5% compost, or with 5% biochar at 2.5% and 5% compost rates. Maximal microbial biomass was achieved with 5% poultry litter biochar and 5% compost, and microbial communities in soils amended with poultry litter biochar distinctly clustered away from all other soil treatments. Additionally, poultry litter biochar amended soils had the highest enzyme activity rates for ß-glucosidase, N-acetyl-ß-D-glucosaminidase, and esterase. These results suggest that soil reclamation using biochar and compost can improve mine-impacted soil biogeophysical characteristics, and potentially improve future remediation efforts.

Biochar Affects Essential Nutrients of Carrot Taproots and Lettuce Leaves.

Essential nutrient concentrations in crops can affect human health. While biochar has the potential as a soil amendment to improve crop yields, it may also affect the concentrations of nutrients such as Ca, Fe, K, Mg, Mn, and Zn in edible portions of crops. To better characterize effects of biochar on important human nutrients in food crops, we evaluated the effects of biochar on lettuce (Lactuca sativa L. cv. Black-Seeded Simpson) leaf and carrot [Daucus carota subsp. sativus (Hoffm.) Schübl. cv. Tendersweet] developing taproot nutrients. Plants were grown in pots in a greenhouse using sandy loam (Coxville, fine, kaolinitic, thermic Typic Paleaquults) and loamy sand (Norfolk, fine-loamy, kaolinitic, thermic Typic Kandiudults,) series soils, amended with biochar produced from four feedstocks: pine chips (PC), poultry litter (PL), swine solids (SS), and switchgrass (SG); and two blends of PC plus PL [Pc/PL, 50%/50% (55) and 80%/20% (82) by weight]. Biochar was produced at 350, 500, and 700 °C from each feedstock. Lettuce leaf and carrot taproot total nutrient concentrations were determined by inductively coupled plasma analysis. Biochar (especially at least in part manure-based, i.e., PL, SS, 55, and 82 at nearly all temperatures) primarily decreased nutrient concentrations in lettuce leaves, with Ca, Mg, and Zn affected most. Carrot taproot nutrient concentrations also deceased, but to a lesser extent. Some biochars increased leaf or taproot nutrient concentrations, especially K. This study indicated that biochar can both decrease and increase leaf and taproot nutrient concentrations important for human health. Thus, potential effects on nutrients in plants should be carefully considered when biochar is used as a soil amendment with vegetable crops.

Biochar compost blends facilitate switchgrass growth in mine soils by reducing Cd and Zn bioavailability.

Biochars have the potential to reclaim mine-impacted soils; however, their variable physico-chemical properties incite speculation about their successful remediation performance. This investigation examined the capability of biochars produced from three different feedstocks along with a compost blend to improve switchgrass growth conditions in a mine-impacted soil by examining influences on soil pH, grass metal contents, and soil-extractable metal concentrations. Cadmium (Cd)- and zinc (Zn)-contaminated mine soil was collected from a site near Webb City, Missouri, USA-a location within the Tri-State Mining District. In a full factorial design, soil was treated with a 0%, 2.5%, and 5% (w/w) compost mixture (wood chips + beef cattle manure), and 0%, 2.5% and 5% of each biochar pyrolyzed from beef cattle manure, poultry litter, and lodgepole pine feedstocks. Switchgrass (Panicum virgatum, 'Cave-In-Rock' variety) was grown in a greenhouse for 50 days and the mass of shoots (above-ground biomass) and roots was assessed, while soil pH, deionized H2O- and 0.01 M CaCl2-extractable Cd and Zn concentrations were measured. Poultry litter biochar and compost had the greatest ability to raise soil pH (from 4.40 to 6.61), beef cattle manure biochar and compost moderately raised pH (from 4.4 to 5.92), and lodgepole pine biochar and compost weakly raised pH (from 4.40 to 5.05). Soils treated with beef cattle manure biochar, poultry litter biochar significantly reduced deionized H2O- and 0.01 M CaCl2-extractable Cd and Zn concentrations, while lodgepole pine biochar-treated soils showed mixed results. Switchgrass shoot and root masses were greatest in soil treated with compost in combination with either beef cattle manure biochar or poultry litter biochar. Soils treated with 5% beef cattle manure biochar + 5% compost had greater reductions in total Cd and Zn concentrations measured in switchgrass shoots and roots compared to the other two treatments. The three biochars and compost mixtures applied to heavy metal, mine-impacted soil had considerable performance dissimilarities for improving switchgrass productivity. Switchgrass growth was noticeably improved after treatment with the compost in combination with biochar from beef cattle manure or poultry litter. This may be explained by the increased soil pH that promoted Zn and Cd precipitation and organic functional groups that reduced soil-available heavy metal concentrations. Our results imply that creating designer biochars is an important management component in developing successful mine-site phytostabilization programs.

Remediation of an acidic mine spoil: Miscanthus biochar and lime amendment affects metal availability, plant growth, and soil enzyme activity.

Biochar may be a tool for mine spoil remediation; however, its mechanisms for achieving this goal remain unclear. In this study, Miscanthus (Miscanthus giganteus) biochar was evaluated for its ability to reclaim acidic mine spoils (pH < 3) through reducing metal availability, improving soil microbial enzymatic activity, and initial growth of grass seedlings. Biochar was applied at 0, 1, 2.5 and 5% (w/w) along with lime/no lime and fertilizer additions. Blue Wildrye (Elymus glaucus cv. 'Elkton') was planted and later the shoots and roots were collected and metal concentrations determined. Afterwards, each pot was leached with deionized water, and the leachate analyzed for pH, electrical conductivity (EC), dissolved organic carbon (DOC) and soluble metal concentrations. After drying, the spoil was extracted with 0.01 M CaCl2 and Mehlich 3 (M3) to determine extractable Al, Cu, and Zn concentrations. Additionally, microbial activity was measured using a fluorescent ß-glucosidase and N-acetyl-ß-d-glucosaminidase assay. Spoil treated with lime and biochar had significantly greater pH and EC values. Significantly greater ß-glucosidase activity occurred only in the 5% biochar plus lime treatment, while N-acetyl-ß-d-glucosaminidase activities were not altered. Metal concentrations in rye shoot and roots were mixed. Lime additions significantly reduced extractable metal concentrations. Increasing biochar rates alone significantly reduced leachate DOC concentrations, and subsequently reduced leachable metal concentrations. Surprisingly, miscanthus biochar, by itself, was limited at mitigation, but when combined with lime, the combination was capable of further reducing extractable metal concentrations and improving ß-glucosidase enzyme activity.