2-Methyl-4-chlorophenoxyacetic acid (MCPA) sorption and desorption as a function of biochar properties and pyrolysis temperature.

2-Methyl-4-chlorophenoxyacetic acid (MCPA) is a highly mobile herbicide that is frequently detected in global potable water sources. One potential mitigation strategy is the sorption on biochar to limit harm to unidentified targets. However, irreversible sorption could restrict bioefficacy thereby compromising its usefulness as a vital crop herbicide. This research evaluated the effect of pyrolysis temperatures (350, 500 and 800°C) on three feedstocks; poultry manure, rice hulls and wood pellets, particularly to examine effects on the magnitude and reversibility of MCPA sorption. Sorption increased with pyrolysis temperature from 350 to 800°C. Sorption and desorption coefficients were strongly corelated with each other (R2 = 0.99; P < .05). Poultry manure and rice hulls pyrolyzed at 800°C exhibited irreversible sorption while for wood pellets at 800°C desorption was concentration dependent. At higher concentrations some desorption was observed (36% at 50 ppm) but was reduced at lower concentrations (1-3% at < 5 ppm). Desorption decreased with increasing pyrolysis temperature. Sorption data were analyzed with Langmuir, Freundlich, Dubinin-Radushkevich and Temkin isotherm models. Freundlich isotherms were better predictors of MCPA sorption (R2 ranging from 0.78 to 0.99). Poultry manure and rice hulls when pyrolyzed at higher temperatures (500 and 800°C) could be used for remediation efforts (such as spills or water filtration), due to the lack of desorption observed. On the other hand, un-pyrolyzed feedstocks or biochars created at 350°C could perform superior for direct field applications to limit indirect losses including runoff and leaching, since these materials also possess the ability to release MCPA subsequently to potentially allow herbicidal action.

The Role of Nanoengineered Biochar Activated with Fe for Sulfanilamide Removal from Soils and Water.

Biochar is a nanoengineered sorbent proposed to control the contamination derived from the presence of residual concentrations of sulfonamides in soil. In this work, we evaluated the sorption of sulfanilamide (SFA) in commercial biochar (BC) produced at 500 °C from oak hardwood (Quercus ilex) and its analog activated with 2% (w/w) Fe (BC-Fe). Subsequently, the effect on dissipation and transport of SFA in untreated soil and soil treated with BC and BC-Fe was also assessed. Laboratory batch studies revealed that BC-Fe increased the sorption of SFA as compared to the pristine BC with Kd of 278 and 98 L/kg, respectively. The dissipation of SFA in either untreated soil or soil treated with BC or BC-Fe was similar, displaying half-lives ranging between 4 and 6.4 days. Conversely, the concurrent determination of sorption during the incubation experiment showed that lower amounts of SFA in solution at the beginning of the experiments were bioavailable in BC-Fe-treated soil when compared to the rest of the treatments shortly after application. Leaching column studies confirmed the amendment's capability to bind the SFA compound. Therefore, the decrease in bioavailability and movement of SFA in treated soils suggest that biochar soil application can reduce SFA soil and water contamination. According to our results, BC surface modification after Fe activation may be more appropriate for water decontamination than for soil since there were no significant differences between the two types of biochar when added to the soil. Therefore, these outcomes should be considered to optimize the SFA mitigation potential of biochar.

Microbial Response to Phytostabilization in Mining Impacted Soils Using Maize in Conjunction with Biochar and Compost.

Even after remediation, mining impacted soils can leave behind a landscape inhospitable to plant growth and containing residual heavy metals. While phytostabilization can be used to restore such sites by limiting heavy metal spread, it is reliant on soil capable of supporting plant growth. Manure-based biochars, coupled with compost, have demonstrated the ability to improve soil growth conditions in mine impacted soils, however there is a paucity of information regarding their influence on resident microbial populations. The objective of this study was to elucidate the impact of these soil amendments on microbial community structure and function in mine impacted soils placed under phytostabilization management with maize. To this aim, a combination of phospholipid fatty acid (PLFA) and enzymatic analyses were performed. Results indicate that microbial biomass is significantly increased upon addition of biochar and compost, with maximal microbial biomass achieved with 5% poultry litter biochar and compost (62.82 nmol g-1 dry soil). Microbial community structure was impacted by biochar type, rate of application, and compost addition, and influenced by pH (r2 = 0.778), EC (r2 = 0.467), and Mg soil concentrations (r2 = 0.453). In three of the four enzymes analyzed, poultry litter biochar treatments were observed with increased activity rates that were often significantly greater than the unamended control. Overall, enzyme activities rates were influenced by biochar type and rate, and addition of compost. These results suggest that using a combination of biochar and compost can be utilized as a management tool to support phytostabilization strategies in mining impacted soils.

Relative proportions of organic carbon functional groups in biochars as influenced by spectral data collection and processing.

Solid-state 13C Nuclear Magnetic Resonance (NMR) and synchrotron-based X-ray Absorption Near-Edge Structure (XANES) have applications for determining the relative proportions of organic C functional groups in materials. Spectral data obtained by NMR is typically processed using integration (INTEG) whereas XANES spectral data is typically processed using deconvolution (DECONV). The objective of this study was to examine the impact of spectral data collection and processing on the estimated relative proportions of organic C functional groups in biochars. Biochars showed large variations in aromatic C (45-97%), alkyl C (0-23%), O-alkyl C (1-41%), phenolic C (0-20%) and carboxylic C (0-20%). NMR had a better ability than XANES to differentiate % aromatic C across biochars, and the mean % aromatic C was always greater for NMR-INTEG and NMR-DECONV than for XANES-INTEG or XANES-DECONV. NMR-INTEG showed significant associations with NMR-DECONV and XANES-INTEG for % aromatic C and alkyl C, but there were no significant associations between NMR and XANES for % O-alkyl C, phenolic C and carboxylic C. As well, there was no association between NMR-INTEG and XANES-DECONV for any organic C functional group, and in some cases, spectral data collection and processing influenced the quantification of organic C functional groups in a given biochar to the extent that the differences observed were as large as differences observed between biochars when analyzed using the same spectral data collection and processing technique. We conclude that great caution must be taken when comparing studies that determined organic C functional groups in materials using NMR-INTEG versus XANES-DECONV.

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.

Biochar changes the bioavailability and bioefficacy of the allelochemical coumarin in agricultural soils.

BACKGROUND: Allelochemicals can act as biopesticides or enhance the action of synthetic pesticides. In this work, we assessed the bioavailability of the allelochemical coumarin in soils amended with fresh or field-aged biochars (BCs). The fresh BC from oak wood (Fresh BC) was prepared at 550 °C and was buried for aging in two different places: in a sandy loam soil in Spain for 15 months (Aged BC_1) and a sandy loam soil in USA for six months (Aged BC_2). RESULTS: Sorption experiments showed that all BCs were able to increase the affinity of soil towards coumarin, with the distribution coefficient following the order: unamended soil < Aged BC_2-amended soil < Aged BC_1-amended soil < Fresh BC-amended soil. All biochars ensure greater persistence of coumarin and the effect was more pronounced at high chemical dose (10 mg kg-1 ). Conversely, leaching studies in soil columns revealed that BCs were able to maintain coumarin within the first 5 cm of top-soil with total amount extracted ranging between 17% and 22% for BC-amended soil and <1% for unamended soil. Leaching was only observed when coumarin was added at the highest rate. Likewise, the bioefficacy of coumarin against lettuce was enhanced only at 10 kg ha-1 with BC-amended soil. CONCLUSIONS: Biochar application to agricultural soils is a promising tool for the management of natural compounds with potential use as biopesticides, such as coumarin, because it increases sorption, persistence and, in some cases, bioefficacy. The results reveal that this effect still persists with aging of BC in soils.

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.

Dynamic Effect of Fresh and Aged Biochar on the Behavior of the Herbicide Mesotrione in Soils.

In this study, we assessed the sorption, dissipation, and leaching of the herbicide mesotrione in soil amended with fresh and field-aged biochars, when added to the soil. The aging process was performed by burying the fresh biochar at 10 cm depth in three soils located in different points across the USA [Wisconsin (ABC_WI), Idaho (ABC_ID), and South Carolina (ABC_SC)] for six months. ABC_ID and ABC_SC slightly increased the sorption of mesotrione in soils, whereas ABC_WI removed greater amounts of herbicide from the solution. This was attributed to differences in water-soluble components and metal content of this aged biochar. Consequently, the persistence of the herbicide in the amended soils with fresh biochar and ABC_ID and ABC_SC were similar to that in unamended soils, while ABC_WI slightly increased mesotrione half-life. Differences between treatments were detected in leaching studies although no direct relationship with the dissipation batch studies was observed. Mesotrione leaching could not be detected in soil columns amended with ABC_WI and was high for the rest of treatments. The outcomes from this work demonstrate that temporal variability of biochar sorption capacities due to soil exposure can occur altering mesotrione's behavior in biochar-amended soils.

Sorption of ammonium and nitrate to biochars is electrostatic and pH-dependent.

Biochars are potentially effective sorbents for NH4+ and NO3- in water treatment and soil applications. Here we compare NH4+ and NO3- sorption rates to acid-washed biochars produced from red oak (Quercus rubra) and corn stover (Zea mays) at three pyrolysis temperatures (400, 500 and 600 °C) and a range of solution pHs (3.5-7.5). Additionally, we examined sorption mechanisms by quantification of NH4+ and NO3- sorption, as well as Ca2+ and Cl- displacement for corn stover biochars. Solution pH curves showed that NH4+ sorption was maximized (0.7-0.8 mg N g-1) with low pyrolysis temperature (400 °C) biochar at near neutral pH (7.0-7.5), whereas NO3- sorption was maximized (1.4-1.5 mg N g-1) with high pyrolysis temperatures (600 °C) and low pH (3.5-4). The Langmuir (r2 = 0.90-1.00) and Freundlich (r2 = 0.81-0.97) models were good predictors for both NH4+ (pH 7) and NO3- (pH 3.7) sorption isotherms. Lastly, NH4+ and NO3- displaced Ca2+ and Cl-, respectively, from previously CaCl2-saturated corn stover biochars. Results from the pH curves, Langmuir isotherms, and cation displacement curves all support the predominance of ion exchange mechanisms. Our results demonstrate the importance of solution pH and chemical composition in influencing NH4+ and NO3- sorption capacities of biochar.

Carbon Dosing Increases Nitrate Removal Rates in Denitrifying Bioreactors at Low-Temperature High-Flow Conditions.

Nitrogen losses from croplands contribute to impairment of water bodies. This laboratory experiment evaluated various C sources for use in a denitrifying bioreactor, a conservation practice designed to reduce N losses. The nitrate removal efficiency of candidate treatments (corn cobs [CC], corn cobs with modified coconut coir [CC+MC], corn cobs with modified coconut coir and modified macadamia shell biochar [CC+MC+MBC], wood chips [WC], wood chips with hardwood biochar [WC+BC], and wood chips with continuous sodium acetate addition [WC+A]) were tested with up-flow direction. Effluent was sampled after a repeated weekly flow regime with hydraulic residence times of 1.5, 8, 12, and 24 h. Column temperatures were 15°C for 14 wk (warm), 5°C for 13 wk (cold), and again 15°C for 7 wk (rewarm). Cumulative nitrate N load reduction was greatest for WC+A (80, 80, and 97% during the warm, cold, and rewarm runs, respectively). Corn cob treatments (CC, CC+MC, and CC+MC+MBC) had the second greatest cumulative load reductions for all three temperature experiments, and WC and WC+BC had the lowest performance under these conditions. The nitrate removal rate was optimum at the 1.5-h hydraulic residence time for the WC+A treatment: 43, 30, and 121 g N m d for the warm, cold, and rewarm runs, respectively. Furthermore, acetate addition greatly improved wood chip performance and could be used to enhance nitrate N removal under the cold and high-flow-rate conditions of springtime drainage for the north-central United States.

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.

Glyphosate sorption/desorption on biochars - interactions of physical and chemical processes.

BACKGROUND: Biochar, a carbon-rich product of biomass pyrolysis, could limit glyphosate transport in soil and remediate contaminated water. The present study investigates the sorption/desorption behavior of glyphosate on biochars prepared from different hardwoods at temperatures ranging from 350 to 900 °C to elucidate fundamental mechanisms. RESULTS: Glyphosate (1 mg L-1 ) sorption on biochars increased with pyrolysis temperature and was highest on 900 °C biochars; however, total sorption was low on a mass basis (<0.1 mg g-1 ). Sorption varied across feedstock materials, and isotherms indicated concentration dependence. Biochars with a greater fraction of micropores exhibited lower sorption capacities, and specific surface groups were also found to be influential. Prepyrolysis treatments with iron and copper, which complex glyphosate in soils, did not alter biochar sorption capacities. Glyphosate did not desorb from biochar with CaCl2 solution; however, up to 86% of the bound glyphosate was released with a K2 HPO4 solution. CONCLUSION: Results from this study suggest a combined impact of surface chemistry and physical constraints on glyphosate sorption/desorption on biochar. Based on the observed phosphate-induced desorption of glyphosate, the addition of P-fertilizer to biochar-amended soils can remobilize the herbicide and damage non-target plants; therefore, improved understanding of this risk is necessary. © 2017 Society of Chemical Industry.

Biochar Soil Additions Affect Herbicide Fate: Importance of Application Timing and Feedstock Species.

Biochar (BC), solid biomass subjected to pyrolysis, can alter the fate of pesticides in soil. We investigated the effect of soil amendment with several biochars on the efficacy of two herbicides, clomazone (CMZ) and bispyribac sodium (BYP). To this aim, we evaluated CMZ and BYP sorption, persistence, and leaching in biochar-amended soil. Sorption of CMZ and BYP was greater in soil amended with BC produced at high temperature (700 °C). Significant sorption of the neutral CMZ herbicide also occurred in amended soil with BC prepared at low temperature (350 and 500 °C). For both herbicides, desorption possessed higher hysteretic behavior in soil amended with BC made at 700 °C (pyrolysis temperature). Dissipation of CMZ was enhanced after addition of BCs to soil, but no correlation between persistence and sorption was observed. Persistence of BYP was up to 3 times greater when BC made at 700 °C was added to soil. All BCs suppressed the leaching of CMZ and BYP as compared to the unamended soil. Amendment with 700 °C BC inhibited the action of CMZ against weeds, but 350 and 500 °C BCs had no such effect when added to soil. BYP activity was similar to that exhibited by unamended soil after the addition of 700 °C BC. From these results, biochar amendments can be a successful strategy to reduce the environmental impact of CMZ and BYP in soil. However, the phytotoxicity of soil-applied herbicides will depend on BC sorption characteristics and the pesticide's chemical properties, as well as the pesticide application timing (e.g., pre- or postemergence). According to our results, proper biochar screening with intended pesticides in light of the application mode (pre- or postemergence) is required prior to use to ensure adequate efficacy.

Metolachlor Sorption and Degradation in Soil Amended with Fresh and Aged Biochars.

Addition of organic amendments such as biochar to soils can influence pesticide sorption-desorption processes and, in turn, the amount of pesticide readily availability for transport and biodegradation. Sorption-desorption processes are affected by both the physical and chemical properties of soils and pesticides, as well as soil-pesticide contact time, or aging. Changes in sorption-desorption of metolachlor with aging in soil amended with three macadamia nut shell biochars aged 0 (BCmac-fr), 1 year (BCmac-1yr), and 2 years (BCmac-2yr) and two wood biochars aged 0 (BCwood-fr) and 5 years (BCwood-5yr) were determined. Apparent sorption coefficient (Kd-app) values increased with incubation time to a greater extent in amended soil as compared to unamended soils; Kd-app increased by 1.2-fold for the unamended soil, 2.0-fold for BCwood-fr, 1.4-fold for BCwood-5yr, 2.4-fold for BCmac-fr, 2.5-fold for BCmac-1yr, and 1.9-fold for BCmac-4yr. The increase in calculated Kd-app value was the result of a 15% decrease in the metolachlor solution concentration extractable with CaCl2 solution with incubation time in soil as compared to a 50% decrease in amended soil with very little change in the sorbed concentration. Differences could possibly be due to diffusion to less accessible or stronger binding sites with time, a faster rate of degradation (in solution and on labile sites) than desorption, or a combination of the two in the amended soils. These data show that transport models would overpredict the depth of movement of metolachlor in soil if effects of aging or biochar amendments are not considered.

Soil Functional Zone Management: A Vehicle for Enhancing Production and Soil Ecosystem Services in Row-Crop Agroecosystems.

There is increasing global demand for food, bioenergy feedstocks and a wide variety of bio-based products. In response, agriculture has advanced production, but is increasingly depleting soil regulating and supporting ecosystem services. New production systems have emerged, such as no-tillage, that can enhance soil services but may limit yields. Moving forward, agricultural systems must reduce trade-offs between production and soil services. Soil functional zone management (SFZM) is a novel strategy for developing sustainable production systems that attempts to integrate the benefits of conventional, intensive agriculture, and no-tillage. SFZM creates distinct functional zones within crop row and inter-row spaces. By incorporating decimeter-scale spatial and temporal heterogeneity, SFZM attempts to foster greater soil biodiversity and integrate complementary soil processes at the sub-field level. Such integration maximizes soil services by creating zones of 'active turnover', optimized for crop growth and yield (provisioning services); and adjacent zones of 'soil building', that promote soil structure development, carbon storage, and moisture regulation (regulating and supporting services). These zones allow SFZM to secure existing agricultural productivity while avoiding or minimizing trade-offs with soil ecosystem services. Moreover, the specific properties of SFZM may enable sustainable increases in provisioning services via temporal intensification (expanding the portion of the year during which harvestable crops are grown). We present a conceptual model of 'virtuous cycles', illustrating how increases in crop yields within SFZM systems could create self-reinforcing feedback processes with desirable effects, including mitigation of trade-offs between yield maximization and soil ecosystem services. Through the creation of functionally distinct but interacting zones, SFZM may provide a vehicle for optimizing the delivery of multiple goods and services in agricultural systems, allowing sustainable temporal intensification while protecting and enhancing soil functioning.

Pesticide sorption and leaching potential on three Hawaiian soils.

On the Hawaiian Islands, groundwater is the principal source of potable water and contamination of this key resource by pesticides is of great concern. To evaluate the leaching potential of four weak acid herbicides [aminocyclopyrachlor, picloram, metsulfuron-methyl, biologically active diketonitrile degradate of isoxaflutole (DKN)] and two neutral non-ionizable herbicides [oxyfluorfen, alachlor], their sorption coefficients were determined on three prevalent soils from the island of Oahu. Metsulfuron-methyl, aminocylcopyrachlor, picloram, and DKN were relatively low sorbing herbicides (K(oc) = 3-53 mL g(-1)), alachlor was intermediate (K(oc) = 120-150 mL g(-1)), and oxyfluorfen sorbed very strongly to the three soils (K(oc) > 12,000 mL g(-1)). Following determination of K(oc) values, the groundwater ubiquity score (GUS) indices for these compounds were calculated to predicted their behavior with the Comprehensive Leaching Risk Assessment System (CLEARS; Tier-1 methodology for Hawaii). Metsulfuron-methyl, aminocyclopyrachlor, picloram, and DKN would be categorized as likely leachers in all three Hawaiian soils, indicating a high risk of groundwater contamination across the island of Oahu. In contrast, oxyfluorfen, regardless of the degradation rate, would possess a low and acceptable leaching risk due to its high sorption on all three soils. The leaching potential of alachlor was more difficult to classify, with a GUS value between 1.8 and 2.8. In addition, four different biochar amendments to these soils did not significantly alter their sorption capacities for aminocyclopyrachlor, indicating a relatively low impact of black carbon additions from geologic volcanic inputs of black carbon. Due to the fact that pesticide environmental risks are chiefly dependent on local soil characteristics, this work has demonstrated that once soil specific sorption parameters are known one can assess the potential pesticide leaching risks.

Characterization and selection of biochar for an efficient retention of tricyclazole in a flooded alluvial paddy soil.

Biochars, from different organic residues, are increasingly proposed as soil amendments for their agronomic and environmental benefits. A systematic detection method that correlates biochar properties to their abilities to adsorb organic compounds is still lacking. Seven biochars obtained after pyrolysis at different temperatures and from different feedstock (alperujo compost, rice hull, and woody debris), were characterized and tested to reveal potential remedial forms for pesticide capture in flooded soils. Biochar properties were determined by nuclear magnetic resonance (NMR) spectroscopy, Fourier transform infrared spectroscopy, specific surface area (SSA) assessment and scanning electron microscopy. In addition, dissolved organic matter (DOM) from these biochars was extracted and quantified in order to evaluate the effect on pesticide sorption. The biochars from alperujo compost presented very high affinity to the fungicide tricyclazole (55.9, 83.5, and 90.3% for B1, B4, and B5, respectively). This affinity was positively correlated with the pyrolysis temperature, the pH, the increased SSA of the biochars, and the enhanced aromaticity. Sorptive capacities were negatively related to DOM contents. The amendment with a mixture of compost and biochar endows the alluvial soil with high sorptive properties (from K(fads(soil)) = 9.26 to K(fads(mixture)) = 17.89) without impeding the slow release of tricyclazole.

Denitrification kinetics in biomass- and biochar-amended soils of different landscape positions.

Knowledge of how biochar impacts soil denitrification kinetics as well as the mechanisms of interactions is essential in order to better predict the nitrous oxide (N2O) mitigation capacity of biochar additions. This study had multiple experiments in which the effect of three biochar materials produced from corn stover (Zea mays L.), ponderosa pine wood residue (Pinus ponderosa Douglas ex Lawson and C. Lawson), switchgrass (Panicum virgatum L.), and their corresponding biomass materials (corn stover, ponderosa pine wood residue, and switchgrass) on cumulative N2O emissions and total denitrification in soils from two different landscape positions (crest and footslope) were studied under varying water-filled pore space (40, 70, and 90% WFPS). Cumulative N2O emissions were reduced by 30 to 70% in both crest and footslope soils. The effect of biochars and biomass treatments on cumulative N2O emissions and total denitrification were only observed at ≥40% WFPS. The denitrification enzyme activity (DEA) kinetic parameters, K s (half-saturation constant), and V max (maximum DEA rate) were both significantly reduced by biochar treatments, with reductions of 70-80% in footslope soil and 80-90 % in the crest soil. The activation energy (E a) and enthalpy of activation of DEA (ΔH) were both increased with biochar application. The trends in DEA rate constants (K s and V max) were correlated by the trends of thermodynamic parameters (activation energy E a and enthalpy of activation ΔH) for denitrifying enzyme activity (DEA). The rate constant V max/K s evaluated the capacity of biochars to mitigate the denitrification process. Denitrifying enzyme kinetic parameters can be useful in evaluating the ability of biochars to mitigate N2O gas losses from soil.

Influence of soil biochar aging on sorption of the herbicides MCPA, nicosulfuron, terbuthylazine, indaziflam, and fluoroethyldiaminotriazine.

Sorption of four herbicides and a metabolite of indaziflam on a fresh macadamia nut biochar and biochars aged one or two years in soil was characterized. On fresh biochar, the sorption was terbuthylazine (Kd = 595) > indaziflam (Kd = 162) > MCPA (Kd = 7.5) > fluoroethyldiaminotriazine (Kd = 0.26) and nicosulfuron (Kd = 0). Biochar surface area increased with aging attributed to the loss of a surface film. This was also manifested in a decline in water extractable organic carbon with aging. Correspondingly, an increase in the aromaticity was observed. The higher surface area and porosity in aged biochar increased sorption of indaziflam (KdBC-2yr = 237) and fluoroethyldiaminotriazine (KdBC-1yr = 1.2 and KdBC-2yr = 3.0), but interestingly decreased sorption of terbuthylazine (KdBC-1yr = 312 and KdBC-2yr = 221) and MCPA (KdBC-1yr = 2 and KdBC-2yr = 2). These results will facilitate development of biochars for specific remediation purposes.

Phosphorus reclamation through hydrothermal carbonization of animal manures.

Projected shortages of global phosphate have prompted investigation of methods that could be employed to capture and recycle phosphate, rather than continue to allow the resource to be essentially irreversibly lost through dilution in surface waters. Hydrothermal carbonization of animal manures from large farms was investigated as a scenario for the reclamation of phosphate for agricultural use and mitigation of the negative environmental impact of phosphate pollution. Hydrothermal reaction conditions were identified for poultry, swine, and cattle manures that resulted in hydrochar yields of 50-60% for all three manures, and >90% of the total phosphorus present in these systems was contained in the hydrochars as precipitated phosphate salts. Phosphate recovery was achieved in yields of 80-90% by subsequent acid treatment of the hydrochars, addition of base to acid extracts to achieve a pH of 9, and filtration of principally calcium phosphate. Phosphate recovery was achieved in yields of 81-87% based on starting manures by subsequent acid treatment of the hydrochars, addition of base to acid extracts to achieve a pH of 9, and filtration of principally calcium phosphate. Swine and cattle manures produced hydrochars with combustion energy contents comparable to those of high-end sub-bituminous coals.