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.

Evaluation of TiO2 Based Photocatalytic Treatment of Odor and Gaseous Emissions from Swine Manure with UV-A and UV-C.

It is essential to mitigate gaseous emissions that result from poultry and livestock production to increase industry sustainability. Odorous volatile organic compounds (VOCs), ammonia (NH3), hydrogen sulfide (H2S), and greenhouse gases (GHGs) have detrimental effects on the quality of life in rural communities, the environment, and climate. This study's objective was to evaluate the photocatalytic UV treatment of gaseous emissions of odor, odorous VOCs, NH3, and other gases (GHGs, O3-sometimes considered as by-products of UV treatment) from stored swine manure on a pilot-scale. The manure emissions were treated in fast-moving air using a mobile lab equipped with UV-A and UV-C lights and TiO2-based photocatalyst. Treated gas airflow (0.25-0.76 m3∙s-1) simulates output from a small ventilation fan in a barn. Through controlling the light intensity and airflow, UV dose was tested for techno-economic analyses. The treatment effectiveness depended on the UV dose and wavelength. Under UV-A (367 nm) photocatalysis, the percent reduction of targeted gases was up to (i) 63% of odor, (ii) 51%, 51%, 53%, 67%, and 32% of acetic acid, propanoic acid, butanoic acid, p-cresol, and indole, respectively, (iii) 14% of nitrous oxide (N2O), (iv) 100% of O3, and 26% generation of CO2. Under UV-C (185 + 254 nm) photocatalysis, the percent reductions of target gases were up to (i) 54% and 47% for p-cresol and indole, respectively, (ii) 25% of N2O, (iii) 71% of CH4, and 46% and 139% generation of CO2 and O3, respectively. The results proved that the UV technology was sufficiently effective in treating odorous gases, and the mobile lab was ready for farm-scale trials. The UV technology can be considered for the scaled-up treatment of emissions and air quality improvement inside livestock barns. Results from this study are needed to inform the experimental design for future on-farm research with UV-A and UV-C.

Design and Testing of Mobile Laboratory for Mitigation of Gaseous Emissions from Livestock Agriculture with Photocatalysis.

Livestock production systems generate nuisance odor and gaseous emissions affecting local communities and regional air quality. There are also concerns about the occupational health and safety of farmworkers. Proven mitigation technologies that are consistent with the socio-economic challenges of animal farming are needed. We have been scaling up the photocatalytic treatment of emissions from lab-scale, aiming at farm-scale readiness. In this paper, we present the design, testing, and commissioning of a mobile laboratory for on-farm research and demonstration of performance in simulated farm conditions before testing to the farm. The mobile lab is capable of treating up to 1.2 m3/s of air with titanium dioxide, TiO2-based photocatalysis, and adjustable UV-A dose based on LED lamps. We summarize the main technical requirements, constraints, approach, and performance metrics for a mobile laboratory, such as the effectiveness (measured as the percent reduction) and cost of photocatalytic treatment of air. The commissioning of all systems with standard gases resulted in ~9% and 34% reduction of ammonia (NH3) and butan-1-ol, respectively. We demonstrated the percent reduction of standard gases increased with increased light intensity and treatment time. These results show that the mobile laboratory was ready for on-farm deployment and evaluating the effectiveness of UV treatment.

Pilot-Scale Testing of UV-A Light Treatment for Mitigation of NH3, H2S, GHGs, VOCs, Odor, and O3 Inside the Poultry Barn.

Poultry farmers are producing eggs, meat, and feathers with increased efficiency and lower carbon footprint. Technologies to address concerns about the indoor air quality inside barns and the gaseous emissions from farms to the atmosphere continue to be among industry priorities. We have been developing and scaling up a UV air treatment that has the potential to reduce odor and other gases on the farm scale. In our recent laboratory-scale study, the use of UV-A (a less toxic ultraviolet light, a.k.a. "black light") and a special TiO2-based photocatalyst reduced concentrations of several important air pollutants (NH3, CO2, N2O, O3) without impact on H2S and CH4. Therefore, the objectives of this research were to (1) scale up the UV treatment to pilot scale, (2) evaluate the mitigation of odor and odorous volatile organic compounds (VOCs), and (3) complete preliminary economic analyses. A pilot-scale experiment was conducted under commercial poultry barn conditions to evaluate photocatalyst coatings on surfaces subjected to UV light under field conditions. In this study, the reactor was constructed to support interchangeable wall panels and installed on a poultry farm. The effects of a photocatalyst's presence (photocatalysis and photolysis), UV intensity (LED and fluorescent), and treatment time were studied in the pilot-scale experiments inside a poultry barn. The results of the pilot-scale experiments were consistent with the laboratory-scale one: the percent reduction under photocatalysis was generally higher than photolysis. In addition, the percent reduction of target gases at a high light intensity and long treatment time was higher. The percent reduction of NH3 was 5-9%. There was no impact on H2S, CH4, and CO2 under any experimental conditions. N2O and O3 concentrations were reduced at 6-12% and 87-100% by both photolysis and photocatalysis. In addition, concentrations of several VOCs responsible for livestock odor were reduced from 26 to 62% and increased with treatment time and light intensity. The odor was reduced by 18%. Photolysis treatment reduced concentrations of N2O, VOCs, and O3, only. The initial economic analysis has shown that LEDs are more efficient than fluorescent lights. Further scale-up and research at farm scale are warranted.

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.

The Proof-of-the Concept of Biochar Floating Cover Influence on Swine Manure pH: Implications for Mitigation of Gaseous Emissions From Area Sources.

Mitigation of potentially hazardous and malodor compounds emitted from animal waste is needed to improve the sustainability of livestock agriculture. Bacteria control the generation of these compounds and also depend on the pH of manure. Influencing swine manure pH, especially on the liquid-air interface, may lead to a reduction of emission of odorous and hazardous compounds. The objective of this experiment was to test highly alkaline and porous (HAP) modified biochar with pH = 9.2 and red oak (RO) biochar with pH = 7.5 influence on swine manure pH acquired from the outdoor storage and deep pit storage under a barn. HAP and RO biochars were topically applied on the outdoor-stored (pH = 7.55), and pit (pH = 8.00) manures and spatial pH (every 1 mm of depth) were measured on days 0, 2, and 4. Results showed that HAP biochar increased outdoor-stored manure pH on day 4, particularly within the top 10 mm of depth, where pH ranged from 7.79 to 8.90, while in the case of RO pH ranged between 7.46 and 7.66, i.e., similar to control (7.57-7.64). Both biochars decreased pit-stored manure pH within the top 10 mm of depth (in comparison with the control pH of 8.36-8.47) to 8.19-8.30 (HAP), and 8.18-8.29 (RO) on day 4. However, differences were not considerable. The reason for the insignificant effect of biochars on pit manure was likely due to its higher buffer capacity in comparison with the outdoor-stored manure.

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.

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.

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.