Keri B. Cantrell

Biochar: A Synthesis of Its Agronomic Impact beyond Carbon Sequestration

Biochar has been heralded as an amendment to revitalize degraded soils, improve soil carbon sequestration, increase agronomic productivity, and enter into future carbon trading markets. However, scientific and economic technicalties may limit the ability of biochar to consistently deliver on these expectations. Past research has demonstrated that biochar is part of the black carbon continuum with variable properties due to the net result of production (e.g., feedstock and pyrolysis conditions) and postproduction factors (storage or activation). Therefore, biochar is not a single entity but rather spans a wide range of black carbon forms. Biochar is black carbon, but not all black carbon is biochar. Agronomic benefits arising from biochar additions to degraded soils have been emphasized, but negligible and negative agronomic effects have also been reported. Fifty percent of the reviewed studies reported yield increases after black carbon or biochar additions, with the remainder of the studies reporting alarming decreases to no significant differences. Hardwood biochar (black carbon) produced by traditional methods (kilns or soil pits) possessed the most consistent yield increases when added to soils. The universality of this conclusion requires further evaluation due to the highly skewed feedstock preferences within existing studies. With global population expanding while the amount of arable land remains limited, restoring soil quality to nonproductive soils could be key to meeting future global food production, food security, and energy supplies; biochar may play a role in this endeavor. Biochar economics are often marginally viable and are tightly tied to the assumed duration of agronomic benefits. Further research is needed to determine the conditions under which biochar can provide economic and agronomic benefits and to elucidate the fundamental mechanisms responsible for these benefits.

Impact of pyrolysis temperature and manure source on physicochemical characteristics of biochar

While pyrolysis of livestock manures generates nutrient-rich biochars with potential agronomic uses, studies are needed to clarify biochar properties across manure varieties under similar controlled conditions. This paper reports selected physicochemical results for five manure-based biochars pyrolyzed at 350 and 700°C: swine separated-solids; paved-feedlot manure; dairy manure; poultry litter; and turkey litter. Elemental and FTIR analyses of these alkaline biochars demonstrated variations and similarities in physicochemical characteristics. The FTIR spectra were similar for (1) turkey and poultry and (2) feedlot and dairy, but were distinct for swine biochars. Dairy biochars contained the greatest volatile matter, C, and energy content and lowest ash, N, and S contents. Swine biochars had the greatest P, N, and S contents alongside the lowest pH and EC values. Poultry litter biochars exhibited the greatest EC values. With the greatest ash contents, turkey litter biochars had the greatest biochar mass recoveries, whereas feedlot biochars demonstrated the lowest.

Livestock waste-to-bioenergy generation opportunities

The use of biological and thermochemical conversion (TCC) technologies in livestock waste-to-bioenergy treatments can provide livestock operators with multiple value-added, renewable energy products. These products can meet heating and power needs or serve as transportation fuels. The primary objective of this work is to present established and emerging energy conversion opportunities that can transform the treatment of livestock waste from a liability to a profit center. While biological production of methanol and hydrogen are in early research stages, anaerobic digestion is an established method of generating between 0.1 to 1.3m3m(-3)d(-1) of methane-rich biogas. The TCC processes of pyrolysis, direct liquefaction, and gasification can convert waste into gaseous fuels, combustible oils, and charcoal. Integration of biological and thermal-based conversion technologies in a farm-scale hybrid design by combining an algal CO2-fixation treatment requiring less than 27,000m2 of treatment area with the energy recovery component of wet gasification can drastically reduce CO2 emissions and efficiently recycle nutrients. These designs have the potential to make future large scale confined animal feeding operations sustainable and environmentally benign while generating on-farm renewable energy.

Qualitative analysis of volatile organic compounds on biochar

Qualitative identification of sorbed volatile organic compounds (VOCs) on biochar was conducted by headspace thermal desorption coupled to capillary gas chromatographic-mass spectrometry. VOCs may have a mechanistic role influencing plant and microbial responses to biochar amendments, since VOCs can directly inhibit/stimulate microbial and plant processes. Over 70 biochars encompassing a variety of parent feedstocks and manufacturing processes were evaluated and were observed to possess diverse sorbed VOC composition. There were over 140 individual chemical compounds thermally desorbed from some biochars, with hydrothermal carbonization (HTC) and fast pyrolysis biochars typically possessing the greatest number of sorbed volatiles. In contrast, gasification, thermal or chemical processed biochars, soil kiln mound, and open pit biochars possessed low to non-detectable levels of VOCs. Slow pyrolysis biochars were highly variable in terms of their sorbed VOC content. There were no clear feedstock dependencies to the sorbed VOC composition, suggesting a stronger linkage with biochar production conditions coupled to post-production handling and processing. Lower pyrolytic temperatures (⩽350°C) produced biochars with sorbed VOCs consisting of short carbon chain aldehydes, furans and ketones; elevated temperature biochars (>350°C) typically were dominated by sorbed aromatic compounds and longer carbon chain hydrocarbons. The presence of oxygen during pyrolysis also reduced sorbed VOCs. These compositional results suggest that sorbed VOCs are highly variable and that their chemical dissimilarity could play a role in the wide variety of plant and soil microbial responses to biochar soil amendment noted in the literature. This variability in VOC composition may argue for VOC characterization before land application to predict possible agroecosystem effects.

The potential impacts of biomass feedstock production on water resource availability

Biofuels are a major topic of global interest and technology development. Whereas bioenergy crop production is highly dependent on water, bioenergy development requires effective allocation and management of water. The objectives of this investigation were to assess the bioenergy production relative to the impacts on water resource related factors: (1) climate and weather impact on water supplies for biomass production; (2) water use for major bioenergy crop production; and (3) potential alternatives to improve water supplies for bioenergy. Shifts to alternative bioenergy crops with greater water demand may produce unintended consequences for both water resources and energy feedstocks. Sugarcane and corn require 458 and 2036 m(3) water/m(3) ethanol produced, respectively. The water requirements for corn grain production to meet the US-DOE Billion-Ton Vision may increase approximately 6-fold from 8.6 to 50.1 km(3). Furthermore, climate change is impacting water resources throughout the world. In the western US, runoff from snowmelt is occurring earlier altering the timing of water availability. Weather extremes, both drought and flooding, have occurred more frequently over the last 30 years than the previous 100 years. All of these weather events impact bioenergy crop production. These events may be partially mitigated by alternative water management systems that offer potential for more effective water use and conservation. A few potential alternatives include controlled drainage and new next-generation livestock waste treatment systems. Controlled drainage can increase water available to plants and simultaneously improve water quality. New livestock waste treatments systems offer the potential to utilize treated wastewater to produce bioenergy crops. New technologies for cellulosic biomass conversion via thermochemical conversion offer the potential for using more diverse feedstocks with dramatically reduced water requirements. The development of bioenergy feedstocks in the US and throughout the world should carefully consider water resource limitations and their critical connections to ecosystem integrity and sustainability of human food.

Thermochemical conversion of livestock wastes: Carbonization of swine solids

Slow pyrolysis or carbonization promotes the conversion of animal manures such as swine manure into charcoal. In this paper, the carbonizing kinetics of swine solids taken from different treatment stages were investigated with a thermogravimetric analyzer. Compared to their biologically stabilized counterpart (lagoon sludge) with an activation energy of 160 kJ mol(-1), the activation energies for fresh swine solid samples such as homogenized flushed manure and dewatered solids were much lower between 92 and 95 kJ mol(-1). Compared to the kinetics of first order decomposition of cellulose, the pyrolytic decomposition of the swine manures were more complex with the reaction orders varying at 3.7 and 5.0. The two different mathematical methods employed in this paper yielded the similar values of activation energy (E) and pre-exponential factor (A), confirming the validity of these methods. The results of this study provide useful information for development of farm-scale swine solid carbonization process.

Carbon mineralization in two ultisols amended with different sources and particle sizes of pyrolyzed biochar.

Biochar produced during pyrolysis has the potential to enhance soil fertility and reduce greenhouse gas emissions. The influence of biochar properties (e.g., particle size) on both short- and long-term carbon (C) mineralization of biochar remains unclear. There is minimal information on the potential effects of biochar particle sizes on their breakdowns by soil microorganism, so it is unknown if the particle size of biochar influences C mineralization rate and/or stability in soils. In order to evaluate the effect of different sources (BS) and particle sizes (BF) of biochar on C loss and/or stability in soils, an incubation study on C mineralization of different biochar sources and particle sizes was established using two soils (ST): Norfolk soil (fine loamy, kaolinitic, thermic, typic Kandiudults) and Coxville soil (fine loamy kaolinitic, thermic, Paleaquults). In separate incubation vessels, these soils were amended with one of two manure-based biochars (poultry litters, PL; swine solids, SS) or one of two lignocellulosic-based biochars (switchgrass, SG; pine chips, PC) which were processed into two particle sizes (dust, <0.42 mm; pellet, >2 mm). The amount of CO2 evolved varied significantly between soils (p≤0.0001); particle sizes (p≤0.0001) and the interactions of biochar source (p≤0.001) and forms of biochars (p≤0.0001) with soil types. Averaged across soils and sources of biochar, CO2-C evolved from dust-sized biochar (281 mg kg(-1)) was significantly higher than pellet-sized biochar (226 mg kg(-1)). Coxville soils with SS biochar produced the greatest average CO2-C of 428 mg kg(-1) and Norfolk soils with PC had the lowest CO2-C production (93 mg kg(-1)). Measured rates of carbon mineralization also varied with soils and sources of biochar (Norfolk: PL>SS>SG≥PC; Coxville: PC>SG>SS>PL). The average net CO2-C evolved from the Coxville soils (385 mg kg(-1)) was about threefold more than the CO2-C evolved from the Norfolk soils (123 mg kg(-1)). Our results suggest different particle sizes and sources of biochar as well as soil type influence biochar stability.

Biochar elemental composition and factors influencing nutrient retention

Biochar is the carbonaceous solid byproduct of the thermochemical conversion of a carbon-bearing organic material, commonly high in cellulose, hemicelluloses, or lignin content, for the purposes of carbon sequestration and storage. More specifically, the thermal conversion process known as pyrolysis occurs when carbon-containing substances are introduced to elevated temperatures in the absence of oxygen at varying residence times, yielding biochar. Several pyrolysis techniques employed to produce biochar differ in the temperature of reaction and residence time in the reactor. Different reactor residence times are described as slow (hours to days), fast (seconds to minutes), and flash (seconds). Fast or flash pyrolysis typically occurs around 500oC with residence times less than 500 milliseconds to 1 second and produces relatively greater gas yields with a concomitant decrease in biochar yield (~ 12%). Slow pyrolysis temperatures have ranged from 350 to 750oC but with residence times ranging from minutes to days. Slow pyrolysis yields a greater quantity of biochar (between 25 to 35%). Pyrolysis temperature and type may be varied to maximize the desired biochar end-product. In general, increasing pyrolysis temperature tends to increase biochar total carbon, potassium, and magnesium content, pH, and surface area, and decrease cation exchange capacity. Slow pyrolysis, in general, tends to produce biochars with greater nitrogen, sulfur, available phosphorus, calcium, magnesium, surface area, and cation exchange capacity as compared to fast pyrolysis. In addition to altering temperature and time, the importance of feedstock source needs to be recognized when utilizing biochar in situations such as a soil conditioner. Over the last 10 years biochar research and use has expanded exponentially and so have the feedstocks utilized. Biochars have now been created from corn, wheat, barley and rice straw, switchgrass, peanut, pecan, and hazelnut shells, sugarcane bagasse, coconut coir, food waste, hardwood and softwood species, poultry and turkey litter, swine, dairy, and cattle manure, and biosolids to name a few. Feedstock source influences end-product characteristics, and in general most plant-based biochars containing elevated carbon content and lesser quantities of necessary plant nutrients as compared to manure-based biochars. It has been demonstrated that the mineral content of the feedstock has a significant effect on product distribution, with higher amounts of chloride salts reducing the amount of the solid biochar product. In addition, chloride and other inorganic salts also impact the chemical composition of the liquid, gas, and char pyrolysis products, potentially producing products with higher economic values. Existing studies indicate that even the trace amounts of minerals present in the various biomass sources and feedstock mixtures do have an impact on the chemical compositions of the products. Furthermore, both temperature and residence time, along with feedstock source or mixtures of sources, affect end-product characteristics.

Retention of Heavy Metals in a Typic Kandiudult Amended with Different Manure-based Biochars

Although nutrient-rich manure biochars are expected to be an effective heavy metal stabilizer in agricultural and contaminated soils, systematic studies are lacking to predict the influence of manure variety and pyrolysis temperature on metal-binding potentials. In this study, biochars produced from five manure varieties (dairy, paved feedlot, swine solids, poultry litter, and turkey litter) at two pyrolytic temperatures (350 and 700°C) were examined for the stabilization of Pb, Cu, Ni, and Cd in a weathered, acidic Norfolk loamy sand (fine-loamy, kaolinitic, thermic, Typic Kandiudult). Equilibrium concentrations in the aqueous phase were determined for heavy metals (Cu, Ni, Cd, and Pb) and additional selected elements (Na, P, S, Ca, Mg, Al, and K); these were analyzed by positive matrix factorization to quantitatively determine the factors responsible for the biochars ability to bind the selected heavy metals in soil. Concurrently with the greatest increase in pH and highest equilibrium Na, S, and K concentrations, poultry litter, turkey litter, and feedlot 700°C biochar exhibited the greatest heavy metal retention. In contrast, manure varieties containing disproportionately high (swine) and low (dairy) ash, P, and other elements were the least effective stabilizers. Regardless of the manure type, proton nuclear magnetic resonance analyses showed the removal of leachable aliphatic and nitrogen-containing heteroaromatic functional groups at the higher (700°C) pyrolysis temperature. Consistently greater Cu retention by the 700°C biochar indicated the mobilization of Cu by 350°C biochar-born dissolved organic carbon; however, the influence of other temperature-dependent biochar characteristics cannot be ruled out.

Efficacy of biochar to remove Escherichia coli from stormwater under steady and intermittent flow

Biofilters, designed to facilitate the infiltration of stormwater into soil, are generally ineffective in removing bacteria from stormwater, thereby causing pollution of groundwater and receiving surface waters. The bacterial removal capacity of biofilters has been shown to be lower in the presence of natural organic matter (NOM) and during intermittent infiltration of stormwater. To improve the removal of fecal indicator bacteria (Escherichia coli) under these conditions, we amended sand with 5% (by weight) biochar, a carbonaceous geomedia produced by pyrolysis of biomass, and investigated the removal and remobilization of E. coli. Three types of biochar were used to evaluate the role of biochar properties on the removal. Compared to sand, biochar not only retained up to 3 orders of magnitude more E. coli, but also prevented their mobilization during successive intermittent flows. In the presence of NOM, the removal capacity of biochar was lower, but remained higher than sand alone. The improved retention with the biochar amendment is attributed to an increase in the attachment of E. coli at the primary minimum and to an increase in the water-holding capacity of biochar-amended sand, which renders driving forces such as moving air-water interfaces less effective in detaching bacteria from grain surfaces. Biochars with lower volatile matter and polarity appear to be more effective in removing bacteria from stormwater. Overall, our results suggest that a biochar amendment to biofilter media has the potential to effectively remove bacteria from stormwater.