Minori Uchimiya

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.

Immobilization of heavy metal ions (CuII, CdII, NiII, and PbII) by broiler litter-derived biochars in water and soil.

Chars, a form of environmental black carbon resulting from incomplete burning of biomass, can immobilize organic contaminants by both surface adsorption and partitioning mechanisms. The predominance of each sorption mechanism depends upon the proportion of organic to carbonized fractions comprising the sorbent. Information is currently lacking in the effectiveness of char amendment for heavy metal immobilization in contaminated (e.g., urban and arms range) soils where several metal contaminants coexist. The present study employed sorbents of a common biomass origin (broiler litter manure) that underwent various degrees of carbonization (chars formed by pyrolysis at 350 and 700 degrees C and steam-activated analogues) for heavy metal (Cd(II), Cu(II), Ni(II), and Pb(II)) immobilization in water and soil. ATR-FTIR, (1)H NMR, and Boehm titration results suggested that higher pyrolysis temperature and activation lead to the disappearance (e.g., aliphatic -CH(2) and -CH(3)) and the formation (e.g., C-O) of certain surface functional groups, portions of which are leachable. Both in water and in soil, pH increase by the addition of basic char enhanced the immobilization of heavy metals. Heavy metal immobilization resulted in nonstoichiometric release of protons, that is, several orders of magnitude greater total metal concentration immobilized than protons released. The results suggest that with higher carbonized fractions and loading of chars, heavy metal immobilization by cation exchange becomes increasingly outweighed by other controlling factors such as the coordination by pi electrons (C=C) of carbon and precipitation.

Influence of Pyrolysis Temperature on Biochar Property and Function as a Heavy Metal Sorbent in Soil

While a large-scale soil amendment of biochars continues to receive interest for enhancing crop yields and to remediate contaminated sites, systematic study is lacking in how biochar properties translate into purported functions such as heavy metal sequestration. In this study, cottonseed hulls were pyrolyzed at five temperatures (200, 350, 500, 650, and 800 °C) and characterized for the yield, moisture, ash, volatile matter, and fixed carbon contents, elemental composition (CHNSO), BET surface area, pH, pHpzc, and by ATR-FTIR. The characterization results were compared with the literature values for additional source materials: grass, wood, pine needle, and broiler litter-derived biochars with and without post-treatments. At respective pyrolysis temperatures, cottonseed hull chars had ash content in between grass and wood chars, and significantly lower BET surface area in comparison to other plant source materials considered. The N:C ratio reached a maximum between 300 and 400 °C for all biomass sources considered, while the following trend in N:C ratio was maintained at each pyrolysis temperature: wood≪cottonseed hull≈grass≈pine needle≪broiler litter. To examine how biochar properties translate into its function as a heavy metal (NiII, CuII, PbII, and CdII) sorbent, a soil amendment study was conducted for acidic sandy loam Norfolk soil previously shown to have low heavy metal retention capacity. The results suggest that the properties attributable to the surface functional groups of biochars (volatile matter and oxygen contents and pHpzc) control the heavy metal sequestration ability in Norfolk soil, and biochar selection for soil amendment must be made case-by-case based on the biochar characteristics, soil property, and the target function.

Screening biochars for heavy metal retention in soil: Role of oxygen functional groups

Oxygen-containing carboxyl, hydroxyl, and phenolic surface functional groups of soil organic and mineral components play central roles in binding metal ions, and biochar amendment can provide means of increasing these surface ligands in soil. In this study, positive matrix factorization (PMF) was first employed to fingerprint the principal components responsible for the stabilization of heavy metals (Cu, Ni, Cd, Pb) and the release of selected elements (Na, Ca, K, Mg, S, Al, P, Zn) and the pH change in biochar amended soils. The PMF analysis indicated that effective heavy metal stabilization occurred concurrently with the release of Na, Ca, S, K, and Mg originating from soil and biochar, resulting in as much as an order or magnitude greater equilibrium concentrations relative to the soil-only control. In weathered acidic soil, the heavy metal (especially Pb and Cu) stabilization ability of biochar directly correlated with the amount of oxygen functional groups revealed by the O/C ratio, pH(pzc), total acidity, and by the (1)H NMR analysis. Equilibrium speciation calculation showed minor influence of hydrolysis on the total soluble metal concentration, further suggesting the importance of binding by surface ligands of biochar that is likely to be promoted by biochar-induced pH increase.

Contaminant immobilization and nutrient release by biochar soil amendment: Roles of natural organic matter

Contamination of soil interstitial waters by labile heavy metals such as Cu(II), Cd(II), and Ni(II) is of worldwide concern. Carbonaceous materials such as char and activated carbon have received considerable attention in recent years as soil amendment for both sequestering heavy metal contaminants and releasing essential nutrients like sulfur. Information is currently lacking in how aging impacts the integrity of biochars as soil amendment for both agricultural and environmental remediation purposes. Major contributors to biochar aging in soils are: sorption of environmental constituents, especially natural organic matter (NOM), and oxidation. To investigate the impact of NOM and organic fractions of chars, we employed broiler litter-derived chars and steam-activated carbons that underwent varying degrees of carbonization, in the presence and absence of NOM having known carboxyl contents. For aging by oxidation, we employed phosphoric acid activated carbons that underwent varying degrees of oxidation during activation. The results suggest that the organic fractions of biochars, and NOM having high carboxyl contents can mobilize Cu(II) retained by alkaline soil. Base treatment of broiler litter-derived char formed at low pyrolysis temperature (350 degrees C) improved the immobilization of all heavy metals investigated, and the extent of immobilization was similar to, or slightly greater than pecan shell-derived phosphoric acid activated carbons. Portions of total sulfur were released in soluble form in soil amended with broiler litter-derived carbons, but not pecan shell-derived phosphoric acid activated carbons.

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.

Influence of soil properties on heavy metal sequestration by biochar amendment: 1. Copper sorption isotherms and the release of cations.

The amendment of carbonaceous materials such as biochars and activated carbons is a promising in situ remediation strategy for both organic and inorganic contaminants in soils and sediments. Mechanistic understandings in sorption of heavy metals on amended soil are necessary for appropriate selection and application of carbonaceous materials for heavy metal sequestration in specific soil types. In this study, copper sorption isotherms were obtained for soils having distinct characteristics: clay-rich, alkaline San Joaquin soil with significant heavy metal sorption capacity, and eroded, acidic Norfolk sandy loam soil having low capacity to retain copper. The amendment of acidic pecan shell-derived activated carbon and basic broiler litter biochar lead to a greater enhancement of copper sorption in Norfolk soil than in San Joaquin soil. In Norfolk soil, the amendment of acidic activated carbon enhanced copper sorption primarily via cation exchange mechanism, i.e., release of proton, calcium, and aluminum, while acid dissolution of aluminum cannot be ruled out. For San Joaquin soil, enhanced copper retention by biochar amendment likely resulted from the following additional mechanisms: electrostatic interactions between copper and negatively charged soil and biochar surfaces, sorption on mineral (ash) components, complexation of copper by surface functional groups and delocalized π electrons of carbonaceous materials, and precipitation. Influence of biochar on the release of additional elements (e.g., Al, Ca) must be carefully considered when used as a soil amendment to sequester heavy metals.

Retention of Heavy Metals by Carboxyl Functional Groups of Biochars in Small Arms Range Soil

Long-term effectiveness of biochar for heavy metal stabilization depends upon biochars sorptive property and recalcitrance in soil. To understand the role of carboxyl functional groups on heavy metal stabilization, cottonseed hull biochar and flax shive steam-activated biochar having a low O/C ratio (0.04-0.06) and high fixed carbon content (~80% dry weight basis) were oxidized using concentrated H(2)SO(4)/HNO(3) and 30% HNO(3). Oxidized and unoxidized biochars were characterized for O/C ratio, total acidity, pH, moisture, ash, volatile matter, and fixed carbon contents, Brunauer-Emmett-Teller surface area, and attenuated total reflectance Fourier transform infrared spectral features. Characterized biochars were amended (2%, 5%, 10%, and 20% in grams of biochar per gram of soil) on a sandy, slightly acidic (pH 6.27) heavy metal contaminated small arms range soil fraction (<250 μm) having low total organic carbon (0.518%) and low cation exchange capacity (0.95 cmol(c) kg(-1)). Oxidized biochars rich in carboxyl functional groups exhibited significantly greater Pb, Cu, and Zn stabilization ability compared to unoxidized biochars, especially in pH 4.9 acetate buffer (standard solution for the toxicity characteristic leaching procedure). Oppositely, only oxidized biochars caused desorption of Sb, indicating a counteracting impact of carboxyl functional groups on the solubility of anions and cations. The results suggested that appropriate selection of biochar oxidant will produce recalcitrant biochars rich in carboxyl functional groups for a long-term heavy metal stabilization strategy in contaminated soils.

Reversible redox chemistry of quinones: impact on biogeochemical cycles.

The role of quinone biomolecules and quinone moieties of natural organic matter (NOM) as the electron transfer mediator in essential biogeochemical processes such as iron bioreduction and contaminant degradation has received considerable interests in the past decade. Hypothesized electron shuttling mechanism must be evaluated based on the availability and stability of quinones under a given environmental setting. The goal of this review is to examine the source, reactivity, and fate of potential quinone catalysts with respect to chemical interactions (e.g., with other quinones and nucleophiles) that will inevitably occur in complex environmental media. We will first discuss natural and anthropogenic sources of quinones in aqueous environments, and fundamental transformation pathways including cross reaction, autoxidation, and addition reactions. We will then assess how the described sources (molecular structure) and transformation pathways (stability) will impact the ability of a quinone molecule to catalyze a biogeochemical process. Thermodynamics and kinetics of electron transfer reactions with both the electron donor (e.g., hydrogen sulfide as a bulk reductant) and the terminal electron acceptor (e.g., nitroaromatic explosives in contaminant degradation), and stability towards irreversible side reactions are the key factors determining the geochemical conditions under which the catalysis by a quinone molecule will be operative.

Sorption of deisopropylatrazine on broiler litter biochars.

Biochars have received increasing attention in recent years because of a large-scale soil amendment to improve soil fertility, immobilize contaminants, and to serve as a recalcitrant carbon stock. Information is currently lacking in factors controlling the sorption capacity of manure-derived biochars. In this study, sorption isotherms for deisopropylatrazine, a stable metabolite of the widely applied herbicide atrazine, were obtained in acidic aqueous media (pH 5.5) for broiler litter-derived biochars formed by pyrolysis at 350 and 700 °C with and without steam activation at 800 °C. An increase in the Freundlich distribution coefficient (KF) and isotherm nonlinearity (nF) was observed with pyrolysis temperature and steam-activation, suggesting that the surface area and aromaticity (degree of carbonization) are the factors controlling the sorption capacity of chars at low surface coverage. At high surface coverage, the isotherms became increasingly linear, suggesting sorption on noncarbonized fraction of biochars. In binary-solute experiments, the sorption of deisopropylatrazine was significantly diminished by Cu(II), further suggesting the predominance of the surface adsorption mechanism at low surface coverage of biochars.