Differentiating Inorganics in Biochars Produced at Commercial Scale Using Principal Component Analysis.
ABSTRACT: Characterizing the inorganic phase of biochar, beyond determining element concentration, is needed for appropriate application of these materials because mineral forms also influence element availability and behavior. Inorganics in 13 biochars (produced from Poultry litter, switchgrass, and different types of wood) were characterized by proximate analysis, chemical analysis, powder X-ray diffraction (XRD), and scanning electron microscopy with energy-dispersive X-ray (SEM-EDX) spectroscopy. Principal component analysis (PCA) was used to compare biochars and characterize associations between elements. The biochars were produced using commercial-scale reactors and represent materials with properties relevant to field application. Bulk inorganic concentration and composition were responsible for differentiating biochars after PCA of chemical data. In comparison, differentiation based on PCA of diffractogram fingerprints was more nuanced. Here, contributions from cellulose and turbostratic crystalline C influenced separation between samples. It was also sensitive to mineral forms of Ca (whewellite and calcite). Differences in crystalline C and Ca minerals separated two biochars generated from the same willow feedstock using the same pyrolysis conditions at different temperatures. PCA of 606 SEM-EDX point scans revealed that inorganics belong to four main clusters containing Ca, Fe, [Al, Si], and [Cl, K, Mg, Na, P, S] consistent with XRD identification of calcite, magnetic Fe-oxide, silicates, and sylvite. It further suggested that amorphous P-containing minerals associated with Ca (not identified through XRD) were constituents of willow and poultry litter-derived biochars. However, unlike PCA of XRD, it was not able to differentiate the two biochars derived from willow. The three analysis methods provided different perspectives on the properties of the biochar inorganic phase. Combining information from multiple methods is needed to better understand the inorganic composition of biochars.
Project description:Biochar production and use are part of the modern agenda to recycle wastes, and to retain nutrients, pollutants, and heavy metals in the soil and to offset some greenhouse gas emissions. Biochars from wood (eucalyptus sawdust, pine bark), sugarcane bagasse, and substances rich in nutrients (coffee husk, chicken manure) produced at 350, 450 and 750°C were characterized to identify agronomic and environmental benefits, which may enhance soil quality. Biochars derived from wood and sugarcane have greater potential for improving C storage in tropical soils due to a higher aromatic character, high C concentration, low H/C ratio, and FTIR spectra features as compared to nutrient-rich biochars. The high ash content associated with alkaline chemical species such as KHCO3 and CaCO3, verified by XRD analysis, made chicken manure and coffee husk biochars potential liming agents for remediating acidic soils. High Ca and K contents in chicken manure and coffee husk biomass can significantly replace conventional sources of K (mostly imported in Brazil) and Ca, suggesting a high agronomic value for these biochars. High-ash biochars, such as chicken manure and coffee husk, produced at low-temperatures (350 and 450°C) exhibited high CEC values, which can be considered as a potential applicable material to increase nutrient retention in soil. Therefore, the agronomic value of the biochars in this study is predominantly regulated by the nutrient richness of the biomass, but an increase in pyrolysis temperature to 750°C can strongly decrease the adsorptive capacities of chicken manure and coffee husk biochars. A diagram of the agronomic potential and environmental benefits is presented, along with some guidelines to relate biochar properties with potential agronomic and environmental uses. Based on biochar properties, research needs are identified and directions for future trials are delineated.
Project description:Biochars result from the pyrolysis of biomass waste of plant and animal origin. The interest in these materials stems from their potential for improving soil quality due to increased microporosity, carbon pool, water retention, and their active capacity for metal adsorption from soil and irrigation water. Applications in agriculture have been studied under different conditions, but the overall results are still unclear. Char structure, which varies widely according to the pyrolysis process and the nature of feedstock, is thought to be a major factor in the interaction of chars with soil and their metal ion adsorption/chelation properties. Furthermore, biochar nutrients and their elemental content can modify soil fertility. Therefore, the use of biochars in agricultural settings should be examined carefully by conducting experimental trials. Three key problems encountered in the use of biochar involve (i) optimizing pyrolysis for biomass conversion into energy and biochar, (ii) physicochemically characterizing biochar, and (iii) identifying the best possible conditions for biochar use in soil improvement. To investigate these issues, two types of wood pellets, plus digestate and poultry litter, were separately converted into biochar using different technologies: pyrolysis/pyrogasification or catalytic (thermo)reforming. The following physicochemical features for the different biochar batches were measured: pH, conductivity, bulk density, humidity and ash content, particle size, total organic substances, and trace element concentrations. Fine porous structure analysis and total elemental analysis were performed using environmental scanning electron microscopy along with energy-dispersive X-ray spectrometry (EDX). Phytotoxicity tests were performed for each biochar. Finally, we were able to (i) differentiate the biochars according to their physicochemical properties, microstructure, elemental contents, and original raw biomass; (ii) correlate the whole biochar features with their respective optimal concentrations when used as plant fertilizers or soil improvers; and (iii) show that biochars from animal origin were phytotoxic at lower concentrations than those from plant feedstock.
Project description:In this study, different types of magnetic biochar nanocomposites were synthesized using the co-precipitation method. Two biochar materials, namely, sewage sludge biochar and woodchips biochar, were prepared at two different temperatures, viz., 450 and 700 °C. These biochars were further modified with magnetic nanoparticles (Fe3O4). The modified biochar nanocomposites were characterized using field emission-scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), transmission electron microscopy (TEM), Brunauer-Emmett-Teller (BET), SQUID analysis, X-ray photoelectron spectroscopy (XPS), and Fourier-transform infrared spectroscopy (FTIR). The potential of prepared adsorbents was examined for the removal of hexavalent chromium (Cr(VI)) and Acid orange 7 (AO7) dye from water as a function of various parameters, namely, contact time, pH of solution, amount of adsorbents, and initial concentrations of adsorbates. Various kinetic and isotherm models were tested to discuss and interpret the adsorption mechanisms. The maximum adsorption capacities of modified biochars were found as 80.96 and 110.27 mg g-1 for Cr(VI) and AO7, respectively. Magnetic biochars showed high pollutant removal efficiency after 5 cycles of adsorption/desorption. The results of this study revealed that the prepared adsorbents can be successfully used for multiple cycles to remove Cr(VI) and AO7 from water. Graphical Abstract.
Project description:Biochars were produced with magnesium chloride as an additive for the sorption of hexavalent chromium dissolved in water using five types of straw (from taro, corn, cassava, Chinese fir, and banana) and one type of shell (Camellia oleifera) as the raw materials. The removal of hexavalent chromium by the six biochars mainly occurred within 60 min and then gradually stabilized. The kinetics of the adsorption process were second order, the Langmuir model was followed, and the adsorption of Cr(VI) by the six biochars was characterized by Langmuir monolayer chemisorption on a heterogeneous surface. Banana straw biochar (BSB) had the best performance, which perhaps benefitted from its special structure and best adsorption effect on Cr(VI), and the theoretical adsorption capacity was calculated as 125.00 mg/g. For the mechanism analysis, Mg-loaded biochars were characterized before and after adsorption by Fourier transform infrared spectroscopy (FTIR), X-ray diffractometry (XRD), and scanning electron microscopy/energy dispersive spectroscopy (SEM-EDS). The adsorption mechanism differed from the adsorption process of conventional magnetic biochar, and biochar interactions with Cr(VI) were controlled mainly by electrostatic attraction, complexation, and functional group bonding. In summary, the six Mg-loaded biochars exhibit great potential advantages in removing Cr(VI) from wastewater and have promising potential for practical use, especially BSB, which shows super-high adsorption performance.
Project description:The effects of feedstock type and biomass conversion conditions on the speciation of sulfur in biochars are not well-known. In this study, the sulfur content and speciation in biochars generated from pyrolysis and gasification of oak and corn stover were determined. We found the primary determinant of the total sulfur content of biomass to be the feedstock from which the biochar is generated, with oak and corn stover biochars containing 160 and 600-800 ppm sulfur, respectively. In contrast, for sulfur speciation, we found the primary determinant to be the temperature combined with the thermochemical conversion method. The speciation of sulfur in biochars was determined using X-ray absorption near-edge structure (XANES), ASTM method D2492, and scanning electron microscopy-energy-dispersive spectroscopy (SEM-EDS). Biochars produced under pyrolysis conditions at 500-600 °C contain sulfate, organosulfur, and sulfide. In some cases, the sulfate contents are up to 77-100%. Biochars produced in gasification conditions at 850 °C contain 73-100% organosulfur. The increase of the organosulfur content as the temperature of biochar production increases suggests a similar sulfur transformation mechanism as that in coal, where inorganic sulfur reacts with hydrocarbon and/or H2 to form organosulfur when the coal is heated. EDS mapping of a biochar produced from corn stover pyrolysis shows individual sulfur-containing mineral particles in addition to the sulfur that is distributed throughout the organic matrix.
Project description:Biochar application to soils has been investigated as a means of improving soil fertility and mitigating climate change through soil carbon sequestration. In the present work, the invasive shrub "Eupatorium adenophorum" was utilized as a sustainable feedstock for making biochar under different pyrolysis conditions in Nepal. Biochar was produced using several different types of kilns; four sub types of flame curtain kilns (deep-cone metal kiln, steel shielded soil pit, conical soil pit and steel small cone), brick-made traditional kiln, traditional earth-mound kiln and top lift up draft (TLUD). The resultant biochars showed consistent pH (9.1 ± 0.3), cation exchange capacities (133 ± 37 cmolc kg-1), organic carbon contents (73.9 ± 6.4%) and surface areas (35 to 215 m2/g) for all kiln types. A pot trial with maize was carried out to investigate the effect on maize biomass production of the biochars made with various kilns, applied at 1% and 4% dosages. Biochars were either pretreated with hot or cold mineral nutrient enrichment (mixing with a nutrient solution before or after cooling down, respectively), or added separately from the same nutrient dosages to the soil. Significantly higher CEC (P< 0.05), lower Al/Ca ratios (P< 0.05), and high OC% (P<0.001) were observed for both dosages of biochar as compared to non-amended control soils. Importantly, the study showed that biochar made by flame curtain kilns resulted in the same agronomic effect as biochar made by the other kilns (P > 0.05). At a dosage of 1% biochar, the hot nutrient-enriched biochar led to significant increases of 153% in above ground biomass production compared to cold nutrient-enriched biochar and 209% compared to biochar added separately from the nutrients. Liquid nutrient enhancement of biochar thus improved fertilizer effectiveness compared to separate application of biochar and fertilizer.
Project description:We used diffuse reflectance Fourier-transform infrared (DR-FTIR) spectroscopy, X-ray diffraction (XRD), and chemical and isotopic analyses to characterize the light fraction of four contrasting soils (control and biocharamended soils) to determine changes in biochar properties after aging. Two Eucalyptus saligna Sm. wood biochars, produced at 450°C (B450) and 550°C (B550), were incubated separately in each of the four soils for up to 12 mo at 20, 40, and 60°C. Total C and isotopic (?13C) methods were used to quantify the amounts of biochar C and native C mineralized during incubation. The DR-FTIR spectra of the light fraction showed distinct absorption bands representing native soil organic C, biochar C, and mineral constituents present in the soils; the mineral bands were consistent with XRD data of the clay fraction of the four soils. Analysis of the DR-FTIR spectra in the ?(C-H) bands showed that the ratio of the aromatic ?(C-H) bands systematically increased relative to the aliphatic ?(C-H) bands with increasing mineralization of biochar C in the B550 amended soils, and this relationship was unique for each soil type. In contrast, this relationship was not observed for the B450 amended soils that contained a relatively smaller proportion of aromatic C.
Project description:Sewage sludge biochars were obtained at different pyrolysis temperatures from 300°C to 900°C and their macro- and microscale properties were analyzed. The biochar's plant-available nutrients and humus-like substances in the water-extractable phase and fixed nutrients in the solid fraction were evaluated for their potential agronomic implications. FT-IR, Raman, XRD, XPS, and SEM techniques were used to investigate the chemical structure, functional groups, and microcrystal structure on the surface of the biochar. The results revealed minor chemical changes and dramatic mass loss in the biochar obtained at 300-500°C, whereas significant chemical changes in the biochar were obtained at 600-900°C. The concentrations of plant-available nutrients as well as fulvic- and humic-acid-like materials decreased in the biochar samples obtained at higher temperatures. These results implied that the biochar samples pyrolyzed at 300-500°C could be a direct nutrient source and used to neutralize alkaline soil. The surface area and porosity of the biochar samples increased with temperature, which increased their adsorption capacity. Rearrangement occurred at higher temperature 600-900°C, resulting in the biochar becoming increasingly polyaromatic and its graphite-like carbon becoming organized.
Project description:This dataset is the supplementary data for the summited research article Li et al., 2017  and provides detailed data profiles to support the explication about mineral constituents' effect on temperature-dependent structural characterization of carbon fractions in sewage sludge-derived biochar. The elemental compositions of major inorganics in the sewage sludge were detected by X-ray fluorescence spectrometry (XRF, S2-Ranger, Bruker).The images from scanning electron microscope (SEM) were compared between unwashed and acid-washed samples, and revealed the effect of acid washing on the surface morphology and porosity of sewage sludge and the biochar. Peak deconvolution was conducted for the (002) peak of X-ray diffraction (XRD) patterns from the acid-washed samples, which provided information on structural parameters of the carbon stacking structure and the temperature-dependent structure evolution of sewage sludge biochar. Peak deconvolution was also carried out for Raman data of the samples with/without consideration of mineral constituents (aluminosilicates). Results of Raman peak deconvolution showed structure ordering evolution with pyrolysis temperature and evidenced the contribution of mineral constituents to the Raman signals.
Project description:Effects of biochars on soil silicon dissolution kinetics remain unaddressed. Si-rich rice husk (RH) and rice straw (RS), and Si-deficient wood sawdust (WB) and orange peel (OP) were applied to prepare biochars at 300-700?°C. The silicon dissolution of Si-rich biochars was relatively high in comparison with Si-deficient biochars, and increased with the pyrolysis temperature. The mechanism of silicon release is suggested to be controlled by a protective carbon-silicon interaction, as accompanied by carbon release. After mixing with soil, the addition of Si-rich biochar leads up to 72.7-121% improvement in silicon dissolution in a high-silicon soil (HSS) compared to 147-243% improvement in a low-silicon soil (LSS). The total cumulative amount of silicon dissolved decreased compared to the theoretical value due to the adsorption of silicic acid by the biochar. The addition of WB700 or OP700 as Si-deficient biochars leads to a cumulative Si dissolution decrease of 15.7 and 12.1%, respectively. The adsorption of silicic acid in the biochar and the protection of soil dissolved Fe make biochar a reservoir of soil silicon. Thus, Si-rich biochar could serve as a source of Si with slow release, while Si-deficient biochar could serve as an extra Si sink in agricultural paddy soil.