Systematic evaluation of methods for iron-impregnation of biochar and effects on arsenic in flooded soils.

There is a need for innovative strategies to decrease the mobility of metal(loids) including arsenic (As) and cadmium (Cd) in agricultural soils, including rice paddies, so as to minimize dietary exposure to these toxic elements. Iron (Fe)-modified biochars (FBCs) are used to immobilize As and Cd in soil-water systems, but there is a lack of clarity on optimal methods for preparing FBCs because there are only limited studies that directly compare BCs impregnated with Fe under different conditions. There is also a lack of information on the long-term performance of FBCs in flooded soil environments, where reductive dissolution of Fe (oxy)hydroxide phases loaded onto biochar surfaces may decrease the effectiveness of FBCs. This study uses material characterization methods including FTIR, SEM-EDX, BET, and adsorption isotherm experiments to investigate the effects of Fe-impregnation methods (pH, pyrolysis sequence, and sonication) on the morphology and mineralogy of Fe loaded onto the biochar surface, and to FBC adsorbent properties for arsenate (As(V)), arsenite (As(III)), and Cd. Acidic impregnation conditions favored the adsorption of As(III) onto amorphous Fe phases that were evenly distributed on the biochar surface, including within the biochar pore structure. The combination of sonication with acidic Fe-impregnation conditions led to the best adsorption capacities for As(V) and As(III) (4830 and 11,166 µg As g-1 biochar, respectively). Alkaline Fe-impregnation conditions led to the highest Cd adsorption capacity of 3054 µg Cd g-1 biochar, but had poor effectiveness as an As adsorbent. Amending soil with 5% (w/w) of an acid-impregnated and sonicated FBC was more effective than an alkaline-impregnated FBC or ferrihydrite in decreasing porewater As concentrations. The acid-impregnated FBC also had greater longevity, decreasing As by 54% and 56% in two flooded phases, probably due to the greater stability of Fe(III) within the biochar pore structure that may have a direct chemical bond to the biochar surface. This study demonstrates that FBCs can be designed with selectivity towards different As species or Cd and that they can maintain their effectiveness under anaerobic soil conditions. This is the first study to systematically test how impregnation conditions affect the stability of FBCs in soils under multiple drying-rewetting cycles.

Using the Conditional Process Analysis Model to Characterize the Evolution of Carbon Structure in Taxodium ascendens Biochar with Varied Pyrolysis Temperature and Holding Time.

Temperature determines biochar structure during pyrolysis. However, differences in holding time and feedstock types may affect this relationship. The conditional process analysis model was used in this paper to investigate the potential to affect this mechanism. The branch and leaf parts of Taxodium ascendens were separately pyrolyzed at 350, 450, 650, and 750 °C, and kept for 0.5, 1, and 2 h at each target temperature. We measured the fixed carbon and ash contents and the elemental composition (C, H, O and N) of the raw materials and their char samples. After plotting a Van Krevelen (VK) diagram to determine the aromatization of chars, the changes in the functional groups were analyzed using Fourier transform infrared (FTIR), Raman, and X-ray photoelectron spectroscopy (XPS). The results revealed that pyrolysis at temperatures between 450 and 750 °C accounted for the aromatization of biochar because the atomic H/C ratio of branch-based chars (BC) decreased from 0.53-0.59 to 0.15-0.18, and the ratio of leaf-based chars (LC) decreased from 0.56-0.68 to 0.20-0.22; the atomic O/C ratio of BC decreased from 0.22-0.27 to 0.08-0.11, while that of LC decreased from 0.26-0.28 to 0.18-0.21. Moreover, the average contents of N (1.89%) and ash (13%) in LC were evidently greater than that in BC (N:0.62%; Ash: 4%). Therefore, BC was superior to LC in terms of the stability of biochar. In addition, the increasing ID/IG and ID/I(DR+GL) ratios in BC and LC indicated an increasing amount of the amorphous aromatic carbon structure with medium-sized (2~6 rings) fused benzene rings. According to the CPA analysis, an extension of the holding time significantly enhanced the increase in aromatic structures of LC with temperature. But this extension slightly reduced the growth in aromatic structures of BC. All indicate that holding time and feedstock types (branch or leaf feedstock) could significantly affect the variation in biochar aromatic structure with respect to temperature.

Temperature and moisture mediated changes in chemical and microbial properties of biochars in an Anthrosol.

Sequestration of soil carbon is considered as a promising strategy for mitigating climate change. As a source of recalcitrant carbon, biochar has been widely used in agricultural soil as a mean of stabilizing soil organic carbon (SOC). However, limited reports focused on the changes of biochar itself in soil when compared with the bulk SOC after biochar addition. To explore how environmental conditions influence the stability of biochar, isolated straw-derived biochar particles (0.25-2 mm) were embedded in an Anthrosol for 12 months under varied environmental conditions of incubation temperature (15 °C, 25 °C and 35 °C) and moisture (60 % and 150 % of saturated water content). Within the early 1 month of incubation, pH and inorganic nitrogen contents of biochar changed significantly as a function of moisture and temperature (p < 0.01), whereas water extractable organic carbon (WEOC) content was only influenced by moisture content (p < 0.01). The highest temperature (35 °C) and saturated water content (150 %) induced the largest aging response reflected by increases in oxygen-containing surface functional groups of biochar, including C-O-C (51.35 % - 149 %) and N-C-O (65.55 % - 119 %). Pearson correlation and RDA analysis indicated that the chemical properties of biochar contribute more to the carbon-source utilization properties of biochar colonized microbial community within 1 month of incubation, while the bulk soil chemical properties (pH, DOC, MBC and NO3-) had a higher contribution until the end of incubation. Moisture rather than temperature was the dominant factor in regulating the functional diversity of biochar colonized microbial community.

Stability of biochar in mineral soils: Assessment methods, influencing factors and potential problems.

Amendment of biochar into mineral soils has been reported a promising strategy for carbon sequestration and greenhouse gas mitigation due to its high stability. Currently, most studies on the stability of biochar are mainly focused on the assessment methods and influencing factors. The assessment methods include qualitative evaluation of physical and chemical properties, and utilization of kinetic mineralization models on the basis of laboratory incubation. As a result, these assessment methods are difficult to accurately reflect the real impact of the interaction between biochar and environmental factors. This article reviews the existing assessment methods, influencing factors, and the impact of environmental aging on the stability of biochar. It is found that under the influence of environmental factors, existing assessment methods are likely to overestimate the stability of biochar in mineral soils. Therefore, more emphases should be laid on the analyses of the deficiencies in the existing assessment methods on the stability of biochar in the consideration of practical applications. Long-term field experiment is strongly recommended to establish a more accurate assessment model on biochar stability for the evaluation of its carbon sequestration potential in mineral soils.

Stabilization of dissolvable biochar by soil minerals: Release reduction and organo-mineral complexes formation.

Biochar has two existing forms in the moist soil environment, free dissolvable biochar (particle size < 0.45 µm) and undissolvable particles (particle size > 0.45 µm). The release and decomposition of dissolvable biochar from bulk biochar particles is a primary C loss pathway in biochar-amended soils, which would be reduced by their interactions with soil minerals. Most previous studies focused on the effect of feedstock types and pyrolysis conditions on dissolvable biochar stability, while few studies researched the interaction between dissolvable biochar and soil components, for instance the soil minerals, and its effect on the stability of dissolvable biochar. In this study, bentonite and goethite were selected as model soil minerals because of their differences in structure and surface types: negatively charged 2:1 type phyllosilicate (bentonite) and positively charged crystalline mineral (goethite). Dry-wet cycling was conducted to determine the effect of these two minerals on the release of dissolvable biochar from walnut shell-derived biochar particles. The stability of dissolvable biochar was measured by chemical oxidation and biodegradation. Both soil minerals reduced the release of dissolvable biochar by over 34% with the presence of Ca2+. Mechanisms of "Ca2+ bridging", "ligand exchange" and "van der Waals attraction" contributed to the formation of dissolvable biochar-bentonite complexes, and Ca2+ promoted dissolvable biochar inserting into bentonite interlayer space, expanding d-spacing from 1.25 nm to 1.55 nm. However, "Ca2+ bridging" barely formed on goethite because of charge repulsion, indicating that the dissolvable biochar was bound with goethite mainly by "van der Waals attraction" and "ligand exchange". Due to organo-mineral complexes formation, the chemical oxidation extent of dissolvable biochar was reduced by 22.8-36.5%, and the biodegradation extent was reduced by 72.7-85.0%, since the soil minerals are more effective to prevent the dissolvable biochar from being biodegraded. This study proved soil minerals and Ca2+ were beneficial for enhancing biochar stability, these observations assisted in assessing the biochar ability for long-term carbon sequestration.

Chemical stabilization of Cd-contaminated soil using fresh and aged wheat straw biochar.

Metal mining and smelting activities can introduce a substantial amount of potentially toxic elements (PTE) into the environment that can persist for an extended period. That can limit the productivity of the land and creates dangerous effects on ecosystem services. The effectiveness of wheat straw biochar to immobilize Cd in contaminated soil due to metal smelting activities was investigated in this study. The biochar carbon stability and long-term provisioning of services depend on the biochar production conditions, nature of the feedstock, and the biotic and abiotic environmental conditions in which the biochar is being used. Within this context, three types of wheat straw biochar were produced using a screw reactor at 400 °C, 500 °C, and 600 °C and tested in a laboratory incubation study. Soil was amended with 2 wt% of biochar. Both fresh and aged forms of biochar were used. Biochars produced at lower temperatures were characterized by lower pH, a lower amount of stable C, and higher amounts of acidic surface functional groups than the freshly produced biochars at higher production temperatures. At the end of the 6 months of incubation time, compared to the soil only treatment, fresh and aged forms of wheat straw biochar produced at 600 °C reduced the Cd concentration in soil pore water by 22% and 15%, respectively. Our results showed that the aged forms of biochar produced at higher production temperatures (500 °C and 600 °C) immobilized Cd more efficiently than the aged forms of lower temperature biochar (400 °C). The findings of this study provide insights to choose the production parameters in wheat straw biochar production while considering their aging effect to achieve successful stabilization of Cd in contaminated soils.

Mechanisms of Pb and/or Zn adsorption by different biochars: Biochar characteristics, stability, and binding energies.

Biochar has been widely studied as an amendment for use in remediation of water and soil contaminated with heavy metals such as Pb2+ and Zn2+, but the effects of biochar characteristics, including stability, on the competitive adsorption of Pb2+ and Zn2+ by biochars from various sources are incompletely understood. In this work, biochars from three different feedstocks, including rice straw (RS), chicken manure (CM), and sewage sludge (SS), were prepared at two pyrolysis temperatures, 550 and 350 °C, and tested to investigate the influence of their stabilities and other characteristics on their adsorption of Pb2+ and Zn2+ in both single- and binary-metal systems. RS biochar had the highest carbon and hydrogen contents, greatest number of functional groups (e.g., OH and C=C/C=O), highest pH, most negative surface charge, and highest physical stability, and thus the highest adsorption capacity for Pb2+ and Zn2+. Pyrolysis at the higher temperature resulted in a slight decrease in aromatic functional groups on biochar surfaces but higher adsorption capacities for Pb2+ and Zn2+ due to the decreased biochar particle size and increased specific surface area. FTIR, XRD, and XPS analyses indicated that Pb2+ and Zn2+ were absorbed on the biochars primarily via chemical complexation with aromatic functional groups. Quantum chemistry calculations confirmed that these functional groups (e.g., -OH and-COOH) tended to bind more strongly with Pb2+ than with Zn2+ due to the former's lower binding energies, which also accounted for the notable decrease in adsorption of Zn2+ in the presence of Pb2+. In addition, compared to carboxyl groups, hydroxyl groups had smaller binding energies and stronger metal complexation. These findings provide a theoretical basis for improved understanding of potential applications of biochars in environmental remediation.

Evaluation of change in biochar properties derived from different feedstock and pyrolysis temperature for environmental and agricultural application.

In recent years, the application of biochar has increased significantly for sustainable and efficient carbon sequestration, improving soil quality and enhancement of plant growth. The biochar is mostly made from agricultural residues and waste materials. The objective of this study was to assess the changes in physicochemical, surface morphology, and mineral composition of different biochars with varying pyrolysis temperature. Eighteen different types of biochars were prepared through pyrolysis of feedstock at four different temperatures (350 °C, 450 °C, 550 °C and 650 °C). The feedstock used for the preparation of biochar were organic waste materials such as pine saw dust, rice husk, food waste, poultry litter and paper sludge. Pyrolysis temperatures and feedstock types significantly influenced biochar properties. For instance, pH of poultry litter and paper sludge biochar has increased from 6.2 to 10.3, BET surface area of saw dust and rice husk increased from 3.39 to 443.79 m2 g-1 and 11.61 to 280.97 m2 g-1 while cation exchange capacity value decreased with the increase in temperature. Paper sludge and poultry litter had the highest ash content value (57.20 ± 0.02 and 44.10 ± 0.02) whereas saw dust, rice husk and food waste biochar have highest fixed carbon value (55.31 ± 0.15, 48.47 ± 0.31 and 58.85 ± 0.22) at 650 °C. Degree of aromaticity increased and polarity reduced significantly with pyrolysis temperature. Rice husk and saw dust biochar prepared at higher temperature were more stable among all and thus recalcitrant in nature. X-ray diffraction results revealed mineral like quartz in saw dust and poultry litter biochar, sylvite, potassium iodate, calcium sulfide in food waste biochar and calcium carbonate in paper sludge biochar. Scanning Electron Microscopy showed increase in number of pores as well as pore size specially for the saw dust, and rice husk biochar. This study suggested that biochar prepared at higher temperature (550 °C and 650 °C) are more suitable for carbon sequestration and agricultural purpose.

Driving forces linking microbial community structure and functions to enhanced carbon stability in biochar-amended soil.

Biochar induces various priming effects on native soil organic carbon (nSOC), whereas the underlying mechanisms linking these to soil microbial community structure and functions remain unclear. To investigate soil microbial community structure and functions associated with priming effects, rice straw (RS) and the derived biochar samples (RS400 and RS700, pyrolyzed at 400 °C and 700 °C, respectively) were applied to a sandy loam soil for a 33- and 200-day incubation. Using stable C isotopic ratios, CO2-C emissions from biochar/feedstock and nSOC were quantitatively identified and indicated an enhanced C stability of RS700 over that of RS and RS400. A decreased soil pH and increased dissolved organic carbon and NH4+-N concentrations with the RS amendment are driving forces that lead to an enhanced soil microbial activity and a higher abundance of heterotrophic microbes, especially Proteobacteria and Acidobacteria, which contribute to high CO2 emissions. The enhanced C stability of biochar and nSOC over that of pristine feedstock was primarily attributable to a stable and high soil pH, which minimized the disturbance of soil heterotrophic microbial community structure and functions, favoring the growth of Actinobacteria, Proteobacteria, and Ascomycota. The biochar amendment in soil enriched the metabolic pathways of biosynthesis and the decomposition of secondary metabolites, polycyclic aromatic hydrocarbons (PAHs) degradation, and electron transfer carriers.

Enhanced biochar stabilities and adsorption properties for tetracycline by synthesizing silica-composited biochar.

The silica-composited biochars (SBC) were synthesized by adding silica particulates into bamboo biomass during pyrolysis at 700 °C to examine the effect of silica addition on biochar stabilities and adsorption properties for tetracycline (TC). Silica addition increased the total pore volume and average pore diameter of biochar due to the abundant mesopores in SBC, but decreased specific surface area due to the blockage of biochar pore with silica particles. Biochar stability was obviously enhanced with silica addition due to the decreased atomic ratio of H/C and O/C, the reduced C loss amount after chemical oxidation treatment, and the increased thermal stability. The adsorption capacities of SBC for TC were greatly enhanced with silica addition and increased with the increasing silica addition amount, which can be attributed to the facilitating effect of π-π electron donor acceptor (EDA) interaction and pore-filling effect. In addition, silica addition can also effectively enhance the oxidation resistance of biochar for TC adsorption, since the decreased degree (δ) of TC adsorption amounts on the biochars after chemical oxidation decreased with the increasing silica addition level. The observed positive correlations between δ values and the corresponding C loss amount of biochars after chemical oxidation suggested that the high carbon stability was favorable for the maintenance of biochar adsorption capacity. These results can provide a new way to improve biochar stabilities, aging resistance, and adsorption properties for organic pollutants.