Enhancing the adsorption function of biochar by mechanochemical graphitization for organic pollutant removal

• Mechanochemical treatment reduced the calcination temperature for biochar synthesis. • Biochar is converted to graphite after mechanochemical treatment. • Biochar was reduced to nanoscale after mechanochemical treatment. Biochar (BC) has been extensively studied as adsorbent for the treatment of water pollution. Despite the distinct advantages, the high calcination temperature and low adsorption capacity of pristine BC limit its practical applications. Most of the former studies focused on the structure and/or surface modification to improve the adsorption capacity of BC. However, the harsh experiment conditions involved in the biochar modification limited the application in industrial level. Herein, we introduced mechanical treatment into BC preparation to reduce the calcination temperature and improve the adsorption capacity simultaneously. The results indicated that the calcination temperature was reduced and the adsorption capacity of the treated BC was improved after mechanochemical treatment. Characterization of the samples disclosed that BCs were graphitized with the particle size reduced to nanoscale after treatment. Adsorption tests indicated that the mechanochemically treated BCs showed much better removal performance of organic contaminants than that of pristine BCs. For instance, among four pristine BCs (BC600, BC700, BC800, and BC900), only BC900 has strong adsorption capacity for MB, while BC600 has low adsorption capacity (1.2 mg/g). By comparison, the adsorption capacity of MB increased greatly to 173.96 mg/g by BC600-500/1 (treated at 500 r/min for 1 hour). To optimize the mechanochemical treatment, the effects of rotation speed and agitation duration were also investigated.     

Co-pyrolysis of swine manure with agricultural plastic waste: Laboratory-scale study

Manure-derived biochar is the solid product resulting from pyrolysis of animal manures. It has considerable potential both to improve soil quality with high levels of nutrients and to reduce contaminants in water and soil. However, the combustible gas produced from manure pyrolysis generally does not provide enough energy to sustain the pyrolysis process. Supplementing this process may be achieved with spent agricultural plastic films; these feedstocks have large amounts of available energy. Plastic films are often used in soil fumigation. They are usually disposed in landfills, which is wasteful, expensive, and environmentally unsustainable. The objective of this work was to investigate both the energetics of co-pyrolyzing swine solids with spent plastic mulch films (SPM) and the characteristics of its gas, liquid, and solid byproducts. The heating value of the product gas from co-pyrolysis was found to be much higher than that of natural gas; furthermore, the gas had no detectable toxic fumigants. Energetically, sustaining pyrolysis of the swine solids through the energy of the product gas could be achieved by co-pyrolyzing dewatered swine solids (25% m/m) with just 10% SPM. If more than 10% SPM is used, the co-pyrolysis would generate surplus energy which could be used for power generation. Biochars produced from co-pyrolyzing SPM and swine solid were similar to swine solid alone based on the surface area and the ¹H NMR spectra. The results of this study demonstrated the potential of using pyrolysis technology to manage two prominent agricultural waste streams (SPM and swine solids) while producing value-added biochar and a power source that could be used for local farm operations.     

Adsorption of Pb(II) on variable charge soils amended with rice-straw derived biochar

Two Ultisols and one Oxisol from tropical regions of southern China were incubated with rice straw biochar to investigate the effect of biochar on their surface charge and Pb(II) adsorption using batch methods. The incorporation of biochar induced a remarkable increase in soil cation exchange capacity after 30 d of incubation. The incorporation of biochar significantly increased the adsorption of Pb(II) by these variable charge soils; the enhancement of adsorption of Pb(II) by these soils increased with the addition level of biochar. Adsorption of Pb(II) involved both electrostatic and non-electrostatic mechanisms; however, biochar mainly increased Pb(II) adsorption through the non-electrostatic mechanism via the formation of surface complexes between Pb²⁺ and functional groups on biochar. There was greater enhancement of biochar on the non-electrostatic adsorption of Pb(II) by the variable charge soils at relatively low pH. Therefore, the incorporation of biochar decreased the activity and availability of Pb(II) to plants through increased non-electrostatic adsorption of Pb(II) by acidic variable charge soils.     

Textural and chemical properties of swine-manure-derived biochar pertinent to its potential use as a soil amendment

Biochars have received increasing attention in recent years because of their properties pertaining to soil fertility and contaminant immobilization as well as serving as carbon sinks. In this work, a series of biochars were produced from dried swine manure waste by slow pyrolysis at different temperatures (i.e., 673-1073 K). The characterization of the resulting biochars was examined for its relevance to its potential use as soil amendment. It was found that the pore properties, ash contents and pH values of all swine-manure-derived biochars basically increased as temperature increased, while the yield and nitrogen/oxygen contents decreased with increasing temperature as a result of pyrolytic volatilization during pyrolysis. From the organic and inorganic elements analyses, the manure-derived biochar was rich in soil nutrients such as N, P, Ca, Mg, and K. Furthermore, the pore, surface and chemical properties were also consistent with the observations of the SEM-EDS, XRD and FTIR. This result suggested that the mesoporous manure-derived biochar could be used as an excellent medium to soil environment.     

Effects of biochar and greenwaste compost amendments on mobility, bioavailability and toxicity of inorganic and organic contaminants in a multi-element polluted soil

Applying amendments to multi-element contaminated soils can have contradictory effects on the mobility, bioavailability and toxicity of specific elements, depending on the amendment. Trace elements and PAHs were monitored in a contaminated soil amended with biochar and greenwaste compost over 60 days field exposure, after which phytotoxicity was assessed by a simple bio-indicator test. Copper and As concentrations in soil pore water increased more than 30 fold after adding both amendments, associated with significant increases in dissolved organic carbon and pH, whereas Zn and Cd significantly decreased. Biochar was most effective, resulting in a 10 fold decrease of Cd in pore water and a resultant reduction in phytotoxicity. Concentrations of PAHs were also reduced by biochar, with greater than 50% decreases of the heavier, more toxicologically relevant PAHs. The results highlight the potential of biochar for contaminated land remediation.     

Matrix effect on the performance of headspace solid phase microextraction method for the analysis of target volatile organic compounds (VOCs) in environmental samples

Solid phase microextraction (SPME) is a fast, cheap and solvent free methodology widely used for environmental analysis. A SPME methodology has been optimized for the analysis of VOCs in a range of matrices covering different soils of varying textures, organic matrices from manures and composts from different origins, and biochars. The performance of the technique was compared for the different matrices spiked with a multicomponent VOC mixture, selected to cover different VOC groups of environmental relevance (ketone, terpene, alcohol, aliphatic hydrocarbons and alkylbenzenes). VOC recovery was dependent on the nature itself of the VOC and the matrix characteristics. The SPME analysis of non-polar compounds, such as alkylbenzenes, terpenes and aliphatic hydrocarbons, was markedly affected by the type of matrix as a consequence of the competition for the adsorption sites in the SPME fiber. These non-polar compounds were strongly retained in the biochar surfaces limiting the use of SPME for this type of matrices. However, this adsorption capacity was not evident when biochar had undergone a weathering/aging process through composting. Polar compounds (alcohol and ketone) showed a similar behavior in all matrices, as a consequence of the hydrophilic characteristics, affected by water content in the matrix. SPME showed a good performance for soils and organic matrices especially for non-polar compounds, achieving a limit of detection (LD) and limit of quantification (LQ) of 0.02 and 0.03 ng g⁻¹ for non-polar compounds and poor extraction for more hydrophilic and polar compounds (LD and LQ higher 310 and 490 ng g⁻¹). The characteristics of the matrix, especially pH and organic matter, had a marked impact on SPME, due to the competition of the analytes for active sites in the fiber, but VOC biodegradation should not be discarded in matrices with active microbial biomass.     

Efficient degradation of organic pollutants by S-NaTaO3/biochar under visible light and the photocatalytic performance of a permonosulfate-based dual-effect catalytic system

Removing large concentrations of organic pollutants from water efficiently and quickly under visible light is essential to developing photocatalytic technology and improving solar energy efficiency. This study used a simple hydrothermal method to prepare a non-metallic, S-doped NaTaO₃ (S-NTO) photocatalyst, which was then loaded onto biochar (BC) to form a S-NTO/BC composite photocatalyst. After uniform loading onto BC, the S-NTO particles transformed from cubic to spherical. The photogenerated electron-hole pair recombination probability of the composite photocatalyst was significantly lower than those of the NTO particles. The light absorption range of the catalyst was effectively widened from 310 nm UV region to visible region. In addition, a dual-effect catalytic system was constructed by introducing peroxymonosulfate (PMS) into the environment of the pollution to be degraded. The Rhodamine B, Methyl Orange, Acid Orange 7, tetracycline, and ciprofloxacin degradation efficiency at 40 mg/L reached 99.6%, 99.2%, 84.5%, 67.1%, and 70.7%, respectively, after irradiation by a 40 W lamps for 90 min. The high-efficiency visible-light catalytic activity of the dual-effect catalytic system was attributed to doping with non-metallic sulfur and loading of catalysts onto BC. The development of this dual-effect catalytic system provides new ideas for quickly and efficiently solving the problem of high-concentration organic pollution in aqueous environments, rationally and fully utilizing solar energy, and expanding the application of photocatalytic technology to practice.     

One-step preparation of a novel graphitic biochar/Cu0/Fe3O4 composite using CO2-ambiance pyrolysis to activate peroxydisulfate for dye degradation

Herein,a one-step co-pyrolysis protocol was adopted for the first time to prepare a novel pyrogenic carbon-Cu⁰/Fe₃O₄ heteroatoms (FCBC) in CO₂ ambiance to discern the roles of each component in PDS activation.During co-pyrolysis,CO₂ catalyzed formation of reducing gases by biomass which facilitated reductive transformation of Fe³⁺ and Cu²⁺ to Cu⁰ and Fe₃O₄,respectively.According to the a...     

Decontamination of Cr(VI) facilitated formation of persistent free radicals on rice husk derived biochar

PFRs were produced on biochar during Cr(VI) decontamination. PFRs formation on biochar was owing to the oxidization of phenolic-OH by Cr(VI). Appearance of excessive oxidant led to the consumption of PFRs on biochar. Biochar charred at high temperature possessed great performance to Cr(VI) removal. This study investigated the facilitation of Cr(VI) decontamination to the formation of persistent free radicals (PFRs) on rice husk derived biochar. It was found that Cr(VI) remediation by biochar facilitated the production of PFRs, which increased with the concentration of treated Cr(VI). However, excessive Cr(VI) would induce their decay. Biochar with high pyrolysis temperature possessed great performance to Cr(VI) removal, which was mainly originated from its reduction by biochar from Inductively Coupled Plasma Optical Emission Spectroscopy and X-ray Photoelectron Spectroscopy. And the corresponding generation of PFRs on biochar was primarily ascribed to the oxidization of phenolic hydroxyl groups by Cr(VI) from Fourier Transform Infrared Spectroscopy analysis, which was further verified by the H₂O₂ treatment experiments. The findings of this study will help to illustrate the transformation of reactive functional groups on biochar and provide a new insight into the role of biochar in environmental remediation.