Proper management of waste crop residues has been an environmental concern for years. Yellow mealworms (larvae of Tenebrio molitor Linnaeus, 1758) are major insect protein source. In comparison with normal feed wheat bran (WB), we tested five common lignocellulose-rich crop residues as feedstock to rear mealworms, including wheat straw (WS), rice straw (RS), rice bran (RB), rice husk (RH), and corn straw (CS). We then used egested frass for the production of biochar in order to achieve clean production. Except for WS and RH, the crop residues supported mealworms’ life activity and growth with consumption of the residues by 90% or higher and degraded lignin, hemicellulose and cellulose over 32 day period. The sequence of degradability of the feedstocks is RS > RB > CS > WS > RH. Egested frass was converted to biochar which was tested for metal removal including Pb(II), Cd(II), Cu(II), Zn(II), and Cr(VI). Biochar via pyrolysis at 600 °C from RS fed frass (FRSBC) showed the best adsorption performance. The adsorption isotherm fits the Langmuir model, and kinetic analysis fits the Pseudo-Second Order Reaction. The heavy metal adsorption process was well-described using the Intra-Particle Diffusion model. Complexation, cation exchange, precipitation, reduction, deposition, and chelation dominated the adsorption of the metals onto FRSBC. The results indicated that crop residues (WS, RS, RB, and CS) can be utilized as supplementary feedstock along with biochar generated from egested frass to rear mealworms and achieve clean production while generating high-quality bioadsorbent for environment remediation and soil conditioning.

Metals are released from biochar (BC) in either the free or dissolved organic carbon (DOC)-combined form. The complexation of metals with DOC influences their toxicity and bioavailability in the environment. The endogenous release of metal species with heterogeneous DOC from BC is very complex; this process has been neglected and remains unaddressed in the literature to date. In this study, the yield and chemical properties of labile DOC from BC were characterized, and the release of endogenous metal/metalloid elements (K, Mg, Mn, Fe, Al, Cu, and Si) and their species from BC with various pyrolysis temperatures and particle sizes were systematically investigated under various solution chemistries. The results showed that pyrolysis temperature of BC significantly influenced the yield and composition of DOC and DOC-metal/metalloid complexes, while particle size had lower impact. The yield of BC-derived DOC significantly decreased and the components gradually changed from low-molecular weight and low-aromaticity hydrophilic humic acid-like substances to complex high-molecular weight and high-aromaticity hydrophobic substances as pyrolysis temperature increased from 200 to 700 °C. The release of total dissolved metals decreased with increasing pyrolysis temperature, while the highest total dissolved Si was released from BC with the moderate pyrolysis temperature (500 °C). The metal elements were mainly released in the DOC-combined form, while the released Si was mainly in the free form in the neutral water environment. The release of DOC increased while that of dissolved metals decreased with increasing solution pH. The release of total dissolved metals/metalloids increased but the ratio of the DOC-combined metals/metalloids decreased with increasing solution ionic strength. These results provide new insight into the understanding of endogenous metal/metalloid release from BC in the natural environment.

Dissolved organic carbon (DOC) has a major influence upon sorption/desorption and transport of hydrophobic organic contaminants (HOCs) in soil environments. However, the molecular mechanisms of DOC sorption and its effects on aged HOC desorption in contaminated soils still remain largely unclear. Here, effects of three different DOC (one from commercial peat and two from biochars produced at 300 °C and 500 °C pyrolysis temperatures, respectively) and oxalate (as a reference) on abiotic desorption behavior of aged phenanthrene from three agricultural soils were investigated. Results showed that desorption of aged phenanthrene from soils was predominantly dependent on soil organic carbon content. The presence of DOC and oxalate resulted in higher desorption of phenanthrene compared to water alone, and the effects were positively related to soil organic carbon content and DOC/oxalate concentration. The facilitating effects of DOC were further increased during the second consecutive desorption, whereas oxalate had no such effect. Ultra-high-resolution Fourier transform-ion cyclotron resonance-mass spectrometry confirmed the molecular fractionation of DOC at the soil-water interface during DOC sorption. Specifically, the DOC molecules with O-rich moieties were preferentially adsorbed, whereas the molecules with phenolic and aromatic structures were selectively retained in the soil solutions through competitive displacement and co-sorption reactions during sorption. The enriched phenyl structures in the retained DOC facilitated its association with phenanthrene in the solutions and thus the release of phenanthrene from the soils. In contrast, oxalate replaced some organic carbon from the soils and thus released the associated phenanthrene into the solutions. Our findings highlight the importance of the molecular composition and structure of DOC for the desorption of phenanthrene in soil-water environments, which may help improve our understanding of the release and transport of organic compounds in the environments.

Biochar has been used to remove heavy metals from aqueous solutions. In this study, a sulfurized wood biochar (SWB) by direct impregnation with elemental sulfur was produced and evaluated along with pristine wood biochar (WB) for adsorption characteristics and mechanism of mercury. Mercury adsorption by WB and SWB was well described by Langmuir model and pseudo second order model and the maximum adsorption capacities of WB and SWB were 57.8 and 107.5 mg g⁻¹, respectively. Intraparticle diffusion model showed that mercury adsorption was fast due to boundary layer and slow adsorption due to diffusion into biochar pores. Although, mercury adsorption by both WB and SWB was predominantly influenced by the pH, temperature, salt concentration, and biochar dosage, the SWB showed a relatively stable mercury adsorption compared to WB under different conditions, suggesting the strong affinity of SWB for mercury. The XPS analysis showed different adsorption mechanisms of mercury between WB and SWB. In particular, mercury adsorption in WB was due to Hg-Cπ bond formation and interaction with carboxyl and hydroxyl groups, whereas in SWB it is primarily due to mercury interaction with C-SOₓ-C and thiophenic groups in addition to Hg-Cπ bond formation and interaction with carboxyl groups. The SEM-EDS mapping also demonstrated that mercury in SWB was related to carbon, oxygen and sulfur. Overall, the sulfurized biochar was effective for removing mercury from aqueous solution, and its direct production through pyrolysis with elemental sulfur impregnation of wood chips could make it an economic option as absorbent for treating mercury-rich wastewater.

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.

Biochar addition to soil may change the hydrophobicity of amended soil and influence soil hydraulic properties. Soil hydrophobicity, i.e. soil water repellency (SWR) can interrupt water infiltration and form preferential flow leading to a potential risk of soil erosion or groundwater pollution. Up to date, the effect of different biochars on soil hydrophobicity remains unclear and the association of SWR with soil hydraulic properties is still unknown. To link the biochar hydrophobicity to SWR and soil water holding capacity (WHC), the surface structure and chemical composition of 27 biochars with different feedstocks and pyrolysis temperatures were characterized, and the SWR and soil WHC of biochar-added soil were investigated. Carboxylic groups on the biochar surface, surface area and pore volume were mostly influenced by pyrolysis temperature, which suggested the dominant factor determining the severity of biochar hydrophobicity was pyrolysis temperature. Hydrophilic soil became hydrophobic after biochar amendment. A higher addition rate led to a stronger SWR of hydrophilic soil. Biochar addition increased soil WHC of hydrophilic soil with low total organic carbon (TOC) content. Biochar did not have significant influence on SWR and soil WHC of hydrophobic soil with high TOC content. It implied that the influence of biochar on SWR and soil hydraulic properties mainly depended on soil original hydrophobicity and TOC content. Therefore, the properties of biochar and influence on soil hydrophobicity and hydraulic properties should be considered before processing biochar application.

The capacity of biochar to take up heavy metals from contaminated soil and water is influenced by the pyrolysis temperature. We have prepared three biochar samples from Jerusalem artichoke stalks (JAS) by pyrolysis at 300, 500 and 700 °C, denoted as JAS300, JAS500, and JAS700, respectively. A variety of synchrotron-based techniques were used to assess the effect of pyrolysis temperature on the molecular properties and copper (Cu) sorption capacity of the samples. The content of oxygen-containing functional groups in the biochar samples decreased, while that of aromatic structures and alkaline mineral components increased, with a rise in pyrolysis temperature. Scanning transmission X-ray microscopy indicated that sorbed Cu(II) was partially reduced to Cu(I), but this process was more evident with JAS300 and JAS700 than with JAS500. Carbon K-edge X-ray absorption near edge structure spectroscopy indicated that Cu(II) cations were sorbed to biochar via complexation and Cu-π bonding. With rising pyrolysis temperature, Cu(II)-complexation weakened while Cu-π bonding was enhanced. In addition, the relatively high ash content and pH of JAS500 and JAS700 facilitated Cu precipitation and the formation of langite on the surface of biochar. The results of this investigation will aid the conversion of halophyte waste to useable biochar for the effective remediation of Cu-contaminated soil and water.

As a global pollutant, microplastics have attracted attention from the public and researchers. However, the lack of standard and time-saving methods for analysis has become one of the bottlenecks in microplastics research. Here, we demonstrate TGA coupled to FTIR to identify and quantify certain microplastics in environment. Samples were pyrolyzed in TGA and the pyrolysis gases were analyzed by FTIR. Combining TGA and FTIR data adds discriminatory power as temperature profiles and absorption spectra differ among several common plastics. To quantify on a mass basis, we calibrated on characteristic IR peaks at temperatures of maximum weight loss for individual polymers. The method can distinguish PVC, PS and was validated by spiking samples with known quantities of microplastics. The result of field sample experiments showed that TGA-FTIR can be used to identify and quantify PVC and PS in bivalves, seawater and soil. And the method may be applicable to environmental samples.

This work comprises results of the laboratory tests on formation and potential release of contaminants from underground gasification of lignites. Four large scale and multi-day trials were carried out using ex-situ gasification facilities. Two different kinds of lignite were tested, i.e. Velenje lignite (Slovenia) and Oltenia lignite (Romania). Gasification tests were conducted in the artificial coal seams under two distinct pressure regimes—atmospheric and high pressure regime (35 bar and 10 bar for the Velenje and Oltenia samples respectively). The UCG wastewater samples were periodically collected from the gas purification module to measure the rate of the wastewater and contaminants production at each phase of the experiment and to assess the effect of gasification pressure and lignite physicochemical properties. The group of target contaminants included: phenols, aromatic hydrocarbons, and some non-specific water parameters. The effect of gasification pressure was confirmed, especially for BTEX and phenols and significant drops in the contents of these compounds were observed at elevated pressures. The effect of pressure was more pronounced for the geologically older coal (Velenje), i.e. drop in the average concentrations from 1994 μg/l (atmospheric) to 804 μg/l (35 bar) and from 733 mg/l (atmospheric) to 17 mg/l (35 bar) for BTEX and total phenols, respectively. The differences in the macromolecular structure and ash content of the both coals were found to be the main reason behind the differences in the contents of organic and inorganic species respectively. The study also shown that composition of UCG wastewaters significantly varied over the time of the particular experiments, which reflected changes in the gasification thermodynamic conditions and development of oxidation and pyrolysis zones. During the atmospheric gasification experiments, the values of BTEX for the Velenje lignite dropped from 3434 μg/l to 1364 μg/l and for the Oltenia lignite from 1833 μg/l to 978 μg/l. A similar downward trend in the concentrations of BTEX was observed for the pressurized experiments. For the Velenje trial a drop from 1111.6 μg/l to 211.2 μg/l and for the Oltenia - from 1695 μg/l to 688 μg/l was observed. Concentrations of phenolic compounds during the atmospheric gasification experiments varied significantly during both atmospheric trials and no significant trends were noticed.

In this study, a novel Fe–Mn–Ce oxide-modified biochar composite (FMCBC) was synthesized via pyrolysis to enhance the adsorption capacity of biochar (BC). Scanning electron microscopy-energy-dispersive X-ray spectroscopy confirmed that Fe, Mn, and Ce were successfully loaded onto the surface of the BC. A series of adsorption experiments showed that the FMCBC exhibited improved adsorption of As(III) in an aqueous environment. The adsorption process was well expressed by the pseudo-second-order kinetic model. The adsorption capacity of FMCBC reached 8.74 mg L⁻¹, which was 3.27 times greater than that of BC. The pH of the solution significantly influenced the adsorption of As(III), where the amount of As(III) adsorbed by FMCBC was maximized at pH 3. A high phosphate concentration inhibited adsorption, whereas nitrate and sulfate ions promoted As(III) adsorption and increased the FMCBC adsorption capacity. Similarly, with increasing humic acid concentration, the adsorption capacity of FMCBC for As(III) decreased; however, a low concentration of humic acid promoted adsorption. X-ray photoelectron spectroscopy analysis revealed that the adsorption of As(III) by FMCBC occurred through redox and surface complexation reactions. Therefore, FMCBC has excellent potential for purifying arsenic-contaminated water.