Polymer Coatings Affect Transport and Remobilization of Colloidal Activated Carbon in Saturated Sand Columns: Implications for In Situ Groundwater Remediation.

Colloidal activated carbon (CAC) is an emerging technology for the in situ remediation of groundwater impacted by per- and polyfluoroalkyl substances (PFAS). In assessing the long-term effectiveness of a CAC barrier, it is crucial to evaluate the potential of emplaced CAC particles to be remobilized and migrate away from the sorptive barrier. We examine the effect of two polymer stabilizers, carboxymethyl cellulose (CMC) and polydiallyldimethylammonium chloride (PolyDM), on CAC deposition and remobilization in saturated sand columns. CMC-modified CAC showed high mobility in a wide ionic strength (IS) range from 0.1 to 100 mM, which is favorable for CAC delivery at a sufficient scale. Interestingly, the mobility of PolyDM-modified CAC was high at low IS (0.1 mM) but greatly reduced at high IS (100 mM). Notably, significant remobilization (release) of deposited CMC-CAC particles occurred upon the introduction of solution with low IS following deposition at high IS. In contrast, PolyDM-CAC did not undergo any remobilization following deposition due to its favorable interactions with the quartz sand. We further elucidated the CAC deposition and remobilization behaviors by analyzing colloid-collector interactions through the application of Derjaguin-Landau-Verwey-Overbeek theory, and the inclusion of a discrete representation of charge heterogeneity on the quartz sand surface. The classical colloid filtration theory was also employed to estimate the travel distance of CAC in saturated columns. Our results underscore the roles of polymer coatings and solution chemistry in CAC transport, providing valuable guidelines for the design of in situ CAC remediation with maximized delivery efficiency and barrier longevity.

Evaluation of acetanilide and antipyrine adsorption on lignin-derived activated carbons.

In this study, the removal of two emerging pollutants (EPs), antipyrine and acetanilide, through adsorption on activated carbons (ACs) prepared by chemical activation of Organosolv lignin with H3PO4 were evaluated. ACs with different pore size distribution were obtained at different impregnation ratios (H3PO4/lignin, 0.5-3.0 w/w) and activating temperatures (500-900 °C). The porosity and surface chemistry of the ACs were determined, and a bimodal size distribution of micropores and narrow mesopores was observed for the different ACs. These ACs were tested for antipyrine and acetanilide adsorption in aqueous solutions in a batch system at 20 °C and low concentration levels (0.5-10 ppm). In general, the ACs exhibited higher adsorption affinity to acetanilide than to antipyrine due to its smaller molecular size. Langmuir adsorption isotherm was able to describe the adsorption equilibrium data. A new Linear Driving Force (2-LDF) kinetic model, based on the bimodal size distribution of micropores and narrow mesopores observed for the ACs has been developed. The new model provided a more accurate description of the batch adsorption rates than that obtained from conventional kinetic models, and also enabled to relate the pore size distribution of the adsorbent with the adsorption kinetics. The validity of this model was checked in small-scale column fixed bed adsorption for the AC showing the highest affinity for both EP. The kinetic model and equilibrium adsorption isotherm obtained from the batch experiments were successfully used to provide an accurate description of the bed service time and the full breakthrough profile of acetanilide and antipyrine.

Conversion of char from pyrolysis of plastic wastes into alternative activated carbons for heavy metal removal.

The valorization of post-consumer mixed plastics in pyrolysis processes represents an abundant reservoir of carbon that can be effectively converted into useful chars. This process not only holds appeal in terms of improving plastic waste concerns but also contributes to the reduction of greenhouse gas emissions, thus aligning with the principles of a circular economy paradigm. In this study, the char produced from the pyrolysis of post-consumer mixed plastic waste has been activated with Na2CO3, KOH, NaOH, and K2CO3 to improve the textural, structural, and composition characteristics, leading to improved adsorption capability. These characteristics were studied by N2 adsorption-desorption isotherms, scanning electron microscopy, elemental and immediate analysis, and X-ray photoelectron spectroscopy. The developed surface area (SBET) was 573, 939, 704 and 592 m2 g-1 for Na2CO3, KOH, NaOH and K2CO3 activated carbons, respectively. These activated chars (ACs) were tested for the adsorption of heavy metals in both synthetic waters containing Pb, Cd, and Cu and industrial wastewater collected at an agrochemical production plant. Na2CO3-AC was the best performing material. The metal uptake in synthetic waters using a batch set-up was 40, 13 and 12 mg g-1 for Pb, Cd and Cu. Experiments in a column set-up using Na2CO3-AC resulted in a saturation time of 290, 16, and 80 min for Pb, Cd, and Cu synthetic waters, respectively, and metal uptakes of 26.8, 4.1, and 7.9 mg g-1, respectively. The agrochemical effluents, containing mainly Cr, Cu, Mn, and Zn were tested in a plug-flow column. The metal uptake notably decreased compared to synthetic water due to a competition effect for active sites.

Influence of different stalks on the metallization degree of FeCl3-derived magnetic biochar through pyrolysis behavior and compositional differences.

To investigate the effect of stalk type on the metallization degrees in FeCl3-derived magnetic biochar (MBC), MBC was synthesized via an impregnation-pyrolysis method using six different stalks. The Fe0 content in MBC significantly influenced its magnetic properties and ostensibly governed its catalytic capabilities. Analysis of the interaction between stalks and FeCl3 revealed that the variation in metallization degrees, resulting from FeCl2 decomposition (6.1%) and stalk-mediated reduction (20.7%), was directly responsible for the observed differences in MBC metallization. The presence of oxygen-containing functional groups and fixed carbon appeared to promote metallization in MBC induced by reduction. A series of statistical analyses indicated that the cellulose, lignin, and hemicellulose content of the stalks were key factors contributing to differences in MBC metallization degrees. Further exploration revealed that hemicellulose and cellulose were more effective than lignin in enhancing metallization through FeCl2 decomposition and reduction. Constructing stalk models demonstrated that the variance in the content of these three biomass components across the six stalk types could lead to differences in the metallization degree attributable to reduction and FeCl2 decomposition, thereby affecting the overall metallization degree of MBC. A prediction model for MBC metallization degree was developed based on these findings. Moreover, the elevated Si content in some stalks facilitated the formation of Fe2(SiO4), which subsequently impeded the reduction process. This study provides a theoretical foundation for the informed selection of stalk feedstocks in the production of FeCl3-derived MBC.

Activated carbon fiber as an efficient co-catalyst toward accelerating Fe2+/Fe3+ cycling for improved removal of antibiotic cefaclor via electro-Fenton process using a gas diffusion electrode.

The electro-Fenton (EF) based on gas-diffusion electrodes (GDEs) reveals promising application prospective towards recalcitrant organics degradation because such GDEs often yields superior H2O2 generation efficiency and selectivity. However, the low efficiency of Fe2+/Fe3+ cycle with GDEs is always considered to be the limiting step for the EF process. In this study, activated carbon fiber (ACF) was firstly employed as co-catalyst to facilitate the performance of antibiotic cefaclor (CEC) decomposition in EF process. It was found that the addition of ACF co-catalyst achieved a rapid Fe2+/Fe3+ cycling, which significantly enhanced Fenton's reaction and hydroxyl radicals (•OH) generation. X-ray photoelectron spectroscopy (XPS) results indicated that the functional groups on ACF surface are related to the conversion of Fe3+ into Fe2+. Moreover, DMSO probing experiment confirmed the enhanced •OH production in EF + ACF system compared to conventional EF system. When inactive BDD and Ti4O7/Ti anodes were paired to EF system, the addition of ACF could significantly improve mineralization degree. However, a large amount of toxic byproducts, including chlorate (ClO3-) and perchlorate (ClO4-), were generated in these EF processes, especially for BDD anode, due to their robust oxidation capacity. Higher mineralization efficiency and less toxic ClO4- generation were obtained in the EF + ACF process with Ti4O7/Ti anode. This presents a novel alternative for efficient chloride-containing organic removal during wastewater remediation.

Nitrogen-doped activated carbon-based steel slag composite material as an accelerant for enhancing the resilience of flexible biogas production process against shock loads: Performance, mechanism and modified ADM1 modeling.

Anaerobic digestion for flexible biogas production can lead to digestion inhibition under high shock loads. While steel slag addition has shown promise in enhancing system buffering, its limitations necessitate innovation. This study synthesized the nitrogen-doped activated carbon composite from steel slag to mitigate intermediate product accumulation during flexible biogas production. Material characterization preceded experiments introducing the composite into anaerobic digestion systems, evaluating its impact on methane production efficiency under hydraulic and concentration sudden shocks. Mechanistic insights were derived from microbial community and metagenomic analyses, facilitating the construction of the modified Anaerobic Digestion Model No. 1 (ADM1) to quantitatively assess the material's effects. Results indicate superior resistance to concentration shocks with substantial increment of methane production rate up to 33.45% compared with control group, which is mediated by direct interspecies electron transfer, though diminishing with increasing shock intensity. This study contributes theoretical foundations for stable flexible biogas production and offers an effective predictive tool for conductor material reinforcement processes.

Sugarcane bagasse biochar boosts maize growth and yield in salt-affected soil by improving soil enzymatic activities.

Salinization is a leading threat to soil degradation and sustainable crop production. The application of organic amendments could improve crop growth in saline soil. Thus, we assessed the impact of sugarcane bagasse (SB) and its biochar (SBB) on soil enzymatic activity and growth response of maize crop at three various percentages (0.5%, 1%, and 2% of soil) under three salinity levels (1.66, 4, and 8 dS m-1). Each treatment was replicated three times in a completely randomized block design with factorial settings. The results showed that SB and SBB can restore the impact of salinization, but the SBB at the 2% addition rate revealed promising results compared to SB. The 2% SBB significantly enhanced shoot length (23.4%, 26.1%, and 41.8%), root length (16.8%, 20.8%, and 39.0%), grain yield (17.6%, 25.1%, and 392.2%), relative water contents (11.2%, 13.1%, and 19.2%), protein (17.2%, 19.6%, and 34.9%), and carotenoid (16.3, 30.3, and 49.9%) under different salinity levels (1.66, 4, and 8 dS m-1, respectively). The 2% SBB substantially drop the Na+ in maize root (28.3%, 29.9%, and 22.4%) and shoot (36.1%, 37.2%, and 38.5%) at 1.66, 4, and 8 dS m-1. Moreover, 2% SBB is the best treatment to boost the urease by 110.1%, 71.7%, and 91.2%, alkaline phosphatase by 28.8%, 38.8%, and 57.6%, and acid phosphatase by 48.4%, 80.1%, and 68.2% than control treatment under 1.66, 4 and 8 dS m-1, respectively. Pearson analysis showed that all the growth and yield parameters were positively associated with the soil enzymatic activities and negatively correlated with electrolyte leakage and sodium. The structural equational model (SEM) showed that the different application percentage of amendments significantly influences the growth and physiological parameters at all salinity levels. SEM explained the 81%, 92%, and 95% changes in maize yield under 1.66, 4, and 8 dS m-1, respectively. So, it is concluded that the 2% SBB could be an efficient approach to enhance the maize yield by ameliorating the noxious effect of degraded saline soil.

Silica-magnesium coupling in lignin-based biochar: A promising remediation for composite heavy metal pollution in environment.

Lignin hydrothermal silica-carbon material served as a backbone for MgCl2 activation to prepare lignin-based silicon/magnesia biochar (ALB/Si-Mg) for Cd2+, Pb2+, Cu2+, and Zn2+ removal from water and soil environment. Characterization studies revealed a 1017.71-fold increase in the specific surface area of ALB/Si-Mg compared to the original lignin biochar (ALB), producing abundant oxygen functional groups (OC-O, Si-O, Mg-O), and mineral matter (Mg2SiO4 and MgO). Crucially, batch adsorption experiments demonstrated that the adsorption capacity of ALB/Si-Mg for Cd2+, Pb2+, Cu2+, and Zn2+ was 848.17, 665.07, 151.84, and 245.78 mg/g, which were 29.09-140.45 times of the ALB. Soil remediation experiments showed that applying ALB/Si-Mg increased soil effective silicon (109.04%-450.2%) and soil exchangeable magnesium (276.41%-878.66%), enhanced plant photosynthesis, and notably reduced the bioavailability of heavy metals in soil as well as the content of heavy metals in Pakchoi, thereby promoting Pakchoi growth and development. The presence of oxygen-containing functional groups on ALB/Si-Mg, along with Mg2SiO4 and MgO nanoparticles, enhanced the adsorption capacity for heavy metals through the promotion of heavy metal precipitation, ion exchange, and complexation mechanisms. This study establishes the groundwork for the coupling of silica and magnesium elements in biochar and the remediation of composite heavy metal environmental pollution.

Unveiling drastic influence of cross-interactions in hydrothermal carbonization of spirulina with cellulose, lignin or poplar on nature of hydrochar and activated carbon.

Spirulina platensis contains abundant nitrogen-containing organics, which might react with derivatives of cellulose/lignin during hydrothermal carbonization (HTC), probably affecting yield, property of hydrochar, and pore development in activation of hydrochar. This was investigated herein by conducting co-HTC of spirulina platensis with cellulose, lignin, and sawdust at 260 °C and subsequent activation of the resulting hydrochars with K2C2O4 at 800 °C. The results showed that cross-condensation of spirulina platensis-derived proteins with cellulose/lignin-derived ketones and phenolics did take place in the co-HTC, forming more π-conjugated heavier organics, retaining more nitrogen species in hydrochar, reducing yields of hydrochar, making the hydrochar more aromatic and increasing the thermal stability and resistivity towards activation. This enhanced the yield of activated carbon (AC) by 7 %-20 % and significantly increased specific surface area of the AC from activation of hydrochar of spirulina platensis + lignin to 2074.5 m2/g (859.3 m2/g from spirulina platensis only and 1170.1 m2/g from lignin only). Furthermore, more mesopores from activation of hydrochar of spirulina platensis + cellulose (47 %) and more micropores from activation of hydrochar of spirulina + sawdust (93 %) was generated. The AC from spirulina platensis + lignin with the developed pore structures generated sufficient sites for adsorption of tetracycline from aqueous phase and minimized steric hindrance for mass transfer with the abundant mesopores (43 %).

Effects of biodegradable microplastics coexistence with biochars produced at low and high temperatures on bacterial community structure and phenanthrene degradation in soil.

The increasing use of biodegradable plastics may result in more serious pollution of microplastics which often coexist with biochar in soil, this will affect how organic pollutants move and transform in the soil. This work investigated the effect of biodegradable polybutylene adipate-co-terephthalate (PBAT) coexistence with biochars produced at temperatures of 400 and 700 °C (W4 and W7) on soil bacterial communities and phenanthrene degradation. The results showed that coexistence of PBAT and biochar paticles greatly boosted the relative abundance of Nocardioides while decreased the relative abundance of Sphingomonas as compared to soils with a single addition of PBAT or biochar. Changes in soil Eh values were the most influential factor in bacterial communities (more than 40% contribution). The degradation ratio of phenanthrene when PBAT coexisted with W7 (39.6 ± 3.6%) was not significantly different from the treatment with a single W7 addition (35.0 ± 2.3%, P＞0.05), and was related to phenanthrene degradation in the adsorbed state of W7 in soil. In contrast, the degradation ratio of phenanthrene in PBAT coexisting with W4 (35.1 ± 3.5%) was intermediate between that of single PBAT (49.8 ± 0.9%) and W4 (13.7 ± 5.8%) treatments. This was primarily due to changes in the experiment's initial bioavailable phenanthrene content. Furthermore, after the introduction of earthworms, phenanthrene degradation ratio in coexistence treatments were very similar to that described above in the absence of earthworms. Except for two treatments that contain W7, phenanthrene degradation ratio in the other treatments was increased by the presence of earthworms (up to 23%), which is related to the enhanced relative abundance of polycyclic aromatic hydrocarbon-degraders. Our findings indicated that PBAT coexistence with high-temperature or low-temperature biochar had a completely different impact on bacterial communities and phenanthrene degradation in soil.

Microplastic inhibits the sorption of trichloroethylene on modified biochar.

Biochar (BC) was used to remove trichloroethylene (TCE) from soil and water phases, and BC modification changed the sorption behavior of pollutants. Microplastics are emerging pollutants in the soil and water phases. Whether microplastics can affect the sorption of TCE by modified BC is not clear. Thus, batch sorption kinetics and isotherm experiments were conducted to elucidate the sorption of TCE on BC, and BC combined with polyethylene (PE) or polystyrene (PS). The results showed that HCl and NaOH modification increased TCE sorption on BC, while HNO3 modification inhibited TCE sorption on BC. When PE/PS and BC coexisted, the TCE sorption capacity decreased significantly on BC-CK + PE, BC-HCl + PE, BC-HNO3 + PE, BC-NaOH + PE, and BC-NaOH + PS, which was likely due to the preferential sorption of PE/PS on BC samples. We concluded that microplastics can change TCE sorption behavior and inhibit TCE sorption on BC samples. Thus, the interaction of BC and microplastics should be considered when BC is used for TCE removal in soil and water remediation.

Sugarcane bagasse-derived biochar modified by alkali for enriching surface functional groups to effectively treat ammonium-contaminated water.

In this study, sugarcane bagasse (SB), which was preliminarily treated with H3PO4, was utilized to produce biochar (SB-BC). The SB-BC was subsequently modified with KOH to enrich oxygen-containing functional groups (OCFGs) for the enhanced adsorption of NH4+ from wastewater. Batch tests revealed that KOH-modified SB-BC (SB-MBC) increased the maximum Langmuir adsorption capacity of NH4+ by approximately twofold, from 27.1 mg/g for SB-BC to 53.1 mg/g for SB-MBC. The optimal operational conditions for NH4+ adsorption onto SB-MBC were pH of 7.0 and a biochar dose of 3.0 g/L for the removal of 50 mg/L NH4+ at room temperature (25 ± 2 °C) over 180 min of contact. The enhanced adsorption capacity of NH4+ onto SB-MBC was due to the important contribution of the OCFGs enriched on the surface of biochar, which was increased by about fourfold, after being modified by KOH. The NH4+ adsorption dynamics were better fitted by the Elovich and the NH4+ adsorption isotherms were better described by Langmuir and Sips models, showing that the adsorption process was dominated by monolayer chemisorption. The properties of the adsorption materials before and after adsorption of NH4+ confirmed that cation exchange, electrostatic attraction and surface complexation were the main mechanisms controlling the adsorption process. The desorption and reusability tests of NH4+-saturated SB-MBC revealed that NH4+ adsorption slightly decreased after three successive sorption‒desorption cycles. The findings suggested that SB-MBC is a promising and feasible adsorbent for the effective treatment of NH4+-contaminated water sources. Future work should conduct tests for treatment of NH4+-rich real wastewater and utilize NH4+-saturated SB-MBC as slow releasing fertilizer for plants growth.

Rice husk biochar is more effective in blocking the cadmium and lead accumulation in two Brassica vegetables grown on a contaminated field than sugarcane bagasse biochar.

Heavy metal-contaminated soil has a great impact on yield reduction of vegetable crops and soil microbial community destruction. Biochar-derived waste biomass is one of the most commonly applied soil conditioners in heavy metal-contaminated soil. Different heavy metal-contaminated soil added with suitable biochars represent an intriguing way of the safe production of crops. This study investigated the effects of two types of biochar [rice husk biochar (RHB) and sugarcane bagasse biochar (SBB)] on Cd and Pb accumulation in Shanghaiqing (SHQ, a variety of Brassica campestris L.) and Fengyou 737 (FY, a variety of Brassica napus), as well as on the soil microbial community, through a field experiment. RHB and SBB were characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, and Brunauer-Emmet-Teller method. The results showed that RHB and SBB displayed the higher pH, cation exchange capacity and pore properties, and the addition of RHB and SBB enhanced soil pH and rhizosphere microorganisms promoting vegetables yield. RHB treatments were more effective than SBB in reducing upward transfer of Cd and Pb, blocking the accumulation of Cd and Pb in the edible parts of SHQ and FY, and decreasing soil Cd and Pb bioavailability. Additionally, RHB and SBB changed the composition of the rhizosphere soil microbial community. The application of biochar promoted the growth of ecologically beneficial bacteria (Nitrospira, Opitutus, and Gemmatimonas) and fungi (Mortierella and Holtermanniella), whereas reducing the enrichment of plant pathogenic fungi (Alternaria, Stagonosporopsis, Lectera, and Periconia) in rhizosphere soil. Our findings demonstrated that the application of RHB significantly reduces Cd and Pb accumulation in the edible parts by decreasing the soil Cd and Pb bioavailability and altering the rhizosphere microbial community composition in two Brassica vegetables grown on Cd/Pb-contaminated soils. Thus, the application of two biochar, especially RHB is a feasible strategy for the safe production of vegetable crops in Cd/Pb co-contaminated soils.

Polyvinyl chloride nanoplastics transport inhibited in natural sandy soil by iron-modified biochar.

The small particle size of nanoplastics allows them to migrate through soil and make them highly bioavailable, posing a potential threat to groundwater. Measures are urgently needed to reduce the migration of nanoplastics in soil. However, there is limited research available on this topic. In this study, two types of iron-modified biochar (magnetic corncob biochar (MCCBC) and magnetic walnut shell biochar (MWSBC)) were selected and their effects on the transport of polyvinyl chloride nanoplastics (PVC-NPs) in natural sandy soil columns under different ionic types and strengths were investigated. The results show that the transport of PVC-NPs in single sandy soil columns was rapid and efficient, with the estimated breakthrough rate of 85.10%. However, the presence of MCCBC and MWSBC (0.5%, w/w) significantly inhibited the transport of PVC-NPs in sandy soil columns (p < 0.05), and MCCBC had a stronger inhibitory effect on the transport of PVC-NPs than MWSBC. This can be attributed to the fact that the adsorption of PVC-NPs on adsorbents followed the order as: MCCBC > MWSBC > sandy soil. The retention of PVC-NPs by MCCBC and MWSBC is determined by ionic type and ionic strength. The presence of coexisting ions enhanced the inhibitory effect of iron-modified biochar on the transport of PVC-NPs, with the following order: Ca2+ > SO2- 4 > Cl- > NO- 3. The inhibitory effect of MCCBC and MWSBC on the transport of PVC-NPs in soil columns increased with increasing ionic strengths. Furthermore, MCCBC and MWSBC inhibited the migration of PVC-NPs in a rainwater-soil system. The mechanisms by which MCCBC and MWSBC affect the transport of PVC-NPs in soil columns were considered to enhancing adsorption and decreasing soil pore volume. The results provide new insights into the management of soil nanoplastic pollution.

An in-situ biochar-enhanced anaerobic membrane bioreactor for swine wastewater treatment under various organic loading rates.

A biochar-assisted anaerobic membrane bioreactor (BC-AnMBR) was conducted to evaluate the performance in treating swine wastewater with different organic loading rates (OLR) ranging from 0.38 to 1.13 kg-COD/(m3.d). Results indicated that adding spent coffee grounds biochar (SCG-BC) improved the organic removal efficiency compared to the conventional AnMBR, with an overall COD removal rate of > 95.01%. Meanwhile, methane production of up to 0.22 LCH4/gCOD with an improvement of 45.45% was achieved under a high OLR of 1.13 kg-COD/(m3.d). Furthermore, the transmembrane pressure (TMP) in the BC-AnMBR system was stable at 4.5 kPa, and no irreversible membrane fouling occurred within 125 days. Microbial community analysis revealed that the addition of SCG-BC increased the relative abundance of autotrophic methanogenic archaea, particularly Methanosarcina (from 0.11% to 11.16%) and Methanothrix (from 16.34% to 24.05%). More importantly, Desulfobacterota and Firmicutes phylum with direct interspecific electron transfer (DIET) capabilities were also enriched with autotrophic methanogens. Analysis of the electron transfer pathway showed that the concentration of c-type cytochromes increased by 38.60% in the presence of SCG-BC, and thus facilitated the establishment of DIET and maintained high activity of the electron transfer system even at high OLR. In short, the BC-AnMBR system performs well under various OLR conditions and is stable in the recovery energy system for swine wastewater.

Fluoride removal from coal mining water using novel polymeric aluminum modified activated carbon prepared through mechanochemical process.

Defluoridation of coal mining water is of great significance for sustainable development of coal industry in western China. A novel one-step mechanochemical method was developed to prepare polymeric aluminum modified powder activated carbon (PAC) for effective fluoride removal from coal mining water. Aluminum was stably loaded on the PAC through facile solid-phase reaction between polymeric aluminum (polyaluminum chloride (PACl) or polyaluminum ferric chloride (PAFC)) and PAC (1:15 W/W). Fluoride adsorption on PACl and PAFC modified PAC (C-PACl and C-PAFC) all reached equilibrium within 5 min, at rate of 2.56 g mg-1 sec-1 and 1.31 g mg-1 sec-1 respectively. Larger increase of binding energy of Al on C-PACl (AlF bond: 76.64 eV and AlFOH bond: 77.70 eV) relative to that of Al on C-PAFC (AlF bond: 76.52 eV) explained higher fluoride uptake capacity of C-PACl. Less chloride was released from C-PACl than that from C-PAFC due to its higher proportion of covalent chlorine and lower proportion of ionic chlorine. The elements mapping and atomic composition proved the stability of Al loaded on the PAC as well as the enrichment of fluoride on both C-PACl and C-PAFC. The Bader charge, formation energy and bond length obtained from DFT computational results explained the fluoride adsorption mechanism further. The carbon emission was 7.73 kg CO2-eq/kg adsorbent prepared through mechanochemical process, which was as low as 1:82.3 to 1:8.07 × 104 compared with the ones prepared by conventional hydrothermal methods.

Sustainable Biochar Nanosheets Derived from Sweet Sorghum Residues via Superbase Pretreatment.

Two-dimensional (2D) sheet-like biochar as promising alternatives to graphene nanosheets has gained significant attention in materials science while being highly restricted by its complicated synthetic steps. In this study, the dimethyl sulfoxide/potassium hydroxide (DMSO/KOH) superbase system was first used to pretreat sweet sorghum residues (SS) and then carbonized to prepare sheet-like biochar. Ascribing to the strong nucleophilicity of DMSO/KOH, a synergistic effect was achieved by partially removing non-cellulosic components in SS and swelling the amorphous region of cellulose, leaving more layered cellulose behind (∼46.5 wt %), which was favorable for the formation of 2D biochar nanosheets with high graphitization degrees (∼93.1%). This strategy was also suitable for other biomass fibers (e.g., straw, wood powders, and nuclear shells) to obtain sheet-like biochar. The resulting sheet-like biochar could be compounded with cellulose nanofibers to achieve the structural design of composites and solve the molding problem of biochar, which was beneficial for dyeing wastewater treatment. Thus, this work provides insight into a simple strategy for developing 2D ultrathin sheet-like biochar from sustainable biomass wastes.

Different photoreduction processes of Cr(VI) on cellulose-rich and lignin-rich biochar.

In this study, a series of biochar were prepared via pyrolyzing cellulose-rich pakchoi (PBC) and lignin-rich corncob (CBC) to explore the photoreduction process of Cr(VI). X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy confirmed higher oxygenated functional groups in PBC (48.9%-57.1%), whereas CBC exhibited more aromatization properties due to the stable aromatic network in lignin. For PBC, the valence bands decreased from 1.42 eV to 1.20 eV with the increase of pyrolysis temperature from 300 °C to 500 °C; however, an opposite trend was observed for CBC. The photoreduction of Cr(VI) clearly showed that both PBC and CBC had the best performance at the carbonization temperature of 300 °C (named PBC300 and CBC300). It is noted that PBC300 exhibited the most effective photoreduction of Cr(VI), which was about 1.3 times higher than that of CBC300. The maximum reduction capacities of Cr(VI) were 68.2 mg g-1 on PBC300 and 66.1 mg g-1 on CBC300 at pH∼2.0. Compared with the insoluble char substances, dissolved black carbons made more contributions for Cr(VI) photoreduction, ∼70% in PBC and almost 100% in CBC, which suggested that in the case of PBC, the insoluble char and the corresponding dissolved black carbons play an important role in the photoreduction of Cr(VI). However, only dissolved black carbons contributed to Cr(VI) photoreduction on CBC. As the key reaction pathway, the interfacial electron transport dominated Cr(VI) reduction on PBC and CBC. Moreover, the radical of •O2- had some contribution to the reduction of Cr(VI) only in the PBC system. Interestingly, •OH could promote the photoreduction of Cr(VI) in both PBC and CBC systems, which might be due to the fact that •OH facilitated the formation of small molecule fragments. These findings provide an essential basis for evaluating the environmental impact of photocatalytic behaviors of biochar.

Super facile one-step synthesis of sugarcane bagasse derived N-doped porous biochar for adsorption of ciprofloxacin.

A new N-doped biochar derived from sugarcane bagasse (NSB) was prepared by one-pot pyrolysis with sugarcane bagasse as feedstock, melamine as nitrogen source and NaHCO3 as pore-forming agent, and then NSB was used to adsorb ciprofloxacin (CIP) in water. The optimal preparation conditions of NSB were determined based on the evaluation index of adsorbability of NSB for CIP. SEM, EDS, XRD, FTIR, XPS and BET characterizations were used to analyze the physicochemical properties of the synthetic NSB. It was found that the prepared NSB had excellent pore structure, high specific surface area and more nitrogenous functional groups. Meanwhile, it was demonstrated that the synergistic interaction between melamine and NaHCO3 increased the pores of NSB and the largest surface area of NSB was 1712.19 m2/g. The CIP adsorption capacity of 212 mg/g was obtained under optimal parameters as follows: NSB amount 0.125 g/L, initial pH 6.58, adsorption temperature 30 °C, CIP initial concentration 30 mg/L and adsorption time 1 h. The isotherm and kinetics studies elucidated that the adsorption of CIP conformed both D-R model and Pseudo-second-order kinetic model. The high CIP adsorption capacity of NSB for CIP was due to the combined filling pore, π-π conjugation and hydrogen bonding. All results demonstrated that adsorption of CIP by the low-cost N-doped biochar of NSB is a reliable technology for the disposal of CIP wastewater.

In situ self-sacrificial synthesis of polypyrrole/biochar composites for efficiently removing short- and long-chain perfluoroalkyl acid from contaminated water.

Efficient removal of perfluoroalkyl acids (PFAAs), especially short-chain ones, from contaminated water is of great challenge and is urgently called for so as to safeguard the ecosystem and human health. Herein, polypyrrole (PPy) functionalized biochar (BC) composites were innovatively synthesized by an in situ self-sacrificial approach to allow efficient capture of PFAAs with different chain lengths. Compared with conventional PPy-based composites synthesized by direct polymerization using FeCl3 as an oxidizing agent, PPy/BC composites were fabricated utilizing freshly generated Fe3+ as an oxidizing agent from self-sacrificial Fe3O4 for pyrrole monomers in situ polymerizing on BC. As a result, with the support of BC and gradual release of Fe3+, PPy overcame its tendency to aggregate and became uniformly dispersed on BC, and meanwhile, PPy could well tailor the surface chemistry of BC to endow its positively charged surface. Consequently, the composites exhibited strong sorption capacities of 3.89 and 1.53 mmol/g for short-chain perfluorobutanoic acid (PFBA) and perfluorobutane sulfonic acid (PFBS), 2.55 and 1.22 mmol/g for long-chain perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS), respectively, which were superior to those of pristine BC, commercial activated carbon, and anion exchange resins reported. Additionally, they could effectively remove 17 different classes of per- and polyfluoroalkyl substances (PFAS) (removal >95%) from actual PFAS-contaminated water, and the spent sorbent could be well regenerated and reused at least 5 times. An integrated analysis indicated that such an outstanding PFAA sorption performance on PPy/BC composites could be mainly attributed to surface adsorption enhanced by electrostatic attractions (anion exchange interaction) with the traditional hydrophobic interaction and pore filling of less contribution, particularly for short-chain analogues. These results are expected to inform the design of BC with greater ability to remove PFAS from water and the new sorbent could help water facilities comply with PFAS regulations.