Ammonia and phosphorus removal from agricultural runoff using cash crop waste-derived biochars

• Orange tree residuals biochar had a better ability to adsorb ammonia. • Modified tea tree residuals biochar had a stronger ability to remove phosphorus. • Partially-modified biochar could remove ammonia and phosphorus at the same time. • The real runoff experiment showed an ammonia nitrogen removal rate of about 80%. • The removal rate of total phosphorus in real runoff experiment was about 95%. Adsorption of biochars (BC) produced from cash crop residuals is an economical and practical technology for removing nutrients from agricultural runoff. In this study, BC made of orange tree trunks and tea tree twigs from the Laoguanhe Basin were produced and modified by aluminum chloride (Al-modified) and ferric sulfate solutions (Fe-modified) under various pyrolysis temperatures (200°C–600°C) and residence times (2–5 h). All produced and modified BC were further analyzed for their abilities to adsorb ammonia and phosphorus with initial concentrations of 10–40 mg/L and 4–12 mg/L, respectively. Fe-modified Tea Tree BC 2h/400°C showed the highest phosphorus adsorption capacity of 0.56 mg/g. Al-modified Orange Tree BC 3h/500°C showed the best performance for ammonia removal with an adsorption capacity of 1.72 mg/g. FTIR characterization showed that P = O bonds were formed after the adsorption of phosphorus by modified BC, N-H bonds were formed after ammonia adsorption. XPS analysis revealed that the key process of ammonia adsorption was the ion exchange between K⁺ and NH₄⁺. Phosphorus adsorption was related to oxidation and interaction between PO₄^3– and Fe³⁺. According to XRD results, ammonia was found in the form of potassium amide, while phosphorus was found in the form of iron hydrogen phosphates. The sorption isotherms showed that the Freundlich equation fits better for phosphorus adsorption, while the Langmuir equation fits better for ammonia adsorption. The simulated runoff infiltration experiment showed that 97.3% of ammonia was removed by Al-modified Orange tree BC 3h/500°C, and 92.9% of phosphorus was removed by Fe-modified Tea tree BC 2h/400°C.     

PM-support interfacial effect and oxygen mobility in Pt,Pd or Rh-loaded (Ce,Zr,La)O2 catalysts

• Pt/CZL exhibits the optimum catalytic performance for HC and NO_x elimination. • The strong PM-Ce interaction favors the oxygen mobility and DOSC. • Pd/CZL shows higher catalytic activity for CO conversion due to more O_latt species. • Great oxygen mobility at high temperature broadens the dynamic operation window. • The relationship between DOSC and catalytic performance is revealed. The physicochemical properties of Pt-, Pd- and Rh- loaded (Ce,Zr,La)O₂ (shorted for CZL) catalysts before/after aging treatment were systematically characterized by various techniques to illustrate the relationship of the dynamic oxygen storage/release capacity and redox ability with their catalytic performances for HC, NO_x and CO conversions. Pt/CZL catalyst exhibits the optimum catalytic performance for HC and NO_x elimination, which mainly contribute to its excellent redox ability and dynamic oxygen storage/release capacity (DOSC) at lower temperature due to the stronger PM (precious metals)-support interaction. However, the worse stability of Pt-O-Ce species and volatile Pt oxides easily result in the dramatical decline in catalytic activity after aging. Pd/CZL shows higher catalytic activity for CO conversion by reason of more O_latt species as the active oxygen for CO oxidation reaction. Rh/CZL catalyst displays the widest dynamic operation window for NO_x elimination as a result of greater oxygen mobility at high temperature, and the ability to retain more Rh-O-Ce species after calcined at 1100°C effectively restrains sintering of active RhO_x species, improving the thermal stability of Rh/CZL catalyst.     

Characterization of value-added chemicals derived from the thermal hydrolysis and wet oxidation of sewage sludge

• Hydrothermal treatment can greatly improve resource recovery from sewage sludge. • tCOD removal during WO was ~55% compared with ~23% after TH. • TOC solubilization during hydrothermal treatment followed first-order kinetics. • Solids and carbon balance confirmed loss of organics during thermal hydrolysis. • Reaction pathways for thermal hydrolysis and wet oxidation are proposed. We evaluated the effect of hydrothermal pretreatments, i.e., thermal hydrolysis (TH) and wet oxidation (WO) on sewage sludge to promote resource recovery. The hydrothermal processes were performed under mild temperature conditions (140°C–180°C) in a high pressure reactor. The reaction in acidic environment (pH= 3.3) suppressed the formation of the color imparting undesirable Maillard’s compounds. The oxidative conditions resulted in higher volatile suspended solids (VSS) reduction (~90%) and chemical oxygen demand (COD) removal (~55%) whereas TH caused VSS and COD removals of ~65% and ~27%, respectively at a temperature of 180°C. During TH, the concentrations of carbohydrates and proteins in treated sludge were 400–1000 mg/L and 1500–2500 mg/L, respectively. Whereas, WO resulted in solids solubilization followed by oxidative degradation of organics into smaller molecular weight carboxylic acids such as acetic acid (~400–500 mg/L). Based on sludge transformation products generated during the hydrothermal pretreatments, simplified reaction pathways are predicted. Finally, the application of macromolecules (such as proteins), VFAs and nutrients present in the treated sludge are also discussed. The future study should focus on the development of economic recovery methods for various value-added compounds.     

Effect of gastric fluid on adsorption and desorption of endocrine disrupting chemicals on microplastics

• Effect of gastric fluid on EDCs adsorption-desorption to microplastics was evaluated. • The gastric fluid enhanced desorption of EDCs on the surface of microplastics. • Adsorption and desorption isotherms fitted the Freundlich model well. • Desorption ratios of EE2 (55%–59%) on PVC were larger than that of E2 (49%–55%). • Decrease in pH and increase in ionic strength in gastric fluid strengthen desorption. Microplastics and endocrine disrupting chemicals are emerging pollutants in the marine environment because of their potential hazards. The effect of gastric fluid on the adsorption and desorption of 17β-estradiol (E2) and 17α-ethynylestradiol (EE2) to microplastics was investigated. The adsorption and desorption isotherms of E2/EE2 on microplastics could be well fitted by the Freundlich model while the Gibbs free energy of these processes were negative, proving that the reaction occurred spontaneously on the heterogeneous surface of the microplastics. Desorption ratios of EE2 (55%–59%) on PVC were larger than that of E2 (49%–55%) to indicate that EE2 was less stable in gastric fluid, which could be explained by the fact that the hydrophobicity of EE2 was greater than E2. E2/EE2 were more easily desorbed from PVC in the gastric fluid and the desorption amount (5.25–12.91/7.19–17.86 μg/g) increased by 2.51 times in comparison with that in saline solution (2.22–7.81/2.87–10.80 μg/g). The decrease of pH and the increase of ionic strength in gastric fluid could further strengthen desorption of E2/EE2 from PVC. The promotion of gastric juice on desorption of PVC was achieved by reducing the hydrophobicity of the PVC surface. The desorption rate of E2/EE2 at 18°C and 38°C was respectively 44%–47%/46%–50% and 49%–55%/56%–59%, indicating that PVC loaded with E2/EE2 had a relatively greater risk of releasing pollutants in the gastric fluid of constant temperature marine organisms while higher temperatures exposed higher hazards for variable temperature animals. The interaction between microplastics and pollutants might be mainly hydrophobic interaction.     

The combined effects of biomass and temperature on maximum specific ammonia oxidation rate in domestic wastewater treatment

• Actual SAORs was determined using MLVSS and temperature. • Measured SAOR decreased with increasing MLVSS 1.1‒8.7 g/L. • Temperature coefficient (θ) decreased with increasing MLVSS. • Nitrification process was dynamically simulated based on laboratory-scale SBR tests. • A modified model was successfully validated in pilot-scale SBR systems. Measurement and predicted variations of ammonia oxidation rate (AOR) are critical for the optimization of biological nitrogen removal, however, it is difficult to predict accurate AOR based on current models. In this study, a modified model was developed to predict AOR based on laboratory-scale tests and verified through pilot-scale tests. In biological nitrogen removal reactors, the specific ammonia oxidation rate (SAOR) was affected by both mixed liquor volatile suspended solids (MLVSS) concentration and temperature. When MLVSS increased 1.6, 4.2, and 7.1-fold (1.3‒8.9 g/L, at 20°C), the measured SAOR decreased by 21%, 49%, and 56%, respectively. Thereby, the estimated SAOR was suggested to modify when MLVSS changed through a power equation fitting. In addition, temperature coefficient (θ) was modified based on MLVSS concentration. These results suggested that the prediction of variations ammonia oxidation rate in real wastewater treatment system could be more accurate when considering the effect of MLVSS variations on SAOR.     

Antioxidative potential of metformin: Possible protective mechanism against generating OH radicals

• Metformin consumes O₂−• and OH• induced by PM are proposed. • OH• dominated the oxidation of metformin compared with O₂−• • Metformin can prevent the harm of ROS induced by PM to human health. • Antioxidative potential of metformin was first proposed to provide measures. Exposure to particulate matter (PM) can lead to the excessive accumulation of reactive oxygen species (ROS), which causes oxidative stress and endangers human health. In this study, the effects of metformin on PM-induced radicals were investigated, and the antioxidation reaction mechanism of metformin was analyzed by the density functional theory (DFT) method. The corresponding results revealed that the consumption rate of dithiothreitol (DTT) increased as the metformin concentration (0–40 mmol/L) increased under exposure to PM active components. Moreover, the OH radical content decreased as the metformin concentration increased. This result may be related to the consumption of PM-induced OH radicals by metformin, which promotes the DTT consumption rate. Additionally, because the initiation reaction has a high barrier, the oxidation reaction rate between metformin and •O₂− is not very fast, although various catalysts may be present in the human environment. Importantly, we found that the barrier of metformin induced by OH radicals is only 9.6 kcal/mol while the barrier of metformin induced by oxygen is 57.9 kcal/mol, which shows that the rate of the •OH-initiated oxidative reaction of metformin is much faster and that this reaction path occurs more easily. By sample analysis, the mean OH radical generation was 55 nmol/min/g (ranging from 5 to 105 nmol/min/g) on haze days and 30 nmol/min/g (ranging from 10 to 50 nmol/min/g) on non-haze days. Moreover, OH radical generation was higher on haze days than on neighboring non-haze days. Taken together, all data suggest that metformin could consume the PM-induced radicals, such as OH radicals and •O₂−, thereby providing health protection.     

TiO2@palygorskite composite for the efficient remediation of oil spills via a dispersion-photodegradation synergy

• A novel and multi-functional clay-based oil spill remediation system was constructed. • TiO₂@PAL functions as a particulate dispersant to break oil slick into tiny droplets. • Effective dispersion leads to the direct contact of TiO₂ with oil pollutes directly. • TiO₂ loaded on PAL exhibits efficient photodegradation for oil pollutants. • TiO₂@PAL shows a typical dispersion-photocatalysis synergistic remediation. Removing spilled oil from the water surface is critically important given that oil spill accidents are a common occurrence. In this study, TiO₂@Palygorskite composite prepared by a simple coprecipitation method was used for oil spill remediation via a dispersion-photodegradation synergy. Diesel could be efficiently dispersed into small oil droplets by TiO₂@Palygorskite. These dispersed droplets had an average diameter of 20–30 mm and exhibited good time stability. The tight adsorption of TiO₂@Palygorskite on the surface of the droplets was observed in fluorescence and SEM images. As a particulate dispersant, the direct contact of TiO₂@Palygorskite with oil pollutants effectively enhanced the photodegradation efficiency of TiO₂ for oil. During the photodegradation process, •O₂⁻and •OH were detected by ESR and radical trapping experiments. The photodegradation efficiency of diesel by TiO₂@Palygorskite was enhanced by about 5 times compared with pure TiO₂ under simulated sunlight irradiation. The establishment of this new dispersion-photodegradation synergistic remediation system provides a new direction for the development of marine oil spill remediation.     

Degradation of polyacrylamide (PAM) and methane production by mesophilic and thermophilic anaerobic digestion: Effect of temperature and concentration

• PAM degradation in thermophilic AD in comparison with mesophilic AD. • PAM degradation and its impact on thermophilic and mesophilic AD. • Enhanced methane yield in presence of PAM during thermophilic and mesophilic AD. • PAM degradation and microbial community analysis in thermophilic and mesophilic AD. Polyacrylamide (PAM) is generally employed in wastewater treatment processes such as sludge dewatering and therefore exists in the sludge. Furthermore, it degrades slowly and can deteriorate methane yield during anaerobic digestion (AD). The impact or fate of PAM in AD under thermophilic conditions is still unclear. This study mainly focuses on PAM degradation and enhanced methane production from PAM-added sludge during 15 days of thermophilic (55°C) AD compared to mesophilic (35°C) AD. Sludge and PAM dose from 10 to 50 g/kg TSS were used. The results showed that PAM degraded by 76% to 78% with acrylamide (AM) content of 0.2 to 3.3 mg/L in thermophilic AD. However, it degraded only 27% to 30% with AM content of 0.5 to 7.2 mg/L in mesophilic AD. The methane yield was almost 230 to 238.4 mL/g VSS on the 8th day in thermophilic AD but was 115.2 to 128.6 mL/g VSS in mesophilic AD. Mechanism investigation revealed that thermophilic AD with continuous stirring not only enhanced PAM degradation but also boosted the organics release from the sludge with added PAM and gave higher methane yield than mesophilic AD.     

A novel strategy for gas mitigation during swine manure odour treatment using seaweed and a microbial consortium

• Comprehensive mitigation of gas emissions from swine manure was investigated. • Additives addition for mitigation of gas from the manure has been developed. • Sargassum horneri, seaweed masking strategy controlled gas by 90%-100%. • Immediate reduction in emitted gas and improving air quality has been determined. • Microbial consortium with seaweed completely controlled gas emissions by 100%. Gas emissions from swine farms have an impact on air quality in the Republic of Korea. Swine manure stored in deep pits for a long time is a major source of harmful gas emissions. Therefore, we evaluated the mitigation of emissions of ammonia (NH₃), hydrogen sulfide (H₂S) and amine gases from swine manure with biological products such as seaweed (Sargassum horneri) and a microbial consortium (Bacillus subtilis (1.2 × 10⁹ CFU/mL), Thiobacillus sp. (1.0 × 10¹⁰ CFU/mL) and Saccharomyces cerevisiae (2.0 × 10⁹ CFU/mL)) used as additives due to their promising benefits for nutrient cycling. Overall, seaweed powder masking over two days provided notable control of over 98%-100% of the gas emissions. Furthermore, significant control of gas emissions was especially pronounced when seaweed powder masking along with a microbial consortium was applied, resulting in a gas reduction rate of 100% for NH₃, amines and H₂S over 10 days of treatment. The results also suggested that seaweed powder masking and a microbial consortium used in combination to reduce the gas emissions from swine manure reduced odour compared with that observed when the two additives were used alone. Without the consortium, seaweed decreased total volatile fatty acid (VFA) production. The proposed novel method of masking with a microbial consortium is promising for mitigating hazardous gases, simple, and environmentally beneficial. More research is warranted to determine the mechanisms underlying the seaweed and substrate interactions.     

Cattle manure biochar and earthworm interactively affected CO2 and N2O emissions in agricultural and forest soils: Observation of a distinct difference

• Earthworms increase CO₂ and N₂O emissions in agricultural and forest soil. • 10% biochar suppresses CO₂ and N₂O emissions in forest soil. • Biochar interacted with earthworm to significant affect CO₂ and N₂O emissions. The application of manure-derived biochar offers an alternative to avoid the direct application of manure to soil causing greenhouse gas emission. Soil fauna, especially earthworms, can markedly stimulate carbon dioxide (CO₂) and nitrous oxide (N₂O) emissions from soil. This study therefore investigated the effect of cattle manure biochar (added at rates of 0, 2%, or 10%, coded as BC0, BC2 and BC10, respectively) application, with or without earthworm Aporrectodea turgida, on emissions of CO₂ and N₂O and changes of physic-chemical properties of agricultural and forest soils in a laboratory incubation experiment. The BC10 treatment significantly enhanced cumulative CO₂ emissions by 27.9% relative to the untreated control in the agricultural soil. On the contrary, the BC2 and BC10 treatments significantly reduced cumulative CO₂ emissions by 16.3%–61.1% and N₂O emissions by 92.9%–95.1% compared to the untreated control in the forest soil. The addition of earthworm alone significantly enhanced the cumulative CO₂ and N₂O fluxes in agricultural and forest soils. Cumulative CO₂ and N₂O fluxes were significantly increased when BC2 and BC10 were applied with earthworm in the agricultural soil, but were significantly reduced when BC10 was applied with earthworm in the forest soil. Our study demonstrated that biochar application interacted with earthworm to affect CO₂ and N₂O emissions, which were also dependent on the soil type involved. Our study suggests that manure biochar application rate and use of earthworm need to be carefully studied for specific soil types to maximize the climate change mitigation potential of such management practices.     

Adsorption characteristics of ciprofloxacin onto g-MoS2 coated biochar nanocomposites

• The g-MoS₂ coated composites (g-MoS₂-BC) were synthesized. • The coated g-MoS₂ greatly increased the adsorption ability of biochar. • The synergistic effect was observed for CIP adsorption on g-MoS₂-RC700. • The adsorption mechanisms of CIP on g-MoS₂-BC were proposed. The g-MoS₂ coated biochar (g-MoS₂-BC) composites were synthesized by coating original biochar with g-MoS₂ nanosheets at 300°C(BC300)/700°C (BC700). The adsorption properties of the g-MoS₂-BC composites for ciprofloxacin (CIP) were investigated with an aim to exploit its high efficiency toward soil amendment. The specific surface area and the pore structures of biochar coated g-MoS₂ nanosheets were significantly increased. The g-MoS₂-BC composites provided more π electrons, which was favorable in enhancing the π-π electron donor-acceptor (EDA) interactions between CIP and biochar. As a result, the g-MoS₂-BC composites showed faster adsorption rate and greater adsorption capacity for CIP than the original biochar. The coated g-MoS₂ nanosheets contributed more to CIP adsorption on the g-MoS₂-BC composites due to their greater CIP adsorption capacity than the original biochar. Moreover, the synergistic effect was observed for CIP adsorption on g-MoS₂-BC700, and suppression effect on g-MoS₂-BC300. In addition, the adsorption of CIP onto g-MoS₂-BC composites also exhibited strong dependence on the solution pH, since it can affect both the adsorbent surface charge and the speciation of contaminants. It was reasonably suggested that the mechanisms of CIP adsorption on g-MoS₂-BC composites involved pore-filling effects, π-π EDA interaction, electrostatic interaction, and ion exchange interaction. These results are useful for the modification of biochar in exploiting the novel amendment for contaminated soils.     

A Cu-modified active carbon fiber significantly promoted H2S and PH3 simultaneous removal at a low reaction temperature

• Cu_0.15-ACF performs the best for H₂S and PH₃ simultaneous removal. • 550°C and 90°C are separately calcination and reaction temperatures. • The reason why Cu_0.15/ACF shows better performance was found. • The accumulation of H₂PO₄⁻ and SO₄²⁻(H₂O)₆ is the deactivation cause of Cu_0.15/ACF. Poisonous gases, such as H₂S and PH₃, produced by industrial production harm humans and damage the environment. In this study, H₂S and PH₃ were simultaneously removed at low temperature by modified activated carbon fiber (ACF) catalysts. We have considered the active metal type, content, precursor, calcination, and reaction temperature. Experimental results exhibited that ACF could best perform by loading 15% Cu from nitrate. The optimized calcination temperature and reaction temperature separately were 550°C and 90°C. Under these conditions, the most removal capacity could reach 69.7 mg/g and 132.1 mg/g, respectively. Characterization results showed that moderate calcination temperature (550°C) is suitable for the formation of the copper element on the surface of ACF, lower or higher temperature will generate more cuprous oxide. Although both can exhibit catalytic activity, the role of the copper element is significantly greater. Due to the exceptional dispersibility of copper (oxide), the ACF can still maintain the advantages of larger specific surface area and pore volume after loading copper, which is the main reason for better performance of related catalysts. Finally, increasing the copper loading amount can significantly increase the crystallinity and particle size of copper (oxide) on the ACF, thereby improving its catalytic performance. In situ IR found that the reason for the deactivation of the catalyst should be the accumulation of generated H₂PO₄⁻ and SO₄²⁻(H₂O)₆ which could poison the catalyst.     

A novel approach to preparing ultra-lightweight ceramsite with a large amount of fly ash

•Ultra-lightweight ceramsite is prepared with 80% fly ash. •SiO₂, Al₂O₃, and flux contents significantly influence the performance of ceramsite. •The expansion of ceramsite is caused by the formation of a dense glaze and gas. •The bulk density of ultra-lightweight ceramsite is only 340 kg/m³. The disposal of fly ash has become a serious problem in China due to its rapid increase in volume in recent years. The most common method of fly ash disposal is solidification-stabilization-landfill, and the most common reuse is low-value-added building materials. A novel processing method for preparing ultra-lightweight ceramsite with fly ash was developed. The results show that the optimal parameters for preparation of ultra-lightweight ceramsite are as follows: mass ratio of fly ash:kaolin:diatomite= 80:15:5, preheating temperature of 800°C, preheating time of 5 min, sintering temperature of 1220°C, and sintering time of 10 min. The expansion agent is perlite, at 10 wt.% addition. Finally, a ceramsite with bulk density of 340 kg/m³, particle density of 0.68 g/cm³, and cylinder compressive strength of 1.02 MPa was obtained. Because of its low density and high porosity, ultra-lightweight ceramsite has excellent thermal insulation performance, and its strength is generally low, so it is usually used in the production of thermal insulation concrete and its products. The formation of a liquid-phase component on the surface, and generation of a gas phase inside ceramsite during the sintering process, make it possible to control the production of the suitable liquid phase and gas in this system, resulting in an optimization of the expansion behavior and microstructure of ceramsite. These characteristics show the feasibility of industrial applications of fly ash for the production of ultra-lightweight ceramsite, which could not only produce economic benefits, but also conserve land resources and protect the environment.     

Airborne bacteria associated with particulate matter from a highly urbanised metropolis: A potential risk to the population’s health

• The airborne bacteria of Mexico City are representative of urban environments. • Particle material<10 µm influenced the type and quantity of airborne bacteria. • The diversity and richness of bacteria were higher in the rainy season. • The emission & transport of airborne bacteria determine the atmosphere’s microbiome. • Bacterias as Kocuria, Paracoccus, and Staphylococcus were in the air of Mexico City. Bacteria in the air present patterns in space and time produced by different sources and environmental factors. Few studies have focused on the link between airborne pathogenic bacteria in densely populated cities, and the risk to the population’s health. Bacteria associated with particulate matter (PM) were monitored from the air of Mexico City (Mexico). We employed a metagenomic approach to characterise bacteria using the 16S rRNA gene. Airborne bacteria sampling was carried out in the north, centre, and south of Mexico City, with different urbanisation rates, during 2017. Bacteria added to the particles were sampled using high-volume PM₁₀ samplers. To ascertain significant differences in bacterial diversity between zones and seasons, the Kruskal-Wallis, Wilcoxon tests were done on alpha diversity parameters. Sixty-three air samples were collected, and DNA was sequenced using next-generation sequencing. The results indicated that the bacterial phyla in the north and south of the city were Firmicutes, Cyanobacteria, Proteobacteria, and Actinobacteria, while in the central zone there were more Actinobacteria. There were no differences in the alpha diversity indices between the sampled areas. According to the OTUs, the richness of bacteria was higher in the central zone. Alpha diversity was higher in the rainy season than in the dry season; the Shannon index and the OTUs observed were higher in the central zone in the dry season. Pathogenic bacteria such as Kocuria, Paracoccus, and Micrococcus predominated in both seasonal times, while Staphylococcus, Corynebacterium, and Nocardioides were found during the rainy season, with a presence in the central zone.     

Valorization of agro-industrial fruit peel waste to fluorescent nanocarbon sensor: Ultrasensitive detection of potentially hazardous tropane alkaloid

• Transformation of agro-industrial waste to value-added material via green chemistry. • Orange peel is valorized into fluorescent nanodiamond-like carbon (fNDC) sensor. • fNDC detects potentially hazardous drug atropine sulfate (AS). • fNDC recognizes AS in biological fluids and pharmaceuticals. • fNDC assures applications in clinical and forensic toxicology. Millions of tonnes of agro-industrial waste are generated each year globally, with the vast majority of it going untreated, underutilized, and disposed of by burning or landfilling, causing severe environmental distress and economic downturn. A practical solution to this global issue is to use green chemistry to convert this waste into value-added products. Accordingly, in the present study, agro-industrial orange peel waste was valorized into fluorescent nanodiamond-like carbon sensor via a green route involving hydrothermal treatment of microwave carbonized orange peel waste. The developed sensor, used for the fluorescence detection of potentially hazardous drug atropine sulfate, exhibits unique dual linearity over concentration ranges of 300 nM to 1 M and from 1 M to 10 M, as well as ultra-low sensitivity of 34.42 nM and 356.46 nM, respectively. Additionally, the sensor demonstrates excellent reproducibility, high stability, and satisfactory recovery when used to identify and quantify atropine sulfate in biological samples and commercially available pharmaceuticals, indicating promising multidisciplinary applications.     

Catalytic fast pyrolysis of walnut shell for alkylphenols production with nitrogen-doped activated carbon catalyst

• N-doped activated carbon was prepared for catalytic pyrolysis of walnut shell. • Alkylphenols were selectively produced from catalytic pyrolysis process. • The alkylphenols yield increased by 8.5 times under the optimal conditions. • Formation mechanism of alkylphenols was proposed. Alkylphenols are a group of valuable phenolic compounds that can be derived from lignocellulosic biomass. In this study, three activated carbons (ACs) were prepared for catalytic fast pyrolysis (CFP) of walnut shell to produce alkylphenols, including nitrogen-doped walnut shell-derived activated carbon (N/WSAC), nitrogen-doped rice husk-derived activated carbon (N/RHAC) and walnut shell-derived activated carbon (WSAC). Pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) experiments were carried out to reveal the influences of AC type, pyrolytic temperature, and AC-to-walnut shell (AC-to-WS) ratio on the product distributions. Results showed that with nitrogen doping, the N/WSAC possessed stronger capability than WSAC toward the alkylphenols production, and moreover, the N/WSAC also exhibited better effects than N/RHAC to prepare alkylphenols. Under the catalysis of N/WSAC, yields of alkylphenols were significantly increased, especially phenol, cresol and 4-ethylphenol. As the increase of pyrolytic temperature, the alkylphenols yield first increased and then decreased, while high selectivity could be obtained at low pyrolytic temperatures. Such a trend was also observed as the AC-to-WS ratio continuously increased. The alkylphenols production achieved a maximal yield of 44.19 mg/g with the corresponding selectivity of 34.7% at the pyrolytic temperature of 400°C and AC-to-WS ratio of 3, compared with those of only 4.67 mg/g and 6.1% without catalyst. In addition, the possible formation mechanism of alkylphenols was also proposed with the catalysis of N/WSAC.     

Nanoscale zero-valent iron supported on biochar for the highly efficient removal of nitrobenzene

• Biochar supported nanoscale zero-valent iron composite (nZVI/BC) was synthesized. • nZVI/BC quickly and efficiently removed nitrobenzene (NB) in solution. • NB removal by nZVI/BC involves simultaneous adsorption and reduction mechanism. • nZVI/BC exhibited better catalytic activity, stability and durability than nZVI. The application of nanoscale zero-valent iron (nZVI) in the remediation of contaminated groundwater or wastewater is limited due to its lack of stability, easy aggregation and iron leaching. To address this issue, nZVI was distributed on oak sawdust-derived biochar (BC) to obtain the nZVI/BC composite for the highly efficient reduction of nitrobenzene (NB). nZVI, BC and nZVI/BC were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). For nZVI/BC, nZVI particles were uniformly dispersed on BC. nZVI/BC exhibited higher removal efficiency for NB than the simple summation of bare nZVI and BC. The removal mechanism was investigated through the analyses of UV-Visible spectra, mass balance and XPS. NB was quickly adsorbed on the surface of nZVI/BC, and then gradually reduced to aniline (AN), accompanied by the oxidation of nZVI to magnetite. The effects of several reaction parameters, e.g., NB concentration, reaction pH and nZVI/BC aging time, on the removal of NB were also studied. In addition to high reactivity, the loading of nZVI on biochar significantly alleviated Fe leaching and enhanced the durability of nZVI.     

Thermal defluorination behaviors of PFOS,PFOA and PFBS during regeneration of activated carbon by molten salt

• New method of mineralizing PFCs was proposed. • Activated carbon was regenerated while mineralizing PFCs. • Molten NaOH has good mineralization effect on PFOS and PFBS. Current study proposes a green regeneration method of activated carbon (AC) laden with Perfluorochemicals (PFCs) from the perspective of environmental safety and resource regeneration. The defluorination efficiencies of AC adsorbed perfluorooctanesulfonate (PFOS), perfluorooctanoic acid (PFOA) and perfluorobutanesulfonate (PFBS) using three molten sodium salts and one molten alkali were compared. Results showed that defluorination efficiencies of molten NaOH for the three PFCs were higher than the other three molten sodium salts at lower temperature. At 700°C, the defluorination efficiencies of PFOS and PFBS using molten NaOH reached to 84.2% and 79.2%, respectively, while the defluorination efficiency of PFOA was 35.3%. In addition, the temperature of molten salt, the holding time and the ratio of salt to carbon were directly proportional to the defluorination efficiency. The low defluorination efficiency of PFOA was due to the low thermal stability of PFOA, which made it difficult to be captured by molten salt.The weight loss range of PFOA was 75°C–125°C, which was much lower than PFOS and PFBS (400°C–500°C). From the perspective of gas production, fluorine-containing gases produced from molten NaOH-treated AC were significantly reduced, which means that environmental risks were significantly reduced. After molten NaOH treatment, the regenerated AC had higher adsorption capacity than that of pre-treated AC.     

Stabilization of hexavalent chromium with pretreatment and high temperature sintering in highly contaminated soil

• Separate reduction and sintering cannot be effective for Cr stabilization. • Combined treatment of reduction and sintering is effective for Cr stabilization. • Almost all the Cr in the reduced soil is residual form after sintering at 1000°C. This study explored the effectiveness and mechanisms of high temperature sintering following pre-reduction with ferric sulfate (FeSO₄), sodium sulfide (Na₂S), or citric acid (C₆H₈O₇) in stabilizing hexavalent chromium (Cr(VI)) in highly contaminated soil. The soil samples had an initial total Cr leaching of 1768.83 mg/L, and Cr(VI) leaching of 1745.13 mg/L. When FeSO₄ or C₆H₈O₇ reduction was followed by sintering at 1000°C, the Cr leaching was reduced enough to meet the Safety Landfill Standards regarding general industrial solid waste. This combined treatment greatly improved the stabilization efficiency of chromium because the reduction of Cr(VI) into Cr(III) decreased the mobility of chromium and made it more easily encapsulated in minerals during sintering. SEM, XRD, TG-DSC, and speciation analysis indicated that when the sintering temperature reached 1000°C, almost all the chromium in soils that had the pre-reduction treatment was transformed into the residual form. At 1000°C, the soil melted and promoted the mineralization of Cr and the formation of new Cr-containing compounds, which significantly decreased subsequent leaching of chromium from the soil. However, without reduction treatment, chromium continued to leach from the soil even after being sintered at 1000°C, possibly because the soil did not fully fuse and because Cr(VI) does not bind with soil as easily as Cr(III).     

Promotional effect of ion-exchanged K on the low-temperature hydrothermal stability of Cu/SAPO-34 and its synergic application with Fe/Beta catalysts

• K⁺ hinder the structural degradation of Cu/SAPO-34 under humid condition<100°C. • K⁺ on Cu/SAPO-34 brings lower acidity and inferior SCR activity at high temperature. • Fe/Beta was used to compensate the low activity of Cu/SAPO-34 at high temperature. • The hybrid catalysts with KCu/SAPO-34 and Fe/Beta show a great potential for using. K ions were introduced onto Cu/SAPO-34 catalysts via the ion-exchange process in order to improve their stability under low-temperature hydrothermal aging. The changes in structure and copper-species contents of these catalysts upon hydrothermal aging were probed in order to investigate their effects on selective catalytic reduction (SCR) activity. For the fresh Cu/SAPO-34 catalysts, K ions had little influence on the chabazite framework but effected their acidities by exchanging with acid sites. After hydrothermal aging, the structural integrity and amount of active sites decreased on pure Cu/SAPO-34. While the K-loaded catalysts showed improved chabazite structure, acidity, and active site conservation with increasing K loading. However, although the 0.7 wt% K catalyst maintained the same crystallinity, active site abundance, and low-temperature SCR activity as the fresh catalyst upon aging, an apparent decrease in SCR activity at high temperature was observed because of the inevitable decrease in the number of Brönsted acid sites. To compensate for the activity disadvantage of K-loaded Cu/SAPO-34 at high temperature, Fe/Beta catalysts were co-employed with K-loaded Cu/SAPO-34, and a wide active temperature window of SCR activity was obtained. Thus, our study reveals that a combined system comprising Fe/Beta and K-loaded Cu/SAPO-34 catalysts shows promise for the elimination of NO_x in real-world applications.