Henna plant biomass enhanced azo dye removal: Operating performance, microbial community and machine learning modeling.

The bio-reduction of azo dyes is significantly dependent on the availability of electron donors and external redox mediators. In this study, the natural henna plant biomass was supplemented to promote the biological reduction of an azo dye of Acid Orange 7 (AO7). Besides, the machine learning (ML) approach was applied to decipher the intricate process of henna-assisted azo dye removal. The experimental results indicated that the hydrolysis and fermentation of henna plant biomass provided both electron donors such as volatile fatty acid (VFA) and redox mediator of lawsone to drive the bio-reduction of AO7 to sulfanilic acid (SA). The high henna dosage selectively enriched certain bacteria, such as Firmicutes phylum, Levilinea and Paludibacter genera, functioning in both the henna fermentation and AO7 reduction processes simultaneously. Among the three tested ML algorithms, eXtreme Gradient Boosting (XGBoost) presented exceptional accuracy and generalization ability in predicting the effluent AO7 concentrations with pH, oxidation-reduction potential (ORP), soluble chemical oxygen demand (SCOD), VFA, lawsone, henna dosage, and cumulative henna as input variables. The validating experiments with tailored optimal operating conditions and henna dosage (pH 7.5, henna dosage of 2 g/L, and cumulative henna of 14 g/L) confirmed that XGBoost was an effective ML model to predict the efficient AO7 removal (91.6%), with a negligible calculating error of 3.95%. Overall, henna plant biomass addition was a cost-effective and robust method to improve the bio-reduction of AO7, which had been demonstrated by long-term operation, ML modeling, and experimental validation.

Catalytic Strategies for the Upcycling of Polyolefin Plastic Waste.

Chemical upgrading of waste plastics is currently one of the most important methods for addressing plastic pollution. In comparison to the current methods of incineration or landfill, chemical upgrading enables the utilization of carbon and hydrogen elements in waste plastics as resources. This process strongly relies on efficient catalysts and reaction systems. Through catalyst design, waste plastics can be converted into fuels or chemicals under the optimized reaction conditions, extending their life cycles. In this review, we systematically discuss various chemical conversion methods for polyolefin waste plastics, which account for a large proportion of waste plastics. We further explore the remaining challenges and future development trends in this field, including improving product value through product engineering and shifting research perspectives to exploring the tolerance of catalysts toward impurities in practical waste plastic waste rather than using pure plastic feedstock.

Recent advancements in iodide/phosphine-mediated photoredox radical reactions.

Photoredox catalysis plays a crucial role in contemporary synthetic organic chemistry. Since the groundbreaking work of Shang and Fu on photocatalytic decarboxylative alkylations in 2019, a wide range of organic transformations, such as alkylation, alkenylation, cyclization, amination, iodination, and monofluoromethylation, have been progressively achieved using a combination of iodide and PPh3. In this review, we primarily focus on summarizing the recent advancements in inexpensive and readily available iodide/phosphine-mediated photoredox radical transformations.

Synergistic enhanced activation of peroxymonosulfate by heterojunction Co3O4-CuO@CN for removal of oxytetracycline: Performance, mechanism, and stability.

Metal-organic frameworks (MOFs) as precursors for catalysts has drawn growing attentions. In this study, heterojunction Co3O4-CuO doped carbon materials (noted as Co3O4-CuO@CN) were prepared by direct carbonization of CuCo-MOF in air. It was found that the Co3O4-CuO@CN-2 exhibited excellent catalytic activity with the highest Oxytetracycline (OTC) degradation rate of 0.0902 min-1 at 50 mg/L of Co3O4-CuO@CN-2 dosage, 2.0 mM of PMS and 20 mg/L of OTC, which was 4.25 and 4.96 times that of CuO@CN and Co3O4@CN, respectively. Furthermore, Co3O4-CuO@CN-2 was efficient over a wide pH range (pH 1.9-8.4), and possessed good stability and reusability without OTC degradation decrease after five consecutive uses at pH 7.0. In a comprehensive analysis, the rapid regeneration of Cu(II) and Co(II) is responsible for their excellent catalytic performance, and the p-p heterojunction structure formed between Co3O4 and CuO acts as an intermediary of electron transfer to accelerate PMS decomposition. Moreover, it was interesting to find that Cu rather than Co species played a vital role in the PMS activation. The quenching experiments and electron paramagnetic resonance demonstrated that .OH, SO4•-, and 1O2 were the reactive species responsible for oxidation of OTC and the non-radical pathway triggered by 1O2 was dominant.

The Research Status, Potential Hazards and Toxicological Mechanisms of Fluoroquinolone Antibiotics in the Environment.

Fluoroquinolone antibiotics are widely used in human and veterinary medicine and are ubiquitous in the environment worldwide. This paper recapitulates the occurrence, fate, and ecotoxicity of fluoroquinolone antibiotics in various environmental media. The toxicity effect is reviewed based on in vitro and in vivo experiments referring to many organisms, such as microorganisms, cells, higher plants, and land and aquatic animals. Furthermore, a comparison of the various toxicology mechanisms of fluoroquinolone antibiotic residues on environmental organisms is made. This study identifies gaps in the investigation of the toxic effects of fluoroquinolone antibiotics and mixtures of multiple fluoroquinolone antibiotics on target and nontarget organisms. The study of the process of natural transformation toward drug-resistant bacteria is also recognized as a knowledge gap. This review also details the combined toxicity effect of fluoroquinolone antibiotics and other chemicals on organisms and the adsorption capacity in various environmental matrices, and the scarcity of data on the ecological toxicology evaluation system of fluoroquinolone antibiotics is identified. The present study entails a critical review of the literature providing guidelines for the government to control the discharge of pollutants into the environment and formulate policy coordination. Future study work should focus on developing a standardized research methodology for fluoroquinolone antibiotics to guide enterprises in the design and production of drugs with high environmental biocompatibility.

Cascade Radical Trifluoromethylthiolation/Cyclization of Dienes To Access SCF3-Containing Medium-Sized Heterocycles.

A novel radical cascade trifluoromethylthiolation/cyclization of dienes (N-alkyl-2-(1-phenylvinyl)aniline derivatives) with AgSCF3 has been developed. This approach provides simple and efficient access to a wide range of SCF3-containing medium-sized rings (7/8/9-membered heterocycles). Preliminary mechanistic studies suggest that the reaction is realized through a silver-assisted radical cascade cyclization process. The large-scale experiment and modification of the product reveal the promising utility of this protocol.

Valorisation of food waste for valuable by-products generation with economic assessment.

This study assessed the techno-economic feasibility of a biorefinery for valuable by-products (mainly hydrogen, ethanol and fertilizer) generation from food waste. The plant was designed to be built in Zhejiang province (China) with a processing capacity of 100 t food waste per day. It was found that the total capital investment (TCI) and annual operation cost (AOC) of the plant were US$ 7625549 and US$ 2432290.7 year-1, respectively. After the tax, US$ 3141867.6 year-1 of net profit could be reached. The payback period (PBP) was 3.5 years at a 7% discount rate. The internal rate of return (IRR) and return on investment (ROI) were 45.54% and 43.88%, respectively. Shutdown condition could happen with the feed of food waste less than 7.84 t day-1 (2587.2 t year-1) for the plant. This work was beneficial for attracting interests and even investment for valuable by-products generation from food waste in large scale.

Spatiotemporal distribution of opportunistic pathogens and microbial community in centralized rural drinking water: One year survey in China.

Centralized water supply in rural areas, supported by small waterworks (small-central mode) and by municipal water treatment plants (urban-extension mode), is an important guarantee to implement the Rural Revitalization Strategy Plan (2018-2022) in China. Opportunistic pathogens (OPs) could not be evaluated by the national drinking water sanitation standards in China (GB 5749-2022), posing potential microbial risks in rural drinking water. In this study, the spatiotemporal distribution of OPs, microbial community and the associated functional composition under two central water supply modes were investigated by molecular approaches. The results indicated that OPs were widely presented in the rural drinking water regardless of water supply modes, and were more abundant than those in the urban tap water. The insufficient residual chlorine and higher turbidity triggered more microbial proliferation, posing a seasonal variation of OPs gene copy numbers and bacterial community compositions. In warm seasons of summer and autumn, the gene copies of E. coli, M. avium, Pseudomonas spp. and the amoeba host Acanthamoeba spp. achieved up to 4.92, 3.94, 6.75 and 3.74 log10 (gene copies/mL), respectively. Potential functional prediction indicated higher relative abundance of pathogenic genes and infectious risks associated with the rural drinking water under small-central water supply mode. This one-year survey of the spatiotemporal distribution of OPs and microbial community provided scientific insights into microbial safety of rural drinking water, prompting attention on small-central water supply mode against OPs risks.

Synthesis of Bimetallic FeCu-MOF and Its Performance as Catalyst of Peroxymonosulfate for Degradation of Methylene Blue.

Bimetallic MOFs have recently emerged as promising materials for wastewater treatment based on advanced oxidation processes. Herein, a new bimetallic MOF (FeCu-MOF) was fabricated by hydrothermal process. The structural, morphological, compositional and physicochemical properties of the as-synthesized bimetallic FeCu-MOF were characterized by XRD, FT-IR, SEM, TEM, BET, and XPS. TEM and XPS confirmed the homogeneous distribution of CuO2 nanoparticles in the as-synthesized materials. The result of wastewater treatment indicated that 100% of MB was removed by 6.0 mM PMS activated with 0.6 g/L of FeCu-MOF in 30 min. The high catalytic performance of FeCu-MOF was probably due to the accelerated electron and mass transfer resulting from the existence of a homogeneous distribution of unsaturated metal sites and an abundant mesoporous structure. The obtained results from the competitive quenching tests demonstrated that sulfate radicals (SO4•-) were the major species responsible for MB oxidation. In addition, hydroxyl (·OH) and singlet oxygen (1O2) also had a nonnegligible role in the MB removal. Interestingly, the addition of acetate ion (CHCOO-) promoted the removal of MB while other anions (including NO2-, H2PO4-, SO42-, HPO42-, and HCO3-) inhibited the MB removal. Furthermore, a possible mechanism based on both heterogeneous and homogeneous activation of PMS was proposed, along with the MB degradation mechanism.

Coupled process of in-situ sludge fermentation and riboflavin-mediated nitrogen removal for low carbon wastewater treatment.

Volatile fatty acid recovery from waste activated sludge (WAS) was highly suggested to supplement carbon source for nitrogen removal. However, it was not easy to separate them from the metabolites under the ex-situ fermentation. In this study, in-situ WAS fermentation combined in the denitrification system was established to treat low carbon wastewater (COD/TN = 4), and riboflavin was employed as a redox mediator. This coupled process could simultaneously enhance the WAS fermentation and nitrogen removal, and riboflavin could significantly enrich the fermentative bacteria (Firmicutes phylum), denitrifying bacteria (Denitratisoma genus) and related functional genes (narGHJI, napABC, nirKS, nosZ, norBC), generating more available carbon sources for efficient nitrogen removal. This resulted in the effluent TN (<15 mg/L) satisfying the required discharge standard in China. This study provided new insights into the efficient nitrogen removal from low carbon wastewater, realizing the carbon-neutral operation of new concept wastewater treatment plant in China.

Process design and techno-economic analysis of fuel ethanol production from food waste by enzymatic hydrolysis and fermentation.

In this study, fuel ethanol production from food waste using enzymatic hydrolysis and fermentation was evaluated from techno-economic viewpoint. The plant was designed with a capacity of 10 t/d food waste and a lifetime of 15-year. The total capital cost, annual operation cost and annual net profits of the plant were US$ 367,552, US$ 155,959 and US$ 74,995.57, respectively. The plant was economically viable as long as the internal rate of return remained below 29.8%. The shortest payback time was 5 years with discount rate of 5%. The price of fuel ethanol and food waste treatment fee were the most important variables for the economic performance of the plant by sensitivity analysis. This work could provide the basic knowledge for techno-economic analysis of food waste treatment and promote the industrial production of fuel ethanol.

Bioethanol production from expired cookies and economic analysis for practical application.

This work examined the potential of bioethanol production from expired cookies (EC) by the separate hydrolysis and fermentation process. EC was hydrolyzed by glucoamylase with different enzyme addition (3.5 U/g to 140 U/g) to produce the EC hydrolysate. The glucose concentration increased with enzyme addition from 3.5 U/g to 14 U/g and the highest glucose concentration of 21.2 g/L was obtained. The EC hydrolysate was used by Saccharomyces cerevisiae for bioethanol production. The optimal ethanol production obtained from this study was 40.1 g/L in term of economics and efficiency. According to the mass balance, the highest ethanol yield from EC was 0.4 g/g. Techno-economic analysis of the plant with capacity of 5 tons EC/day was also assessed in this study. The total capital cost and annual operation cost were US$540400.7 and US$144543.9/y, respectively. The revenue of the plant was US$390522/y with the sales of 660 t/y ethanol and 412.5 t/y oils. The plant should feed the EC more than 1.04 t/d (334.2 t/y) to avoid the shutdown point. This is the first study to demonstrate the bioethanol production from EC and assess the economic feasibility for industrial application.

Ethanol Production from the Mixture of Waste French Fries and Municipal Wastewater via Separate Hydrolysis and Fermentation.

The potential of bioethanol generation using the mixture of waste French fries (WFF) and municipal wastewater (MWW) via separate hydrolysis and fermentation (SHF) was evaluated in this study. The effect of WFF substrate loading (SL, 10%, 16%, and 20%, w/v) on the SHF was also examined. Both glucose production and hydrolysis efficiency increased with increasing of SL from 10 to 16% and the maximum glucose yield of 0.236 g glucose/g WFF and hydrolysis efficiency of 91.9% were obtained at SL of 16%. However, the glucose production and hydrolysis efficiency decreased when the SL further increased to 20% due to the inhibition on enzyme caused by higher glucose production. The mixture hydrolysate was then used as feedstock for ethanol fermentation. The maximum ethanol production of 22.69 g/L was obtained from SL of 16%. The highest rate of glucose conversion to ethanol was 84.2%. The results demonstrated that the mixture of WFF and MWW could be used for ethanol production by the SHF.

Effect of temperature on fermentative VFAs production from waste sludge stimulated by riboflavin and the shifts of microbial community.

Fermentative volatile fatty acids (VFAs) production from waste activated sludge (WAS) under moderate temperature is a promising way for resource and energy regeneration in municipal wastewater treatment plants (MWTPs). In this study, the effect of temperature on VFAs production and the associated microbial community from riboflavin-assisted WAS fermentation were investigated. Three fermentative reactors under 25, 35 and 55 °C were operated for 30 days, respectively. The results indicated that riboflavin enhanced VFAs production from WAS fermentation under moderate temperatures (25 °C, 35 °C), increasing conversion of organic matters to bioavailable substrates for the subsequent acidification process. Although a small dosage of riboflavin (1.0 ± 0.05 mM) hardly inhibited the methanogenic process, it could mediate the electron sink for VFAs under lower temperatures. This in turn increased the accumulation of acetic and propionic acids (up to 234 mg/g of volatile suspended solids) and their proportions relative to the total VFAs, being efficient electron donors and carbon sources for nutrient removal in MWTPs. Furthermore, microbial communities were shifted in response to temperature, and riboflavin stimulated the special fermentative bacteria under room temperature and mesophilic conditions. The study suggested a feasible and eco-friendly method to improve VFAs production from crude WAS at a relatively lower temperature.

Selective and leaching-resistant palladium catalyst on a porous polymer support for phenol hydrogenation.

Selective hydrogenation of phenol is promising for the utilization of renewable lignocellulose and production of cyclohexanone that usually relies on petroleum, but it is challenging to simultaneously achieve high activity and selectivity. Herein, we report an amino-functionalized nanoporous polymer stabilized palladium nanoparticle catalyst, which is prepared via a one-pot co-polymerization method, as highly active and selective catalysts for the phenol hydrogenation, giving cyclohexanone selectivity over 99.5% with full conversion of phenol under mild reaction conditions without any soluble additives. Importantly, the palladium leaching was efficiently hindered, maintaining the catalytic performances in continuously recycle tests. In contrast, the commercial palladium catalysts exhibit much lower selectivity and obvious deactivation because of the palladium leaching.

Effects of Enzyme Volumes on Hydrolysis and Fermentation for Ethanol Production From Leftover Cooked Rice.

This study aimed to utilize the enzymatic hydrolysis of leftover cooked rice (LCR) for fermentative ethanol production. Effect of glucoamylase volumes (V1: 5 U/g, V2: 25 U/g, and V3: 50 U/g) on the performance of LCR hydrolysis was also evaluated. It was found that the highest chemical oxygen demand (COD) of 77.5 g/L and reducing sugar (RS) of 34.6 g/L were achieved at V3. The LCR hydrolyzate obtained from enzymatic hydrolysis was then used as feedstock for ethanol fermentation. Higher ethanol production was obtained when RS increased from 18.7 g/L (V1) to 23.2 g/L (V2). However, lower ethanol production was found when RS further increased to 34.6 g/L (V3) probably because too high RS concentration led to the inhibition on the yeast. The maximum ethanol production and yield were 21.1 g/L and 0.3 g ethanol/g LCR, respectively. The LCR could be a promising substrate for fermentative ethanol production for industrial application.

Nano-porous bimetallic CuCo-MOF-74 with coordinatively unsaturated metal sites for peroxymonosulfate activation to eliminate organic pollutants: Performance and mechanism.

The importance of clean water resources for maintaining sustainable development of society is self-evident. In this study, bimetallic metal-organic framework (CuCo-MOF-74) was synthesized and characterized by XRD, FT-IR, SEM, TEM, BET, and XPS techniques. The structural analysis results revealed that CuCo-MOF-74 was nano-porous materials with coordinatively unsaturated metal sites. With the addition of PMS, Cu1Co1-MOF-74 exhibited high activity for methylene blue (MB) removal (100% degradation) within 30 min under low 50 mg/L catalyst dosage. The effects of catalyst dosage, PMS dosage, MB concentration, initial pH, and common anions were evaluated. Quenching reactions and EPR studies revealed the coexistence of sulfate radical (SO4•-), hydroxyl radical (·OH), and singlet oxygen (1O2), which was attributed to the potential in-situ recycling of cobalt and copper species (Co(III)→Co(II), Cu(II)→Cu(I))). Fukui index (f0) and dual descriptor (Δf) by Density functional theory (DFT) calculations were applied to predict the most reactive sites of MB. Meanwhile, the possible degradation pathway of MB was proposed with the help of oxidative intermediates identified by UPLC-MS.

Environmental distribution, transport and ecotoxicity of microplastics: A review.

Microplastics (MPs) have become a global environmental pollutant because of their unique properties. The extensive MP toxicity reports have focused on the aquatic environment, while the pervasive MP contamination in the soil and air has largely been overlooked. This review summarizes the abundance, sources and transport of MPs in different environments. It analyzes the toxicity of MPs based on various environmentally relevant bacterial, cellular, plant, aquatic animal and mammalian test groups, using both in vitro and in vivo experiments. The combined toxicity effects of MPs and various other environmental pollutants on ecosystems are also discussed. Currently, data on the adverse effects on combined MP toxicity are very limited. Thus, a systematic assessment of the environmental risk in different environments and in various species from MPs is challenging. Thus, this review proposes the possible risks and identifies the knowledge gaps posed by MPs to food safety and human health.

Pyrolysis kinetic study of cathode material derived from spent lithium ion batteries (LIBs): Comparison of different models.

Separating cathode material and Al foil from spent lithium-ion batteries (LIBs) is a critical step for LIBs recycling. As compared to chemical dissolving and decomposition, the pyrolysis pretreatment is an alternative and simple method. In this work, the pyrolysis kinetics of cathode material were comparatively studied using various isoconversional methods, including Flynn-Wall-Ozawa (FWO), Friedman, Kissinger-Akahira-Sunose, Starink, Tang, and Boswell. The thermal degradation mechanism was investigated by the Coats-Redfern (CR) and master-plot methods as well. The thermogravimetric analysis revealed that cathode material decomposition could be divided into three stages with mass losses of 1.51%, 0.787%, and 0.449%, respectively. Activation energy (Eα) calculated using the six model-free methods showed a similar trend, gradually increasing as the degree of conversion (α) increased from 0.001 to 0.009, and then significantly elevating. The FWO method gave the best fitting and Eα values first increased from 12.032 to 24.433 kJ·mol-1 with α elevating from 0.001 to 0.009, then increased further to 43.187 kJ·mol-1. Both CR and Criado methods indicated that the degradation of cathode material can be explained by the diffusion models.Implications: The rapid growth in the production and consumption of lithium-ion batteries (LIBs) for portable electronic devices and electric vehicles has resulted in an increasing number of spent LIBs. Thermal treatment offers advantages of high-efficiency and simple operation. Understanding the thermal process of spent LIBs and probing its kinetic are significant for the large-scale treatment. Through this study, it will be significant for the reactor designing and optimizing in practice.

Two-stage anaerobic process benefits removal for azo dye orange II with starch as primary co-substrate.

Two-stage anaerobic system (S1: R1 (acidogenic phase) + R2 (methanogenic phase)) and the one-stage control (S0) were established to investigate the effect of phase separation on the removal of an azo dye orange II, i.e., Acid Orange 7 (AO7), with starch as the primary co-substrate. Although final AO7 removal from two systems showed no statistical differences, the first-order rate constants for AO7 removal (kAO7-) and sulfanilic acid (SA) formation (kSA) were higher in S1. Kinetic analysis showed that kAO7- and kSA in S1 were 2.7-fold and 1.7-fold of those in S0, respectively, indicating the benefit of phase separation to the AO7 reduction. However, this benefit only appeared in the period with influent AO7 concentrations higher than 2.14 mM. Otherwise, this advantage would be hidden due to the longer HRT (5 d) and sufficient electron donor (1.0 g starch L-1). Within S1, R1 only contributed about 10% of the entire AO7 removal, and kAO7- in R1 (0.172 h-1) was much lower than in R2 (0.503 h-1). The methanogenic phase rather than acidogenic phase was the main contribution to AO7 removal, because the influent of R2 had more available electron donors and suitable pH condition (pH 6.5-7.0) for the bio-reduction process.