Cover illustration
Front Cover Story (See: Heidelore Fiedler, Mohammad Sadiaa, Thomas Krauss, Abeer Baabish, Leo W.Y. Yeung, 2022, 16(10): 132) Applying a well-established protocol to assess persistent organic pollutants (POPs), human milk samples – as national pools – were analyzed for perfluoroalkane substances (PFAS), which are emerging contaminants. In 101 samples consisting of 86 national pools and 15 pools from States in Brazil obtained between 2008 and 2019, perfluorooctane carboxylic [Detail] ...
● Adsorption of PFASs on MPs and its mechanisms are critically reviewed. ● MPs could alter the transport and transformation of PFASs in aquatic environments. ● Combined toxicity of MPs and PFASs at organismal and molecular levels is discussed.
Microplastics (MPs) are recognized as vectors for the transport of organic contaminants in aquatic environments in addition to their own adverse effects on aquatic organisms. Per- and polyfluoroalkyl substances (PFASs) are widely present in aquatic environments due to their widespread applications, and thus coexist with MPs. Therefore, we focus on the interaction of MPs and PFASs and related combined toxicity in aquatic environments in this work. The adsorption of PFASs on MPs is critically reviewed, and new mechanisms such as halogen bonding, π-π interaction, cation-π interactions, and micelle formation are proposed. Moreover, the effect of MPs on the transport and transformation of PFASs in aquatic environments is discussed. Based on four typical aquatic organisms (shellfish, Daphnia, algae, and fish), the toxicity of MPs and/or PFASs at the organismal or molecular levels is also evaluated and summarized. Finally, challenges and research perspectives are proposed, and the roles of the shapes and aging process of MPs on PFAS biogeochemical processes and toxicity, especially on PFAS substitutes, are recommended for further investigation. This review provides a better understanding of the interactions and toxic effects of coexisting MPs and PFASs in aquatic environments.
● Collaborative treatment of plastics and OS was established to improve oil quality. ● PE addition successfully improved OS pyrolysis process by deploying H/Ceff ratio. ● Higher H/Ceff ratio promoted cracking to obtain more gas and light oil fractions. ● The degradation of PE and OS was promoted each other under their temperature range.
Pyrolysis is an effective method to treat oily sludge (OS) due to its balance between oil recovery and nonhazardous disposal. However, tank bottom OS contains a high content of heavy fractions, which creates obstacles for pyrolysis due to the high activation energy. The incomplete cracking of macromolecules and secondary polymerization decreases the oil quality and causes coking during the operation process. This study introduced polyethylene (PE) into OS to deploy the H/Ceff ratio of feedstocks for pyrolysis. A strong interaction between OS and PE during copyrolysis could be observed from the TG/DTG curves. PE tightly participated in OS degradation, while OS also promoted PE degradation at high temperature. Apparent pits were generated in solid residues from copyrolysis, which was attributed to the uniform and violent gas release. In addition to HCN, other nitrogenous and sulphurous pollutants were inhibited. Accordingly, more gas products were attained after PE addition with more value-added compositions of alkanes and alkenes. Although the oil yield decreased after PE addition, the oil products from copyrolysis possessed higher heating values and higher contents of light fractions with short chains as well as paraffins. Consequently, copyrolysis of OS and PE significantly improved the pyrolysis process and resulted in high oil quality.
● Fe3O4 NPs increased the biomass and chlorophyll content of hemp clones. ● Fe3O4 NPs penetrated and were internalized by root cells. ● Fe3O4 NPs induced the alteration of metabolite profiles in hemp leaves. ● The psychoactive compound THC in hemp leaves was significantly down-regulated.
We investigated the effect of iron oxide nanoparticles (Fe3O4 NPs, ~17 nm in size) on the phenotype and metabolite changes in hemp (Cannabis sativa L.), an annual crop distributed worldwide. Hemp clones were grown in hydroponic cultures with Fe3O4 NPs (50, 100, 200, or 500 mg/L) for four weeks. TEM and ICP-MS were used to determine Fe3O4 NPs uptake and translocation. LC-MS-based metabolomics was employed to explore the deep insight into the effect of Fe3O4 NPs on hemp plants. The results revealed that plant growth enhanced gradually with increasing concentrations of given NPs up to 200 mg/L, which improved the fresh weight and dry weight by 36.13% and 74.68%, respectively, compared to the control. Even at a high dose (500 mg/L), Fe3O4 NPs promoted plant growth, including increased biomass and tissue length. NPs significantly increased the iron and chlorophyll content in plant tissues Increased catalase activity and reduced hydrogen peroxide content in hemp leaves suggested that the Fe3O4 NPs activated the defense system. TEM showed that NPs were abundantly attached to the cell wall and dispersed throughout the root cells. Metabolomics revealed that Fe3O4 NPs induced metabolic reprogramming in hemp leaves, including the up-regulation of carbohydrates and organic acids, and down-regulation of antioxidants, especially tetrahydrocannabinol (THC). The significantly up-regulated metabolites, including peonidin and 2-hydroxycinnamic acid, could be involved in photosynthesis in hemp plants. These results demonstrate the potential of Fe3O4 NPs for promoting hemp growth and decreasing the THC content at low doses.
● A composite aerogel was simply obtained to remove various fluoroquinolones (FQs). ● The structural and textural properties of this composite aerogel are improved. ● Its adsorption capacity was improved at a low content of coexisting Cu2+ or Fe3+ ion. ● Two substructural analogs of FQs are compared to explore the adsorption mechanisms. ● This aerogel after saturated adsorption can be reused directly for Cu2+ adsorption.
3D composite aerogels (CMC-CG) composed of carboxymethyl cellulose and κ-carrageenan were designed and fabricated using the one-pot synthesis technique. The optimized CMC-CG showed a good mechanical property and a high swelling ratio due to its superior textural properties with a proper chemically cross-linked interpenetrating network structure. CMC-CG was utilized for the removal of various fluoroquinolones (FQs) from water and exhibited high adsorption performance because of effective electrostatic attraction and hydrogen bonding interactions. Ciprofloxacin (CIP), a popular FQ, was used as the representative. The optimized CMC-CG had a theoretically maximal CIP uptake of approximately 1.271 mmol/g at the pH of 5.0. The adsorption capacity of CMC-CG was improved in the presence of some cations, Cu2+ and Fe3+ ions, at a low concentration through the bridging effect but was reduced at a high concentration. The investigation of adsorption mechanisms, based on the adsorption kinetics, isotherms and thermodynamic study, Fourier transform infrared spectrometry and X-ray photoelectron spectroscopy analyses before and after adsorption, and changes in the adsorption performance of CMC-CG toward two molecular probes, further indicated that electrostatic attraction was the dominant interaction rather than hydrogen bonding in this adsorption. CMC-CG after saturated adsorption of CIP could be easily regenerated using a dilute NaCl aqueous solution and reused efficiently. Moreover, the disused aerogel could still be reused as a new adsorbent for effective adsorption of Cu2+ ion. Overall, this study suggested the promising applications of this composite aerogel as an eco-friendly, cost-effective, and recyclable adsorbent for the efficient removal of FQs from water.
● Perfluorooctanesulfonic acid and perfluorooctanoic acid highest in human milk. ● All other perfluoroalkane substances had median values of zero (101 samples). ● Branched PFOS recommended to be analyzed separately from linear isomer. ● PFOS and PFOA showed differentiated regional and income distribution. ● Human health risk assessment values not yet available at global level.
Within the global monitoring plan (GMP) established by article 16 of the Stockholm Convention on Persistent Organic Pollutants, perfluorooctane sulfonic acid (PFOS), perfluorooctanoic acid (PFOA), and perfluorohexane sulfonic acid (PFHxS) are recommended for analysis in core matrices to assess occurrence and changes geographically and with time. In 101 samples consisting of 86 national pools and 15 pools from States in Brazil obtained between 2008 and 2019, PFHxS was detected in 17% of the national pools and none in Brazil. PFOA and PFOS had a detection frequency of 100% and 92%, respectively. Other perfluoroalkane substances (PFAS) had either low detection frequencies and median values of zero (carboxylic acids C4–C11; except PFOA) or could not be quantified in any sample (sulfonic acids, C4–C10, and long-chain carboxylic acids, C12–C14). Correlation between PFOA and PFOS was moderately (r = 0.58). Whereas median values were almost identical (18.9 pg/g f.w. for PFOS; 18.6 pg/g f.w. for PFOA), PFOS showed larger ranges (< 6.2 pg/g f.w.–212 pg/g f.w.) than PFOA (< 6.2 pg/g f.w.–63.4 pg/g f.w.). It was shown that wealthier countries had higher PFOA concentrations than poorer countries. No difference in concentrations was found for samples collected in countries having or not having ratified the Stockholm Convention amendments to list PFOS or PFOA. The goal to achieve 50% decrease in concentrations within ten years was met by Antigua and Barbuda, Kenya, and Nigeria for PFOS and by Antigua and Barbuda for PFOA. In a few cases, increases were observed; one country for PFOS, four countries for PFOA.
● An urchin-like OMS/ZIS composite was fabricated by a facile solvothermal method. ● The OMS/ZIS exhibits superior photocatalytic H2 evolution for organics degradation. ● A probable mechanism of dual-functional photocatalysis was proposed in detail. ● This work provides an inspiration for rational design of dual-functional catalysts.
Achieving hydrogen production and simultaneous decomposition of organic pollutants through dual-functional photocatalytic reactions has received increasing attention due to the environmentally friendly and cost-effective characteristics of this approach. In this work, an urchin-like oxygen-doped MoS2/ZnIn2S4 (OMS/ZIS) composite was fabricated for the first time using a simple solvothermal method. The unique microstructure with abundant active sites and fast charge transfer channels further shortened the charge migration distance and compressed carrier recombination. The obtained composite exhibited an efficient H2 evolution reaction rate of 12.8 mmol/g/h under visible light, which was nearly times higher than pristine ZnIn2S4, and the apparent quantum efficiency was 14.9% (420 nm). The results of the simultaneous photocatalytic H2 evolution and organic pollutant decomposition test were satisfactory, resulting in decomposition efficiencies of resorcinol, tetracycline, and bisphenol A that reached 41.5%, 63.5%, and 53.0% after 4 h, respectively, and the highest H2 evolution rate was 672.7 μmol/g/h for bisphenol A. Furthermore, natural organic matter (NOM) abundantly found in actual water was adopted as an electron donor for H production under simulated sunlight irradiation, indicating the promising practicability of simultaneous hydrogen evolution and NOM decomposition. Moreover, the mechanisms of the dual-purpose photocatalytic reactions, as well as the synergistic effect between the molecular structures of the organic pollutants and the corresponding adsorption behavior on the photocatalyst surface were illustrated in detail. These obtained results may serve as an inspiration for the rational design of highly efficient, dual-functional photocatalysts in the future.
● Cu addition enhances CH3OH oxidation and alleviates its inhibitory effect on SCR. ● Cu addition improves the activation of SCR reactants in the presence of methanol. ● Damaged structure by more Cu addition decreases specific surface area and acidity. ● Excessive Cu addition would lead to the narrowing of SCR temperature window.
Simultaneously removal of NOx and VOCs over NH3-SCR catalysts have attracted lots of attention recently. However, the presence of VOCs would have negative effect on deNOx efficiency especially at low temperature. In this study, copper modification onto Sb0.5CeZr2Ox (SCZ) catalyst were performed to enhance the catalytic performance for simultaneous control of NOx and methanol. It was obtained that copper addition could improve the low-temperature activity of both NOx conversion and methanol oxidation, where the optimal catalyst (Cu0.05SCZ) exhibited a deNOx activity of 96% and a mineralization rate of 97% at 250 °C, which are around 10% higher than that of Cu free sample. The characterization results showed that copper addition could obviously enhance the redox capacity of the catalysts. As such, the inhibition effect of methanol incomplete oxidation on NO adsorption and NH3 activation were then lessened and the conversion of surface formamide species were also accelerated, resulting in the rising of NOx conversion at low temperature. However, excessive copper addition would damage the Sb-Ce-Zr oxides solid solution structure owing to Cu-Ce strong interactions, decreasing the surface area and acidity. Meanwhile, due to easier over-oxidation of NH3 with more Cu addition, the temperature window for NOx conversion would become quite narrow. These findings could provide useful guidelines for the synergistic removal of VOCs over SCR catalyst in real application.
● A new model for bloom control in open land scape water was constructed. ● It considers the effects of temperature and light on algae growth. ● It describes threshold curve of nitrogen, phosp horus and hydraulic retention time. ● Light and temperature dependent growth para meters of typical algae were obtained.
The risks posed by algal blooms caused by nitrogen and phosphorus in reclaimed water used in urban water landscapes need to be carefully controlled. In this study, the combined effects of the nitrogen and phosphorus concentrations and the light intensity and temperature on the specific growth rates of algae were determined using Monod, Steele, and Arrhenius models, then an integrated algal growth model was developed. The algae biomass, nitrogen concentration, and phosphorus concentration mass balance equations were used to establish a new control model describing the nitrogen and phosphorus concentration and hydraulic retention time thresholds for algal blooms. The model parameters were determined by fitting the models to data acquired experimentally. Finally, the control model and numerical simulations for six typical algae and mixed algae under standard conditions were used to determine nitrogen/phosphorus concentration and hydraulic retention time thresholds for landscape water to which reclaimed water is supplied (i.e., for a reclaimed water landscape).
● Coastal and marine regions are the most studied for microplastic pollution. ● Tourism is a major cause of microplastic pollution in coastal regions. ● Sediments contain larger microplastics while fish ingest smaller microplastics. ● Inland lakes, rivers, and freshwater fish are impacted by microplastic pollution. ● Microplastics are found in edible salts, however, presence is less in refined salt.
The research on the extent and effects of microplastics pollution in the Global South is only getting started. Bangladesh is a South Asian country with one of the fastest growing economies in the world, however, such exponential economic growth has also increased the pollution threats to its natural and urban environment. In this paper, we reviewed the recent primary research on the assessment of the extent of microplastics pollution in Bangladesh. From the online databases, we developed a compilation of emerging research articles that detected and quantified microplastics in different coastal, marine, and urban environments in Bangladesh. Most of the studies focused on the coastal environment (e.g., beach sediment) and marine fish, while limited data were available for the urban environment. We also discussed the relationship of the type of anthropogenic activities with the observed microplastic pollution. The Cox’s Bazar sea beach in south-east Bangladesh experienced microplastics pollution due to tourism activities, while fishing and other anthropogenic activities led to microplastics pollution in the Bay of Bengal. While microplastics larger than 1 mm were prevalent in the beach sediments, smaller microplastics with size below 0.5 mm were prevalent in marine fish samples. Moreover, the differences in microplastic abundance, size, shape, color, and polymer type found were depended on the sampling sites and relevant anthropogenic activities. It is imperative to identify major sources of microplastics pollution in both natural and urban environment, determine potential environmental and human health effects, and develop mitigating and prevention strategies for reducing microplastics pollution.
● 548 representative nor genes were collected to create complete phylogenetic trees. ● The distribution of nor and nod genes were detected in 18 different phyla. ● The most conserved amino acids in NOR were located adjacent to the active site. ● nor-universal and Clade-specific primers were designed, suggested, and tested.
Nitric oxide reductases (NORs) have a central role in denitrification, detoxification of nitric oxide (NO) in host-pathogen interactions, and NO-mediated cell-cell signaling. In this study, we focus on the phylogeny and detection of qNOR and cNOR genes because of their nucleotide sequence similarity and evolutionary relatedness to cytochrome oxidases, their key role in denitrification, and their abundance in natural, agricultural, and wastewater ecosystems. We also include nitric oxide dismutase (NOD) due to its similarity to qNOR. Using 548 nor sequences from publicly accessible databases and sequenced isolates from N2O-producing bioreactors, we constructed phylogenetic trees for 289 qnor/nod genes and 259 cnorB genes. These trees contain evidence of horizontal gene transfer and gene duplication, with 13.4% of the sequenced strains containing two or more nor genes. By aligning amino acid sequences for qnor + cnor, qnor, and cnor, we identified four highly conserved regions for NOR and NOD, including two highly conserved histidine residues at the active site for qNOR and cNOR. Extending this approach, we identified conserved sequences for: 1) all nor (nor-universal); 2) all qnor (qnor-universal) and all cnor (cnor-universal); 3) qnor of Comamonadaceae; 4) Clade-specific sequences; and 5) nod of Candidatus Methylomirabilis oxyfera. Examples of primer performance were confirmed experimentally.
● The concentrations of 61 progesterones in HWW, PFTE, SBTE were evaluated. ● The removal efficiencies of progesterones by PFT and SBT were identified. ● Compared the removal efficiencies of progeste rones in five disinfection processes.
Progesterones are ubiquitous in hospital wastewater (HWW) with concentrations much higher than those of estrogens and androgens. To ensure that these water systems are safe to use, disinfection is crucial during HWW treatment by providing “front line” defense against biological contaminations. Here, five disinfection processes, namely, chlorine (Cl2), chlorine dioxide (ClO2), ozone (O3), ultraviolet (UV)), and UV/chlorine (UV/Cl2), were selected to investigate their removal efficiencies for progesterones in primary filtration and secondary biological treatment effluents. There were 61 natural and synthetic progesterones detected in HWW, with the natural progesterones being the main components with a concentration of 845.51 ng/L and contributing to 75.08% of the total progesterones. The primary filtration treatment presented insignificant removal effects on the progesterones, while the secondary biological treatment significantly reduced the progesterone content by biodegradation. The order of removal efficiencies of total progesterones by different disinfection processes was UV/Cl2 > Cl 2 > O 3 > ClO 2 > UV. UV/Cl 2 showed the highest removal efficiency against progesterones mainly due to the activation of Cl2 by ultraviolet (UV) photolysis, which helps open the heterocyclic, aromatic, and phenolic rings, thus accelerating progesterone degradation. In addition, the removal efficiencies of natural progesterones in the five disinfection processes were higher than those of synthetic progesterones (progesterone derivatives, 19-nortestosterone derivatives, and 17α-hydroxyprogesterone derivatives).
● A series of Cu-ZSM-5 catalysts were tested for DMF selective catalytic oxidation. ● Cu-6 nm samples showed the best catalytic activity and N2 selectivity. ● Redox properties and chemisorbed oxygen impact on DMF catalytic oxidation. ● Isolated Cu2+ species and weak acidity have effects on the generation of N2.
N, N-Dimethylformamide (DMF), a nitrogen-containing volatile organic compound (NVOC) with high emissions from the spray industry, has attracted increasing attention. In this study, Cu-ZSM-5 catalysts with different CuO particle sizes of 3, 6, 9 and 12 nm were synthesized and tested for DMF selective catalytic oxidation. The crystal structure and physicochemical properties of the catalyst were studied by various characterization methods. The catalytic activity increases with increasing CuO particle size, and complete conversion can be achieved at 300–350 °C. The Cu-12 nm catalyst has the highest catalytic activity and can achieve complete conversion at 300 °C. The Cu-6 nm sample has the highest N2 selectivity at lower temperatures, reaching 95% at 300 °C. The activity of the catalysts is determined by the surface CuO cluster species, the bulk CuO species and the chemisorbed surface oxygen species. The high N2 selectivity of the catalyst is attributed to the ratio of isolated Cu2+ and bulk CuO species, and weak acidity is beneficial to the formation of N2. The results in this work will provide a new design of NVOC catalytic oxidation catalysts.
