Performance and mechanism of diclofenac adsorption onto 3D poly(m-phenylenediamine)-grafted melamine foam via batch experiment and theoretical studies.

Seeking highly efficient adsorbents for pharmaceuticals and personal care products (PPCPs) removal has been a worldwide continuing endeavor. In this study, a new 3D composite material was synthesized by covalently anchoring Poly(m-Phenylenediamine) onto 3D polyvinyl alcohol modified foam framework (PmPD-MF-PVA). PmPD-MF-PVA was characterized and evaluated for its efficacy in removing diclofenac (DCF), a commonly detected PPCPs in both wastewater and surface water. Results showed that the adsorption capacity of PmPD-MF-PVA toward DCF was 1.5 times higher than that of PmPD-MF. The addition of PVA increased deposition area of PmPD, and promoted PmPD loading on the foam surface. Batch adsorption experiments exhibited that the adsorption of DCF was fitted well with Langmuir isotherm and pseudo-second-order kinetic models. The maximum adsorption capacity of PmPD-MF-PVA was 115 mg/g. Meanwhile, PmPD-MF-PVA exhibited better separation ability than the hard-to-separate PmPD. Characterization analysis and density functional theory (DFT) calculation elucidated the main mechanisms of DCF adsorption on PmPD-MF-PVA. Hydrogen bonding and π-π interactions were main drivers for DCF adsorption, followed by electrostatic attraction and hydrophobic forces. This study provides an effective strategy to overcome the drawbacks of PmPD, such as recycling difficulty and agglomeration problems, offering valuable insights for the design of polymers-based adsorbents.

Pharmaceuticals and personal care products contamination in the rivers of Chennai city during the COVID-19 pandemic.

Pharmaceuticals and personal care products (PPCPs) monitoring in surface water is crucial to address the escalating threat of antimicrobial resistance and safeguard public health. This study aimed to investigate the occurrence of 21 different PPCPs, including wastewater chemical markers, antibiotics, and parabens in the surface water of Chennai city using Ultra Performance Liquid Chromatography-Triple Quadrupole Mass Spectrometry (UPLC-MS/MS) analysis. It is noteworthy that chemical markers viz., carbamazepine (CBZ) and caffeine (CAF) were detected in all the sites and contributed to more than 95% of the total PPCPs load indicating a significant intrusion of wastewater. Among the antibiotics, fluoroquinolones were dominant in this study. Interestingly, a significant and strong correlation was seen between fluoroquinolones, CBZ and CAF (R2 = 0.880-0.928, p < 0.05), suggesting similarities in their sources. More than 50% of the sites exhibited a risk for antimicrobial resistance (RQAMR) with RQAMR > 1 for ciprofloxacin, indicating a significant public health concern. The ecotoxicological risk assessment of PPCPs showed no risk to any organisms, except for triclosan, which posed a risk to fish and daphnids at one site near an open drain in Buckingham canal.

Heterogeneous Photocatalytic Degradation of Selected Pharmaceuticals and Personal Care Products (PPCPs) Using Tungsten Doped TiO2: Effect of the Tungsten Precursors and Solvents.

Pharmaceuticals and personal care products (PPCPs) which include antibiotics such as tetracycline (TC) and ciprofloxacin (CIP), etc., have attracted increasing attention worldwide due to their potential threat to the aquatic environment and human health. In this work, a facile sol-gel method was developed to prepare tungsten-doped TiO2 with tunable W5+/W6+ ratio for the removal of PPCPs. The influence of solvents in the synthesis of the three different tungsten precursors doped TiO2 is also taken into account. WCl6, ammonium metatungstate (AMT), and Na2WO4●2H2O not only acted as the tungsten precursors but also controlled the tungsten ratio. The photocatalyst prepared by WCl6 as the tungsten precursor and ethanol as the solvent showed the highest photodegradation performance for ciprofloxacin (CIP) and tetracycline (TC), and the photodegradation performance for tetracycline (TC) was 2.3, 2.8, and 7.8 times that of AMT, Na2WO4●2H2O as the tungsten precursors and pristine TiO2, respectively. These results were attributed to the influence of the tungsten precursors and solvents on the W5+/W6+ ratio, sample crystallinity and surface properties. This study provides an effective method for the design of tungsten-doped TiO2 with tunable W5+/W6+ ratio, which has a profound impact on future studies in the field of photocatalytic degradation of PPCPs using an environmentally friendly approach.

Temperature-modulated morphological changes in MIL-88B(Fe)-derived iron-based materials triggering generation of the peroxymonosulfate nonradical pathway to degrade carbamazepine: The key role of iron nanoparticles and CN.

Temperature modulation of the synthesis process of MOF-derived composites is not well understood for changes in the peroxymonosulfate catalytic domain. This study synthesized a carbon-based nitrogen-doped (MN@C) MOF-derived composite catalyst derived from MIL-88B(Fe) (Materials Institute Lavoisier) by modulating temperature changes and calcination. Combined with density-functional theory calculations (DFT) analyses showed that changes in iron nanoparticles (FeNP) and CN content caused the alterations of the degradation pathways. MN@C-9 exhibited outstanding activation performance (100 % carbamazepine (CBZ) removal within 10 min). The system maintained efficient operation in different aqueous environments and a wide pH range and demonstrated efficient removal of many pollutants typical of pharmaceuticals and personal care products (PPCPs). After comprehensively analyzing the results of liquid chromatography mass spectrometry (LC-MS) and toxicity prediction, the possible degradation pathways were reasonably speculated, and the toxicity of the byproducts was greatly reduced. This study provides a potential and efficient catalyst preparation strategy for water purification.

Pharmaceuticals and personal care products and heavy metals in the Ganga River, India: Distribution, ecological and human health risk assessment.

In the present study, pharmaceuticals and personal care products (PPCPs), endocrine disrupting compounds (EDCs), and heavy metals (HMs), were measured in water and sediment of the Ganga River during summer and winter seasons for two consecutive years. Additionally, this study estimated the ecological and human health risks associated with PPCPs, EDCs, and HMs. HMs detected in the range of not detected (n.d.) to 23.59 µg/L and 0.01-391.44 µg/g in water and sediment samples, respectively. All studied HMs were within the permissible limits, except for As in water, and Cr and Ni in sediment. The geo-accumulation index (Igeo) indicated that Cr (0.71-5.98) and Pb (0.90-3.90) had high Igeo compared to other metals in sediment samples. Pb showed the highest ecological risk, followed by Cd, Co, Ni, Cu, Cr, As, and Zn. The maximum potential ecological risk index was observed at site G8. The hazard index (HI) value for water (0.08-0.89) and sediment (0.02-0.29) intake by adults remained within the acceptable limits, except at sites G8 (1.27) and G9 (1.34) for water intake. However, for children, the HI value was above the acceptable limit for water intake at sites G4 to G13 and for sediment at site G8. Among the studied compounds, metformin, triclosan, triclocarban, diclofenac, and methylparaben were the most abundant compounds present in the Ganga River. PPCPs and EDCs detected in the range of n.d. to 5850.04 ng/L and n.d. to 1080.41 ng/g in water and sediment samples, respectively. The environmental risk assessment identifies the maximum ecological risk in water exhibited by triclocarban followed by 17α-ethinylestradiol (EE2), diclofenac, and triclosan, while in sediment, the maximum ecological risk exhibited by triclocarban, followed by EE2, 17 ß-estradiol (E2), triclosan, and diclofenac. However, none of the compounds showed human health risk, except for EE2, E2, and atenolol.

Differentiated adsorption of acetaminophen and diclofenac via alkyl chain-modified quaternized SBA-15: Insights from molecular simulation.

The increasing presence of pharmaceuticals and personal care products (PPCPs) in aquatic systems pose significant environmental concerns. This study addresses this issue by synthesizing quaternized mesoporous SBA-15 (QSBA) with varied alkyl chain lengths of C1QSBA, C8QSBA, and C18QSBA. QSBA utilizes dual mechanisms: hydrophobic interactions via the alkyl chain and electrostatic attraction/ion exchange via the ammonium group. Diclofenac (DCF) and acetaminophen (ACT) were selected as target PPCPs due to their contrasting dissociation properties and hydrophobicity, which are the main characteristics of PPCPs. The adsorption of DCF and ACT revealed that longer alkyl chains enhanced the adsorption capacity of ACT through hydrophobic interactions, whereas dissociated DCF (DCF-) adsorption was superior owing to its high hydrophobicity (log Kow = 4.5) and electrostatic attraction. pH levels between 6 and 8 resulted in a high affinity for DCF-. Notably, among the three alkyl chains, only C18QSBA exhibited the most effective adsorption for DCF-. These PPCPs adsorption trends were confirmed through molecular simulations of adsorption under conditions in which competing ions coexisted. The molecular simulations show that while DCF- has lower adsorption energy than Cl-, OH-, and H3O+ ions in QSBA, enhancing its adsorption under various pH conditions. Conversely, ACT exhibits a higher adsorption energy, which reduces its adsorption efficiency. This suggests the potential application of QSBA with long alkyl chains in the treatment of highly hydrophobic and negatively charged PPCPs. Furthermore, this study emphasizes the importance of simulating adsorption under competing ion conditions.

Simultaneous removal of nutrients and pharmaceuticals and personal care products using two-stage woodchip bioreactor-biochar treatment systems.

The co-occurrence of nutrients and pharmaceuticals and personal care products (PPCPs) in sewage effluent can degrade water quality of the receiving watersheds. This study investigated the simultaneous removal of excess nutrients and PPCP contaminants by developing a novel woodchip bioreactor and biochar (B2) treatment system. The result revealed that woodchip bioreactors could effectively remove nitrate via a denitrification process and adsorb some PPCPs. Biochar as a secondary treatment system significantly reduced the concentrations of PPCPs and dissolved reactive phosphorus (DRP) (p < 0.05), compared to the woodchip bioreactor. The removal efficiencies of all targeted contaminants by the B2 system were evaluated using various hydraulic retention times (HRTs) and biochar types (pelletized versus granular biochar). Longer HRTs and smaller biochar particles (granular biochar) could enhance the removal efficiencies of targeted contaminants. Average contaminant removals were 77.25 % for nitrate-N, 99.03 % for DRP, 69.51 % for ibuprofen, 73.65 % for naproxen, 91.09 % for sitagliptin, and 96.96 % for estrone, with woodchip bioreactor HRTs of 12 ± 1.4 h and granular biochar HRTs of 2.1 ± 0.1 h. Notably, the second-stage biochar systems effectively mitigated by-products leaching from woodchip bioreactors. The presence of PPCPs in the woodchip bioreactors enriched certain species, such as Methylophilus (69.6 %), while inhibiting other microorganisms and reducing microbial community diversity. Furthermore, a scaled-up B2 system was analyzed and assessed, indicating that the proposed engineering treatment system could provide decades of service in real-world applications. Overall, this study suggests that the B2 system has promising applications for addressing emerging and conventional contaminants.

Enhanced removal of PPCPs and antibiotic resistance genes in saline wastewater using a bioelectrochemical-constructed wetland system.

Pharmaceuticals and personal care products (PPCPs) are insufficiently degraded in saline wastewater treatment processes and are found at high concentrations and detection frequencies in aquatic environments. In this study, the wetland plant Thalia dealbata was selected using a screening plant experiment to ensure good salt tolerance and high efficiency in removing PPCPs. An electric integrated vertical-flow constructed wetland (E-VFCW) was developed to improve the removal of PPCPs and reduce the abundance of antibiotic resistance genes (ARGs). The removal efficiency of ofloxacin, enrofloxacin, and diclofenac in the system with anaerobic cathodic and aerobic anodic chambers is higher than that of the control system (41.84 ± 2.88%, 47.29 ± 3.01%, 53.29 ± 2.54%) by approximately 20.31%, 16.04%, and 35.25%. The removal efficiency of ibuprofen in the system with the aerobic anodic and anaerobic cathodic chamber was 28.51% higher than that of the control system (72.41 ± 3.06%) and promotes the reduction of ARGs. Electrical stimulation can increase the activity of plant enzymes, increasing their adaptability to stress caused by PPCPs, and PPCPs are transferred to plants. Species related to PPCPs biodegradation (Geobacter, Lactococcus, Hydrogenophaga, and Nitrospira) were enriched in the anodic and cathodic chambers of the system. This study provides an essential reference for the removal of PPCPs in saline-constructed wetlands.

Sequential Reductive Dechlorination of Triclosan by Sediment Microbiota Harboring Organohalide-Respiring Dehalococcoidia.

Aquatic ecosystems represent a prominent reservoir of xenobiotic compounds, including triclosan (TCS), a broad-spectrum biocide extensively used in pharmaceuticals and personal care products. As a biogeochemical hotspot, the potential of aquatic sediments for the degradation of TCS remains largely unexplored. Here, we demonstrated anaerobic biotransformation of TCS in a batch microcosm established with freshwater sediment. The initial 43.4 ± 2.2 µM TCS was completely dechlorinated to diclosan, followed by subsequent conversion to 5-chloro-2-phenoxyphenol, a monochlorinated TCS (MCS) congener. Analyses of community profile and population dynamics revealed substrate-specific, temporal-growth of Dehalococcoides and Dehalogenimonas, which are organohalide-respiring bacteria (OHRB) affiliated with class Dehalococcoidia. Dehalococcoides growth was linked to the formation of diclosan but not MCS, yielding 3.6 ± 0.4 × 107 cells per µmol chloride released. A significant increase in Dehalogenimonas cells, from 1.5 ± 0.4 × 104 to 1.5 ± 0.3 × 106 mL-1, only occurred during the reductive dechlorination of diclosan to MCS. Dehalococcoidia OHRB gradually disappeared following consecutive transfers, likely due to the removal of sediment materials with strong adsorption capacity that could alleviate TCS's antimicrobial toxicity. Consequently, a solid-free, functionally stable TCS-dechlorinating consortium was not obtained. Our results provide insights into the microbial determinants controlling the environmental fate of TCS.

Analytical Methods for the Determination of Pharmaceuticals and Personal Care Products in Solid and Liquid Environmental Matrices: A Review.

Among the various compounds regarded as emerging contaminants (ECs), pharmaceuticals and personal care products (PPCPs) are of particular concern. Their continuous release into the environment has a negative global impact on human life. This review summarizes the sources, occurrence, persistence, consequences of exposure, and toxicity of PPCPs, and evaluates the various analytical methods used in the identification and quantification of PPCPs in a variety of solid and liquid environmental matrices. The current techniques of choice for the analysis of PPCPs are state-of-the-art liquid chromatography coupled to mass spectrometry (LC-MS) or tandem mass spectrometry (LC-MS2). However, the complexity of the environmental matrices and the trace levels of micropollutants necessitate the use of advanced sample treatments before these instrumental analyses. Solid-phase extraction (SPE) with different sorbents is now the predominant method used for the extraction of PPCPs from environmental samples. This review also addresses the ongoing analytical method challenges, including sample clean-up and matrix effects, focusing on the occurrence, sample preparation, and analytical methods presently available for the determination of environmental residues of PPCPs. Continuous development of innovative analytical methods is essential for overcoming existing limitations and ensuring the consistency and diversity of analytical methods used in investigations of environmental multi-class compounds.

Impact of seawater temperature and physical-chemical properties on sorption of pharmaceuticals, stimulants, and biocides to marine particles.

Pharmaceuticals, stimulants, and biocides enter the environment via wastewater from urban, domestic, and industrial areas, in addition to sewage, aquaculture and agriculture runoff. While some of these compounds are easily degradable in environmental conditions, others are more persistent, meaning they are less easily degraded and can stay in the environment for long periods of time. By exploring the adsorptive properties of a wide range of pharmaceuticals, stimulants, and biocides onto particles relevant for marine conditions, we can better understand their environmental behaviour and transport potential. Here, the sorption of 27 such compounds to inorganic (kaolin) and biotic (the microalgae Cryptomonas baltica) marine particles was investigated. Only two compounds sorbed to microalgae, while 23 sorbed to kaolin. The sorption mechanisms between select pharmaceuticals and stimulants and kaolin was assessed through exploring adsorption kinetics (caffeine, ciprofloxacin, citalopram, fluoxetine, and oxolinic acid) and isotherms (ciprofloxacin, citalopram, and fluoxetine). Temperature was shown to have a significant impact on partitioning, and the impact was more pronounced closer to maximum sorption capacity for the individual compounds.

Optimizing entropy weight model to accurately predict variation of pharmaceuticals and personal care products in the estuaries and coasts of the South China.

Pharmaceuticals and personal care products (PPCPs) have raised increasing concern worldwide due to their continuous release and potential hazards to the ecosystem and human health. This study optimized the entropy weight model (EW-WRSR) that combines entropy weight with multi-criteria decision analysis to investigate pollution patterns of PPCPs in the coasts and estuaries. The results revealed that occurrences of PPCPs from the 1940s to the present were consistent with using PPCPs, different types of human activities, and local urban development. This helped better understand the history of PPCP contamination and evaluate the uncertainty of EW-WRSR. The model predicted hotspots of PPCPs that were consistent with the actual situation, indicating that PPCPs mainly enter the nearshore ecosystem by the form of sewage discharge and residual aquaculture. This study can provide method that identifying highly contaminated regions on a global scale.

Occurrence and risks of PPCPs of a typical mountainous region: Implications for sustainable urban water systems.

Urban wastewater treatment plants (WWTPs) and drinking water treatment plants (DWTPs) play vital roles in the urban water cycle, ensuring access to safe drinking water and maintaining aquatic ecosystems. This study comprehensively assessed the occurrence and risks of pharmaceuticals and personal care products (PPCPs) in urban WWTPs and DWTPs. Our findings revealed widespread PPCPs presence, with concentrations ranging from <1 ng/L to several thousand ng/L. Significant regional disparities in occurrence and composition were observed linked to population types and economic structures. Furthermore, strong correlations were observed between DWTPs and WWTPs indicating consistent transport and transformation patterns of PPCPs within the urban water cycle. Approximately two-thirds of PPCPs were degraded post-WWTP treatment, with about one-tenth persisting in drinking water following surface water dilution and purification processes. Thus, we suggested that controlling the total concentration of the five priority PPCPs in the effluent from the WWTP to <1100 ng/L have potential to reduce the environmental and health risk of PPCPs. Additionally, this research identified influential water quality parameters, such as pH, dissolved oxygen, and temperature, through redundancy analysis. This research underscores the importance of establishing emission standards to mitigate PPCP-related risks and supports sustainable urban water system advancement.

Occurrence and risks of pharmaceuticals, personal care products, and endocrine-disrupting compounds in Chinese surface waters.

The continuous and rapid increase of chemical pollution in surface waters has become a pressing and widely recognized global concern. As emerging contaminants (ECs) in surface waters, pharmaceutical and personal care products (PPCPs), and endocrine-disrupting compounds (EDCs) have attracted considerable attention due to their wide occurrence and potential threat to human health. Therefore, a comprehensive understanding of the occurrence and risks of ECs in Chinese surface waters is urgently required. This study summarizes and assesses the environmental occurrence concentrations and ecological risks of 42 pharmaceuticals, 15 personal care products (PCPs), and 20 EDCs frequently detected in Chinese surface waters. The ECs were primarily detected in China's densely populated and highly industrialized regions. Most detected PPCPs and EDCs had concentrations between ng/L to µg/L, whereas norfloxacin, caffeine, and erythromycin had relatively high contamination levels, even exceeding 2000 ng/L. Risk evaluation based on the risk quotient method revealed that 34 PPCPs and EDCs in Chinese surface waters did not pose a significant risk, whereas 4-nonylphenol, 4-tert-octylphenol, 17α-ethinyl estradiol, 17ß-estradiol, and triclocarban did. This review provides a comprehensive summary of the occurrence and associated hazards of typical PPCPs and EDCs in Chinese surface waters over the past decade, and will aid in the regulation and control of these ECs in Chinese surface waters.

Occurrence and Environmental Risk Assessment of Contaminants of Emerging Concern in Brazilian Surface Waters.

We investigated the occurrence and the environmental risk of eight contaminants of emerging concern (CECs; acetaminophen, naproxen, diclofenac, methylparaben, 17ß-estradiol, sulfathiazole, sulfadimethoxine, and sulfamethazine) in three Brazilian water bodies, namely, the Monjolinho River Basin (São Paulo State), the Mogi Guaçu River (São Paulo State), and the Itapecuru River (Maranhão State) in three sampling campaigns. The CECs were only quantified in surface water samples collected at the Monjolinho River Basin. Acetaminophen, naproxen, and methylparaben were detected in the range of <200 to 575.9 ng L-1, <200 to 224.7 ng L-1, and <200 to 303.6 ng L-1, respectively. The detection frequencies of the three measured compounds were between 33% and 67%. The highest concentrations of CECs were associated with intense urbanization and untreated sewage discharge. Furthermore, CEC concentrations were significantly correlated with total organic carbon, electrical conductivity, and dissolved oxygen levels, suggesting that domestic pollution from urban areas is an important source in the distribution of CECs in the Monjolinho River Basin. The environmental risk assessment indicated a high risk for acetaminophen (risk quotient [RQ] values between 2.1 and 5.8), a medium risk for naproxen (RQs between 0.6 and 0.7), and a low risk for methylparaben (RQs < 0.1) to the freshwater biota of the Monjolinho River Basin. Our findings show potential threats of CECs in Brazilian water bodies, especially in vulnerable areas, and reinforce the need for improvements in environmental regulations to include monitoring and control of these compounds in aquatic systems. Environ Toxicol Chem 2024;43:2199-2210. © 2024 SETAC.

Tracing residual patterns and microbial communities of pharmaceuticals and personal care products from 17 urban landfills leachate in China.

Landfill leachate contributes significantly to the presence of pharmaceuticals and personal care products (PPCPs) in the environment, and is a crucial source of contamination. To examine the occurrence of PPCPs and microbial communities, this study comprehensively investigated the concentrations of PPCPs and the abundance of microorganisms in the leachate from 17 municipal landfills across China. Generally, Lidocaine, Linear alkylbenzene sulfonate-C11, and Triclocarban, which are closely associated with human activities, exhibited a detection frequency of 100 % in the leachate. Driven by consumer demand, analgesic and antipyretic drugs have emerged as the most prominent PPCPs in leachate (accounting for 39.9 %). Notably, the Ibuprofen peaked at 56.3 µg/L. Regarding spatial distribution, the contamination of PPCPs in leachates from the eastern regions of China was significantly higher than that in other regions, owing to the level of economic development and demographic factors. Furthermore, the 16S rRNA results revealed significant differences in microbial communities among the leachates from different areas. Although the impact of PPCPs on microbial communities may not be as significant as that of environmental factors, most positive correlations between PPCPs and microorganisms indicate their potential role in providing nutrients and creating favorable conditions for microbial growth. Overall, this research offers new perspectives on the residual features of PPCPs and the microbial community structure in leachates from various regions in China.

Influence of anthropogenic activities on the trace organic contamination of lakes.

Anthropogenic activities and urbanization can lead to the discharge of organic compounds into surface waters. It is important to investigate these relationships further to mitigate contamination better and prioritize protection efforts. This study aimed to verify the effect of specific anthropogenic factors on lake water contamination caused by trace organic contaminants (TrOCs) such as pharmaceuticals, pesticides and consumer product additives. Data on the detection and concentration levels of 54 TrOCs, major anthropogenic land use, and human activities from a large-scale study on Canadian lakes were used to reach this goal. The association of population and livestock densities, the presence of wastewater treatment plants (WWTPs) and hospitals as well as the agricultural and urban land use in the lakes' watersheds on lake water contamination was investigated by applying negative binomial and ordinal logistic regression models. These models were also controlled for lake/watershed area ratio, lake depth, water, residence time, watershed slope, precipitation, and sampling date. The statistical analysis confirmed that agricultural land use, urban land use, and WWTPs plants in lake watersheds are significantly associated with the number of TrOCs detected (incidence rate ratio > 1, p < 0.001) and the summed concentration of targeted TrOCs (odds ratio > 1, p < 0.001). Agricultural land use (odds ratio = 1.58, p < 0.001) and urban land use (odds ratio = 1.19, p < 0.02) were also significantly associated with the summed concentration of the targeted pesticides. This latter outcome thus suggests that urban centers are also important contributors to the concentration levels of pesticides in lakes. Overall, these results demonstrate that even in complex ecosystems such as lakes, it is possible to use a limited number of factors to explain anthropogenic contamination. This can help policymakers make informed decisions on contamination mitigation and provide insights into watershed management.

Unmasking Spatial Heterogeneity in Phytotoxicology Mechanisms Induced by Carbamazepine by Mass Spectrometry Imaging and Multiomics Analyses.

Previous studies have highlighted the toxicity of pharmaceuticals and personal care products (PPCPs) in plants, yet understanding their spatial distribution within plant tissues and specific toxic effects remains limited. This study investigates the spatial-specific toxic effects of carbamazepine (CBZ), a prevalent PPCP, in plants. Utilizing desorption electrospray ionization mass spectrometry imaging (DESI-MSI), CBZ and its transformation products were observed predominantly at the leaf edges, with 2.3-fold higher concentrations than inner regions, which was confirmed by LC-MS. Transcriptomic and metabolic analyses revealed significant differences in gene expression and metabolite levels between the inner and outer leaf regions, emphasizing the spatial location's role in CBZ response. Notably, photosynthesis-related genes were markedly downregulated, and photosynthetic efficiency was reduced at leaf edges. Additionally, elevated oxidative stress at leaf edges was indicated by higher antioxidant enzyme activity, cell membrane impairment, and increased free fatty acids. Given the increased oxidative stress at the leaf margins, the study suggests using in situ Raman spectroscopy for early detection of CBZ-induced damage by monitoring reactive oxygen species levels. These findings provide crucial insights into the spatial toxicological mechanisms of CBZ in plants, forming a basis for future spatial toxicology research of PPCPs.

Persulfate photolysis and limited irrigation of recycled wastewater for turfgrass growth: Accumulation of pharmaceutical and personal care products and physiological responses.

Recycled wastewater effluent irrigation and implementing limited irrigation rates are two promising strategies for water conservation in agriculture. However, one major challenge is the accumulation and translocation of Pharmaceutical and Personal Care Products (PPCPs) from recycled water to crops. This study investigated the effects of UV persulfate (UV/PS) treatment of recycled water and limited irrigation rate on PPCPs accumulation and physiological responses of St. Augustine turfgrass via a 14-week field trial. Carbamazepine (CBZ), sulfamethoxazole (SMX), triclosan (TCS), fluoxetine (FLX) and diclofenac (DCF) were spiked at 0.1-1.5 µg/L into recycled water and two limited irrigation rates corresponding to 60 % and 80 % of reference Evapotranspiration (ETo) were applied. Results showed that UV/PS removed 60 % of CBZ and > 99 % of other PPCPs from recycled water. Irrigation with UV/PS treated recycled water resulted in approximately a 60 % reduction in CBZ accumulation and complete removal of SMX, DCF, FLX and TCS in both turfgrass leaves and roots. A more limited irrigation rate at 60 % ETo resulted in a higher accumulation of CBZ accumulation compared to 80 % ETo. Similarly, the canopy temperature increased under 60 % ETo irrigation rate compared to 80 % ETo, suggesting that turfgrass under 60 % ETo was more prone to water stress. Applying a 60 % ETo irrigation rate was not sufficient to maintain the turfgrass quality in the acceptable range. A negative correlation between the visual quality and cumulative mass of PPCPs in turfgrass leaves at different irrigation rates was observed, yet irrigation rate was the major driver of turfgrass overall quality and health. Insights from this study will help to integrate recycled water with treatment and limited irrigation, thereby enhancing agricultural water reuse practices.

Pyrazine-based iron metal organic frameworks (Fe-MOFs) with modulated O-Fe-N coordination for enhanced hydroxyl radical generation in Fenton-like process.

Rational design of coordination environment of Fe-based metal-organic frameworks (Fe-MOFs) is still a challenge in achieving enhanced catalytic activity for Fenten-like advanced oxidation process. Here in, novel porous Fe-MOFs with modulated O-Fe-N coordination was developed by configurating amino terephthalic acid (H2ATA) and pyrazine-dicarboxylic acid (PzDC) (Fe-ATA/PzDC-7:3). PzDC ligands introduce pyridine-N sites to form O-Fe-N coordination with lower binding energy, which affect the local electronic environment of Fe-clusters in Fe-ATA, thus decreased its interfacial H2O2 activation barrier. O-Fe-N coordination also accelerate Fe(II)/Fe(III) cycling of Fe-clusters by triggering the reactive oxidant species mediated Fe(III) reduction. As such, Fe-ATA/PzDC-7:3/H2O2 system exhibited excellent degradation performance for typical antibiotic sulfamethoxazole (SMX), in which the steady-state concentration of hydroxyl radical (OH) was 1.6 times higher than that of unregulated Fe-ATA. Overall, this study highlights the role of O-Fe-N coordination and the electronic environment of Fe-clusters on regulating Fenton-like catalytic performance, and provides a platform for precise engineering of Fe-MOFs.