The concentration of persistent organic pollutants (POPs) makes remarkable difference to environmental fate. In the field of passive sampling, the partition coefficients between polystyrene-divinylbenzene resin (XAD) and air (i.e., KXAD₋A) are indispensable to obtain POPs concentration, and the KXAD₋A is generally thought to be governed by temperature and molecular structure of POPs. However, experimental determination of KXAD₋A is unrealistic for countless and novel chemicals. Herein, the Abraham solute descriptors of poly parameter linear free energy relationship (pp-LFER) and temperature were utilized to develop models, namely pp-LFER-T, for predicting KXAD₋A values. Two linear (MLR and LASSO) and four nonlinear (ANN, SVM, kNN and RF) machine learning algorithms were employed to develop models based on a data set of 307 sample points. For the aforementioned six models, R²ₐdⱼ and Q²ₑₓₜ were both beyond 0.90, indicating distinguished goodness-of-fit and robust generalization ability. By comparing the established models, the best model was observed as the RF model with R²ₐdⱼ = 0.991, Q²ₑₓₜ = 0.935, RMSEₜᵣₐ = 0.271 and RMSEₑₓₜ = 0.868. The mechanism interpretation revealed that the temperature, size of molecules and dipole-type interactions were the predominant factors affecting KXAD₋A values. Concurrently, the developed models with the broad applicability domain provide available tools to fill the experimental data gap for untested chemicals. In addition, the developed models were helpful to preliminarily evaluate the environmental ecological risk and understand the adsorption behavior of POPs between XAD membrane and air.

Wastewater treatment plants (WWTPs) are almost the only place where plastic fragments are artificially removed, resulting in mass accumulation of nanoplastics (NPs). In this research, four different concentrations (0 mg/L, 0.1 mg/L, 1 mg/L, 10 mg/L) of polystyrene nanoplastics (PS-NPs) were used to investigate the cell damage and nitrogen inhibition of activated sludge, exposed in a self-assembled SBR reactor for 30 days. Intracellular reactive oxides (ROS) and extracellular lactate dehydrogenase (LDH) increased with the rise of exposure concentration, and morphological analysis disclosed the creases, collapse, and even rupture of cell membranes. However, exposure damage (PS-NPs ≤ 1 mg/L) appeared to be reversible, attributed to that extracellular polymeric substances (EPS) secretion can thicken the three protective layers outside the membrane. PS-NPs did not disrupt the EPS chemical structure, but increased humic acid content. Prolonged exposure time (from 15 to 30 days) was directly related to the nitrogen inhibition. Due to the habitat changes under PS-NPs exposure, abundance and diversity of microorganisms in the original activated sludge decreased significantly, and the dominant phylum was occupied by Patescibacteria (PS-NPs = 10 mg/L). Changes in enzyme activities of AMO, NR, NIR, and NOR with exposure concentration may explain the conversion of nitrogen in SBR. This research broadens our horizons to understand the response mechanism of activated sludge bacteria to PS-NPs exposure individually and collectively.

Distribution in ice is regarded as one of important transport modes for pollutants in seasonal freeze-up waters in cold regions. However, the distribution characteristics and mechanisms of fluorinated antibiotics as emerging contaminants during the water freezing process remain unclear. Here, florfenicol and norfloxacin were selected as model fluorinated antibiotics to investigate their ice-water distribution. Effects of antibiotic molecular structure on the distribution were explored through comparative studies with their non-fluorinated structural analogs. Results showed that phase changes during the ice growth process redistributed the antibiotics, with antibiotic concentrations in water 3.0–6.4 times higher than those in ice. The solute-rich boundary layer with a concentration gradient was presented at the ice-water interface and controlled by constitutional supercooling during the freezing process. The ice-water distribution coefficient (KIW) values of antibiotics increased by 34.8%–38.0% with a doubling of the cooling area. The solute distribution coefficient (Kbₛ) values of antibiotics at −20 °C were 65.6%–70.3% higher than at −10 °C. The KIW and Kbₛ values of all antibiotics were negatively correlated with their water solubilities. The fluorine substituents influenced the binding energies between antibiotics and ice, resulting in a 1.1-fold increase in the binding energy of norfloxacin on the ice surface relative to its structural analog pipemidic acid. The results provide a new insight into the transport behaviors of fluorinated pharmaceuticals in ice-water systems.

In this critical review, we explored the most recent advances about the fate of antibiotics on biological wastewater treatment plants (WWTP). Although the occurrence of these pollutants in wastewater and natural streams has been investigated previously, some recent publications still expose the need to improve the detection strategies and the lack of information about their transformation products. The role of the antibiotic properties and the process operating conditions were also analyzed. The pieces of evidence in the literature associate several molecular properties to the antibiotic removal pathway, like hydrophobicity, chemical structure, and electrostatic interactions. Nonetheless, the influence of operating conditions is still unclear, and solid retention time stands out as a key factor. Additionally, the efficiencies and pathways of antibiotic removals on conventional (activated sludge, membrane bioreactor, anaerobic digestion, and nitrogen removal) and emerging bioprocesses (bioelectrochemical systems, fungi, and enzymes) were assessed, and our concern about potential research gaps was raised. The combination of different bioprocess can efficiently mitigate the impacts generated by these pollutants. Thus, to plan and design a process to remove and mineralize antibiotics from wastewater, all aspects must be addressed, the pollutant and process characteristics and how it is the best way to operate it to reduce the impact of antibiotics in the environment.

The on-going and extensive use of neonicotinoids occur in orchards. However, it is still unknown whether and how orchard management affects soil properties, especially the contents and structure of soil organic matter during orchard development, and their further influences on neonicotinoid persistence. Here, surface soil samples were collected from the citrus orchards with different cultivation ages (1, 10, 14, and 20 years), and their physicochemical properties were determined. Changes in the chemical structure of soil organic matter (SOM) were furtherly examined using solid-state CP/TOSS ¹³C NMR. Then, the sorption isotherms of imidacloprid in these soils were investigated. The sorption coefficient (Kd) of imidacloprid at Cₑ of 0.05 mg/L in the orchard soils increased by 19.4–23.3%, along a 20-year chronosequence of cultivation, which should be mainly ascribed to the increase of SOM. However, the organic carbon-normalized sorption coefficient (Kₒc, sorption per unit mass of OM) of imidacloprid declined with increasing cultivation ages. Moreover, the polar and aliphatic domains of SOM had a significantly positive relation to the Kₒc of imidacloprid, suggesting its key role in governing imidacloprid sorption. The results highlighted that reasonable management measures could be adopted to control the occurrence and fate of neonicotinoids in soils, mainly by affecting the content and quality of SOM.

There is limited research on the ingestion of microplastic particles (MPs) by fish from the southern part of the Mediterranean Sea. This study provides the occurrence of small MPs (≤3 μm) in the gastrointestinal tract and muscle of adult benthopelagic fish Serranus scriba (L.1758), caught along Tunisian coasts. MPs were extracted from selected tissues using a potassium hydroxide digestion method (KOH 10%) and then quantified, and their chemical structure was characterized through Raman microspectroscopy. The results highlighted that MPs were present in all samples. The average abundance of MPs per gram of fish tissue identified through successive filters of 3 μm, 1.2 μm, and 0.45 μm differed significantly among the sites. The properties of the MPs extracted indicated that polyethylene-vinyl-acetate (PEVA: 33.45%), high density polyethylene (HD-PE: 17.33%), and fragments were the most abundant plastic types and shape found, respectively. Among those, most MPs were found at a size class of 3–1.2 μm (∼60%), especially in the muscle, suggesting a high transfer of MPs into the human diet. Our field work also aimed to explore the effects observed in the gastrointestinal tract with a battery of biomarkers assessing oxidative stress and neurotoxicity. The preliminary results of this study showed the existence of a link between small MPs, sites, and their associated urban activities and induced oxidative stress. However, more detailed studies are required to evaluate the transfer of MPs into tissues and the potential impacts of this transfer on human health.

Solid phase extraction has been increasingly applied for the detection of organic micropollutants (OMPs). However, time-consuming and high-cost disadvantages also limit the widespread use of this method, especially for the extraction of large-volume field water samples. In this study, a gas chromatography-mass spectrometry (GC-MS) method based on the magnetic microsphere (M150) solid-phase-extraction (MSPE) was established to investigate the OMPs in source water throughout the whole Huai River. In brief, the results demonstrated that the extraction efficiency of the M150 was superior to that of C₁₈ and HLB for the selected OMPs, including species of polycyclic aromatic hydrocarbons (PAHs), organochlorine pesticides (OCPs), phthalate esters (PAEs) and nitrobenzenes (NBs), and the method detection limits of M150 for these OMPs were comparable to those of C₁₈ and HLB. The optimized conditions of extraction and elution were the 100 mg/L dosages of microspheres, extraction time of 60 min and pH of 2, and the eluent with a similar polarity, hydrophobicity and molecular structure to the OMPs rendered higher elution efficiencies. A total of 21 types of OMPs affiliating to PAHs, OCPs, PAEs and NBs were detected by the established method, with the total concentrations of 505–2310 ng/L in source water of the Huai River. Spatial differences of the OMPs were also observed, demonstrating the link between pollutant profiles and geographical locations. This study provides an alternative to enrich OMPs in filed water samples, and it reveals pollutant profiles of source water throughout the whole Huai River.

A comprehensive study of the removal of selected biologically active compounds (pharmaceuticals and pesticides) from different water types was conducted using bare TiO₂ nanoparticles and TiO₂/polyaniline (TP-50, TP-100, and TP-150) nanocomposite powders. In order to investigate how molecular structure of the substrate influences the rate of its removal, we compared degradation efficiency of the initial substrates and degree of mineralization for the active components of pharmaceuticals (propranolol, and amitriptyline) and pesticides (sulcotrione, and clomazone) in double distilled (DDW) and environmental waters. The results indicate that the efficiency of photocatalytic degradation of propranolol and amitriptyline was higher in environmental waters: rivers (Danube, Tisa, and Begej) and lakes (Moharač, and Sot) in comparison with DDW. On the contrary, degradation efficacy of sulcotrione and clomazone was lower in environmental waters. Further, of the all catalysts applied, bare TiO₂ and TP-100 were found to be most effective in the mineralization of propranolol and amitriptyline, respectively, while TP-150 appeared to be the most efficient in terms of sulcotrione and clomazone mineralization. Also, there was no significant toxicity observed after the irradiation of pharmaceuticals or pesticides solutions using appropriate catalysts on rat hepatoma (H-4-II-E), mouse neuroblastoma (Neuro-2a), human colon adenocarcinoma (HT-29), and human fetal lung (MRC-5) cell lines. Subsequently, detection and identification of the formed intermediates in the case of sulcotrione photocatalytic degradation using bare TiO₂ and TP-150 showed slightly different pathways of degradation. Furthermore, tentative pathways of sulcotrione photocatalytic degradation were proposed and discussed.

Chemicals in consumer products have become the focus of recent regulatory developments including California's Safer Consumer Products Act. However, quantifying the amount of chemicals released during the use and post-use phases of consumer products is challenging, limiting the ability to understand their impacts. Here we present a comprehensive framework, OrganoRelease, for estimating the release of organic chemicals from the use and post-use of consumer products given limited information. First, a novel Chemical Functional Use Classifier estimates functional uses based on chemical structure. Second, the quantity of chemicals entering different product streams is estimated based on market share data of the chemical functional uses. Third, chemical releases are estimated based on either chemical product categories or functional uses by using the Specific Environmental Release Categories and EU Technological Guidance Documents. OrganoRelease connects 19 unique functional uses and 14 product categories across 4 data sources and provides multiple pathways for chemical release estimation. Available user information can be incorporated in the framework at various stages. The Chemical Functional Use Classifier achieved an average accuracy above 84% for nine functional uses, which enables the OrganoRelease to provide release estimates for the chemical, mostly using only the molecular structure. The results can be can be used as input for methods estimating environmental fate and exposure.

Carbazole in source water is a potential precursor for toxic chlorocarbazoles in drinking water when chlorine is used as a disinfection agent in drinking water treatment plants. However, the reactivity of carbazole and the specific structures and predominant analogues of chlorocarbazoles produced during aqueous chlorination remain unknown. In this study, the aqueous chlorination of carbazole was performed to characterize its reactivity and the chlorinated products. Chlorocarbazoles generated from carbazole were identified by a comprehensive two-dimensional gas chromatography-mass spectrometry method, and their molecular structures were predicted by the Fukui index of electrophilic attack, f−1(r). As a result, the comprehensive chlorination pathway of carbazole was extrapolated with a total of nine chlorocarbazoles identified, including two monochlorocarbazoles (3-chlorocarbazole and 1-chlorocarbazole), four dichlorocarbazoles (3,6-dichlorocarbazole, 1,6-dichlorocarbazole, 1,3-dichlorocarbazole and 1,8-dichlorocarbazole), two trichlorocarbazoles (1,3,6-trichlorocarbazole and 1,3,8-trichlorocarbazole) and one tetrachlorocarbazole (1,3,6,8-tetrachlorocarbazole). The f−1(r) value indicates that the C1, C3, C6 and C8 atoms of carbazole were the favored positions for electrophilic attack, with the C3 and C6 atoms being the predominant sites for chlorine substitution. 3-Chlorocarbazole, 3,6-dichlorocarbazole, 1,3,6-trichlorocarbazole and 1,3,6,8-tetrachlorocarbazole were the major analogues of each chlorocarbazole group; however, the production of minor analogues such as 1-chlorocarbazole and 1,6-dichlorocarbazole should not be overlooked. The chlorination of carbazole was a pseudo first order reaction with a reaction rate of 0.1836 nmol/(L· h) and half-life of 3.77 h (pH = 6.4, Cl2 = 4.7 mg/L), and the chlorination rate of carbazole was approximately 5 times faster than that of an known chlorination precursor pyrene. These results showed that Fukui index was efficacious to predict the chlorination sites of aromatic compounds, and that carbazole is readily transformed into toxic chlorocarbazoles in drinking water treatment plants that use chlorine as a disinfection agent.