In response to the growing worldwide plastic pollution problem, the field of nanoplastics research is attempting to determine the risk of exposure to nanoparticles amidst their ever-increasing presence in the environment. Since little is known about the attributes of environmental nanoplastics (concentration, composition, morphology, and size) due to fundamental limitations in detection and quantification of smaller plastic particles, researchers often improvise by engineering nanoplastic particles with various surface modifications as models for laboratory toxicological testing. Polystyrene and other commercially available or easily synthesized polymer materials functionalized with surfactants or fluorophores are typically used for these studies. How surfactants, additives, fluorophores, the addition of surface functional groups for conjugation, or other changes to surface attributes alter toxicological profiles remains unclear. Additionally, the limited polymers used in laboratory models do not mimic the vast range of polymer types comprising environmental pollutants. Nanomaterials are tricky materials to investigate due to their high surface area, high surface energies, and their propensity to interact with molecules, proteins, and biological probes. These unique properties can often invalidate common laboratory assays. Extreme care must be taken to ensure that results are not artefactual. We have gathered zeta potential values for various polystyrene nanoparticles with different functionalization, in different solvents, from the reported literature. We also discuss the effects of surface engineering and solvent properties on interparticle interactions, agglomeration, particle-protein interactions, corona formation, nano-bio interfaces, and contemplate how these parameters might confound results. Various toxicological exemplars are critically reviewed, and the relevance and shortfalls of the most popular models used in nanoplastics toxicity studies published in the current literature are considered.

The aim of this study was to recover Sc as the main product and Fe as a by-product from Hungarian bauxite residue/red mud (RM) waste material by solvent extraction (SX). Moreover, a new technique was developed for the selective separation of Sc and Fe from real RM leachates. The presence of high Fe content (∼38%) in RM makes it difficult to recover Sc because of the similarity of their physicochemical properties. Pyrometallurgical and hydrometallurgical methods were applied to remove the Fe prior to SX. Two protocols based on organophosphorus compounds (OPCs) were proposed, and the main extractants were evaluated: bis(2-ethylhexyl) phosphoric acid (D2EHPA/P204) and tributyl phosphate (TBP). The results showed that SX using diethyl ether and tri-n-octylamine (N₂₃₅) was efficient in extracting Fe(III) from the HCl leachate as HFeC1₄. Over 97% of Sc was extracted by D2EHPA extractant under the following conditions; 0.05 mol/L of D2EHPA concentration, A/O phase ratio of 3:1, pH 0–1, 10 min of shaking time, and a temperature of 25 °C. Sc(OH)₃ as a precipitate was efficiently obtained by stripping from the D2EHPA organic phase by 2.5 mol/L of NaOH with a stripping efficiency of 95%. In the TBP system, 99% of Sc was extracted under the following conditions: 12.5% vol of TBP, an A/O phase ratio of 3:1, 10 min of shaking time, and a temperature of 25 °C. The Sc contained in the TBP organic phase could be efficiently stripped by 1 mol/L of HCl with a stripping efficiency of 92.85%.

Health risks of typical benzene series and halocarbons (BSHs) in a densely populated area near a large-scale chemical industrial park were investigated. Ambient and indoor air and tap water samples were collected in summer and winter; and the concentration characteristics, sources, and exposure risks of typical BSH species, including five benzene series (benzene, toluene, ethylbenzene, o-xylene, m,p-xylene) and five halocarbons (dichloromethane, trichloromethane, trichloroethylene, tetrachloromethane, and tetrachloroethylene), were analysed. The total mean concentrations of BSHs were 53.32 μg m⁻³, 36.29 μg m⁻³, and 26.88 μg L⁻¹ in indoor air, ambient air, and tap water, respectively. Halocarbons dominated the total BSHs with concentrations relatively higher than those in many other industrial areas. Industrial solvent use, industrial processes, and vehicle exhaust emissions were the principal sources of BSHs in ambient air. The use of household products (e.g., detergents and pesticides) was the principal source of indoor BSHs. Inhalation is the primary human exposure route. Ingestion of drinking water was also an important exposure route but had less impact than inhalation. Lifetime non-cancer risks of individual and cumulative BSHs were below the threshold (HQ = 1), indicating no significant lifetime non-cancer risks in the study area. However, tetrachloromethane, benzene, trichloromethane, ethylbenzene, and trichloroethylene showed potential lifetime cancer risk. The cumulative lifetime cancer risks exceeded the tolerable benchmark (1 × 10⁻⁴), indicating a lifetime cancer risk of BSHs to residents near the chemical industry park. This study provides valuable information for the management of public health in chemical industrial parks.

In this work, valorisation pathways of brewers’ spent grains (BSG) towards biofuels production under the biorefinery concept were studied utilizing experimental data that provide a common base for straightforward comparison. The dehydration and the recovery of used oil, bioethanol and biogas from BSG were studied. The process units involved were thoroughly investigated and optimized. The oil extraction efficiency reached up to 70% using solid-liquid extraction process with hexane as solvent. The optimal ethanol yield achieved was 45% after the application of acid pretreatment, enzymatic hydrolysis with CellicCTec2 and fermentation with S. Cerevisiae. As far as biogas potential is concerned, the raw BSG, defatted BSG and stillage presented values equal to 379 ± 19, 235 ± 21 and 168 ± 39 mL biogas/g for respectively. Through the combination of the proposed schemes, three biorefinery scenarios were set up able to produce biodiesel, bioethanol and/or biogas. Material flow diagrams were set up in order to assess these schemes. Given that BSG could ensure ‘green’ energy production in the range of 4.5–7.0 million MJ/y if the European BSG potential is fully valorised, BSG could substantially contribute to the biofuel energy strategy.

Dietary exposure to chemicals alters the diversity of microbiome communities and can lead to pathophysiological changes in the gastrointestinal system. The organochlorine pesticide dieldrin is a persistent environmental contaminant that bioaccumulates in fatty tissue of aquatic organisms. The objectives of this study were to determine whether environmentally-relevant doses of dieldrin altered gastrointestinal morphology and the microbiome of zebrafish. Adult zebrafish at ∼4 months of age were fed a measured amount of feed containing either a solvent control or one of two doses of dieldrin (measured at 16, and 163.5 ng/g dry weight) for 4 months. Dieldrin body burden levels in zebrafish after four-month exposure were 0 (control), 11.47 ± 1.13 ng/g (low dose) and 18.32 ± 1.32 ng/g (high dose) wet weight [mean ± std]. Extensive histopathology at the whole organism level revealed that dieldrin exposure did not induce notable tissue pathology, including the gastrointestinal tract. A repeated measure mixed model analysis revealed that, while fish gained weight over time, there were no dieldrin-specific effects on body weight. Fecal content was collected from the gastrointestinal tract of males and 16S rRNA gene sequencing conducted. Dieldrin at a measured feed dose of 16 ng/g reduced the abundance of Firmicutes, a phylum involved in energy resorption. At the level of class, there was a decrease in abundance of Clostridia and Betaproteobacteria, and an increase in Verrucomicrobiae species. We used a computational approach called predicted relative metabolomic turnover (PRMT) to predict how a shift in microbial community composition affects exchange of metabolites. Dieldrin was predicted to affect metabolic turnover of uroporphyrinogen I and coproporphyrinogen I [enzyme]−cysteine, hydrogen selenide, selenite, and methyl-selenic acid in the fish gastrointestinal system. These pathways are related to bacterial heme biosynthesis and selenium metabolism. Our study demonstrates that dietary exposures to dieldrin can alter microbiota composition over 4 months, however the long-term consequences of such impacts are not well understood.

Bioaccessibility extractions are increasingly applied to measure the fraction of pollutants in soil, sediment and biochar, which can be released under environmentally or physiologically relevant conditions. However, the bioaccessibility of hydrophobic organic chemicals (HOCs) can be markedly underestimated when the sink capacity of the extraction medium is insufficient. Here, a novel method called “Membrane Enhanced Bioaccessibility Extraction” (MEBE) applies a semipermeable membrane to physically separate an aqueous desorption medium that sets the desorption conditions from an organic medium that serves as acceptor phase and infinite sink. The specific MEBE method combines HOC (1) desorption into a 2-hydroxypropyl-β-cyclodextrin solution, (2) transfer through a low-density polyethylene (LDPE) membrane and (3) release into ethanol, serving as analytical acceptor phase. The surface to volume ratio within the LDPE membrane is maximized for rapid depletion of desorbed molecules, and the capacity ratio between the acceptor phase and the environmental sample is maximized to achieve infinite sink conditions. Several experiments were conducted for developing, optimizing and pre-testing the method, which was then applied to four soils polluted with polycyclic aromatic hydrocarbons. MEBE minimized sample preparation and yielded a solvent extract readily analyzable by HPLC. This study focused on the proof-of-principle testing of the MEBE concept, which now can be extended and applied to other samples and desorption media.

The present work reported a high-throughput strategy for the analysis of 21 perfluorinated compounds (PFCs) in drinking water, tap water, river water and plant effluent from southern China by supramolecular solvent (SUPARS) vortex-mixed microextraction combined with high performance liquid chromatography-Orbitrap high resolution mass spectrometry (HPLC-Orbitrap HRMS). The SUPRAS without heating assistance is less solvent-consumption, meeting the requirements for green environmental protection and sustainable development. Parameters in the microextraction such as volume of dodecanol and tetrahydrofuran (THF), vortexing extraction and centrifugation time, salt concentration were investigated. The optimal extraction conditions were 250 μL of undecanol, 1.0 mL of THF and 20.0% (w/v, 4 g) NaCl. Under the optimum conditions, method limit of detection and method limit of quantitation in the ranges of 0.01–0.08 μg/L and 0.03–0.25 μg/L, good recoveries (72.5–117.8%) and intra-day precision (1.1–11.2%, n = 6), high enrichment factors (48–78) were obtained. The developed method was successfully applied for analysis of PFCs in 13 drinking water, tap water, river water and plant effluent samples collected from southern China. Perfluorobutane sulfonic acid was detected in one river water with concentration of 0.48 μg/L and 1H,1H,2H,2H-Perfluorooctane sulfonic acid was detected in one river water and two plant effluent samples with concentrations in the range of 0.14–0.67 μg/L.

Solvent stabilizer 1,4-dioxane, an emerging recalcitrant groundwater contaminant, was commonly added to chlorinated solvents such as trichloroethene (TCE), and the impact of co-disposal on contaminant transport processes remains uncertain. A series of batch equilibrium experiments was conducted with variations of 1,4-dioxane and TCE composition to evaluate aqueous dissolution of the two components and their sorption to aquifer sediments. The solubility of TCE increased with increasing amounts of 1,4-dioxane, indicating that 1,4-dioxane acts as a cosolvent causing solubility enhancement of co-contaminants. The solubilization results compared favorably with predictions using the log-linear cosolvency model. Equilibrium sorption coefficients (Kd and Kf) were also measured for different 1,4-dioxane and TCE compositions, and the findings indicate that both contaminants adsorb to aquifer sediments and TCE Kd values increased with increasing organic matter content. However, the Kd for TCE decreased with increases in 1,4-dioxane concentration, which was attributed to cosolvency impacts on TCE solubility. These findings further advance our understanding of the mass-transfer processes controlling groundwater plumes containing 1,4-dioxane, and also have implications for the remediation of 1,4-dioxane contamination.

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous environmental contaminants with a number of them being carcinogenic. One of the approaches to assess human exposure to PAHs is to measure their urinary metabolites, monohydroxyl polycyclic aromatic hydrocarbons (OH-PAHs), with a method allowing for high throughput and short turn-around time. We developed a method to quantify nine urinary OH-PAHs by using supported liquid phase extraction (SLE) and isotope dilution gas chromatography tandem mass spectrometry (GC-MS/MS). SLE demonstrated advantages over the traditionally used liquid-liquid extraction techniques. The target analytes with spiked deuterated and ¹³C-labeled internal standards were extracted from urine by SLE after enzymatic cleavage of the glucuronide and sulfate conjugates. The extracted analytes were then derivatized with N-Methyl-N-(trimethylsilyl) trifluoroacetamide (MSTFA), and analyzed by GC-MS/MS. Six solvent mixtures were evaluated as the SLE extraction solvent, and pentane:chloroform (7:3, v/v) was selected due to its best overall analytical performance. Method detection limits for the 9 analytes ranged from 2.3 to 13.8 pg/mL. Precision and accuracy were satisfactory. SLE and internal isotope labeled standard combination reduced matrix effect effectively. This new method using SLE sample preparation techniques coupled with GC-MS/MS proves applicable to urinary measurements for PAH exposure studies for general population.

The impact of pesticides on organisms may strongly depend on temperature. While many species will be exposed to pesticides and warming both in the parental and offspring generations, transgenerational effects of pesticides under warming are still poorly studied, particularly for behaviour. We therefore studied the single and combined effects of exposure to the pesticide chlorpyrifos (CPF) and warming both within and across generations on antipredator behaviour of larvae of the vector mosquito Culex pipiens. Within each generation pesticide exposure and warming reduced the escape diving time, making the larvae more susceptible to predation. Pesticide exposure of the parents did not affect offspring antipredator behaviour. Yet, parental exposure to warming determined how warming and the pesticide interacted in the offspring generation. When parents were reared at 24 °C, warming no longer reduced offspring diving times in the solvent control, suggesting an adaptive transgenerational effect to prepare the offspring to better deal with a higher predation risk under warming. Related to this, the CPF-induced reduction in diving time was stronger at 20 °C than at 24 °C, except in the offspring whose parents had been exposed to 24 °C. This dependency of the widespread interaction between warming and pesticide exposure on an adaptive transgenerational effect of warming is an important finding at the interface of global change ecology and ecotoxicology.