With the recent ban of triclosan (TCS) and triclocarban (TCC) from some personal care products, many replacement antimicrobial compounds have been used. Yet the potential health risk and environmental impact of these replacement compounds are largely unknown. Here we investigated the toxicological effects of three commonly used replacement antimicrobials, benzalkonium chloride (BAC), benzethonium chloride (BEC), and chloroxylenol (CX) to two model organisms, the nematode C. elegans and zebrafish (Danio rerio), and compared them to the banned TCS and TCC. We found that these replacement compounds are not any safer than the banned antimicrobials. In the worm, at least one of the three, BAC, showed comparable toxicity to TCS from organismal to molecular levels, with toxic effects occurring at lower hundred μg/L to lower mg/L levels. In the fish, all three compounds at the tested concentration ranges (0.05–5 mg/L) showed toxicity effects to zebrafish embryos, indicated by hatching delay or inhibition, embryonic mortality, morphological malformations, and neurotoxicity. BAC was the most toxic among the three, with acute lethal toxicity occurring at environmentally relevant concentrations (hundreds of μg/L), which is comparable to the banned TCC. However, the toxicity effects of BAC and TCC occurred within different time windows, potentially suggesting different mechanisms of toxicity. CX was the only compound that induced a “body curvature” phenotype among the five compounds examined, suggesting a unique mode of toxic action for this compound. Furthermore, all five compounds except TCS induced neurotoxicity in fish larvae, indicated by alterations in secondary motoneuron axonal projections. Such neurotoxicity has been largely understudied for these antimicrobials in the past years and calls for further investigations in terms of its underlying mechanisms and ecological significance. These findings strongly indicate that scrutiny should be put on these replacement compounds before their introduction into massive use in personal care products.

This study investigated the effects of different long-term fertilizations on humic substances (HSs), humic acids (HAs) and humins, functioning as redox mediators for various microbial redox biotransformations, including 2,2′,4,4′,5,5′- hexachlorobiphenyl (PCB₁₅₃) dechlorination, dissimilatory iron reduction, and nitrate reduction, and their electron-mediating natures. The redox activity of HSs for various microbial redox metabolisms was substantially enhanced by long-term application of organic fertilizer (pig manure). As a redox mediator, only humin extracted from soils with organic fertilizer amendment (OF-HM) maintained microbial PCB₁₅₃ dechlorination activity (1.03 μM PCB₁₅₃ removal), and corresponding HA (OF-HA) most effectively enhanced iron reduction and nitrate reduction by Shewanella putrefaciens. Electrochemical analysis confirmed the enhancement of their electron transfer capacity and redox properties. Fourier transform infrared analysis showed that C=C and C=O bonds, and carboxylic or phenolic groups in HSs might be the redox functional groups affected by fertilization. This research enhances our understanding of the influence of anthropogenic fertility on the biogeochemical cycling of elements and in situ remediation ability in agroecosystems through microorganisms’ metabolisms.

Ozone (O₃) and nitrogen dioxide (NO₂) are thought to play primary roles in aggravating air pollution-induced health problems. However, the effects of joint O₃/NO₂ on the allergenicity of pollen allergens are unclear. Humulus japonicus pollen allergen 1 (Hum j1) is a profilin protein that causes widespread pollinosis in eastern Asia. In order to study the effects of combined O₃/NO₂ on the allergenicity of Hum j1, tandem six-histidine peptide tag (His6)-fused recombinant Hum j1 (rHum j1) was expressed in a prokaryotic system and purified through His6 affinity chromatography. The purified rHum j1 was used to immunize SD rats. Rat sera with high titers of IgG and IgE antibodies against rHum j1 were used for allergenicity quantification. The rHum j1 was exposed to O₃/NO₂, and changes in allergenicity of the exposed rHum j1 were assayed using the immunized rat antibodies. Tandem LC-MS/LC (liquid chromatography-mass spectrometer/liquid chromatography spectrometer) chromatography and UV and circular dichroism (CD) spectroscopy were used to study the structural changes in rHum j1. Our data demonstrated that a novel disulfide bond between the sulfhydryl groups of two neighboring cysteine molecules was formed after the rHum j1 exposure to joint O₃/NO₂, and therefore IgE-binding affinity was increased and the allergenicity was reinforced. Our results provided clues to elucidate the mechanism behind air pollution-induced increase in pollinosis prevalence.

Polyfluorinated iodine alkanes (PFIs) are a kind of emerging chemicals with endocrine disrupting effects. Based on the different binding preferences of PFIs to estrogen receptor alpha and beta isoforms (ERα and β), two representative PFIs, dodecafluoro-1,6-diiodohexane (PFHxDI) and tridecafluorohexyl iodide (PFHxI), were selected to evaluate their effects on the proliferation of two kinds of breast cancer cells with different ERα/β expression levels, MCF-7 and T47D. The cell viability assay showed PFHxDI could cause higher cellular toxicity than did PFHxI in both MCF-7 and T47D. MCF-7 with relatively higher ERα/β expression ratio was more vulnerable to the cytotoxic treatments of PFHxI and PFHxDI when compared with T47D cells with relatively lower ERα/β expression ratio. EdU incorporation and cell cycle analysis revealed that, similar to 17β-estrodiol (E₂), non-cytotoxic levels of PFHxDI could significantly promote the proliferation of MCF-7 by increasing cell population at S phase (p < 0.01), while T47D proliferation was not influenced by PFHxI exposure due to cell cycle arrest at G2/M phase. The cellular responses caused by estrogenic PFIs were dominantly mediated by their preferential binding affinities for ER isoforms, which would be helpful in the accurate assessment for their potential influences on the breast cancer progression.

The concentrations, distributions, and bioaccumulation of nine organophosphate flame retardants (OPFRs) were investigated in both abiotic and biotic media, comprising river water, sediment, and crucian carp. The highest concentrations were observed in liver (6.22–18.1 ng/g ww), and the levels in muscle (4.23–7.75 ng/g ww) and gonad (3.08–7.70 ng/g ww) were similar. In whole blood, tris(2-butoxyethyl) phosphate (TBOEP; 31.1–256 ng/mL) accounted for 90% of the total OPFR concentration. Distributions of OPFRs differed between biotic and abiotic media, as tris(2-chloroethyl) phosphate (TCEP), tris(1-chloro-2-propyl) phosphate (TCIPP), and TBOEP were dominant in abiotic media, whereas triethyl phosphate (TEP), tri-n-butyl phosphate (TNBP), TCEP, and TBOEP dominated in crucian carp. The TNBP had remarkable accumulation potential among nine OPFRs, which the TNBP concentrations in muscle increased with increased total length and body weight. The higher perfusion rate of TNBP to female eggs were observed rather than to male gonads as the concentrations were higher in males than in females, while the opposite results were observed in gonad. Moreover, the concentration of TNBP in female muscle began to decrease near maximum growth as a sexually dimorphic difference in crucian carp. This is the first study to simultaneously investigate the fate of OPFRs in biotic and abiotic media and to show sex differences.

Unknown compounds with (anti-)androgenic activities enter the aquatic environment via municipal wastewater treatment plants (WWTPs). Progestins are well-known environmental contaminants capable of interfering with androgen receptor (AR) signaling pathway. The aim of the present study was to determine if 15 selected progestins have potential to contribute to (anti-)androgenic activities in municipal wastewaters and the respective recipient surface waters. AR-specific Chemically Activated LUciferase gene eXpression bioassay in agonistic (AR-CALUX) and antagonistic (anti-AR-CALUX) modes and liquid chromatography tandem atmospheric pressure chemical ionization/atmospheric photoionization with hybrid quadrupole/orbital trap mass spectrometry operated in high resolution product scan mode (LC-APCI/APPI-HRPS) methods were used to assess (anti-)androgenic activity and to detect the target compounds, respectively. The contribution of progestins to (anti-)androgenic activities was evaluated by means of a biologically and chemically derived toxicity equivalent approach. Androgenic (0.08–59 ng/L dihydrotestosterone equivalents – DHT EQs) and anti-androgenic (2.4–26 μg/L flutamide equivalents – FLU EQs) activities and progestins (0.19–75 ng/L) were detected in selected aquatic environments. Progestins displayed androgenic potencies (0.01–0.22 fold of dihydrotestosterone) and strong anti-androgenic potencies (9–62 fold of flutamide). Although they accounted to some extent for androgenic (0.3–29%) and anti-androgenic (4.6–27%) activities in influents, the progestins’ contribution to (anti-)androgenic activities was negligible (≤2.1%) in effluents and surface waters. We also tested joint effect of equimolar mixtures of target compounds and the results indicate that compounds interact in an additive manner. Even if progestins possess relatively strong (anti-)androgenic activities, when considering their low concentrations (sub-ng/L to ng/L) it seems unlikely that they would be the drivers of (anti-)androgenic effects in Czech aquatic environments.

Because the freely dissolved fraction of highly hydrophobic organic chemicals is bioavailable, knowing the partition coefficient between dissolved organic carbon and water (KDOCw) is crucial to estimate the freely dissolved fraction from the total concentration. A kinetic method was developed to obtain KDOCw that required a shorter experimental time than equilibrium methods. The equilibrium partition coefficients of four polychlorinated biphenyls (PCBs) (2,4,4′-trichlorobiphenyl (PCB 28), 2,2′,3,5′-tetrachlorobiphenyl (PCB 44), 2,2′,4,5,5′-pentachlorobiphenyl (PCB 101), and 2,2′,4,4′,5,5′-hexachlorobiphenyl (PCB 153)) between dissolved organic carbon and seawater (KDOCsw) were determined using seawater samples from the Korean coast. The log KDOCsw values of PCB 28 were measured by equilibrating PCB 28, the least hydrophobic congener, with seawater samples, and the values ranged from 6.60 to 7.20. For the more hydrophobic PCBs (PCB 44, PCB 101, and PCB 153), kinetic experiments were conducted to determine the sorption rate constants (k2) and their log KDOCsw values were obtained by comparing their k2 with that of PCB 28. The calculated log KDOCsw values were 6.57–7.35 for PCB 44, 6.23–7.44 for PCB 101, and 6.35–7.73 for PCB 153. The validity of the proposed method was further confirmed using three less hydrophobic polycyclic aromatic hydrocarbons. This kinetic method shortened the experimental time to obtain the KDOCsw values of the more hydrophobic PCBs, which did not reach phase equilibrium.

Coastal zone is of great importance in the provision of various valuable ecosystem services. However, it is also sensitive and vulnerable to environmental changes due to high human populations and interactions between the land and ocean. Major threats of pollution from over enrichment of nutrients, increasing metals and persistent organic pollutants (POPs), and climate change have led to severe ecological degradation in the coastal zone, while few studies have focused on the combined impacts of pollution and climate change on the coastal ecosystems at the global level. A global overview of nutrients, metals, POPs, and major environmental changes due to climate change and their impacts on coastal ecosystems was carried out in this study. Coasts of the Eastern Atlantic and Western Pacific were hotspots of concentrations of several pollutants, and mostly affected by warming climate. These hotspots shared the same features of large populations, heavy industry and (semi-) closed sea. Estimation of coastal ocean capital, integrated management of land-ocean interaction in the coastal zone, enhancement of integrated global observation system, and coastal ecosystem-based management can play effective roles in promoting sustainable management of coastal marine ecosystems. Enhanced management from the perspective of mitigating pollution and climate change was proposed.

Heavy metal tolerance of microorganisms is the basis of heavy metal removal by growing cells. In this study, a cross-protection effect generated by salt stress significantly enhanced the cadmium tolerance of multi-stress-tolerant Pichia kudriavzevii. Comparative transcriptome analysis using RNA-Seq linked with physiological and biochemical observation was used to elucidate the underlying mechanisms of the improved cadmium tolerance. The expression of cadmium transport related genes (GSTY2, GLR1, GLO2, YCF1 and YOR1), GSH content and GST activity were elevated by salt stress, suggesting enhanced cadmium conjugation and detoxification in yeast cells. The inhibited cadmium uptake by ZRT1 and enhanced cadmium efflux by YOR1 contributed to the decrease in the intracellular cadmium concentration. The improved expression of antioxidant enzyme genes (SOD1, SOD2, SOD6, CAT1 and PRXIID), along with the enhanced activities of antioxidant enzymes (SOD, CAT and POD) resulted in a decrease in cadmium-induced ROS production, protein carbonylation, lipid peroxidation and cell death. The abundant expression of heat shock protein genes (HSP12, HSP10 and SSC1) and genes related to trehalose synthesis (TPS1 and TSL1) induced by salt stress protected yeast cells against complex stress conditions, contributing to the improved cadmium tolerance. These findings will be useful to develop cadmium-tolerant yeasts for cadmium removal by growing cells.

Microplastics and nanoplastics in aquatic systems have become a global concern because of their persistence and adverse consequences to ecosystems and potentially human health. Though wastewater treatment plants (WWTPs) are considered a potential source of microplastics in the environment, the role of extracellular polymeric substances (EPS) of activated sludge on the fate of nanoplastics is not clear. In this study, the role of EPS in the influence of polystyrene nanoparticles (PS-NPs) on the endogenous respiration of activated sludge was investigated for the first time. The results showed that the acute inhibition of activated sludge by PS-NPs was enhanced with increasing PS-NPs concentration. X-ray photoelectron spectroscopy (XPS) results indicate that the functional groups involved in the interactions between PS-NPs and EPS were carbonyl and amide groups and the side chains of lipids or amino acids. Furthermore, the Fourier transform infrared (FTIR) spectroscopy results show that the protein secondary structures in EPS were changed by PS-NPs and lead to the bioflocculation of activated sludge, which provides a better understanding on the fate of nanoplastics in WWTPs.