The effects of polystyrene microbeads (micro-PS; mix of 2 and 6 μm; final concentration: 32 μg L−1) alone or in combination with fluoranthene (30 μg L−1) on marine mussels Mytilus spp. were investigated after 7 days of exposure and 7 days of depuration under controlled laboratory conditions. Overall, fluoranthene was mostly associated to algae Chaetoceros muelleri (partition coefficient Log Kp = 4.8) used as a food source for mussels during the experiment. When micro-PS were added in the system, a fraction of FLU transferred from the algae to the microbeads as suggested by the higher partition coefficient of micro-PS (Log Kp = 6.6), which confirmed a high affinity of fluoranthene for polystyrene microparticles. However, this did not lead to a modification of fluoranthene bioaccumulation in exposed individuals, suggesting that micro-PS had a minor role in transferring fluoranthene to mussels tissues in comparison with waterborne and foodborne exposures. After depuration, a higher fluoranthene concentration was detected in mussels exposed to micro-PS and fluoranthene, as compared to mussels exposed to fluoranthene alone. This may be related to direct effect of micro-PS on detoxification mechanisms, as suggested by a down regulation of a P-glycoprotein involved in pollutant excretion, but other factors such as an impairment of the filtration activity or presence of remaining beads in the gut cannot be excluded. Micro-PS alone led to an increase in hemocyte mortality and triggered substantial modulation of cellular oxidative balance: increase in reactive oxygen species production in hemocytes and enhancement of anti-oxidant and glutathione-related enzymes in mussel tissues. Highest histopathological damages and levels of anti-oxidant markers were observed in mussels exposed to micro-PS together with fluoranthene. Overall these results suggest that under the experimental conditions of our study micro-PS led to direct toxic effects at tissue, cellular and molecular levels, and modulated fluoranthene kinetics and toxicity in marine mussels.

1H-HRMAS NMR-based metabolomics was used to better understand the toxic effects on maize root tips of organochlorine pesticides (OCPs), namely lindane (γHCH) and chlordecone (CLD). Maize seedlings were exposed to 2.5 μM γHCH (mimicking basic environmental contaminations) for 7 days and compared to 2.5 μM CLD and 25 μM γHCH for 7 days (mimicking hot spot contaminations). The 1H-HRMAS NMR-based metabolomic profiles provided details of the changes in carbohydrates, amino acids, tricarboxylic acid (TCA) cycle intermediates and fatty acids with a significant separation between the control and OCP-exposed root tips. First of all, alterations in the balance between glycolysis/gluconeogenesis were observed with sucrose depletion and with dose-dependent fluctuations in glucose content. Secondly, observations indicated that OCPs might inactivate the TCA cycle, with sizeable succinate and fumarate depletion. Thirdly, disturbances in the amino acid composition (GABA, glutamine/glutamate, asparagine, isoleucine) reflected a new distribution of internal nitrogen compounds under OCP stress. Finally, OCP exposure caused an increase in fatty acid content, concomitant with a marked rise in oxidized fatty acids which could indicate failures in cell integrity and vitality. Moreover, the accumulation of asparagine and oxidized fatty acids with the induction of LOX3 transcription levels under OCP exposure highlighted an induction of protein and lipid catabolism. The overall data indicated that the effect of OCPs on primary metabolism could have broader physiological consequences on root development. Therefore, 1H-HRMAS NMR metabolomics is a sensitive tool for understanding molecular disturbances under OCP exposure and can be used to perform a rapid assessment of phytotoxicity.

Urban and peri-urban forests provide a multitude of Ecosystem Services to the citizens. While the capacity of removing carbon dioxide and gaseous compounds from the atmosphere has been tested, their capacity to sequestrate particles (PM) has been poorly investigated. Mediterranean forest ecosystems are often located nearby or inside large urban areas. This is the case of the city of Rome, Italy, which hosts several urban parks and is surrounded by forested areas. In particular, the Presidential Estate of Castelporziano is a 6000 ha forested area located between the Tyrrhenian coast and the city (25 km downtown of Rome). Under the hypothesis that forests can ameliorate air quality thanks to particle deposition, we measured fluxes of PM1, 2.5 and 10 with fast optical sensors and eddy covariance technique. We found that PM1 is mainly deposited during the central hours of the day, while negligible fluxes were observed for PM 2.5 and 10. A Hybrid Single–Particle Lagrangian Integrated Trajectory model (HYSPLIT v4) simulated PM emission from traffic areas in the city of Rome and showed that a significant portion of PM is removed by vegetation in the days when the plume trajectory meets the urban forest.

More than a decade ago, the Stockholm Convention on Persistent Organic Pollutants (POPs), one of the multilateral environmental agreements administered by the United Nations Environment Programme (UNEP), entered into force. The objective of this Convention is to protect human health and the environment by controlling the releases of POPs. According to its Article 16, the effectiveness of the Stockholm Convention shall be evaluated using comparable monitoring data on the presence of POPs as well as their regional and global environmental transport. Here, we present a time series analysis on atmospheric POP concentrations from 15 monitoring stations in North America and Europe that provide long-term data and have started operations between 1990 and 2003. We systematically searched for temporal trends and significant structural changes in temporal trends that might result from the provisions of the Stockholm Convention. We find that such structural changes do occur, but they are related mostly to effects of national regulations enforced prior to the implementation of the Stockholm Convention, rather than to the enforcement of the provisions laid out in the Convention. One example is that concentrations of polychlorinated biphenyls, many of which started to decrease rapidly during the 1990s. Also effects of chemical transport and fate, for instance the re-volatilization of POPs from secondary sources, are thought to be a cause of some of the observed structural changes. We conclude that a decade of air monitoring data has not been sufficient for detecting general and statistically significant effects of the Stockholm Convention. Based on these lessons, we present recommendations for the future operation of existing monitoring programs and advocate for a stricter enforcement of the provisions of the Stockholm Convention, in the current absence of proof for its effectiveness.

Difenoconazole is a widely used triazole fungicide and has been reported to have negative impacts on zebrafish embryos. To investigate the mechanism of its developmental toxicity, zebrafish embryos were exposed to 0.5 and 2.0 mg/L difenoconazole for 96 h. The morphological and physiological indicators of embryo development were tested. The total cholesterol (TCHO) level, triglyceride (TG) level and malondialdehyde (MDA) content were measured at 96 hpf (hours post-fertilization). In addition, the transcription of genes related to embryo development, the antioxidant system, lipid synthesis and metabolism was quantified. Our results showed that a large suite of symptoms were induced by difenoconazole, including hatching regression, heart rate decrease, growth inhibition and teratogenic effects. 0.5 mg/L difenoconazole could significantly increase the TG content of zebrafish embryos at 96 hpf, while no apparent change in the TCHO and MDA level was observed post 96 h exposure. Q-PCR (quantitative real-time polymerase chain reaction) results showed that the transcription of genes related to embryonic development was decreased after exposure. Genes related to hatching, retinoic acid metabolism and lipid homeostasis were up-regulated by difenoconazole.

In recent years, phosphorus-containing flame retardants (PFRs) have been frequently detected in various environmental media and biota - and in humans - as the result of steady increase in global usage of PFRs. However, studies on the potential health and ecological risks of PFRs are still scarce. In this study, we investigated the thyroid hormone-disrupting activity and ecological risk of nine frequently detected PFRs by in vitro, in vivo and in silico approaches. Results from the dual-luciferase reporter gene assay showed that tributyl phosphate (TNBP), tricresyl phosphate (TMPP), tris(2-chloroisopropyl)phosphate (TCIPP) and tris(2-chloro-1-(chloromethyl)ethyl)phosphate (TDCIPP) exerted thyroid receptor β (TRβ) antagonistic activity, with the values of RIC20 of 5.2 × 10−7, 2.7 × 10−7, 1.2 × 10−6 and 6.8 × 10−6 M, respectively. Molecular docking platform simulations suggested that the observed effects may be attributed to direct binding of PFRs to TR. Results from the T-screen assay indicated that TNBP and TMPP showed T3 antagonistic activity and thus significantly decreased the viability of GH3 cell lines in the presence of T3. The exposure assay using Xenopus tropicalis embryos revealed the potential teratogenic effect of TNBP, TMPP, TCIPP and TDCIPP. In conclusion, our studies revealed that some PFRs were potential thyroid hormone disruptors and may cause health and ecological risks. However, the mode of action of PFRs on TR remains uncertain. The correlation between the predicted affinity and the amplitude of the effect observed in cell based assay is encouraging, but not decisive. Further in vitro binding experiments of TR and PFRs are required. At the same time, the results provided here also demonstrated that multi-model approaches are of great importance to comprehensively evaluate the potential risks of emerging contaminants.

Deposition of dissolved organic nitrogen (DON) in both bulk precipitation (BD) and canopy throughfall (TF) has been measured for the first time in the western Mediterranean. The study was carried out over a year from 2012 to 2013 at four evergreen holm oak forests located in the Iberian Peninsula: two sites in the Province of Barcelona (Northeastern Spain), one in the Province of Madrid (central Spain) and the fourth in the Province of Navarra (Northern Spain). In BD the annual volume weighted mean (VWM) concentration of DON ranged from 0.25 mg l−1 in Madrid to 1.14 mg l−1 in Navarra, whereas in TF it ranged from 0.93 mg l−1 in Barcelona to 1.98 mg l−1 in Madrid. The contribution of DON to total nitrogen deposition varied from 34% to 56% in BD in Barcelona and Navarra respectively, and from 38% in Barcelona to 72% in Madrid in TF. Agricultural activities and pollutants generated in metropolitan areas were identified as potential anthropogenic sources of DON at the study sites. Moreover, canopy uptake of DON in Navarra was found in spring and autumn, showing that organic nitrogen may be a supplementary nutrient for Mediterranean forests, assuming that a portion of the nitrogen taken up is assimilated during biologically active periods.

Aquatic sediments serve as an important sink for engineered nanomaterials (ENMs), such as metal oxide nanoparticles (MeO NPs) and carbon nanotubes (CNTs). Owing to their remarkable properties, ENMs demonstrate significant potential to disturb the adsorption behavior of other contaminants in aquatic sediments, thereby altering the bioavailability and toxicity of these contaminants. Thus far, most studies have investigated the effect of CNTs on the adsorption of other contaminants on sediments. Cerium dioxide nanoparticles (CeO2 NPs), as one of the important MeO NPs, are also inevitably discharged into aquatic sediments because of their widespread use. In this study, we investigated the adsorption behavior of Pb2+ on sediments spiked with CeO2 NPs at a weight ratio of 5.0%. The results showed that the adsorption rates at three stages occurring during adsorption clearly increase for sediments contaminated with CeO2 NPs. Moreover, the results obtained from the adsorption isotherms indicated that the Langmuir isotherm model best fits the isotherm data for both sediments and those contaminated with CeO2 NPs. After spiking the sediments with CeO2 NPs, the theoretical maximum monolayer adsorption capacity (Qmax) for Pb2+ increased from 4.433 to 4.995 mg/g and the Langmuir isotherm coefficient (KL) decreased from 8.813 to 7.730 L/g. The effects of CeO2 NPs on the surface charge and pore surface properties of sediments were also studied as these properties affect the adsorption of several chemicals in sediments. The results showed that pHzpc, SBET, Sext, and average pore size of sediments clearly decrease for sediments contaminated with CeO2 NPs. Hence, the strong adsorption capacity of CeO2 NPs and the changes of sediment surface charge and pore surface properties caused by CeO2 NPs are important factors affecting the adsorption behavior of Pb2+. The potential risk of Pb2+ in aquatic environment may increase with CeO2 NPs buried in sediments.

An association of influenza-like illness (ILI) with outdoor air pollution has been reported. However, the effect of indoor air pollution on ILI was rarely investigated. We aimed to determine an association of indoor air pollution from coal combustion (IAPCC) and lifestyle with ILI risk in housewives, and the modification effect of phase II metabolic enzyme genes. We recruited 403 housewives for a cross-sectional study in Shanxi Province, China, including 135 with ILI frequency (≥1 time per year in the past ten years) as the case group and 268 with ILI frequency (<1 times per year) as the control group. Information on their energy usage characteristics and lifestyle was collected by questionnaires, as well as the single nucleotide polymorphisms (SNPs) of epoxide hydrolase 1 (rs1051740 and rs2234922), N-acetyltransferase 2 (rs1041983), and glutathione S-transferase (rs1695). We used exposure index to indicate the level of IAPCC among housewives. Our results revealed that the exposure index was positively correlated with ILI frequency. A significant dose-response trend between the exposure index and ILI risk was found with or without adjusting for confounders. Cooking frequency in kitchen with coal as primary fuel and ventilation frequency in the living room or bedroom with a coal-fueled stove for heating during the heating season were two important risk factors to affect ILI frequency. Only rs1051740 was found to be associated with exposure index, whereas it didn’t have interaction effect with exposure index on ILI frequency. In conclusion, IAPCC and SNPs of rs1051740 were both associated with ILI frequency.

Widespread contamination of surface water chloride is an emerging environmental concern. Consequently accurate and cost-effective methods are needed to estimate chloride along all river miles of potentially contaminated watersheds. Here we introduce a Bayesian Maximum Entropy (BME) space/time geostatistical estimation framework that uses river distances, and we compare it with Euclidean BME to estimate surface water chloride from 2005 to 2014 in the Gunpowder-Patapsco, Severn, and Patuxent subbasins in Maryland. River BME improves the cross-validation R2 by 23.67% over Euclidean BME, and river BME maps are significantly different than Euclidean BME maps, indicating that it is important to use river BME maps to assess water quality impairment. The river BME maps of chloride concentration show wide contamination throughout Baltimore and Columbia-Ellicott cities, the disappearance of a clean buffer separating these two large urban areas, and the emergence of multiple localized pockets of contamination in surrounding areas. The number of impaired river miles increased by 0.55% per year in 2005–2009 and by 1.23% per year in 2011–2014, corresponding to a marked acceleration of the rate of impairment. Our results support the need for control measures and increased monitoring of unassessed river miles.