This work evaluates the degradation of benzoic acid, a tracer from biomass burning, by different oxidation agents (Fe (III); H₂O₂; sunlight; and combinations of the previous ones) in model solutions and in real atmospheric waters. The extent of reactions was assessed by Ultraviolet–Visible and molecular fluorescence spectroscopies. The oxidation of benzoic acid occurred with the chemical oxidants Fe (III), H₂O₂, Fe (III) and H₂O₂ simultaneously in the presence of sunlight, and with Fe (III) and H₂O₂ simultaneously in the absence of light. The decrease of the pH value from neutral to acid for atmospheric waters generally increased the extent of oxidation. Sunlight was an important oxidation agent, and its combination with chemical oxidants increased the oxidation rate of benzoic acid, possibly due to the photogeneration of hydroxyl radicals. The results also suggested the occurrence of direct and indirect photolysis of benzoic acid in atmospheric waters. Moreover, the oxidation of benzoic acid produced new and more complex chromophoric compounds, which were then degraded. In addition, the nocturnal period is not sufficient for the full degradation of benzoic acid and of the intermediates formed by Fenton-like oxidation. The diurnal period may be enough for their full degradation through photo-Fenton-like oxidation, but this depends on the composition of the atmospheric waters, namely of the chromophoric content. Thus, this study highlights that benzoic acid from biomass burning, and its derivatives, may persist in atmospheric waters for periods of longer than one day, becoming available for other reactions, and may also affect the terrestrial and aquatic ecosystems through the wet depositions.

Particulate matter (PM) is considered an atmospheric pollutant that mostly affects human health. The finest fractions of PM (PM2.5 or less) play a major role in causing chronic diseases.The aim of this study was to investigate the genotoxic effects of PM0.5 collected in five Italian towns using different bioassays. The role of chemical composition on the genotoxicity induced was also evaluated.The present study was included in the multicentre MAPEC_LIFE project, which aimed to evaluate the associations between air pollution exposure and early biological effects in Italian children.PM10 samples were collected in 2 seasons (winter and spring) using a high-volume multistage cascade impactor. The results showed that PM0.5 represents a very high proportion of PM10 (range 10–63%). PM0.5 organic extracts were chemically analysed (PAHs, nitro-PAHs) and tested by the comet assay (A549 and BEAS-2B cells), MN test (A549 cells) and Ames test on Salmonella strains (TA100, TA98, TA98NR and YG1021).The highest concentrations of PAHs and nitro-PAHs in PM0.5 were observed in the Torino, Brescia and Pisa samples in winter. The Ames test showed low mutagenic activity. The highest net revertants/m3 were observed in the Torino and Brescia samples (winter), and the mutagenic effect was associated with PM0.5 (p < 0.01), PAH and nitro-PAH (p < 0.05) concentrations. The YG1021 strain showed the highest sensitivity to PM0.5 samples. No genotoxic effect of PM0.5 extracts was observed using A549 cells except for some samples in winter (comet assay), while BEAS-2B cells showed light DNA damage in the Torino, Brescia and Pisa samples in winter, highlighting the higher sensitivity of BEAS-2B cells, which was consistent with the Ames test (p < 0.01).The results obtained showed that it is important to further investigate the finest fractions of PM, which represent a relevant percentage of PM10, taking into account the chemical composition and the biological effects induced.

Cadmium (Cd), a ubiquitous environmental pollutant, is known to impair placental development. However, the underlying mechanisms remain unclear. The present study used in vivo and in vitro models to investigate the effects of Cd on apoptosis and autophagy in placental trophoblasts and its mechanism. Pregnant mice were exposed to CdCl₂ (4.5 mg/kg) on gestational day (GD) 9. Human JEG-3 cells were exposed to CdCl₂ (0–40 μM) for different time points. Gestational Cd exposure obviously lowered the weight and diameter of mouse placentas. Number of TUNEL-positive cells was markedly elevated in Cd-administered mouse placentas and JEG-3 cells. Correspondingly, Cd significantly up-regulated cleaved caspase-3 protein level, a key indicator of apoptosis, in murine placentas and JEG-3 cells. Simultaneously, Cd also triggered autophagy, as determined by an elevation of LC3B-II and p62 protein, and accumulation of LC3-positive puncta, in placental trophoblasts. Chloroquine an autophagy inhibitor, obviously aggravated Cd-induced apoptosis in JEG-3 cells. By contrast, rapamycin, a specific autophagy inducer, significantly alleviated Cd-triggered apoptosis in JEG-3 cells. Mechanistically, autophagy inhibited Cd-induced apoptosis mainly via degrading caspase-9. Co-localizations of p62, a classical autophagic receptor, and caspase-9 were observed in Cd-stimulated human JEG-3 cells. Moreover, p62 siRNAs pretreatment markedly blocked the degradation of caspase 9 proteins via Cd-activated autophagy in JEG-3 cells. Collectively, our data suggest that activation of autophagy inhibits Cd-induced apoptosis via p62-mediated caspase-9 degradation in placental trophoblasts. These findings provide a new mechanistic insight into Cd-induced impairments of placental and fetal development.

Biomass burning (BB) is one of the largest sources of carbonaceous aerosols with adverse impacts on air quality, visibility, health and climate. BB emits a few specific aromatic acids (p-hydroxybenzoic, vanillic, syringic and dehydroabietic acids) which have been widely used as key indicators for source identification of BB-derived carbonaceous aerosols in various environmental matrices. In addition, measurement of p-hydroxybenzoic and vanillic acids in snow and ice cores have revealed the historical records of the fire emissions. Despite their uniqueness and importance as tracers, our current understanding of analytical methods, concentrations, diagnostic ratios and degradation processes are rather limited and scattered in literature. In this review paper, firstly we have summarized the most established methods and protocols for the measurement of these aromatic acids in aerosols and ice cores. Secondly, we have highlighted the geographical variability in the abundances of these acids, their diagnostic ratios and degradation processes in the environments. The review of the existing data indicates that the concentrations of aromatic acids in aerosols vary greatly with locations worldwide, typically more abundant in urban atmosphere where biomass fuels are commonly used for residential heating and/or cooking purposes. In contrast, their concentrations are lowest in the polar regions which are avoid of localized emissions and largely influenced by long-range transport. The diagnostic ratios among aromatic acids can be used as good indicators for the relative amounts and types of biomass (e.g. hardwood, softwood and herbaceous plants) as well as photochemical oxidation processes. Although studies suggest that the degradation processes of the aromatic acids may be controlled by light, pH and hygroscopicity, a more careful investigation, including closed chamber studies, is highly appreciated.

The wide adoption of combined heat and power (CHP) can not only improve energy efficiency, but also strengthens energy system resiliency. While CHP reduces overall emissions compared to generating the same amount of electricity and heat separately, its on-site nature also means that CHP facilities operate in populated areas, raising concerns over their near-source air quality impact. Evaluation of the near-source impact of distributed CHP is limited by emission data availability, especially in terms of particulate matter (PM). In this paper, we report on stack emission testing results of a community-scale CHP plant with two natural gas turbine units (15 MW each) from measurements conducted in both 2010 and 2015, and assess the near-source air quality impact using an integrated modeling framework using the stack test results, site-specific meteorological data and terrain profiles with buildings. The NOx removal efficiency by selective catalytic reduction (SCR) is estimated to be ∼83% according to the emission testing. The integrated framework employs AERMOD to screen air quality in a 2.7 km × 2.3 km domain from 2011 to 2015 to identify the highest ground-level concentrations (GLCs). Examining the corresponding meteorological conditions, we find that those high GLCs appeared during the stable atmospheric boundary layer with relative high wind speed. Next, the worse-case scenarios identified from the screening process are simulated using the detailed Unsteady Reynolds Averaged Navier-Stokes (URANS) model coupled with a chemistry solver. The results generally show low GLCs of primary PM₂.₅ for this case study. However, our analysis also suggests greater building downwash impacts with the presence of taller and denser urban structures. Therefore, the near-source impact of natural gas-fired CHP in large metropolitan areas is worthy of further investigation.

During the last 70 years 1, 2, 3, 4, 5, 6-Hexachlorocyclohexane (HCH) has been one of the most extensively used pesticides. Only the gamma-isomer has insecticidal properties. For the marketing of gamma-HCH (lindane) the other 85% HCH isomers which are formed as by-products during HCH production had to be separated and became finally hazardous waste. For each tonne of lindane 8–12 tonnes of waste HCH isomers were produced and production of the approximately 600,000 t of lindane has therefore generated 4.8 to 7.2 million tonnes of HCH/POPs waste. These waste isomers were mostly buried in uncontrolled dumps at many sites around the world. The stockpiles and the large contaminated sites can be categorized as “mega-sites”. Countries with HCH legacy problems include Albania, Argentina, Austria, Azerbaijan, Brazil, China, Croatia, Czech Republic, France, Germany, Hungary, India, Italy, Japan, Macedonia, Nigeria, Poland, Romania, Russia, Slovakia, South Africa, Spain, Switzerland, Turkey, The Netherlands, UK, Ukraine and the USA.As lindane and alpha- and beta-HCH have been listed as POPs in the Stockholm Convention since August 2010, the problem of stockpiles of HCH waste is now documented and globally acknowledged.This article describes briefly the legacy of HCH and lindane that has been created. Three of the mega-sites are being discussed and demonstrate the increase in pollution footprint over time. Recent developments in the EU (including the Sabinanigo project in Aragon/Spain) and on a global level are presented. A short overview is given on lack of activities and on actions of countries within their obligations as Parties of the Stockholm Convention. Furthermore, current country activities supported by the Global Environment Facility (GEF), the “financing mechanism” of the convention, are listed. Finally, conclusions and recommendations are formulated that will contribute to the solution of this problem over the next 25 years.

Microplastics (MPs) are now one of the major environmental problems due to the large amount released in aquatic and terrestrial ecosystems, as well as their diffuse sources and potential impacts on organisms and human health. Still the molecular and cellular targets of microplastics’ toxicity have not yet been identified and their mechanism of actions in aquatic organisms are largely unknown. In order to partially fill this gap, we used a mass spectrometry based functional proteomics to evaluate the modulation of protein profiling in zebra mussel (Dreissena polymorpha), one of the most useful freshwater biological model. Mussels were exposed for 6 days in static conditions to two different microplastic mixtures, composed by two types of virgin polystyrene microbeads (size = 1 and 10 μm) each one. The mixture at the lowest concentration contained 5 × 105 MP/L of 1 μm and 5 × 105 MP/L of 10 μm, while the higher one was arranged with 2 × 106 MP/L of 1 μm and 2 × 106 MP/L of 10 μm.Proteomics’ analyses of gills showed the complete lack of proteins’ modulation after the exposure to the low-concentrated mixture, while even 78 proteins were differentially modulated after the exposure to the high-concentrated one, suggesting the presence of an effect-threshold. The modulated proteins belong to 5 different classes mainly involved in the structure and function of ribosomes, energy metabolism, cellular trafficking, RNA-binding and cytoskeleton, all related to the response against the oxidative stress.

In the present study, the competitive adsorption of Cu²⁺, Pb²⁺, and Cd²⁺ by a novel natural adsorbent (i.e., argillaceous limestone) modified with chitosan (C-AL) was investigated. The results demonstrated that both intraparticle diffusion and chemisorption marked significant contributions to the Cu²⁺ adsorption process by both raw argillaceous limestone (R-AL) and C-AL in mono-metal adsorption systems. Antagonism was found to be the predominant competitive effect for Cu²⁺, Pb²⁺ and Cd²⁺ adsorptions by C-AL in the multi-metal adsorption system. The three-dimensional simulation and FTIR analysis revealed that the presence of Cu²⁺ suppressed Pb²⁺ and Cd²⁺ adsorptions, while the effect of Cd²⁺ on Cu²⁺ and Pb²⁺ adsorptions was insignificant. The spectroscopic analyses evidenced that amide groups in C-AL played a crucial role in metal adsorption. The preferential adsorptions of Pb²⁺ > Cu²⁺ > Cd²⁺ were likely due to the different affinities of the metals to the lone pair of electrons on the N atom from the amide groups and/or the O atoms from the –OH and -COO⁻ groups on C-AL. The interactions between C-AL and metal ions and between various metal species influenced their competitive adsorption behaviors. C-AL exhibited a superior metal adsorption capacity in comparison with that the capacities of other natural adsorbents reported during the last decade, suggesting its potential practical applications.

Adenosine triphosphate-binding cassette (ABC) transporters, including P-glycoprotein (Pgp) and multi-resistance associated proteins (Mrps), have been considered important participants in the self-protection of zebrafish embryos against environmental pollutants, but their possible involvement in the efflux and detoxification of quantum dots (QDs), as well as their regulation mechanism are currently unclear. In this work, gene expression alterations of ABC transporters, nuclear receptors, and oxidative stress signaling in zebrafish embryos after the treatment of mercaptopropionic acid (MPA)CdTe QDs and MPA-CdSCdTe QDs were investigated. It was observed that both QDs caused concentration-dependent delayed hatching effects and the subsequent induction of transporters like mrp1&2 in zebrafish embryos, indicating the protective role of corresponding proteins against CdTe QDs. Accompanying these alterations, expressions of nuclear receptors including the pregnane X receptor (pxr), aryl hydrocarbon receptor (ahr) 1b, and peroxisome proliferator-activated receptor (ppar)-β were induced by QDs in a concentration- and time-dependent manner. Moreover, elevated oxidative stress, reflected by the reduction of glutathione (GSH) level and superoxide dismutase (SOD) activities, as well as the dramatic induction of nuclear factor E2 related factor (nrf) 2, was also found. More importantly, alterations of pxr and nrf2 were more pronounced than that of mrps, and these receptors exhibited an excellent correlation with delayed hatching rate in the same embryos (R² > 0.8). Results from this analysis demonstrated that the induction of mrp1 and mrp2 could be important components for the detoxification of QDs in zebrafish embryos. These transporters could be modulated by nuclear receptors and oxidative stress signaling. In addition, up-regulation of pxr and nrf2 could be developed as toxic biomarkers of CdTe QDs.

Sublethal insecticide exposure poses risks for many non-target organisms and is a challenge for successful implementation of integrated pest management (IPM) programs. Next to detrimental effects of short-term insecticide exposure on fitness-related traits of organisms, also properties such as chemical signaling traits can be altered, which mediate intra- and interspecific communication. We investigated the effects of different durations of larval sublethal exposure to the pyrethroid lambda-cyhalothrin on performance traits of larvae and adults of the herbivorous mustard leaf beetle, Phaedon cochleariae. Moreover, by applying a direct contact and olfactometer bioassays, we determined the reaction of a generalist predator, the ant Myrmica rubra, towards insecticide-exposed and unexposed herbivore larvae and their secretions. Already short-term sublethal insecticide exposure of a few days caused a prolonged larval development and a reduced adult body mass of males. These effects may result from an insecticide-induced reduction in energy reserves. Furthermore, ants responded more frequently to insecticide-exposed than to unexposed larvae of P. cochleariae and their secretions. This increased responsiveness of ants towards insecticide-exposed larvae may be due to an insecticide-induced change in synthesis of chrysomelidial and epichrysomelidial, the dominant compounds of the larval secretion, which act defensive against various generalist predators. In conclusion, the results highlight that short-term insecticide exposure can impair the fitness of an herbivorous species due to both direct toxic effects and an increased responsiveness of predators. Consequently, exposure of single non-target species can have consequences for ecological communities in both natural habitats and IPM programs.