The persistent organic pollutants (POPs) due to their physicochemical properties can be widely spread all over the globe; as such they represent a serious threat to both humans and wildlife. According to Stockholm convention out of 24 officially recognized POPs, 16 are pesticides. The atmospheric life times of pesticides, up to now were estimated based on their gas-phase reactivity. It has been only speculated that sorption to aerosol particles may increase significantly the half‐lives of pesticides in the atmosphere. The results presented here challenge the current view of the half-lives of pesticides in the lower boundary layer of the atmosphere and their impact on air quality and human health. We demonstrate that semivolatile pesticides which are mostly adsorbed on atmospheric aerosol particles are very persistent with respect to the highly reactive hydroxyl radicals (OH) that is the self-cleaning agent of the atmosphere. The half-lives in particulate phase of difenoconazole, tetraconazole, fipronil, oxadiazon, deltamethrin, cyprodinil, permethrin, and pendimethalin are in order of several days and even higher than one month, implying that these pesticides can be transported over long distances, reaching the remote regions all over the world; hence these pesticides shall be further evaluated prior to be confirmed as POPs.

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Abstract. Changes in engine technologies and after-treatment devices can profoundly alter the chemical composition of the emitted pollutants. To investigate these effects, we characterized the emitted particles' chemical composition of three diesel and four gasoline Euro 5 light-duty vehicles tested at a chassis dynamometer facility. The dominant emitted species was black carbon (BC) with emission factors (EFs) varying from 0.2 to 7.1 mg km−1 for direct-injection gasoline (GDI) vehicles, from 0.02 to 0.14 mg km−1 for port fuel injection (PFI) vehicles, and 0.003 to 0.9 mg km−1 for diesel vehicles. The organic matter (OM) EFs varied from 5 to 103 µg km−1 for GDI gasoline vehicles, from 1 to 8 µg km−1 for PFI vehicles, and between 0.15 and 65 µg km−1 for the diesel vehicles. The first minutes of cold-start cycles contributed the largest PM fraction including BC, OM, and polycyclic aromatic hydrocarbons (PAHs). Using a high-resolution time-of-flight mass spectrometer (HR-ToF-AMS), we identified more than 40 PAHs in both diesel and gasoline exhaust particles including methylated, nitro, oxygenated, and amino PAHs. Particle-bound PAHs were 4 times higher for GDI than for PFI vehicles. For two of the three diesel vehicles the PAH emissions were below the detection limit, but for one, which presented an after-treatment device failure, the average PAHs EF was 2.04 µg km−1, similar to the GDI vehicle's values. During the passive regeneration of the catalysed diesel particulate filter (CDPF) vehicle, we measured particles of diameter around 15 nm mainly composed of ammonium bisulfate. Transmission electron microscopy (TEM) images revealed the presence of ubiquitous metal inclusions in soot particles emitted by the diesel vehicle equipped with a fuel-borne-catalyst diesel particulate filter (FBC-DPF). X-ray photoelectron spectroscopy (XPS) analysis of the particles emitted by the PFI vehicle showed the presence of metallic elements and a disordered soot surface with defects that could have consequences on both chemical reactivity and particle toxicity. Our findings show that different after-treatment technologies have an important effect on the emitted particles' levels and their chemical composition. In addition, this work highlights the importance of particle filter devices' condition and performance.

A molecular derivatization method followed by gas chromatographic separation coupled with mass spectrometric detection was used to study photolytic degradation of I2 adsorbed on solid SiÜ2 particles. This heterogeneous photodegradation of I2 is studied at ambient temperature in synthetic air to better understand I2 atmospheric dispersion and environmental fate. The obtained laboratory results show a considerably enhanced atmospheric lifetime of molecular iodine adsorbed on solid media. The heterogeneous atmospheric residence time (x) of I2 is calculated to be x»187 minutes, i.e., x»3 hours. The obtained heterogeneous lifetime of I2 is shown to be considerably longer than its destruction by its principal atmospheric sink, namely, photolysis. The observed enhanced atmospheric lifetime of I2 on heterogeneous media will likely have direct consequences on the atmospheric transport of I2 that influences the toxicity or the oxidative capacity of the atmosphere.