Dissolved organic matter (DOM) plays a significant role in the photochemical behavior of nano- and micro-plastic particles (NPs/MPs). We investigated the influence of DOM on the mechanism on the photoaging of NPs/MPs with different molecular structures under UV₃₆₅ irradiation in water. DOM components used in this study are mainly humic acid and fulvic acid. The results showed that DOM promoted the weathering of aliphatic NPs/MPs (polypropylene (PP)), but inhibited or had only a minor effect on the photoaging of aromatic NPs/MPs (polystyrene (PS) NPs/MPs, carboxyl-modified PS NPs, amino-modified PS NPs, and polycarbonate MPs). NPs with a large surface area may adsorb sufficient DOM on the particle surfaces through π-π interactions, which competes with NPs for photon absorption sites, thus, can delay the photoaging of PS NPs. Aromatic MPs may release phenolic compounds that quench •OH, thereby weakening the photoaging process. For aliphatic MPs, the detection of peracid, aldehyde, and ketone groups on the polymer surface indicated that DOM promoted weathering of PP MPs, which was primarily because the generation of •OH due to DOM photolysis may attack the polymer by C–C bond cleavage and hydrogen extraction reactions. This study provides insight into the UV irradiation weathering process of NPs/MPs of various compositions and structures, which are globally distributed in water.

Pollen allergy risk is modified by air pollutants, including ozone, but the chemical modifications induced on pollen grains are poorly understood. Pollen lipidic extract has been shown to act as an adjuvant to the allergenic reaction and therefore, the modification of lipids by air pollutants could have health implications. Birch pollen was exposed in vitro to ozone to explore the reactivity of O₃ on its surface and on its lipidic fraction. Uptake coefficients of ozone were determined for ozone concentration of 117 ppb on the surface of native birch pollen (8.6 ± 0.8 × 10⁻⁶), defatted pollen (9.9 ± 0.9 × 10⁻⁶), and for crushed pollen grains (34±3 × 10⁻⁶). The mass of ozone uptaken was increased by a factor of four for crushed pollen compared to native pollen showing a higher susceptibility to ozone of cytoplasmic granules and broken pollen grains. A total mass of extractible lipids of 27 mg per gram of birch pollen was found and a fraction of these lipids was identified and quantified (fatty acids, alkanes, alkenes and aldehydes). The distribution of lipids was modified by ozone exposure of 115 and 1000 ppb for 16 h with the following reactivity: consumption of alkene, formation of aldehydes and formation of nonanoic acid and octadecanoic acid. The quantity of ozone trapped in the lipidic fraction during 15 min at 115 ppb is enough to contribute to the reactivity of one-third of the alkenes demonstrating that pollen could be susceptible to an atmospheric increase of ozone concentration even for a very short duration complicating the understanding of the link between pollen allergy and pollution.

The synthetic resin industry plays an important role in Volatile organic compounds (VOCs) emissions from industrial sources. However, owing to various products and their different emission characteristics, it is extremely difficult to study the source profiles of synthetic resins. In this study, the product-based pollution characteristics of VOCs from eight synthetic resin enterprises were investigated in Shanghai, China. Up to 133 VOCs were identified, including 106 based on the Photochemical Assessment Monitoring Stations (PAMS) and the Toxic Organics (TO-15) methods, and the remaining 27 were identified based on the new mass spectrometry analysis method. Aromatics (39.7%) and oxygenated VOCs (29.9%) accounted for a relatively high proportion in the synthetic resin industry. The product-based source profiles of each process unit are compiled. Generally, 1,4-dioxane, methyl isobutyl ketone, toluene, benzene, styrene, propane, and dichloromethane are the most abundant species in synthetic resin. Furthermore, the product-based ozone formation potentials (OFPs) and sources reactivity (SR) were calculated, the synthetic resin industry SR range from 0.3 g g⁻¹ to 4.6 g g⁻¹. Results suggest that toluene, benzene, styrene, propylene, ethylene, and oxygenated VOCs (including 1,4-dioxane, methyl isobutyl ketone, and aldehyde) should be preferentially controlled to reduce the OFPs. A three-level classification was established to evaluate the degree of photochemical pollution in different industries. Emission factors were calculated and ranked for eight synthetic resins. A VOC emission inventory of Chinese synthetic resin from 2005 to 2018 was compiled. It is estimated that the Chinese synthetic resin emitted 23.96 Gg of VOCs in 2018. In this study, a product-based VOC source profile and emission inventory of the synthetic resin industry were established for the first time. Finally, combined with product types, processes, and processing equipment, feasible recommendations for reducing VOC emissions in the synthetic resin industry are proposed.

Pine needles are employed as alternative biomonitoring agents in atmospheric studies. In this study, pine (Pinus Pinea) components (needles and branches) and air samples were collected simultaneously to monitor polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides (OCPs) from Gemlik, Turkey between January and December 2016. The relationship between ambient air and pine needles were examined to enlighten the usability of pine components as passive samplers for persistent organic pollutants (POPs) in the Marmara region. Average ∑14PAH concentrations for the ambient air, pine needles, and pine branches were 23.1 ± 18.3 ng/m3, 626 ± 306 ng/g DW and 548 ± 261 ng/g DW respectively. PCB concentrations were 118 ± 74 pg/m3, 7.5 ± 2.1 ng/g DW and 6.8 ± 2.9 ng/g DW and ∑10 OCP concentrations were 122 ± 89 ng/m3,1.3 ± 1.5 ng/g DW and 10.0 ± 3.8 ng/g DW in the same order. Levels of PAHs and PCBs were higher in needles than branches. PAH, PCB and OCP concentrations in pine components tended to decrease with increasing temperatures in spring. PAH compounds with medium and light molecular weighted ones were found to be dominant. On the other hand, the predominant PCB components were the medium-weighted congeners while γ-HCH, Heptachlor endo. Epox. Iso A, endrin aldehyde, and methoxychlor were the dominant OCP species.

Soil contains large amounts of humic acid (HA), iron ions and manganese ions, all of which affect U(VI) migration in the soil. HA interacts with iron and manganese ions to form HA salts (called HA-Fe and HA-Mn in this paper); however, the effects of HA-Fe and HA-Mn on the migration of U(VI) is not fully understood. In this study, HA-Fe and HA-Mn were compounded by HA interactions with ferric chloride hexahydrate and manganese chloride tetrahydrate, respectively. The influence of HA, HA-Fe and HA-Mn on U(VI) immobilization and migration was investigated by bath adsorption experiments and adsorption-desorption experiments using soil columns. The results showed that the presence of HA, HA-Fe and HA-Mn retarded the migration of U(VI) in soil. Supported by X-ray photoelectron spectroscopy (XPS) and BCR sequential extraction analyses, a plausible explanation for the retardation was that HA-Fe and HA-Mn could reduce hexavalent uranium to stable tetravalent uranium and increase the specific gravity of Fe/Mn oxide-bound uranium and organic/sulfide-bound uranium, which made it difficult for them to longitudinally migrate in soil. Scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), and surface area and pore size analyses indicated that the complex formed between the hydroxyl, amino and carboxyl groups of HA-Fe and U(VI) increased the crystallinity of HA-Fe. The reaction between U(VI) and the hydroxyl, amino, aldehyde, keto and chlorine-containing groups of HA-Mn had no effect on the crystallinity of HA-Mn. Notably, the column desorption experiment found that the U(VI) immobilized in the soil remigrated under the effect of rain leaching, and acid rain promoted uranium remigration better than neutral rain. The findings provide some guidance for the decommissioning disposal of uranium contaminated site and it’s risk assessments.

Copper nanoparticles (nCu) are widely used in industry and in daily life, due to their unique physical, chemical, and biological properties. Few studies have focused on nCu phytotoxicity, especially with regard to toxicity mechanisms in crop plants. The present study examined the effect of 15.6 μM nCu exposure on the root morphology, physiology, and gene transcription levels of wheat (Triticum aestivum L.), a major crop cultivated worldwide. The results obtained were compared with the effects of exposing wheat to an equivalent molar concentration of ionic Cu (Cu²⁺ released from CuSO₄) and to control plants. The relative growth rate of roots decreased to approximately 60% and the formation of lateral roots was stimulated under nCu exposure, possibly due to the enhancement of nitrogen uptake and accumulation of auxin in lateral roots. The expression of four of the genes involved in the positive regulation of cell proliferation and negative regulation of programmed cell death decreased to 50% in the Cu²⁺ treatment compared to that of the control, while only one gene was down-regulated to about half of the control in nCu treatment. This explained the decreased root cell proliferation and higher extent of induced cell death in Cu²⁺- than in nCu-exposed plants. The increased methane dicarboxylic aldehyde accumulation (2.17-fold increase compared with the control) and decreased antioxidant enzyme activities (more than 50% decrease compared with the control) observed in the Cu²⁺ treatment in relation to the nCu treatment indicated higher oxidative stress in Cu²⁺- than in nCu-exposed plants. Antioxidant (e.g., proline) synthesis was pronouncedly induced by nCu to scavenge excess reactive oxygen species, alleviating phytotoxicity to wheat exposed to this form of Cu. Overall, oxidative stress and root growth inhibition were the main causes of nCu toxicity.

The volatile metabolome of Rhizobium sp. strain E20-8 exposed to three concentrations of cadmium (2.5, 5.0 and 7.5 μM) was screened using comprehensive two-dimensional gas chromatography coupled to time of flight mass spectrometry (GC × GC–ToFMS), combined with headspace solid phase microextraction (HS-SPME). Cd exposure induced a global increase in the concentration of volatile organic compounds (VOCs) both intra and extracellularly. Peak areas of several linear alkanes, ketones, aldehydes, alcohols, terpenic and volatile sulfur compounds, and one ester (ethyl acetate), were especially increased when compared with the control condition (no Cd). These compounds might originate from the metabolization of toxic membrane peroxidation products, the proteolysis of oxidized proteins or the alteration of metabolic pathways, resulting from the oxidative stress imposed by Cd. Several VOCs are related to oxidative damage, but the production of VOCs involved in antioxidant response (menthol, α-pinene, dimethyl sulfide, disulfide and trisulfide, 1-butanol and 2-butanone) and in cell aggregation (2,3-butanedione, 3-methyl-1-butanol and 2-butanone) is also observed. These results bring new information that highlights the role of VOCs on bacteria response to Cd stress, identify a novel set of biomarkers related with metal stress and provide information to be applied in biotechnological and remediation contexts.

We aimed to investigate whether exposure to low-molecular-weight saturated aliphatic aldehydes induces an airway inflammation related to lung toxicity. In previous studies, we identified that several aldehydes induced inflammatory responses through the secretion of pro-inflammatory cytokines.Here, we elucidate on whether hexanal exposure induces the lung inflammatory response through the secretion of cytokines. Hexanal is one of the aldehydes, which are major components of indoor environmental irritants. Based on a multiplexed cytokine antibody array, we investigated the cytokine expression profiles to identify the significant biomarkers of hexanal exposure and to predict the possibility of adverse effects on pulmonary toxicity using in vitro and in vivo model systems. We identified the cytokines as biomarkers involved in LEPTIN, Interleukin(IL)-10, MCP-1, and VEGF that showed similar expression patterns in both in vitro and in vivo models under hexanal exposure. These cytokines are known to be associated with diverse lung diseases, such as lung fibrosis, chronic obstructive pulmonary disease (COPD), and non-small cell lung cancer.Although further studies are needed to identify the mechanisms that underlie hexanal pulmonary toxicity, these results provide the key cytokine biomarkers in response to hexanal exposure and indicate meaningful mechanistic previewing that can be indirectly attributed to lung disease.

Two types of diluted bitumen (dilbit) and a light crude oil spiked onto the surface of saltwater were irradiated with natural solar light in Ottawa to assess the impact of sunlight to the fate of oxygenated intermediates. Oxygenated components, including carbonyl polycyclic aromatic hydrocarbons (PAHs) and acidic polar fractions (naphthenic acid fraction compounds, NAFCs), were identified after periods of solar exposure under both winter and summer conditions. Carbonyl PAHs and NAFCs were formed in both seasons; however, light crude and summer irradiation produced higher abundance of them than dilbits and winter exposure. The formed NAFCs were abundant with the congeners containing a heteroatom of oxygen only (Oo species), accompanied by the minor amounts of sulfur- and nitrogen-containing acids. The produced Oo species were predominant with the congeners with light molecular weight, high degree of saturation and heavy oxygen numbers. For both carbonyl PAHs and NAFCs, their abundance continually increased throughout the period of winter exposure. In the summer, some carbonyl PAHs and all Oo species increased during the early exposure period; then they decreased with continued exposure for most oils, illustrating their transitional nature. Oxygenated intermediates thus appear to have been created through the photo-oxidation of non-to medium-polar petroleum hydrocarbons or the intermediates of aldehydes or ketones (O1). Oil properties, the duration of exposure, exposure season and the chemical structure of these intermediates are critical factors controlling their fate through photo-oxidation. The observed chemical changes highlight the effects of sunlight on the potential behavior, fate and impact of spilled oil, with the creation of new resin group compounds and the reduction of aromatics and saturates. These results also imply that the ecological effects of spilled oil, after ageing in sunlight, depend on the specific oil involved and the environmental conditions.

The susceptibility for photon-induced degradation of over 800 pharmaceutical compounds present in the LOPAC1280 library, was analyzed by UV/Vis spectroscopy in the absence or presence of TiO2 P25 in water. In general, few compounds were effectively degraded in the absence of the TiO2 photocatalyst (3% of all compounds tested), while in the presence of TiO2, the majority of compounds was converted, often to a large degree. Differences in degree of degradation are evaluated on the basis of molecular weight, as well as the chemical nature of the drug compounds (functional groups and pharmacological classes). In general, if the molecular weight increases, the degradation efficacy decreases. Relatively high degrees of conversion can be achieved for (relatively small) molecules with functional groups such as aldehydes, alcohols, ketones and nitriles. A low degree of conversion was observed for compounds composed of conjugated aromatic systems. Trends in degradation efficacy on the basis of pharmacological class, e.g. comparing hormones and opioids, are not obvious.