Glyphosate and other plant protection products in size-segregated urban aerosol: Occurrence and dimensional trend.

Plant protection products (PPPs) play a fundamental role in the maintenance of agricultural fields and private/public green areas, however they can contaminate zones nearby the application point due to wind drift, resuspension, and evaporation. Several studied have deepened the relationship between PPPs and living beings' health, suggesting that these products might have a negative influence. Some PPPs belong to the class of Emergent Contaminants, which are compounds whose knowledge on the environmental distribution and influence is limited. These issues are even more stressed in urban aerosol, due to the high residential density that characterizes this area. Therefore, this study assessed the contamination caused by polar PPPs, such as herbicides (i.e., Glyphosate), fungicides (i.e., Fosetyl Aluminium), and growth regulators (i.e. Maleic Hydrazide), in size-segregated urban aerosol and evaluated their concentration variability with respect to atmospheric parameters (humidity, temperature, rain). Moreover, hypotheses on possible sources were formulated, exploiting also back-trajectories of air masses. A total of six PPPs were found in the samples: glyphosate was more present in the coarse fraction (2.5-10 µm), Fosetyl Aluminium, chlorate and perchlorate were more present in the coarse/fine fractions (10-1 µm), while cyanuric acid and phosphonic acid were mostly concentrated in the fine/ultrafine fractions (<1 µm). While for the first four we suspect of local sources, such as private gardening, the two latter might derive from the entire Po Valley, a highly polluted area in the North of Italy, and from degradation of other substances.

Occurrence and phase distribution of benzothiazoles in untreated highway stormwater runoff and road dust.

The study about how tyre-derived particles can potentially worsen the water quality and how traffic pollution markers can affect the environment is crucial for environmental management. Road emissions are known to contribute to pollution in various environments, and benzothiazoles and their derivates can be used to trace pollutant inputs related to surface runoff in the aquatic system. A total of eight benzothiazoles were determined in highway stormwater runoff and road dust collected from February to August 2022 near Venice (Casale sul Sile, Veneto Region, Italy). A new analytical method was validated, by using an UHPLC system coupled to a mass spectrometer (triple quadrupole). The target compounds were determined in both dissolved phase and suspended particulate matter of runoff, and the road dust samples were divided into seven fractions depending on particle diameters to understand the fraction partitioning. The results indicate that 2-SO3H-BTH was the most concentrated benzothiazole in all the analysed substrates, suggesting tyre debris as the main source because it is usually used in the vulcanization process. 2-SO3H-BTH reached a mean concentration of 115 ± 59 µg L-1, 4 ± 3 µg L-1, and 411 ± 441 µg Kg-1 for dissolved phase, suspended particulate matter, and road dust, respectively, while 2-OH-BTH and BTH showed values about an order of magnitude lower. The size distribution of most BTHs suggests that they are distributed in the finest fraction of road dust. An exception was given by 2-SCNMeS-BTH being present only in particles with a diameter > 1 mm.

Cortisol, cortisone and DHEAS in epidermis and scales of fish Aphanius fasciatus: HPLC-MS/MS measurement of stress indicators as proxies for natural and human-induced factors.

Fish health can be affected by a multitude of stressors. Acute and chronic stress assessment via specific hormones monitoring has become a trending research topic. Common investigated matrices are blood and plasma, but recently less invasive substrates have been identified. As chemical composition of skin mucus/epidermis has been demonstrated to link with acute stress, and of scales with chronic stress in fish, the aim of the study was firstly to improve the determination of three stress hormones, namely cortisol (COL), cortisone (CON), and dehydroepiandrosterone-3-sulfate (DHEAS), in skin mucus/epidermis and scales of Aphanius fasciatus. Secondly, an evaluation of the impact of different environments on hormones concentrations was carried out. A liquid chromatography coupled to tandem mass spectrometry method (HPLC-MS/MS) and a preanalytical procedure were validated to determine COL, CON and DHEAS. This methodology was applied to compare a pull of field-collected fish with a pull of fish housed in the laboratory for one year. Our results highlighted a significant presence of cortisol and cortisone in epidermis of the latter pull (averagely 0.10 and 0.14 ng mg-1, respectively), while in the first pull both hormones were much less concentrated (averagely 0.006 and 0.008 ng mg-1, respectively). Scales of both pulls showed presence of hormones, with a higher concentration for fish housed in the laboratory, although a relevant difference in concentration was found only for cortisone. DHEAS was always below the limit of detection.

Multigram Synthesis of Pure HMF and BHMF.

5-Hydroxymethylfurfural (HMF) is a bio-based platform chemical that can be used as a building block to produce several compounds with diverse applications. Even though HMF synthesis holds promise for a greener future, the current state of technology and the high production cost limit its competitiveness on an industrial scale. In this prospect, we have developed a multigram-scale procedure for HMF by reacting d-fructose with Purolite CT275DR-an acidic resin-in a dimethyl carbonate (DMC)/tetraethyl ammonium bromide (TEAB) biphasic system. Reactions performed in an autoclave for 2 h at 110 °C using up to 40 gram of d-fructose resulted in an overall HMF yield of 70%. HMF was purified by a custom-made procedure leading to ca 50% of the pure crystalline product; meanwhile, the residual HMF-rich oil was directly reduced to bis(hydroxymethyl)furan (BHMF). Green metrics and the Ecoscale algorithm were used to evaluate the sustainability of the herein-proposed procedure in comparison with previously reported works.