Benzothiazoles as Molecular Markers for Automobile Tire Derived Inputs: Occurrence and Phase Distribution in Highway Runoff and Road Dust

Over the past several decades, discharges of both wastewater and stormwater have been identified as one of the major causes of the deterioration observed in receiving waters (Lamprea and Ruban, 2011). The major sources are vehicle emissions, motor oil, tyre and brake wear, and road particles in urban environments. During rainfall events contaminants are washed into the stormwater system and then discharged. The Italian legislation (Legislative Decree no. 152 of 11 May 1999) provides a complete program for the protection of water bodies from pollution. The decree implements the community directive 91/271/EEC concerning the treatment of urban wastewater, that constitutes the reference standard for the EU member states. The Italian law focuses on the quality of the receiving water body with several monitoring activities for determining the environmental damage. Despite these steps forward, several pollutants are not determined and their impact and fate in the environment are unknown. Furthermore, a comprehensive determination of contaminants of emerging concern (CECs) is crucial to understand the distribution of target compounds in dissolved phase and suspended particulate matter (Feltracco et al., 2022). The accumulation of road dust itself also serves as a notable pollutant source because it can be transported by runoff, and the associated pollutants could adversely affect the water ecosystem. Among the hazardous pollutants in dissolved phase, suspended particulate matter and road dust particles originating from tires, rubbers, and microplastics are often observed (Rosso et al., 2022), together with benzothiazoles. A total of eight benzothiazoles were determined in highway stormwater runoff and road collected from February to April 2022 near Venice (Casale sul Sile, Veneto Region, Italy). A full validated method is presented, by using an ultra-high pressure liquid chromatography coupled to a triple quadrupole mass spectrometer. The target compounds were determined in both dissolved phase and suspended particulate matter of runoff. The road dust samples were divided in seven fractions depending on particles diameters to evaluate the fraction partitioning. The results underline that SO₃H-BTH was the most concentrated benzothiazole derivate in all the analysed substrates, suggesting the presence of tires debris as main source because it is used in the vulcanization processes. The three major compounds in the dissolved phase were inversely correlated with precipitation amount and positively correlated with the number of days after last rain event, while no correlation were found with suspended particulate matter. The road dust samples indicated a clear trend of the majority of benzothiazoles to distribute in the finest fraction (<63 µm). The distribution of 2-SCNMeS-BTH was opposite to the other benzothiazoles, suggesting a different source and environmental behaviour

Assessing glyphosate in water, marine particulate matter, and sediments in the Lagoon of Venice

Lagoon water, suspended particulate matter, and sediment samples from seven sites at Lagoon of Venice were collected from 2019 to 2021 in order to study the presence of the herbicide glyphosate (N-(phosphonomethyl)glycine), among the most widely used agricultural chemicals worldwide, but its occurrence in lagoon water environment has not been deeply investigated. The sites were selected considering a supposed diversity of inputs and of pollution levels. An analytical method based on ion chromatography coupled with tandem mass spectrometry was optimized and validated for lagoon water, marine particulate matter, and sediment samples. Maximum concentrations of glyphosate were 260 and 7 ng L−1 for lagoon water and suspended particulate matter, respectively, and 15 ng g−1 for sediment, with some spatial and temporal fluctuations. Our results demonstrate that glyphosate content in the Venice Lagoon mainly depends on external forcing from river inlets and agricultural lagoon activities

Fragrances as new contaminants in the Venice lagoon

FragranceMaterials (FMs) are omnipresent components of household and Personal Care Products (PCPs). In spite of their widespread use, little is known about their environmental occurrence. We selected 17 among the longest-lasting and most stable fragrance ingredients that are commercially available, namely: Amberketal, Ambrofix, Amyl Salicylate, Benzyl Salicylate, Bourgeonal, Dupical, Hexyl Salicylate, Isobutavan, Lemonile, Mefranal, Myraldene, Okoumal, Oranger Crystals, Pelargene, Peonile, Tridecene-2-Nitrile, Ultravanil. A new analytical method was developed to quantify FMs in water samples and it was applied to perform the first study about the distribution of these compounds in the surface waters of the city of Venice and its lagoon. Total FMs concentrations range from about 30 ng L-1 to more than 10 mu g L-1 in polluted canals during the low tide. Sewage discharges were supposed to be the main sources of the selected FMs in the environment. Salicylates, oestrogenic and allergenic compounds, were in general the most abundant and widespread components. This study reports for the first time the detection of most of the selected FMs in surface waters and represent the first step to understand their environmental fate. (C) 2016 Elsevier B.V. All rights reserved

Fast and sensitive method for determination of domoic acid in mussel tissue

Domoic acid (DA), a neurotoxic amino acid produced by diatoms, is the main cause of amnesic shellfish poisoning (ASP). In this work, we propose a very simple and fast analytical method to determine DA in mussel tissue. The method consists of two consecutive extractions and requires no purification steps, due to a reduction of the extraction of the interfering species and the application of very sensitive and selective HILIC-MS/MS method. The procedural method was validated through the estimation of trueness, extract yield, precision, detection, and quantification limits of analytical method. The sample preparation was also evaluated through qualitative and quantitative evaluations of the matrix effect. These evaluations were conducted both on the DA-free matrix spiked with known DA concentration and on the reference certified material (RCM). We developed a very selective LC-MS/MS method with a very low value of method detection limit (9 ng g-1) without cleanup steps

Fast Liquid Chromatography Coupled with Tandem Mass Spectrometry for the Analysis of Vanillic and Syringic Acids in Ice Cores

The development of new analytical systems and the improvement of the existing ones to obtain high-resolution measurements of chemical markers in samples from ice cores, is one of the main challenges the paleoclimatic scientific community is facing. Different chemical species can be used as markers for tracking emission sources or specific environmental processes. Although some markers, such as methane sulfonic acid (a proxy of marine productivity), are commonly used, there is a lack of data on other organic tracers in ice cores, making their continuous analysis analytically challenging. Here, we present an innovative combination of fast liquid chromatography coupled with tandem mass spectrometry (FLC-MS/MS) to continuously determine organic markers in ice cores. After specific optimization, this approach was applied to the quantification of vanillic and syringic acids, two specific markers for biomass burning. Using the validated method, detection limits of 3.6 and 4.6 pg mL–1 for vanillic and syringic acids, respectively, were achieved. Thanks to the coupling of FLC-MS/MS with the continuous flow analytical system, we obtained one measurement every 30 s, which corresponds to a sampling resolution of a sample every 1.5 cm with a melting rate of 3.0 cm min–1. To check the robustness of the method, we analyzed two parallel sticks of an alpine ice core over more than 5 h. Vanillic acid was found with concentrations in the range of picograms per milliliter, suggesting the combustion of coniferous trees, which are found throughout the Italian Alps.publishedVersio

Characterization of free L- and D-amino acids in size-segregated background aerosols over the Ross Sea, Antarctica

The study of airborne chemical markers is crucial for identifying sources of aerosols, and their atmospheric processes of transport and transformation. The investigation of free amino acids and their differentiation between the L-and D- en-antiomers are even more important to understand their sources and atmospheric fate. Aerosol samples were collected with a high-volume sampler with cascade impactor at Mario Zucchelli Station (MZS) on the coast of the Ross Sea (Antarctica) for two summer campaigns (2018/19 and 2019/20). The total mean concentration of free amino acids in PM10 was 4 +/- 2 pmol m-3 for both campaigns and most of free amino acids were distributed in fine particles. The coarse mode of airborne D-Alanine and dimethylsufoniopropionate in seawater showed a similar trend during both Antarctic campaigns. Thus, the study of D/L Ala ratio in fine, coarse and PM10 fractions indicated the microlayer as the local source. This paper demonstrated that free amino acids follow the trend of DMS and MSA release occurred in the Ross Sea, confirming their applicability as markers for phytoplankton bloom also in paleoclimatic studies

Composti organici idrosolubili come indicatori nello studio dei processi di scambio atmosfera-neve in Antartide

La frazione organica è un’importante componente dell’aerosol atmosferico e i composti organici idrosolubili costituiscono un 40-60% del carbonio organico presente in atmosfera. Tali composti hanno una grande importanza ambientale in quanto possono influenzare l’igroscopicità delle particelle di aerosol e conseguentemente l’abilità di agire come nuclei di condensazione delle nubi. I composti organici idrosolubili possono essere utilizzati come indicatori di specifiche sorgenti di emissione. Processi di trasporto a lunga distanza sono stati studiati utilizzando il levoglucosan, specifico indicatore di combustione di biomassa, [1], mentre la determinazione di amminoacidi e zuccheri nell’aerosol antartico ha permesso di investigare i processi di formazione e di trasformazione del bioaerosol [2,3]. L’Antartide rappresenta un ottimo laboratorio naturale perché risulta lontano da fonti antropogeniche ed emissioni continentali. In questo studio sono state analizzate diverse classi di composti idrosolubili quali amminoacidi, metossifenoli, mono- e disaccaridi, alcol zuccheri, anidrozuccheri, specie anioniche e cationiche e acidi carbossibili in campioni di aerosol atmosferico e neve superficiale raccolti presso il sito costiero di Campo Faraglione vicino alla Stazione Mario Zucchelli (Antartide) durante la XXX spedizione italiana antartica (estate australe 2014-2015). Il principale obiettivo di questo lavoro consiste nello studio dei processi di scambio atmosfera-neve al fine di individuare nuovi indicatori per lo studio delle carote di ghiaccio. La conoscenza dei processi di deposizione e di possibile degradazione delle specie chimiche nel manto nevoso è fondamentale per capire l’applicabilità di tali composti a studi paleoclimatici. Questo lavoro è stato finanziato dal Programma Nazionale di Ricerche in Antartide (PNRA) mediante il progetto “Scambi e relazioni aria-neve per elementi in tracce e composti organici di interesse climatico” (2013/AZ3.04). Bibliografia [1] R. Zangrando et al., (2016), Science of the Total Environment 544, 606–616. [2] E. Barbaro et al., (2015) Atmospheric Environment, 118, 134-144. [3] E. Barbaro et al., (2015) Atmospheric Chemistry and Physics, 15, 5457–5469