Contaminants of emerging concern in water and sediment of the Venice Lagoon, Italy.

This study investigates for the first time the contamination of water and sediment of the Venice Lagoon by twenty Contaminants of Emerging Concern (CECs): three hormones, six pharmaceutical compounds (diclofenac and five antibiotics, three of which are macrolides), nine pesticides (methiocarb, oxadiazon, metaflumizone, triallate, and five neonicotinoids), one antioxidant (BHT), and one UV filter (EHMC). Water and sediment samples were collected in seven sites in four seasons, with the aim of investigating the occurrence, distribution, and possible emission sources of the selected CECs in the studied transitional environment. The most frequently detected contaminants in water were neonicotinoid insecticides (with a frequency of quantification of single contaminants ranging from 73% to 92%), and EHMC (detected in the 77% of samples), followed by BHT (42%), diclofenac (39%), and clarithromycin (35%). In sediment the highest quantification frequencies were those of BHT (54%), estrogens (ranging from 35% to 65%), and azithromycin (46%). Although this baseline study does not highlight seasonal or spatial trends, results suggested that two of the major emission sources of CECs in the Venice Lagoon could be tributary rivers from its drainage basin and treated wastewater, due to the limited removal rates of some CECs in WWTPs. These preliminary results call for further investigations to better map priority emission sources and improve the understanding of CECs environmental behavior, with the final aim of drawing up a site-specific Watch List of CECs for the Venice Lagoon and support the design of more comprehensive monitoring plans in the future.

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.

Australian Black summer smoke signal on Antarctic aerosol collected between New Zealand and the Ross sea.

Open biomass burning (BB) events are a well-known primary aerosol source, resulting in the emission of significant amount of gaseous and particulate matter and affecting Earth's radiation budget. The 2019-2020 summer, known as "Australian Black Summer", showed exceptional duration and intensity of seasonal wildfires, triggered by high temperatures and severe droughts. Since increasing megafires are predicted due to expected climate changes, it is critical to study the impact of BB aerosol on a large scale and evaluate related transport processes. In this study, five aerosol samples (total suspended particles with a diameter >1 µm) were collected during the XXXV Italian Expedition in Antarctica on board of the R/V Laura Bassi from 6th of January to February 16, 2020, along the sailing route from Lyttelton harbor (New Zealand) to Terra Nova Bay (Antarctica). Levoglucosan and its isomers have been analyzed as markers of BB, together with polycyclic aromatic hydrocarbons (PAHs), sucrose and alcohol sugars. Ionic species and carboxylic acids have been analyzed to support the identification of aerosol sources and its aging. Results showed high levoglucosan concentrations (325-1266 pg m-3) during the campaign, suggesting the widespread presence of smoke in the region, because of huge wildfire releases. Backward trajectories indicated the presence of long-range atmospheric transport from South America, probably carrying wildfires plume, in agreement with literature. Regional sources have been suggested for PAHs, particularly for 3-4 rings' compounds; monosaccharides, sucrose, arabitol, and mannitol were related to marine and biogenic contributions. In a warming climate scenario, more frequent and extensive wildfire episodes are expected in Australia, potentially altering albedo, aerosol radiative properties, and cloud interactions. Therefore, it is crucial to strengthens the investigations on the regional climatic effects of these events in Antarctica.

Pesticides monitoring in biological fluids: Mapping the gaps in analytical strategies.

Pesticides play a key-role in the development of the agrifood sector allowing controlling pest growth and, thus, improving the production rates. Pesticides chemical stability is responsible of their persistency in environmental matrices leading to bioaccumulation in animal tissues and hazardous several effects on living organisms. The studies regarding long-term effects of pesticides exposure and their toxicity are still limited to few studies focusing on over-exposed populations, but no extensive dataset is currently available. Pesticides biomonitoring relies mainly on chromatographic techniques coupled with mass spectrometry, whose large-scale application is often limited by feasibility constraints (costs, time, etc.). On the contrary, chemical sensors allow rapid, in-situ screening. Several sensors were designed for the detection of pesticides in environmental matrices, but their application in biological fluids needs to be further explored. Aiming at contributing to the implementation of pesticides biomonitoring methods, we mapped the main gaps between screening and chromatographic methods. Our overview focuses on the recent advances (2016-2021) in analytical methods for the determination of commercial pesticides in human biological fluids and provides guidelines for their application.

Fragrance materials affect life history parameters and gene expression in Daphnia magna: An emerging issue for freshwater ecosystems.

A chronic toxicity test (21 d exposure) with the model organism Daphnia magna was performed to study the single-compound and combined effects of four fragrance materials (FMs), including musk xylene (MX), Celestolide™ (ADBI), Galaxolide™ (HHCB), and ethylene brassylate (MT). Furthermore, the transcriptional responses of ten target genes related to detoxification, molting and reproduction (DHR96, P-gp, CYP360A8, GST, CYP314, EcRb, Vtg, CAT, GPX, and GCLC) were determined by performing a quantitative real-time polymerase chain reaction (qRT‒PCR) after juvenile D. magna was exposed for 48 h. The results showed that MX, ADBI and HHCB affected development and reproduction after chronic exposure at a concentration of 10 µg L-1. Conversely, MT did not affect reproduction, growth or molting during the 21 d exposure. In juvenile D. magna, gene expression was significantly altered by ADBI (DHR96, CYP260A8, and GCLC) and MX (DHR96, CYP360A8, EcRb, Vtg, CYP314, and GCLC) but not by HHCB. These results suggest that compared to biochemical measures, conventional biological endpoints provide more informative data regarding the effects of this FM. Compared to single substances in the chronic test, the mixture of the four FMs showed effects at lower concentrations and increased gene expression for EcRb and CYP314 during juvenile exposure, indicating a possible additive or synergistic effect of the four FMs compared to single compound exposure.

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.

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- enantiomers 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.

An upgraded CFA - FLC - MS/MS system for the semi-continuous detection of levoglucosan in ice cores.

A new Continuous Flow Analysis (CFA) system coupled with Fast Liquid Chromatography - tandem Mass Spectrometry (FLC-MS/MS) has been recently developed for determining organic markers in ice cores. In this work we present an upgrade of this innovative technique, optimized for the detection of levoglucosan in ice cores, a crucial tracer for reconstructing past fires. The upgrade involved a specific optimization of the chromatographic and mass spectrometric parameters, allowing for a higher sampling resolution (down to 1 cm) and the simultaneous collection of discrete samples, for off-line analysis of water stable isotopes and additional chemical markers. The robustness and repeatability of the method has been tested by the analysis of multiple sticks of ice cut from the same shallow alpine ice core, and running the system for several hours on different days. The results show similar and comparable trends between the ice sticks. With this upgraded system, a higher sensitivity and a lower limit of detection (LOD) was achieved compared to discrete analysis of alpine samples for levoglucosan measurements. The new LOD was as low as 66 ng L-1, a net improvement over the previous LOD of 600 ng L-1.

Detection of glyphosate residues in feed, saliva, urine and faeces from a cattle farm: a pilot study.

Forty-two samples of feed, saliva, urines, and faeces collected from a cattle farm were investigated with the aim to evaluate the occurrence of glyphosate in faeces, urine and saliva. Glyphosate in the feed was also quantified to understand how it was assimilated by mammals. All cows excreted glyphosate in their faeces at concentrations between 57 and 983 ng g-1. In contrast, only 55% of urine and one sample of saliva tested positive. Most of the feeds demonstrated a non-negligible presence of glyphosate. In particular, a silage containing soybeans from genetically modified cultivation showed a concentration one order of magnitude higher than the other feeds. This study aims to provide the first complete determination of glyphosate in a cattle farm, considering the possible re-entry into the environment through the spreading of liquid and solid sewage and its possible impact on groundwater.

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.

Airborne polar pesticides in rural and mountain sites of North-Eastern Italy: An emerging air quality issue.

North-Eastern Italy and in particular Veneto Region, stands out as a major centre of agriculture and viticulture which has rapidly expanded in the last decade with high productivity indexes. In this context, assessing atmospheric pollution caused by crop spraying with pesticides in rural areas and their transport to high-altitude remote sites is crucial to provide a basis for understanding possible impacts on the environment and population health. We aim to improve existing methods with a highly sensitive technique by using high pressure anion exchange chromatography coupled to a triple quadrupole mass spectrometer. Thus, a total of fourteen polar pesticides were determined in aerosol samples collected from August to December 2021 at Roncade (Venetian plain) and Col Margherita Observatory (Dolomites). The observatory was chosen as the background site as it is representative of the surrounding alpine region. Some samples revealed a substantial amount of cyanuric acid mainly at Roncade (mean concentration of 10 ± 10 ng m-3), glyphosate and fosetyl-aluminium (0.1 ± 0.2 and 0.1 ± 0.1 ng m-3, respectively). Surprisingly, some pesticides have been also found at Col Margherita, a high mountain background site, with concentrations an order of magnitude lower than at Roncade. This is the first time that fourteen polar pesticides have been assessed in the aerosol phase of the Po' Valley and detected at a high-altitude remote site, and consequently this study provides the first data on their occurrences in Italian aerosols. It represents a basis for the assessment of risks for humans.

Airborne concentrations of SARS-CoV-2 in indoor community environments in Italy.

COVID-19 pandemic raised a debate regarding the role of airborne transmission. Information regarding virus-laden aerosol concentrations is still scarce in community indoors and what are the risks for general public and the efficiency of restriction policies. This work investigates, for the first time in Italy, the presence of SARS-CoV-2 RNA in air samples collected in different community indoors (one train station, two food markets, one canteen, one shopping centre, one hair salon, and one pharmacy) in three Italian cities: metropolitan city of Venice (NE of Italy), Bologna (central Italy), and Lecce (SE of Italy). Air samples were collected during the maximum spread of the second wave of pandemic in Italy (November and December 2020). All collected samples tested negative for the presence of SARS-CoV-2, using both real-time RT-PCR and ddPCR, and no significant differences were observed comparing samples taken with and without customers. Modelling average concentrations, using influx of customers' data and local epidemiological information, indicated low values (i.e. < 0.8 copies m-3 when cotton facemasks are used and even lower for surgical facemasks). The results, even if with some limitations, suggest that the restrictive policies enforced could effectively reduce the risk of airborne transmissions in the community indoor investigated, providing that physical distance is respected.

A review on measurements of SARS-CoV-2 genetic material in air in outdoor and indoor environments: Implication for airborne transmission.

Airborne transmission of SARS-CoV-2 has been object of debate in the scientific community since the beginning of COVID-19 pandemic. This mechanism of transmission could arise from virus-laden aerosol released by infected individuals and it is influenced by several factors. Among these, the concentration and size distribution of virus-laden particles play an important role. The knowledge regarding aerosol transmission increases as new evidence is collected in different studies, even if it is not yet available a standard protocol regarding air sampling and analysis, which can create difficulties in the interpretation and application of results. This work reports a systematic review of current knowledge gained by 73 published papers on experimental determination of SARS-CoV-2 RNA in air comparing different environments: outdoors, indoor hospitals and healthcare settings, and public community indoors. Selected papers furnished 77 datasets: outdoor studies (9/77, 11.7%) and indoor studies (68/77. 88.3%). The indoor datasets in hospitals were the vast majority (58/68, 85.3%), and the remaining (10/68, 14.7%) were classified as community indoors. The fraction of studies having positive samples, as well as positivity rates (i.e. ratios between positive and total samples) are significantly larger in hospitals compared to the other typologies of sites. Contamination of surfaces was more frequent (in indoor datasets) compared to contamination of air samples; however, the average positivity rate was lower compared to that of air. Concentrations of SARS-CoV-2 RNA in air were highly variables and, on average, lower in outdoors compared to indoors. Among indoors, concentrations in community indoors appear to be lower than those in hospitals and healthcare settings.

Year-round measurements of size-segregated low molecular weight organic acids in Arctic aerosol.

Organic acids in aerosols Earth's atmosphere are ubiquitous and they have been extensively studied across urban, rural and polar environments. However, little is known about their properties, transport, source and seasonal variations in the Svalbard Archipelago. Here, we present the annual trend of organic acids in the aerosol collected at Ny-Ålesund and consider their size-distributions to infer their possible sources and relative contributions. A series of carboxylic acids were detected with a predominance of C2-oxalic acid. Pinic acid and cis-pinonic acid were studied in order to better understand the oxidative and gas-to-particle processes occurred in the Arctic atmosphere. Since the water-soluble organic fraction is mainly composed by organic acids and ions, we investigated how the seasonal variation leads to different atmospheric transport mechanisms, focusing on the chemical variations between the polar night and boreal summer. Using major ions, levoglucosan and MSA, the Positive Matrix Factorization (PMF) identified five different possible sources: a) sea spray; b) marine primary production; c) biomass burning; d) sea ice related process and e) secondary products.

Interannual variability of sugars in Arctic aerosol: Biomass burning and biogenic inputs.

The concentrations and particle-size distribution of sugars in Arctic aerosol samples were studied to investigate their potential sources and transport. Sugars are constituents of the water-soluble organic compounds (WSOC) fraction in aerosol particles where some saccharides are used as tracers of Primary Biological Aerosol Particles (PBAPs). Monosaccharides (arabinose, fructose, galactose, glucose, mannose, ribose, xylose), disaccharides (sucrose, lactose, maltose, lactulose), alcohol-sugars (erythritol, mannitol, ribitol, sorbitol, xylitol, maltitol, galactitol) and anhydrosugars (levoglucosan, mannosan and galactosan) were quantified in aerosol samples collected during three different sampling campaigns (spring and summer 2013, spring 2014 and 2015). The mean total concentrations of sugars were 0.4 ± 0.3, 0.6 ± 0.5 and 0.5 ± 0.6 ng m-3 for 2013, 2014 and 2015 spring campaigns, while the mean concentration increased to 3 ± 3 ng m-3 in the summer of 2013. This work identified a reproducibility in the sugars trend during spring, while the summer data in 2013 allowed to us to demonstrate strong local inputs when the ground was free of snow and ice. Furthermore, the study aims to show that the two specific ratios of sorbitol & galactiol to arabinose were diagnostic for the type of biomass that was burnt. This study demonstrates that not only is long-range atmospheric transport significant. But depending on seasonality, local inputs can also play an important role in the chemical composition of sugars in Arctic aerosol.

Characterization of the water soluble fraction in ultrafine, fine, and coarse atmospheric aerosol.

Water soluble organic carbon significantly contributes to aerosol's carbon mass and its chemical composition is poorly characterized due to the huge number of species. In this study, we determined 94 water-soluble compounds: inorganic ions (Cl-, Br-, I-, NO3-, SO42-,K+, Mg+, Na+, NH4+, Ca2+), organic acids (methanesulfonic acid and C2-C7 carboxylic acids), monosaccharides, alcohol-sugars, levoglucosan and its isomers, sucrose, phenolic compounds, free l- and d-amino acids and photo-oxidation products of α-pinene (cis-pinonic acid and pinic acid). The sampling was conducted using a micro-orifice uniform deposit impactor (MOUDI) at the urban area of Mestre-Venice from March to May 2016. The main aim of this work is to identify the source of each detected compound, evaluating its particle size distribution. Clear differences in size distributions were observed for each class of analyzed compounds. The positive matrix factorization (PMF) model was used to identify six factors related to different sources: a) primary biogenic aerosol particles with particle size > 10 µm; b) secondary sulfate contribution; c) biomass burning; d) primary biogenic aerosol particles distributed between 10 and 1 µm; e) an aged sea salt input and f) SOA pinene. Each factor was also characterized by different composition in waters soluble compounds and different particles size distribution.

Free and combined L- and D-amino acids in Arctic aerosol.

Aerosol samples were collected with a high-volume cascade impactor with a 10 day sampling frequency at the Gruvebadet observatory, close to Ny-Ålesund (Svalbard Islands). A total of 42 filters were analyzed for free and combined amino acids, as they are key components of bio-aerosol. This article provides the first investigation of free and combined L- and d-amino acids in Arctic atmospheric particulate matter. The main aim of this study was to determine how these compounds are distributed in size-segregated aerosols after short-range and long-range atmospheric transport and understand the possible sources of amino acids. The total load of free amino acids ranged from 2.0 to 10.8 pmol m-3, while combined amino acids ranged from 5.5 to 18.0 pmol m-3. At these levels amino compounds could play a role in the chemistry of cloud condensation nuclei and fine particles, for example by influencing their buffering capacity and basicity. Free and combined amino acids were mainly found in the fine aerosol fraction (<0.49 µm) and their concentrations could be affect by several sources, the most important of which were biological primary production and biomass burning.