Organic toxicants and emerging contaminants in hospital interiors before and during the SARS-CoV2 pandemic: alkanes and PAHs.

Indoor pollution and deposition dust (DD), in particular, are acquiring concern, due to long exposure time and importance of intake by humans through contact and ingestion. Hospitals look a special category of sites, owing to peculiar contaminants affecting them and to presence of people prone to adverse effects induced by toxicants. Four in-field campaigns aimed at understanding the chemical composition of DD were performed in five Italian hospitals. Measurements were performed before (autumn 2019), during (spring 2021), and after (winter 2022) the peak of SARS-CoV2 and when restrictions caused by pandemic were revoked (winter 2023). Parallel measurements were made outdoors (2022), as well as in a university and a dwelling. Targeted contaminants were n-alkanes and polycyclic aromatic hydrocarbons (PAHs), while iso- and anteiso-alkanes were analyzed to assess the impact of tobacco smoking. Total n-alkanes ranged from 3.9 ± 2.3 to 20.5 ± 4.2 mg/g, with higher percentages of short chain homologs in 2019. PAHs ranged from 0.24 ± 0.22 to 0.83 ± 0.50 mg/g, with light congeners (≤ 228 a.m.u.) always exceeding the heavy ones (≥ 252 a.m.u.). According to carbon preference indexes, alkanes originated overall from anthropogenic sources. Microorganisms resulted to affect a hospital, and tobacco smoke accounted for ~ 4-20‰ of DD mass. As for PAH sources, the diagnostic concentration ratios suggested the concourse of biological matter burning and vehicle emission. Benzo[a]pyrene equivalent carcinogenic and mutagenic potencies of depositions at hospitals ranged ~ 9-39 µg/g and ~ 15-76 µg/g, respectively, which seems of concern for health. DD composition in hospitals was different from that outside the premises, as well as that found at university and at dwelling.

n-Alkanes and Polycyclic Aromatic Hydrocarbons in Deposition Dust and PM10 of Interiors in Touggourt Region, Algeria.

The occurrence of pollutants in environment displays its maximum impact on human health and on the global "quality" of life in the places where humans spend most of their time, i.e., indoors. A field study was undertaken in the region of Touggourt, Algeria. The goal was that of obtaining information on the main sources of indoor pollutant emissions (n-alkanes and polycyclic aromatic compounds) associated with deposition dusts (DDs) and suspended particulates (PM10). A multi-service clinic, two schools, a coffee bar, three houses, and an asphalt distribution center were investigated. Forty-five samples in total were collected, including 31 deposition dusts and 14 airborne particulates. That would improve the current understanding of pollution features in central Algeria reached through previous investigations in the Touggourt region. Capillary gas chromatography coupled with mass spectrometric detection was adopted to determine the concentrations of n-alkanes and PAHs. In deposition dust, total n-alkanes (TNAs) ranged between 37 and 794 ng/(m2 day) in the summer and 33-1,724 ng/(m2 day) in the fall. Meanwhile, TNAs loads in the PM10 samples ranged between 778 and 2,024 ng/m3. According to Carbon Preference Index (CPI), Cmax, and wax n-alkanes (WaxCn) approaches, both DD and PM10 were released overall by anthropogenic sources, though the contribution of natural emissions could not be neglected. Total polycyclic aromatic hydrocarbons (TPAHs) associated with DD ranged from 4.4 ng/(m2 day) to 127 ng/(m2 day) during the summer period, and 2.0-224 ng/(m2 day) in the fall; TPAHs' concentrations in PM10 ranged between 40 ng/m3 and 984 ng/m3. Preliminary information about the sources of PAHs was drawn by calculating the concentration ratios between diagnostic pairs (DRs) of PAHs. According to PAH DR values, the pollution sources influenced at distinct extents all of the sites and locations investigated. Anyway, the PAH occurrence was associated with petrogenic sources, with the prevalence of gasoline fuel cars, at most sites. A wide variability was also observed by comparing the concentrations of pollutants observed in the summer and in the fall. This was in agreement with the results of n-alkanes emissions.

Molecular signatures of organic particulates as tracers of emission sources.

Chemical signature of airborne particulates and deposition dusts is subject of study since decades. Usually, three complementary composition markers are investigated, namely, (i) specific organic compounds; (ii) concentration ratios between congeners, and (iii) percent distributions of homologs. Due to its intrinsic limits (e.g., variability depending on decomposition and gas/particle equilibrium), the identification of pollution sources based on molecular signatures results overall restricted to qualitative purposes. Nevertheless, chemical fingerprints allow drawing preliminary information, suitable for successfully approaching multivariate analysis and valuing the relative importance of sources. Here, the state-of-the-art is presented about the molecular fingerprints of non-polar aliphatic, polyaromatic (PAHs, nitro-PAHs), and polar (fatty acids, organic halides, polysaccharides) compounds in emissions. Special concern was addressed to alkenes and alkanes with carbon numbers ranging from 12 to 23 and ≥ 24, which displayed distinct relative abundances in petrol-derived spills and exhausts, emissions from microorganisms, high vegetation, and sediments. Long-chain alkanes associated with tobacco smoke were characterized by a peculiar iso/anteiso/normal homolog fingerprint and by n-hentriacontane percentages higher than elsewhere. Several concentration ratios of PAHs were identified as diagnostic of the type of emission, and the sources of uncertainty were elucidated. Despite extensive investigations conducted so far, the origin of uncommon molecular fingerprints, e.g., alkane/alkene relationships in deposition dusts and airborne particles, remains quite unclear. Polar organics resulted scarcely investigated for pollution apportioning purposes, though they looked as indicative of the nature of sources. Finally, the role of humans and living organisms as actual emitters of chemicals seems to need concern in the future.

Indexes of tobacco smoke contribution to environmental particulates based on molecular fingerprints of alkanes.

Tobacco smoke (TS) is the source of a number of toxicants affecting the atmosphere and poses a threat to smokers and the whole community. Chemical, physical, and toxicological features of smoking products (vapors as well as mainstream, side stream, and third-hand smoke) have been investigated extensively. Special attention is paid to organic compounds (individually or in combination giving rise to peculiar molecular fingerprints), potentially able to act as "chemical signature" of TS. In this regard, the percent distribution of long-chainnormal, iso, and anteiso alkanes was ascertained as typical of TS. Nevertheless, until now no indexes have been identified as suitable for assessing the global TS contribution to environmental pollution, e.g., the TS percentage in carbonaceous aerosol and in deposited dusts, the only exception consisting in the use of nicotelline as tracer. This paper describes the results of an extensive study aimed at chemically characterizing the nonpolar lipid fraction associated to suspended particulates (PMs) and deposition dusts (DDs) collected at indoor and outdoor locations. Based on the iso, anteiso, and normal C29-C34 alkane profile in the samples as well in tobacco smoke- and no-TS-related emissions (literature data), various parameters describing the distribution of compounds were investigated. Finally, a cumulative variable was identified as the tobacco smoke impact index (TS%) suitable for estimating the TS percentage occurring in the particulate matter. The TS% rates were plotted vs. the exceedance of normal C31 alkane with respect to the average of C29 and C33 homologs, which results higher in TS than in most other emissions, revealing a link in the case of suspended particulates but not of deposited dusts. According to back analysis carried out on all particulate matter sets, it was found that traces of TS affect even remote areas, while inside the smokers' homes the contributions of TS to PM could account for up to ~61% and ~10%, respectively, in PM and DD. This confirms the need of valuing the health risk posed by TS to humans, by means of tools easy to apply in extensive investigations.

Exposure levels and health risk of PAHs associated with fine and ultrafine aerosols in an urban site in northern Algeria.

Size distribution of toxicants in airborne particulates remains insufficiently investigated in Algeria. A 1-year campaign was performed at Bab Ezzouar, Algiers (Algeria), aimed at characterizing particulates for their physical and chemical features. For this purpose, scanning electronic microscopy (SEM), Raman spectroscopy (RaS), and GC-MS methodologies were applied. The samples were collected on daily basis by means of a high-volume sampling (HVS) system equipped with cascade impactor separating three size fractions, i.e., particles with aerodynamic diameters d < 1.0 µm (PM1), 1.0 µm

First Investigation of Seasonal Concentration Behaviors and Sources Assessment of Aliphatic Hydrocarbon in Waters and Sediments from Wadi El Bey, Tunisia.

The contents, composition profiles, and sources of aliphatic hydrocarbons were examined in surface sediment and water samples collected from Wadi El Bey, in Tunisia, during different year seasons in 14 stations receiving domestic effluent, industrial discharge, and agricultural drainage wastes. The target substances were analyzed by gas chromatography coupled with mass spectrometric detection (GC/MS). Total concentrations of n-alkanes (n-C14-n-C38) ranged from 0.08 ± 0.01 to 18.14 ± 0.1 µg/L in waters and 0.22 ± 0.04 to 31.9 ± 24.6 µg/g in sediments, while total aliphatic fraction ranged from 0.08 ± 0.01 to 196 ± 140 µg/L in waters and 0.22 ± 0.04 to 1977 ± 1219 µg/g in sediments, which means that almost all sites were affected by hydrocarbon contents in sediments exceeding the recommended limit (100 µg/g). Various diagnostic indices (ADIs) were used to identify the hydrocarbon sources, namely the concentration ratios of individual compounds (n-C17/pristane, n-C18/phytane, pristane/phytane, n-C29/n-C17, n-C31/n-C19) as well as cumulative quantities (Carbon Preference Index, natural n-alkanes ratio, terrigenous/aquatic compounds ratio, unresolved complex mixture percentage, low molecular weight vs. high molecular weight homologues, Alkane Proxy and Terrestrial Marine Discriminants). In general, these indexes indicated that the origin of aliphatic hydrocarbons affecting sediments and waters of Wadi El Bey were linked to both biogenic and petrogenic inputs, attesting the impact of plankton and terrestrial plants and of oil contamination, respectively. The average carbon chain length computation (ACL), used to further index the chemical environment, ranged from 25.5 to 31.1 in sediments and 47.9-116 in waters. This finding could depend on the severe disturbances suffered by the ecosystem as a consequence of heavy anthropogenic inputs. Petroleum contamination associated with high eutrophication rates in Wadi El Bey must be strictly controlled, due to possible harmful effects induced on ecosystem and humans.

Air pollution survey across the western Mediterranean Sea: overview on oxygenated volatile hydrocarbons (OVOCs) and other gaseous pollutants.

Despite the Mediterranean Sea basin is among the most sensitive areas over the world for climate change and air quality issues, it still remains less studied than the oceanic regions. The domain investigated by the research ship Minerva Uno cruise in Summer 2015 was the Tyrrhenian Sea. An overview on the marine boundary layer (MBL) concentration levels of carbonyl compounds, ozone (O3), and sulfur dioxide (SO2) is reported. The north-western Tyrrhenian Sea samples showed a statistically significant difference in acetone and SO2 concentrations when compared to the south-eastern ones. Acetone and SO2 values were higher in the southern part of the basin; presumably, a blend of natural (including volcanism) and anthropogenic (shipping) sources caused this difference. The mean acetone concentration reached 5.4 µg/m3; formaldehyde and acetaldehyde means were equal to 1.1 µg/m3 and 0.38 µg/m3, respectively. Maximums of 3.0 µg/m3 for formaldehyde and 1.0 µg/m3 for acetaldehyde were detected along the route from Civitavecchia to Fiumicino. These two compounds were also present at levels above the average in proximity of petrol-refining plants on the coast; in fact, formaldehyde reached 1.56 µg/m3 and 1.60 µg/m3, respectively, near Milazzo and Augusta harbors; meanwhile, acetaldehyde was as high as 0.75 µg/m3 at both sites. The levels of formaldehyde agreed with previously reported measurements over Mediterranean Sea and elsewhere; besides, a day/night trend was observed, confirming the importance of photochemical formation for this pollutant. According to this study, Mediterranean Sea basin, which is a closed sea, was confirmed to suffer a high anthropic pressure impacting with diffuse emissions, while natural contribution to pollution could come from volcanic activity, particularly in the south-eastern Tyrrhenian Sea region.

Organic molecular markers in marine aerosols over the Western Mediterranean Sea.

A scientific campaign was undertaken along the Western sector of the Mediterranean Sea in the summer 2015 (26th Jun to 13th Jul), with the goal of gathering information about organic contaminants affecting marine aerosol over the Italian seas and with a special focus on changes in composition due to sources. 24 PM10 atmospheric samples in total were chemically characterized, including polycyclic aromatic hydrocarbons (PAHs), aliphatic hydrocarbons (n-alkanes) and phthalate esters. Contemporarily, regulated gaseous toxicants (i.e. ozone, nitrogen oxides and sulfur dioxide) and meteorological parameters were recorded. Samplings were carried out inshore in front of harbors (N = 7) and along the cruise, both during the vessel shipping (N = 11, transects) and at its stops offshore (N = 6). Total PAH concentrations ranged from 0.03 to 1.94 ng/m3 and raised close to harbors and coastal sites, confirming that continental sources were responsible for the strong increase of pollution levels there compared to offshore. The percent composition and diagnostic ratio rates of PAHs were different for harbors, while transects were in agreement with offshore stops, possibly due to the different impact of pollution sources. n-Alkanes (C21C38) and the corresponding carbon preference index rates (CPI) were assessed; their values ranged 8.7-90 ng/m3 and 1.1-2.9 respectively, which suggested that fossil fuel combustion was the dominant source, though biogenic emission could contribute. Alkyl phthalates revealed wide variability in concentrations among aerosol samples. Moreover, long-range atmospheric transport and particle ageing effect induced by photo-oxidants were important factors controlling the composition of organic aerosols in the Mediterranean Sea air.

Polycyclic aromatic hydrocarbons, phthalates, parabens and other environmental contaminants in dust and suspended particulates of Algiers, Algeria.

Chemicals such as polycyclic aromatic hydrocarbons (PAHs), phthalateesters, parabens, siloxanes and squalene, all of them classified as endocrine-disrupting chemicals (EDCs), have been reported to occur in all environmental compartments. The effects of EDCs on development, reproduction, growth, metabolism and obesity constitute a real public health issue. A list of EDCs (> 40 compounds) were characterised in total suspended particulates (outdoor soot: 92 samples) collected in July-September 2016 in an Algiers urban area; besides, settled indoor dusts (36 samples) were collected between November and December 2016 in schools, homes, manufacture and hospital of the same province. The analytical procedure consisted of ultrasonic bath extraction, column chromatography separation into fractions of different polarity and gas chromatographic-mass spectrometric processing. The total loads of phthalates ranging from 6.0 to 347 ng/m2 (median, 26 ng/m2) were determined in indoor dust and 4.6 to 11.6 ng/m3 (median, 7.9 ng/m3) in outdoor soot; meanwhile, PAHs ranged from 12.1 to 108 ng/m2 (median, 36 ng/m2) in indoor dust and ranged from 5.6 to 7.7 ng/m3 (median 5.7 ng/m3) in outdoor soot. Finally, illicit substances such as cocaine, cannabinol and Δ9-tetrahydrocannabinol were found to range from 0.5 to 11 pg/m3, 4.6 to 9.2 pg/m3 and 11 to 81 pg/m3, respectively, in outdoor soot.

Environmental impact of biogas: A short review of current knowledge.

The social acceptance of biogas is often hampered by environmental and health concerns. In this study, the current knowledge about the impact of biogas technology is presented and discussed. The survey reports the emission rate estimates of the main greenhouse gases (GHG), namely CO2, CH4 and N2O, according to several case studies conducted over the world. Direct emissions of gaseous pollutants are then discussed, with a focus on nitrogen oxides (NOx); evidences of the importance of suitable biomass and digestate storages are also reported. The current knowledge on the environmental impact induced by final use of digestate is critically discussed, considering both soil fertility and nitrogen release into atmosphere and groundwater; several case studies are reported, showing the importance of NH3 emissions with regards to secondary aerosol formation. The biogas upgrading to biomethane is also included in the study: with this regard, the methane slip in the off-gas can significantly reduce the environmental benefits.

Volatilization and oxidative artifacts of PM bound PAHs collected at low volume sampling (1): Laboratory and field evaluation.

Laboratory and field studies were carried out to assess the effects of oxidative degradation and volatilization on PM10 bound polycyclic aromatic hydrocarbons (PAHs), collected at low volume condition according to the EU sampling reference method EN12341:2014 (flow rate 2.3 m3 h-1), on 47 mm quartz filters. For the laboratory experiments, pairs of twin samples were collected in field and, after treatments favoring decomposition or/and volatilization of PAHs on one sample, the PAH amount was compared with that of the corresponding untreated sample. Ozone exposure caused a general PAHs decay with more marked effects on benzo [a]pyrene, perylene and benz [a]anthracene; these compounds showed, similarly to benzo [ghi]perylene, correlations between ozone dose and losses. Treatments with zero air exhibited losses due to volatilization even for 5-ring PAHs up to benzo [a]pyrene, whereas a linear dependence was observed between filter PAH load and losses for benzo [a]anthracene, chrysene and benzofluoranthenes. Concentrations on samples collected simultaneously over 48, 24, 12 and 6 h were compared. Results confirmed a lack of temporal auto-consistency in the PAHs sampling methodology here adopted. In particular higher atmospheric PAH concentrations were ascertained on samples constituted by cumulative filters exposed over shorter sampling times. When 24-h and 2 × 12-h samples were compared, comparable losses were evaluated in the hot and cold seasons. This finding shows that, although in summer meteorology conditions favor sampling artifacts, the effectiveness of these phenomena continue in the winter, probably due to the larger amount of PAH available on the sampling filter (total PAHs ∼ 10 vs 0.5 ng m-3).

Seasonal occurrence, source evaluation and ecological risk assessment of polycyclic aromatic hydrocarbons in industrial and agricultural effluents discharged in Wadi El Bey (Tunisia).

Polycyclic aromatic hydrocarbons are of great concern due to their persistence, bioaccumulation and toxic properties. The occurrence, source and ecological risk assessment of 26 polycyclic aromatic hydrocarbons in industrial and agricultural effluents affecting the Wadi El Bey watershed were investigated by means of gas chromatographic/mass spectrometric analysis (GC/MS). Total PAHs (∑ 26 PAH) ranged from 1.21 to 91.7 µg/L. The 4- and 5-ring compounds were the principal PAHs detected in most of 5 sites examined. Diagnostic concentration ratios and molecular indices were performed to identify the PAH sources. Results show that PAHs could originate from petrogenic, pyrolytic and mixed sources. According to the ecotoxicological assessment, the potential risk associated with PAHs affecting agricultural and industrial effluents ranged from moderate to high for both aquatic ecosystem and human health. The toxic equivalency factor (TEF) approach indicated that benzo[a]pyrene and benz[a]anthracene were the principal responsible for carcinogenic power of samples.

Volatilization and oxidative artifacts of PM bound PAHs at low volume sampling (2): Evaluation and comparison of mitigation strategies effects.

The artifacts induced by oxidative degradation and volatilization were assessed with regards to determination of particulate atmospheric PAHs collected at low volume conditions (2.3 m3 h-1) according to the EU Reference Method EN 12341:2014. In order to evaluate the oxidative degradation, PAH measures carried out through collecting airborne particulate with and without ozone denuders were examined. Simultaneously, the influence of volatilization was investigated by comparing concentrations of PAHs in particulate samples collected over 24-h and 12-h using conventional instruments. Summer and winter/spring campaigns were carried out in order to assess the influence of environmental contour on the artifact processes. Oxidative degradation led to a general decrease of PAH concentrations in both periods; in particular, the highest losses were observed for benzo[a]pyrene and perylene reaching, in average, ca. 20%. In the summer, the effect of volatilization exceeded that of oxidative degradation for light PAHs up to benzo[e]pyrene. In the winter/spring time, the influence of both artifact typologies could be mitigated by splitting the normal 24-h collection interval starting at midnight into two 12-h intervals. A mitigation of the losses could even be obtained by fixing the start time sampling fixed at noon or in the first hours of the day. Finally, the feasibility of collecting PAHs through prolonged sampling (>1 month) at the flow rate of 1.1 L min-1 was preliminarily investigated. Results indicated that this approach is unsuitable for minimizing the oxidative artifacts.

Air quality study in the coastal city of Crotone (Southern Italy) hosting a small-size harbor.

Particulate polycyclic aromatic hydrocarbons (PAHs), n-alkanes, and gaseous pollutants were collected from the harbor and the urban area of Crotone (Southern Italy) in October 2015. The atmospheric concentrations of organic substances associated to PM10 were determined daily, while gaseous pollutants (BTEX, O3, SO2, NOx, NO2, and NH3) were monitored on monthly basis by means of diffusive sampling. Total PAHs reached, on the average, 1.56 ± 0.72, 0.33 ± 0.14, and 0.59 ± 0.37 ng/m3 at the urban monitoring stations (Fiore, Fermi) and at the harbor, respectively. The percent distribution and diagnostic concentration ratios of PAHs were similar at Fermi and harbor, whereas differences were found through comparison with Fiore site. Biogenic n-alkanes (n-C29, and n-C31) were the most abundant components, indicating the important impact of terrestrial higher plants in all sites. On the other hand, n-C23-n-C25 homologs originated from incomplete combustion of fossil fuel were not negligible (CPI2.5 = 2.4) in harbor, confirming the role of anthropogenic sources there. Inside the harbor, SO2 concentrations ranged from 5.6 to 14.8 µg/m3 showing the maximum value within the old part of the harbor (touristic port). A statistical significant difference between the harbor and the surroundings was indeed observed for this pollutant, which is a specific marker of ship emissions. The other gaseous species monitored did not exhibit the same distribution, with exception of NH3 and benzene, whose concentration values ranged from 2.8 to 6.9 µg/m3 and 0.3 to 1.4 µg/m3, respectively, and peaked at the same harbor site. Similarities were found in NOx, NO2, and O3 concentration distributions, showing high values in the New Port area.

Seasonal Distribution, Source Identification, and Toxicological Risk Assessment of Polycyclic Aromatic Hydrocarbons (PAHs) in Sediments from Wadi El Bey Watershed in Tunisia.

Surface sediments were collected from the Watershed of Wadi El Bey in Tunisia to evaluate the degree of polycyclic aromatic hydrocarbons (PAHs) contamination. Sediments were collected during different seasons in 14 sites that received wastes from domestic effluent, industrial discharge, and agricultural drainage wastes. Twenty-six individual PAHs were analyzed. The total PAH contents (Σ PAHs) in surface sediments showed wide variability, ranging from 6.89 ± 0.05 to 340 ± 0.1 ng g-1. The 4-, 5-, and 6-ring compounds were the most abundant PAHs detected at the majority of sites. Diagnostic concentration ratios between pairs of PAHs and molecular indices, calculated with the purpose of drawing information about pollution sources, indicated that PAHs were of both petrogenic and pyrolytic origins. Toxic contaminants concentrations were determined according to the numerical effect-based sediment quality guidelines (SQGs). PAH levels did not exceed the SQGs, indicating that PAHs seem to pose low and occasional toxicity risks. Total carcinogenicity and mutagenicity (TEQBaP and MEQBaP) ranged from 0.08 to 65 ng and from 0.02 to 135.0 ng g-1 of dry weight, respectively. Among the seven carcinogenic PAHs, BaP accounted for the majority of the potency and could potentially be used as a unique indicator of PAH toxicity. This study provides a baseline to promote environmental protection programs and pollution monitoring/control in Watershed and coastal areas.

Psychotropic substances in house dusts: a preliminary assessment.

Psychotropic substances (PSs) are known to affect air and waters, while scarce attention has been paid to their occurrence in settled dusts although they can reach important concentrations there; moreover, no procedures have been developed for this specific purpose. In this study, a list of PSs (i.e., nicotine, cotinine, caffeine, cocaine, cannabinol, Δ9-tetrahydrocannabinol, cannabidiol, amphetamine, heroin, and methadone) were characterized in dusts from Rome and Fiumicino international airport, Italy, and from Ouargla city, Algeria. The analytical procedure, based on ultra-sonic bath extraction, silica column chromatography, and GC-MSD analysis, provided good recovery, uncertainty, sensitivity, and lack of interferences for all substances except amphetamine. In NIST SRM-2585 house dust, nicotine, cotinine, caffeine, cocaine, and cannabinol accounted for ~5.95, 0.87, 4.17, 7.0, and 2.2 µg/g, respectively; on the other hand, methadone, tetrahydrocannabinol, cannabidiol, and heroin (all <0.025 µg/g) were below the detection limit of the method. Two sites at the Fiumicino airport were affected by different loads of PSs (e.g., 0.76 and 2.80 ng/m2 of cocaine). In Ouargla, where dust was collected in a primary school and a dwelling, nicotine ranged from ~60 ± 50 to ~86 ± 89 ng/m2, cocaine was absent, and cannabinoids (0.35 ± 0.43 ng/m2 as total) were found only in the home. In Rome, nicotine, caffeine, cocaine, and cannabinol reached ca. 700, 1470, 0.82, and 2.4 ng/m2, respectively, in a smokers' home, but they were ca. 1300, 25,000, 670, and 1700 ng/m2 in a non-smoker home. In conclusion, all dusts revealed the presence of illicit PSs. Further studies are necessary to understand the links between the PS amounts in airborne particulates and in dusts, as well as the PS origin and fate in interiors.

Pharmaceutical substances in ambient particulates: A preliminary assessment.

Till now, no attention has been paid to pharmaceuticals (PCs) in the air, though they are known to affect waters, soils, foods and biota. This paper describes the first attempt to characterize the PC occurrence in the air. Airborne particulates (PM10 or PM2.5 fractions, from Amsterdam, Netherland, Rome and Rende, Italy) were sampled on quartz fiber filter by means of pumping systems operating at medium-volume conditions (16 or 38.5 L min-1). The samples were solvent extracted through sonication with a dichloromethane:acetone:methanol mixture and reduced close to dryness; three fractions of the residue were separated through column chromatography; they comprised non polar, low polar and very polar organic compounds, respectively, and PCs were in the third one. Chemical analysis was performed by means of gas chromatography coupled with mass spectrometric detection (GC-MSD), after treatment of solutions with methyl,tertzbutylsilyl-trifluoroacetamide (MTBSTFA) to form silyl derivatives of most PCs. The following substances were investigated: acetaminophenol, ibuprofen, ketoprofen, fenoprefen, naproxen, fenofibrate, diclofenac, acetylcysteine and sulfanilamide; p-hydroxybenzoic acid and salicylic acid; and parabens (methyl, ethyl and propyl). Except aspirin, acetamidophenol, acetylcysteine and sulfanilamide, the target compounds could be quantified with good repeatability, reproducibility and percent recoveries (on the average, ∼7.5%, ∼7.1% and 91%, respectively). The PC concentrations ranged <0.1-8.6 ng m-3; season dependent drug profiles could be observed in Rome and Rende.

Influence of transport from urban sources and domestic biomass combustion on the air quality of a mountain area.

The environmental influence of biomass burning for civil uses was investigated through the determination of several air toxicants in the town of Leonessa and its surroundings, in the mountain region of central Italy. Attention was focussed on PM10, polycyclic aromatic hydrocarbons (PAHs) and regulated gaseous pollutants (nitrogen dioxide, ozone and benzene). Two in-field campaigns were carried out during the summer 2012 and the winter 2013. Contemporarily, air quality was monitored in Rome and other localities of Lazio region. In the summer, all pollutants, with the exception of ozone, were more abundant in Rome. On the other hand, in the winter, PAH concentration was higher in Leonessa (15.8 vs. 7.0 ng/m3), while PM10 was less concentrated (22 vs. 34 µg/m3). Due to lack of other important sources and to limited impact of vehicle traffic, biomass burning was identified as the major PAH source in Leonessa during the winter. This hypothesis was confirmed by PAH molecular signature of PM10 (i.e. concentration diagnostic ratios and 206 ion mass trace in the chromatograms). A similar phenomenon (i.e. airborne particulate levels similar to those of the capital city but higher PAH loads) was observed in other locations of the province, suggesting that uncontrolled biomass burning contributed to pollution across the Rome metropolitan area.

Fine particulate-bound polycyclic aromatic hydrocarbons in vehicles in Rome, Italy.

Urban commuters are exposed to elevated levels of air pollutants, especially in heavily polluted areas and traffic congested roads. In order to assess the contribution of commuting to citizens' exposure, measurements of fine particulate (PM2.5) and polycyclic aromatic hydrocarbons (PAHs) were carried out in cars, busses, and metro trains, within the LIFE+ EXPAH Project. Monitoring campaigns were performed in Rome, Italy, from April 2011 to August 2012. Inside the busses, the concentration of total PAHs ranged from 2.7 to 6.6 ng/m3 during the winter and from 0.34 to 1.51 ng/m3 in the summer. In cars, internal concentrations were in the range 2.2-7.3 and 0.46-0.82 ng/m3, respectively, in the 2-year time. Analogous differences between seasons were observed examining the benzo[a]pyrene-equivalent carcinogenicity. In the metro trains, total PAHs ranged from 1.19 to 2.35 ng/m3 and PM2.5 ranged from 17 to 31 µg/m3. The PM2.5 concentration in all transport modes ranged from 10 to 160 µg/m3 during the cold season and 15-48 µg/m3 during the warm time. The average inside-to-outside ratio (R I/O) was found to exceed 1.0 for PM2.5 only in busses, probably due to dust re-suspension caused by crowding and passenger activity. The molecular PAH signature suggests that vehicle emissions and biomass combustion were the major sources of commuters' exposure to these toxicants in Rome. According to linear regression analysis, the PAH concentrations inside the vehicles were linked to those detected outside. Statistically significant differences (p < 0.05) were found between the in-vehicle locations and the urban pollution network stations, with higher PAH values detected, on the average, in these latter.

Cocaine and cannabinoids in the atmosphere of Northern Europe cities, comparison with Southern Europe and wastewater analysis.

This study reports the first investigation of atmospheric illicit drug concentrations in Northern Europe using measurements of cocaine and cannabinoids in Amsterdam, London and Stockholm. Further, these measurements were compared to those made in Rome to explore the geographical and inter-city variability. Co-located measurements of atmospheric particulate mass and PAHs were used to help describe and interpret the illicit drug measurements with respect to atmospheric dispersion. Cocaine concentrations ranged from 0.03 to 0.14ng/m3 in Amsterdam, from 0.02 to 0.33ng/m3 in London and were below quantification limit (3pg/m3) in Stockholm. Cannabinol was the only cannabinoid molecule detected in the three cities. During this campaign, London reported the highest concentrations of cocaine and meaningful differences were detected between the urban background and city centre London sites. Mean cocaine concentrations measured in Amsterdam during March 2011 were also compared with those measured simultaneously in eight Italian cities. The cocaine concentration in Amsterdam was comparable to that measured at an urban background in Milan and at a densely populated site in Florence. Although correlating atmospheric concentrations directly with drug prevalence is not possible using current data, links between concentrations of cocaine and estimates of abuse prevalence assessed by the more routinely used wastewater analysis were also examined. A statistically significant correlation was found between the two sets of data (R2=0.66; p=0.00131). Results confirmed that meteorology, population rate and habits of consumption influence the atmospheric concentrations of drugs. If these confounding factors were better controlled for, the techniques described here could became an easy and cost effective tool to index the impact of cocaine abuse in the area; especially where local hot spots need to be identified.