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The joint use of hourly resolution sampling and analyses with accelerated ion beams such as Particle Induced X-ray Emission (PIXE) technique has allowed the measurement of hourly temporal patterns of particulate matter (PM) composition at many sites in different parts of the world. The demand within the scientific community for this type of analysis has been continuously increasing in recent years, but hourly resolution samplers suitable for PIXE analysis are now discontinued and/or suffer from some technical limitations. In this framework, a new hourly sampler, STRAS (Size and Time Resolved Aerosol Sampler), was developed for the collection of PM10, PM2.5 or PM1. It allows automatic sequential sampling of up to 168 hourly samples (1 week), it is mechanically robust, compact, and easily transportable. To increase PIXE sensitivity, each sample is concentrated on a small surface area on a polycarbonate membrane. The comparison between the elemental concentrations retrieved by STRAS samples and samples collected using a standard sequential sampler operated in parallel shows a very good agreement; indeed, if both the samplers use the same kind of membrane, the concentrations of all detected elements are in agreement within 10 %. [ABSTRACT FROM AUTHOR]

The waste of electrical and electronic equipment (WEEE) is generally considered a secondary raw material for the recovery of valuable components. However, emerging issues regarding the impact of suspended particles arising from WEEE recycling operations are a concern. It was recently demonstrated that samples from three different WEEE plants were rich in organophosphate flame retardants (OPFRs). Since exposure to a xenobiotic can lead to its biotransformation through human metabolism routes, in the present study, the metabolism of eight OPFRs of interest in our sampling campaign (triphenyl phosphate (TPhP), tri-m-tolyl phosphate (TMTP), ethylhexyl diphenyl phosphate (EHDPhP), tributoxyethyl phosphate (TBOEP), diphenyl phosphate (DPhP), trichloroethyl phosphate (TCEP), tris(1,3-dichloropropan-2-yl) phosphate (TDClPP) and bisphenol A bis(diphenyl phosphate) (BDP)) was investigated. Their metabolism was studied at different time points in three matrices: human liver microsomes, human hepatocytes and human skin microsomes. This study, which was run using a common experimental setting, allowed easy comparison of results for each OPFR of interest, and a comparison with other data in the literature was performed. In particular, a number of metabolites not previously described were detected, and for the first time, it was shown that TPhP could be metabolized in human skin microsomes. [ABSTRACT FROM AUTHOR]

Poly- and perfluorinated alkyl substances (PFASs) are widely used in the electrical and electronic appliance industry to the point that waste of electrical and electronic equipment (WEEE), also known as e-waste, creates significant potential for PFAS exposure (by inhalation, ingestion, or dermal exposure) for people handling and recycling e-waste. The aim of this work was the development of an untargeted analytical approach in order to detect the presence of possible unknown PFASs in particulate matter collected in three Italian e-waste facilities through liquid chromatography coupled to high-resolution tandem mass spectrometry (LC-HR-MS/MS) in negative ionization mode. By means of three acquisition experiments, nine compounds were detected as candidate PFASs, and three were definitively confirmed by comparison with their authentic standards. Among these, bistriflimide (bis (trifluoromethylsulfonyl) imide), an ionic liquid with several promising technological applications, was the most abundant compound detected in all three recycling plants. This is the first study associating the presence of fluorinated ionic liquids with e-waste, and as these chemicals are not only toxic and persistent but also highly mobile, our results indicate the need to include them in future PFAS research. Only further data on their actual environmental diffusion will determine whether they are emerging pollutants or not. [ABSTRACT FROM AUTHOR]

Daily fine (PM2.5) and coarse (PM2.5–10) particulate matter samples were collected from rural and urban monitoring stations located in an industrial region of mid-western Turkey, Kütahya city for one year. All fine- and coarse-mode samples were analyzed by both triple quadrupole inductively coupled plasma-mass spectrometry (ICP-MS/MS) and particle-induced X-ray emission (PIXE) techniques. The two techniques were comparatively evaluated and analytic performances were compared for 21 identified elements including Al, As, Br, Ca, Cr, Cu, Fe, Mg, Mn, Mo, Na, Ni, Pb, Rb, S, Se, Sr, Ti, V, Zn, and Zr. MDLs for PIXE were relatively higher than those of ICP-MS/MS by analyzing over 800 PM samples. The highest and lowest MDLs estimated for PIXE were in the range of 5.0 × 10−3 (Na)–9 × 10−6 μg m−3 (Ti) and between 8.5 × 10−5 (S)–6 × 10−8 μg m−3 (As) for ICP-MS/MS, respectively. Other metrics such as percent below the detection limit (% BDL), precision, and SRM recoveries were also used as variables of comparison. % BDL for PIXE varied between 0% (for Zn) and 83% (for Mo) with important marker elements such as Ca, S, K, Cl and Na being 4%, 8%, 11%, 12% and 21%, respectively. For ICP-MS/MS, % BDL varied between 0% (for Mg) and 98% (for Se) and important marker elements such as Na, Al, Ca, Cr, V and S were between 0% and 1% below detection. Absolute atmospheric concentration ratios (CPIXE/CICP-MS/MS) of most elements except for Br, Mg, Na, and Zr were approximately 1, suggesting a good relationship between the two analytical techniques for elemental characterization of PM samples. In terms of atmospheric concentrations, the two techniques yielded almost the same magnitudes for the elements As, Br, Cr, Fe, Mn, Mo, Pb, Rb, Se, Sr, Ti, V, and Zn – hence, they were found to be equally competitive for measurement of these elements. Ca, Si, Ti, Cu, Zn, S, and Cl were detected in 90 to 100% of the samples. Likewise, Na, Mg, Al, S, Ca, Ti, V, Cr, Mn, Fe, Ni, and As were detected by ICP-MS/MS in almost every sample (∼99–100%). [ABSTRACT FROM AUTHOR]

To control the spread of COVID-19, exceptional restrictive measures were taken in March 2020 that imposed a radical change on the lifestyle of millions of citizens around the world, albeit for a short period. The national lockdown, which lasted from 10 March to 18 May 2020 in Italy, was a unique opportunity to observe the variation in air quality in urban environments under conditions comprising almost total traffic restriction and a strong reduction in work activities. In this paper, the data from 17 urban monitoring sites in Tuscany are presented, and the PM and NO2 concentrations in the 2 months before the start of the lockdown and the 2 months after lockdown are compared with the corresponding months of the previous 3 years. The results show that the total loads of PM 2.5 and PM 10 (particulate matter with an aerodynamic diameter smaller than 2.5 and 10 µm , respectively) decreased, but they did not exhibit significant changes compared to previous years, whereas NO2 underwent a drastic reduction. For three of these sites, the chemical composition of the collected samples was measured using thermal–optical techniques, ion chromatography, and particle-induced X-ray emission analysis, and the application of multivariate positive matrix factorization analysis also allowed for PM 10 source identification and apportionment. Using these analyses, it was possible to explain the low sensitivity of PM 10 to the lockdown effects as being due to different, sometimes inverse, behaviors of the different sources that contribute to PM. The results clearly indicate a decline in pollution levels related to urban traffic and an increase in the concentration of sulfate for all sites during the lockdown period. [ABSTRACT FROM AUTHOR]

ABSTRACT An extensive investigation was carried out for the characterisation of the air particulate composition in Florence. The aim was to determine the aerosol elemental concentrations, as well as to [...]

The RHAPS (Redox-Activity And Health-Effects Of Atmospheric Primary And Secondary Aerosol) project was launched in 2019 with the major objective of identifying specific properties of the fine atmospheric aerosol from combustion sources that are responsible for toxicological effects and can be used as new metrics for health-related outdoor pollution studies. In this paper, we present the overall methodology of RHAPS and introduce the phenomenology and the first data observed. A comprehensive physico-chemical aerosol characterization has been achieved by means of high-time resolution measurements (e.g., number size distributions, refractory chemical components, elemental composition) and low-time resolution analyses (e.g., oxidative potential, toxicological assays, chemical composition). Preliminary results indicate that, at the real atmospheric conditions observed (i.e., daily PM1 from less than 4 to more than 50 μg m−3), high/low mass concentrations of PM1, as well as black carbon (BC) and water soluble Oxidative Potential (WSOP,) do not necessarily translate into high/low toxicity. Notably, these findings were observed during a variety of atmospheric conditions and aerosol properties and with different toxicological assessments. Findings suggest a higher complexity in the relations observed between atmospheric aerosol and toxicological endpoints that go beyond the currently used PM1 metrics. Finally, we provide an outlook to companion papers where data will be analyzed in more detail, with the focus on source apportionment of PM1 and the role of source emissions on aerosol toxicity, the OP as a predictive variable for PM1 toxicity, and the related role of SOA possessing redox-active capacity, exposure-response relationships for PM1, and air quality models to forecast PM1 toxicity. [ABSTRACT FROM AUTHOR]

To control the spread of COVID-19, in March 2020 exceptional restrictive measures were taken imposing a radical change in the lifestyle of millions of citizens around the world, albeit for a short period of time. The national lockdown, which in Italy lasted from 10 March to 18 May 2020, was a unique opportunity to observe the variation in air quality in urban environments in a condition of almost total traffic block and a strong reduction in work activities. In this paper, the data from seventeen urban monitoring sites in Tuscany are presented by comparing PM and NO2 of the two months before the start of the lockdown and the two after with the corresponding months of the previous three years. The results show that the total load of PM2.5 and PM10 decreased but it did not exhibit significant changes compared to previous years, while NO2 undergoes a drastic reduction. For three of these sites, the chemical composition of the collected samples was measured by thermo-optical, ion chromatography and PIXE analysis, and the application of multivariate PMF analysis allowed the PM10 source identification and apportionment. Thanks to these analyses it was possible to explain the low sensitiveness of PM10 to the lockdown effects as due to different, sometimes opposite, behaviors of the different sources that contribute to PM. The results clearly indicated a decline in pollution levels related to urban traffic and an increase in the concentration of sulfate for all sites during the lockdown period. [ABSTRACT FROM AUTHOR]

The elemental composition of the fine (PM 2.5) and coarse (PM 2.5-10) fraction of atmospheric particulate matter was measured at an hourly time resolution by the use of a streaker sampler during a winter period at a Central European urban background site in Warsaw, Poland. A combination of multivariate (Positive Matrix Factorization) and wind- (Conditional Probability Function) and trajectory-based (Cluster Analysis) receptor models was applied for source apportionment. It allowed for the identification of five similar sources in both fractions, including sulfates, soil dust, road salt, and traffic- and industry-related sources. Another two sources, i.e., Cl-rich and wood and coal combustion, were solely identified in the fine fraction. In the fine fraction, aged sulfate aerosol related to emissions from domestic solid fuel combustion in the outskirts of the city was the largest contributing source to fine elemental mass (44 %), while traffic-related sources, including soil dust mixed with road dust, road dust, and traffic emissions, had the biggest contribution to the coarse elemental mass (together accounting for 83 %). Regional transport of aged aerosols and more local impact of the rest of the identified sources played a crucial role in aerosol formation over the city. In addition, two intensive Saharan dust outbreaks were registered on 18 February and 8 March 2016. Both episodes were characterized by the long-range transport of dust at 1500 and 3000 m over Warsaw and the concentrations of the soil component being 7 (up to 3.5 µgm-3) and 6 (up to 6.1 µgm-3) times higher than the mean concentrations observed during non-episodes days (0.5 and 1.1 µgm-3) in the fine and coarse fractions, respectively. The set of receptor models applied to the high time resolution data allowed us to follow, in detail, the daily evolution of the aerosol elemental composition and to identify distinct sources contributing to the concentrations of the different PM fractions, and it revealed the multi-faceted nature of some elements with diverse origins in the fine and coarse fractions. The hourly resolution of meteorological conditions and air mass back trajectories allowed us to follow the transport pathways of the aerosol as well. [ABSTRACT FROM AUTHOR]

In this paper, a new methodology coupling aerosol optical and chemical parameters in the same source apportionment study is reported. In addition to results on source contributions, this approach provides information such as estimates for the atmospheric absorption Ångström exponent (α) of the sources and mass absorption cross sections (MACs) for fossil fuel emissions at different wavelengths. A multi-time resolution source apportionment study using the Multilinear Engine (ME-2) was performed on a PM 10 dataset with different time resolutions (24, 12, and 1 h) collected during two different seasons in Milan (Italy) in 2016. Samples were optically analysed by an in-house polar photometer to retrieve the aerosol absorption coefficient bap (in Mm -1) at four wavelengths (λ=405 , 532, 635, and 780 nm) and were chemically characterized for elements, ions, levoglucosan, and carbonaceous components. The dataset joining chemically speciated and optical data was the input for the multi-time resolution receptor model; this approach was proven to strengthen the identification of sources, thus being particularly useful when important chemical markers (e.g. levoglucosan, elemental carbon) are not available. The final solution consisted of eight factors (nitrate, sulfate, resuspended dust, biomass burning, construction works, traffic, industry, aged sea salt); the implemented constraints led to a better physical description of factors and the bootstrap analysis supported the goodness of the solution. As for bap apportionment, consistent with what was expected, biomass burning and traffic were the main contributors to aerosol absorption in the atmosphere. A relevant feature of the approach proposed in this work is the possibility of retrieving a lot of other information about optical parameters; for example, in contrast to the more traditional approach used by optical source apportionment models, here we obtained source-dependent α values without any a priori assumption (α biomass burning =1.83 and α fossil fuels =0.80). In addition, the MACs estimated for fossil fuel emissions were consistent with literature values. It is worth noting that the approach presented here can also be applied using more common receptor models (e.g. EPA PMF instead of multi-time resolution ME-2) if the dataset comprises variables with the same time resolution as well as optical data retrieved by widespread instrumentation (e.g. an Aethalometer instead of in-house instrumentation). [ABSTRACT FROM AUTHOR]

In this paper, a new methodology coupling aerosol optical and chemical parameters in the same source apportionment study is reported. This approach gives additional relevant information such as estimates for the atmospheric Ångström Absorption Exponent (α) of the sources and Mass Absorption Coefficient (MAC) for fossil fuel emissions at different wavelengths. A multi-time source apportionment study using Multilinear Engine ME-2 was performed on a PM10 dataset with different time resolution (24 hours, 12 hours, and 1 hour) collected during two different seasons in Milan (Italy) in 2016. Samples were optically analysed to retrieve the aerosol absorption coefficient bap (in Mm−1) at four wavelengths (λ = 405 nm, 532 nm, 635 nm and 780 nm) and chemically characterised for elements, ions, levoglucosan, and carbonaceous components. Time-resolved chemically speciated data were coupled with bap multi-wavelength measurements and introduced as input data in the multi-time receptor model; this approach was proven to strengthen the identification of sources being particularly useful when important chemical markers (e.g. levoglucosan, elemental carbon, ...) are not available. The final solution consisted in 8 factors (nitrate, sulphate, resuspended dust, biomass burning, construction works, traffic, industry, aged sea salt); the implemented constraints led to a better physical description of factors and the bootstrap analysis supported the goodness of the solution. As for bap apportionment, consistently to what expected, the two factors assigned to biomass burning and traffic were the main contributors to aerosol absorption in atmosphere. A relevant feature of the approach proposed in this work is the possibility of retrieving many other information about optical parameters; for example, opposite to the more traditional approach used by optical source apportionment models, here we obtained the atmospheric Ångström Absorption Exponent (α) of the sources (α biomass burning = 1.83 and α fossil fuels = 0.80), without any a priori assumption. In addition, an estimate for the Mass Absorption Cross section (MAC) for fossil fuel emissions at four wavelengths was obtained and found to be consistent with literature ranges. [ABSTRACT FROM AUTHOR]

The contribution of natural sources to ambient air particulate matter (PM) concentrations is often not considered; however, it may be significant for certain areas and during specific periods of the year. In the framework of the AIRUSE-LIFEC project, state-of-the-art methods have been employed for assessing the contribution of major natural sources (African dust, sea salt and forest fires) to PM concentrations, in southern European urban areas. 24 h measurements of PM10 and PM2.5 mass and chemical composition were performed over the course of a year in five cities: Porto, Barcelona, Milan, Florence and Athens. Net African dust and sea-salt concentrations were calculated based on the methodologies proposed by the EC (SEC 2011/208). The contribution of uncontrolled forest fires was calculated through receptor modelling. Sensitivity analysis with respect to the calculation of African dust was also performed, in order to identify major parameters affecting the estimated net dust concentrations. African dust contribution to PM concentrations was more pronounced in the eastern Mediterranean, with the mean annual relative contribution to PM10 decreasing from 21% in Athens, to 5% in Florence, and around 2% in Milan, Barcelona and Porto. The respective contribution to PM2.5 was calculated equal to 14% in Athens and from 1.3 to 2.4% in all other cities. High seasonal variability of contributions was observed, with dust transport events occurring at different periods in the western and eastern Mediterranean basin. Sea salt was mostly related to the coarse mode and also exhibited significant seasonal variability. Sea-salt concentrations were highest in Porto, with average relative contributions equal to 12.3% for PM10. Contributions from uncontrolled forest fires were quantified only for Porto and were low on an annual basis (1.4 and 1.9% to PM10 and PM2.5, respectively); nevertheless, contributions were greatly increased during events, reaching 20 and 22% of 24 h PM10 and PM2.5 concentrations, respectively. [ABSTRACT FROM AUTHOR]

Particulate matter with aerodynamic diameters lower than 10 μm, (PM10) aerosol samples were collected during summer 2013 within the framework of the Chemistry and Aerosol Mediterranean Experiment (ChArMEx) at two sites located north (Capo Granitola) and south (Lampedusa Island), respectively, of the main Mediterranean shipping route in the Straight of Sicily. The PM10 samples were collected with 12 h time resolutions at both sites. Selected metals, main anions, cations and elemental and organic carbon were determined. The evolution of soluble V and Ni concentrations (typical markers of heavy fuel oil combustion) was related to meteorology and ship traffic intensity in the Straight of Sicily, using a high-resolution regional model for calculation of back trajectories. Elevated concentration of V and Ni at Capo Granitola and Lampedusa are found to correspond with air masses from the Straight of Sicily and coincidences between trajectories and positions of large ships; the vertical structure of the planetary boundary layer also appears to play a role, with high V values associated with strong inversions and a stable boundary layer. The V concentration was generally lower at Lampedusa than at Capo Granitola V, where it reached a peak value of 40 ng m-3. Concentrations of rare earth elements (REEs), La and Ce in particular, were used to identify possible contributions from refineries, whose emissions are also characterized by elevated V and Ni amounts; refinery emissions are expected to display high La / Ce and La / V ratios due to the use of La in the fluid catalytic converter systems. In general, low La / Ce and La / V ratios were observed in the PM samples. The combination of the analyses based on chemical markers, air mass trajectories and ship routes allows us to unambiguously identify the large role of the ship source in the Straight of Sicily. Based on the sampled aerosols, ratios of the main aerosol species arising from ship emission with respect to V were estimated with the aim of deriving a lower limit for the total ship contribution to PM10. The estimated minimum ship emission contributions to PM10 were 2.0 μg m-3 at Lampedusa and 3.0 μg m-3 at Capo Granitola, corresponding with 11 and 8.6 % of PM10, respectively. [ABSTRACT FROM AUTHOR]

London, like many major cities, has a noted air pollution problem, and a better understanding of the sources of airborne particles in the different size fractions will facilitate the implementation and effectiveness of control strategies to reduce air pollution. Thus, the trace elemental composition of the fine and coarse fraction were analysed at hourly time resolution at urban background (North Kensington, NK) and roadside (Marylebone Road, MR) sites within central London. Unlike previous work, the current study focuses on measurements during the summer providing a snapshot of contributing sources, utilising the high time resolution to improve source identification. Roadside enrichment was observed for a large number of elements associated with traffic emissions (Al, S, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, As, Rb and Zr), while those elements that are typically from more regional sources (e.g. Na, Cl, S and K) were not found to have an appreciable increment. Positive Matrix Factorization (PMF) was applied for the source apportionment of the particle mass at both sites with similar sources being identified, including sea salt, airborne soil, traffic emissions, secondary inorganic aerosols and a Zn-Pb source. In the fine fraction, traffic emissions was the largest contributing source at MR (31.9%), whereas it was incorporated within an “urban background” source at NK, which had contributions from wood smoke, vehicle emissions and secondary particles. Regional sources were the major contributors to the coarse fraction at both sites. Secondary inorganic aerosols (which contained influences from shipping emissions and coal combustion) source factors accounted for around 33% of the PM 10 at NK and were found to have the highest contributions from regional sources, including from the European mainland. Exhaust and non-exhaust sources both contribute appreciably to PM 10 levels at the MR site, highlighting the continuing importance of vehicle-related air pollutants at roadside. [ABSTRACT FROM AUTHOR]

Natural sources' contribution to ambient air particulate matter (PM) concentrations is often not considered; however, it may be significant for certain areas and during specific periods of the year. In the framework of the AIRUSE-LIFE+ project, state-of-the-art methods have been employed for assessing the contribution of major natural sources (African dust, sea salt and forest fires) to PM concentrations, in Southern European urban areas. 24 h measurements of PM10 and PM2.5 mass and chemical composition were performed over the course of a year in five cities: Porto, Barcelona, Milan, Florence and Athens. Net African dust and sea salt concentrations were calculated based on the methodologies proposed by EC (SEC 2011/208). The contribution of uncontrolled forest fires was calculated through receptor modelling. Sensitivity analysis with respect to the calculation of African dust was also performed, in order to identify major parameters affecting the estimated net dust concentrations. African dust contribution to PM concentrations was more pronounced in Eastern Mediterranean, with the mean annual relative contribution to PM10 decreasing from 21% in Athens, to 5% in Florence, and around 2% in Milan, Barcelona and Porto. The respective contribution to PM2.5 was calculated equal to 14% in Athens and from 1.3 to 2.4% in all other cities. High seasonal variability of contributions was observed, with dust transport events occurring at different periods in the Western and Eastern Mediterranean basin. Sea salt was mostly related to the coarse mode and also exhibited significant seasonal variability. Sea salt concentrations were highest in Porto, with average relative contributions equal to 12.3% for PM10. Contributions from uncontrolled forest fires were quantified only for Porto and were low on an annual basis (1.4% and 1.9% to PM10 and PM2.5, respectively); nevertheless, contributions were greatly increased during events, reaching 20 and 22% of 24 h PM10 and PM2.5 concentrations, respectively. [ABSTRACT FROM AUTHOR]

A set of PM samples ( n= 121) collected at an urban background location in Elche (in southeastern Spain) from December 2004 to November 2005 was analysed by particle-induced X-ray emission (PIXE) and ion chromatography in order to provide source identification and potential source locations. Positive matrix factorization (PMF) was used to estimate source profiles and their mass contributions. The PMF modelling identified six sources: aged sea salt (9.2%), ammonium sulphate (40.4%), soil dust related to Saharan outbreaks (13.0%), traffic 1 (18.9%), nitrate aerosol and traffic 2 (5.5%) and local soil dust (6.0%). Potential source contribution function (PSCF) was then used to identify potential source locations. Scarce influence from Mediterranean and European regions was found with the exception of the nitrate source, whose potential source areas were northern Italy and eastern France. Primary source regions for the remaining components (ammonium sulphate, soil dust-related to Saharan outbreaks and aged sea salt) with known mass contributions due to long-range transport have a marked Atlantic and North African location, primarily between Morocco and northwestern Algeria. [ABSTRACT FROM AUTHOR]

We describe a new experimental methodology based on the contemporary use of two-stage continuous streaker samplers and optical particle counters. This is a complementary approach to size-segregated particulate matter (PM) sampling, and it is able to give information on the elemental size distribution and to assess the contribution of major PM source to size bins. PM samples in the fine and coarse fraction of PM10 have been collected by a two-stage streaker sampler and analyzed by particle-induced X-ray emission (PIXE) to obtain elemental concentration time series with hourly resolution. PM sources and profiles were singled out by positive matrix factorization (PMF). A multi-linear regression of size-segregated number of particles versus the sources, resolved by PMF, made possible the apportionment of size-segregated particles number in a fast and direct way. Results obtained in three sampling sites, located in different urban districts are discussed. [Copyright &y& Elsevier]