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The adverse effects of atmospheric particulate matter (PM) on health and ecosystems, as well as on meteorology and climate change, are well known to the scientific community. It is therefore undeniable that a good understanding of the sources of PM is crucial for effective control of emissions and to protect public health. One of the major contributions to atmospheric PM is biomass burning, a practice used both in agriculture and home heating, which can be traced and identified by analyzing sugars emitted from the combustion of cellulose and hemicellulose that make up biomass. In this review comparing almost 200 selected articles, we highlight the most recent studies that broaden such category of tracers, covering research publications on residential wood combustions, open-fire or combustion chamber burnings and ambient PM in different regions of Asia, America and Europe. The purpose of the present work is to collect data in the literature that indicate a direct correspondence between biomass burning and saccharides emitted into the atmosphere with regard to distinguishing common sugars attributed to biomass burning from those that have co-causes of issue. In this paper, we provide a list of 24 compounds, including those most commonly recognized as biomass burning tracers (i.e., levoglucosan, mannosan and galactosan), from which it emerges that monosaccharide anhydrides, sugar alcohols and primary sugars have been widely reported as organic tracers for biomass combustion, although it has also been shown that emissions of these compounds depend not only on combustion characteristics and equipment but also on fuel type, combustion quality and weather conditions. Although it appears that it is currently not possible to define a single compound as a universal indicator of biomass combustion, this review provides a valuable tool for the collection of information in the literature and identifies analytes that can lead to the determination of patterns for the distribution between PM generated by biomass combustion.

Magnetite (Fe 3 O 4 ) nano-particles (MNPs) have been found in human tissues and causally linked to serious illnesses. The possible negative role of MNPs has been not still fully ascertained even though MNPs might cause health effects due to their magnetic property, redox activity and surface charge. The origin of MNPs in human tissues still remains to be unambiguously identified since biological processes, natural phenomena and anthropogenic production have been proposed. According to this latter increasingly convincing hypothesis, anthropogenic MNPs might enter mainly in the human body via inhalation, penetrate deeply into the lungs and in the alveoli and also migrate into the blood circulation and gather in the extrapulmonary organs and central nervous system. In order to identify the releasing source of the potentially inhalable MNPs, we pioneered an innovative approach to rapidly investigate elemental profile and morphology of a large number of airborne micron and sub-micron-sized Fe-bearing particles (FePs). The study was performed by collecting a large amount of micron and sub-micron sized inhalable airborne FePs in trafficked and densely frequented areas of Rome (Italy). Then, we have investigated individually the elemental profile and morphology of the collected particles by means of high-spatial resolution scanning electron microscopy, energy dispersive spectroscopy and an automated software purposely developed for the metal-bearing particles analysis. On the basis of specific elemental tracing features, the investigation reveals that almost the total amount of the airborne FePs is released by the vehicle braking systems mainly in the form of magnetite. Furthermore, we point out that our approach might be more generally used to identify the releasing sources of different inorganic airborne particles and to contribute to establish more accurately the impact of specific natural or anthropogenic particles on the environment and human health., (Copyright © 2021 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Laboratory and field studies were carried out to assess the effects of oxidative degradation and volatilization on PM 10 bound polycyclic aromatic hydrocarbons (PAHs), collected at low volume condition according to the EU sampling reference method EN12341:2014 (flow rate 2.3 m 3  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 )., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Homes represent a critical microenvironment in terms of air quality due to the proximity to main particle sources and the lack of proper ventilation systems. Biomass-fed heating systems are still extensively used worldwide, then likely emitting a significant amount of particles in indoor environments. Nonetheless, research on biomass emissions are limited to their effects on outdoor air quality then not properly investigating the emission in indoor environments. To this purpose, the present paper aims to evaluate the exposure to different airborne particle metrics (including both sub- and super-micron particles) and attached carcinogenic compounds in dwellings where three different heating systems were used: open fireplaces, closed fireplaces and pellet stoves. Measurements in terms of particle number, lung-deposited surface area, and PM fraction concentrations were measured during the biomass combustion activities, moreover, PM 10 samples were collected and chemically analyzed to obtain mass fractions of carcinogenic compounds attached onto particles. Airborne particle doses received by people exposed in such environments were evaluated as well as their excess lung cancer risk. Most probable surface area extra-doses received by people exposed to open fireplaces on hourly basis (56 mm 2  h -1 ) resulted one order of magnitude larger than those experienced for exposure to closed fireplaces and pellet stoves. Lifetime extra risk of Italian people exposed to the heating systems under investigation were larger than the acceptable lifetime risk (10 -5 ): in particular, the risk due to the open fireplace (8.8 × 10 -3 ) was non-negligible when compared to the overall lung cancer risk of typical Italian population., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

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 m 3  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., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Nitrous oxide (N2O) is the third most important greenhouse gas after carbon dioxide and methane, and contributes about 6% to the greenhouse effect. Nitrous oxide is a minor component of the atmosphere, and it is a thousand times less than carbon dioxide (CO2). Nevertheless, it is much more potent than CO2 and methane, owing to its long stay in the atmosphere of approximately 120 yr and the high global warmingpotential (GWP) of298 times that of CO2. Although greenhouse gases are natural in the atmosphere, human activities have changed the atmospheric concentrations. Most of the values of emission of nitrous oxide are still obtained by means ofemission factors and not actually measured; the lack ofreal data may result in an underestimation ofcurrent emissions. The emission factors used for the calculation of N2O can be obtained from the "Guidelines for the implementation of the national inventory of emissions" of the Intergovernmental Panel on Climate Change, which refer to all nations for the realization of their inventory. This study will present real data, measured in several Italian cement plants with different characteristics. The work also shows a comparison between N2O concentration measured with in situ-Fourier transform IR (FTIR) and the reference method EN ISO 21258 based on nondispersive IR (NDIR), in order to investigate the interfering compounds in the measurement with NDIR.

A method to measure the emissive concentration of 5-ethylidene-2-norbornene (ENB), a reactive compound used in industrial synthesis of terpolymers, has been developed. The starting points for the development of the presented method are European and Italian reference methods for the quantification of nonreactive volatile organic compounds in industrial emission. In this study, sampling conditions and desorption solvent have been optimized in laboratory and the method was applied in an industrial plant. The laboratory tests showed a good recovery (88-95%). The concentrations of ENB in industrial emission obtained with the developed method were compared with an online gas chromatography-flame ionization results (R (2) > 0.97). In addition, several manual measurements were performed in parallel, and the resulting %RSD repeatability was <9%. The developed method provides a discontinuous technique to measure reactive volatile organic compounds using easy-to-use instruments and assures a very good accuracy and precision even with high-humidity gas flows. The method could be extended to other reactive compounds of the same class.

Purpose: PCDD/Fs, PCBs, and PAHs, ubiquitous environmental pollutants which are part of the POPs, are mainly produced by anthropogenic activities as well as by natural processes. Occurrences of these pollutants in different sites in Trieste are presented. PCDD/Fs distribution and their possible emission sources are discussed., Methods: Air samples were collected in different sites near the industrial area, in the city center, and in a background area, using a high-volume sampler equipped with a quartz fiber filter and a PUF. Each sampling lasted a week., Results: The concentrations of the organochlorinated pollutants are consistent with literature data (ΣPCDD/Fs and Σdl-PCBs were 5-38 fg TEQ/Nm(3) and 4-31 fg TEQ/Nm(3), respectively), and an apparent seasonal trend was found with slightly higher concentrations in the winter and lower levels in both summer campaigns. Moreover, the isomer profile of each sampling campaign was compared to the fingerprint of a sintering plant, a cement plant, and an incinerator, the main industrial activities in Trieste., Conclusions: The organic micropollutants were detected in levels consistent with literature data. The results show that the pollutants are uniformally distributed in the atmosphere of Trieste. PCDD/F fingerprints in each site remained almost identical during summer and winter, confirming the yearly prevalence of the emissions from the nearby sintering plant.

After entry into force of the Stockholm Convention and Aarhus Protocol and in order to implement the upcoming European legal background, the European countries are asked to apply control measures to reduce the release of persistent organic pollutants (POPs) such as dioxins and furans (PCDD/PCDF) and polychlorinated biphenyls as well as to establish POPs release inventories. In this perspective, development of measuring techniques of emissions is a focal issue in acquiring useful information. In this paper, results of various measurement campaigns at different municipal waste incineration (MWI) plants using long-term automated sampling of PCDD/PCDF are presented. The samples collected from both manual and automated campaigns were analyzed following the European Standard EN-1948:2006 by high-resolution gas chromatograph/high-resolution mass spectrometer. Performances of two different commercial systems have been investigated. Anomalous values occurred during one long-term campaign (22.16 pg I-toxic equivalent (TEQ)/Nm(3)), compared to average values (4-5 pg I-TEQ/Nm(3)) of the MWI. At this maximum value, a main occurrence of abnormal and instable operating conditions has been found. Sampling based on long-term basis was found to be more reliable to monitor PCDD/PCDF emissions than occasional short-term sampling. Nevertheless, the results of long-term campaigns demonstrate that emission levels detected in 15-30 days campaigns, when unsteady operating conditions can occur, as start-up and shut down, are not immediately comparable to the typical levels in a 6-8 h, when operating conditions are generally stable. Moreover, there are often differences observed in the congener profiles between short- and long-term campaigns.

A comprehensive clean-up method for quantitative analysis of polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-p-dioxins and dibenzo-furans (PCDD/Fs) in one single extract of environmental samples was developed. Since the chemical nature and toxicity of planar PCBs are similar to those of PCDD/Fs, dioxin-like PCBs and PCDD/Fs are often surveyed together in their exposure assessments. The development of a method for the simultaneous analysis of PCBs and PCDD/Fs in environmental samples is invaluable. The automated clean-up system evaluated in this work consists of three additional steps after traditional extraction: the chromatography on gel permeation (GPC), the concentration of the solvent through the use of an in-line evaporation module and the further purification and separation of PCDDs/Fs and dl-PCBs on an alumina cartridge in the 'SPE module'. In this work, three fly ash samples from an interlaboratory study with different PCDD/F and PCB levels were Soxhlet-extracted and then cleaned up using an automated system. PCDD/Fs and PCBs were determined using isotope dilution and high resolution gas chromatography/high resolution mass spectrometry. The determined values of 17 PCDD/Fs were consistent with the certified values and the relative standard deviations (RSDs) of the determined values were less than 20%. The recoveries of (13)C labeled PCDD/Fs and planar PCBs, and their RSDs were within the ranges specified in EPA1613 and 1668a methods, respectively. An accurate and reliable method was successfully developed and can be used in the simultaneous analysis of PCDD/Fs and planar PCBs in environmental samples., (This journal is © The Royal Society of Chemistry 2012)

Although the worldwide presence of illicit psychotropic compounds in the environment is well known, the social impact of drug abuse on the community has yet to be determined. Besides, the possibility of deriving indicators of the prevalence of drug abuse from the content of illicit substances in the air remains unexplored. In this study, the atmospheric concentrations of psychotropic compounds recorded in Italy were plotted vs. a series of criminal statistics. Meaningful links were found between atmospheric cocaine and the amount of drugs seized, the number of drug related crimes and the demand for clinical treatment recorded in the Italian regions. Atmospheric cocaine and cannabinoids also seemed to be correlated with tumour insurgence and mental disease frequency, respectively. However, further investigations are necessary to elucidate/explain/clarify if the behaviours observed for cocaine vs. the parameters usually adopted to estimate drug abuse prevalence (correspond to an effective relationships)/are directly linked, and to understand why the same approach failed when applied to cannabinoids. Moreover, according to our study illicit drugs are suspected to promote long-term ill health effects even when present at low concentrations the air., (Copyright © 2011 Elsevier B.V. All rights reserved.)

The Stockholm Convention on Persistent Organic Pollutants (POPs) was signed in May 2001 by 127 countries. Currently, 12 substances are regulated by the convention, and the work on finding new candidate chemicals to the convention has started. Among these 12 substances, dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) are the objects of this study. There are no European standard methods for the simultaneous determination of these microorganic compounds, together with polycyclic aromatic hydrocarbons (PAHs) in ambient air--they must be referred to three different methods developed by the U.S. Environmental Protection Agency (EPA). The quali-quantitative analysis of these microorganic pollutants is an important challenge due to the low concentrations at which they may be present. In this study, the development of a simplified, alternative, fast and affordable sampling method for the determination of PAHs, PCDDs, PCDFs and PCBs in ambient air was performed. The sampling time was extended from 24 h to 7 d in order to enrich the sample, to fall within the instrumental limits of detection and to reduce the number of samples to be processed and, therefore, errors that may arise. First of all, experiments with labelled standards were conducted in the research area of Montelibretti (rural station, which is sited about 20 km northeast of Rome), with the purpose of optimizing sampling efficiency. Finally, the method was applied to the analysis of these compounds in the air of a suburban area with small industrial plants in order to evaluate the feasibility of the proposed sampling method system, by comparing concentrations of native compounds acquired during simultaneous daily and weekly sampling.

A monitoring campaign of polychlorinated dibenzo-p-dioxins and dibenzofurans, polyaromatic hydrocarbons (PAHs), and polychlorinated biphenyl was carried out in an Italian iron ore sintering plant by sampling the combustion gases at the electrostatic precipitator (ESP) outlet, at the Wetfine scrubber (WS) outlet, and by collecting the ESP dust. Few data are available on these micropollutants produced in iron ore sintering plants, particularly from Italian plants. This study investigates the PAH emission profiles and the removal efficiency of ESPs and WS. PAHs were determined at the stack, ESP outlet flue gases, and in ESP dust to characterize the emission profiles and the performance of the ESP and the WS for reducing PAH emission. The 11 PAHs monitored are listed in the Italian legislative decree 152/2006. The mean total PAH sum concentration in the stack flue gases is 3.96 microg/N x m3, in ESP outlet flue gases is 9.73 microg/N x m3, and in ESP dust is 0.53 microg/g. Regarding the emission profiles, the most abundant compound is benzo(b)fluoranthene, which has a relative low BaP toxic equivalency factors (TEF) value, followed by dibenzo(a,l)pyrene, which has a very high BaP(TEF) value. The emission profiles in ESP dust and in the flue gases after the ESP show some changes, whereas the fingerprint in ESP and stack flue gases is very similar. The removal efficiency of the ESP and of WS on the total PAH concentration is 5.2 and 59.5%, respectively.

An experimental campaign was carried out in a thermoelectric power plant in Southern Italy in order to evaluate the emissions released during the utilisation of three different fuels, Orimulsion-400, coal and heavy fuel oil (HFO) with high content of sulphur. Macropollutant concentrations in the exhaust gases were recorded by the continuous monitoring system and the Institute on Atmospheric Pollution of the Italian National Research Council (CNR) carried out samplings and analysis of Polycyclic Aromatic Hydrocarbons (PAHs), Polychlorodibenzo-p-dioxins (PCDD) and Polychlorodibenzofurans (PCDF), halogenidric acids and metals. The pollutant concentrations, mass flows and emission factors were compared. Each fuel met the air emission limits for all the pollutants. Coal showed the highest emission levels, whilst HFO and Orimulsion were fairly similar. NOx, SO2 and particulate matter showed constant concentration for all the fuels, while Orimulsion and HFO SO2 concentrations were critical at the highest operating power. Orimulsion showed the lowest PAHs values and PCDDs and PCDFs were much lower than the limits, for all the fuels. Particular attention must be paid with vanadium and nickel during Orimulsion utilisation. For these metals mass balances were carried out.