G. de Gennaro

Sources of high PM2.5 concentrations in Milan, Northern Italy: Molecular marker data and CMB modelling

In Milan (MI), the largest city in Northern Italy, the annually average PM2.5 concentration is above 25 μg m(-3), the value that the EU established as a target for 2010, and the upper limit from 2015 onwards (2008/30/CE). Over a three-year period (2006-2009) PM concentrations and chemical compositions were measured in an urban site (MI), a rural site (OB) and a remote site (ASC) in Northern Italy. Chemical characterization (EC/OC, inorganic ions, elements, C20-C32 n-alkanes, C2-C5 mono and dicarboxylic acids, levoglucosan and PAHs) was carried out on PM2.5 samples from the three sites, and PM10 from MI. Molecular markers were used in Chemical Mass Balance (CMB) modelling to estimate the contributions of primary sources to OC, and then PM mass from each source was reconstructed in MI, OB and ASC for different seasons. Estimates of the traffic (TR) source contribution to PM2.5 mass ranged from 4.1 (± 2.0) μg m(-3) during the summer, to 13.3 (± 6.7) μg m(-3) during the winter in MI. TR was the main primary source for PM2.5 concentrations in MI (17-24%). Its contribution was lower at the OB site (7-9%) and at the remote ASC site (3-4%). TR is a local source, while biomass burning (BB) is a diffuse regional source in Northern Italy: during fall and winter, BB was 25-30% and 27-31% of PM2.5 at MI and OB respectively. Other primary sources accounted for a small amount of the PM2.5, i.e. natural gas combustion (0-1%), plant debris (0-4%), road dust (RD=0-4%; but 15% at ASC during winter and 10% of PM10 at MI during summer) and sea salt (0-1%). Secondary inorganic+organic aerosol constituted the major part of the PM2.5 mass during spring and summer (50-65%) at the three sites.

Determination of nutrients in the presence of high chloride concentrations by column-switching ion chromatography

Determination of inorganic anions in waters of high salinity is one of the most difficult task in analytical chemistry. A simple column-switching method, based on an original chromatographic set-up, for the determination of nutrients (nitrate, nitrite and phosphate) in chloride rich aqueous matrices is presented. A pre-separation system (made of two in line pre-columns, Dionex AG9-HC 4 mm) connected to an analytical column (Dionex AS9-HC 4 mm) by a four way pneumatic valve, allows chloride to be eluted off into the waste and nutrients to be separated and detected by a conductimeter and/or a UV spectrophotometer. Neither chemical pre-treatment nor sample dilution are required; sample matrices presenting a large range of chloride concentrations can be investigated. Moreover by using this technology, automation for routine analysis, low analysis time and low costs can be achieved. LODs of 100, 300, 1000 microg/l for nitrate, nitrite and phosphate, respectively, have been obtained by spiking a synthetic sea water sample containing 20,000 mg/l of chloride and 3000 mg/l of sulphate. Analyte calibration curves of analytes are linear (r>0.99) in the range between the LODs and 60 mg/l. This method was applied to nutrients determination in sea water samples collected near a river outlet.

Chemical characterization of exhaled breath to differentiate between patients with malignant plueral mesothelioma from subjects with similar professional asbestos exposure

Malignant pleural mesothelioma (MPM) is an aggressive tumour whose main aetiology is the long-term exposure to asbestos fibres. The diagnostic procedure of MPM is difficult and often requires invasive approaches; therefore, it is clinically important to find accurate markers for MPM by new noninvasive methods that may facilitate the diagnostic process and identify patients at an earlier stage. In the present study, the exhaled breath of 13 patients with histology-established diagnosis of MPM, 13 subjects with long-term certified professional exposure to asbestos (EXP) and 13 healthy subjects without exposure to asbestos (healthy controls, HC) were analysed. An analytical procedure to determine volatile organic compounds by sampling of air on a bed of solid sorbent and thermal desorption GC-MS analysis was developed in order to identify the compounds capable of discriminating among the three groups. The application of univariate (ANOVA) and multivariate statistical treatments (PCA, DFA and CP-ANN) showed that cyclopentane and cyclohexane were the dominant variables able to discriminate among the three groups. In particular, it was found that cyclohexane is the only compound able to differentiate the MPM group from the other two; therefore, it can be a possible marker of MPM. Cyclopentane is the dominant compound in the discrimination between EXP and the other groups (MPM and HC); then, it can be considered a good indicator for long-term asbestos exposure. This result suggests the need to perform frequent and thorough investigations on people exposed to asbestos in order to constantly monitor their state of health or possibly to study the evolution of disease over time.

Atmospheric Deposition: Sampling Procedures, Analytical Methods, and Main Recent Findings from the Scientific Literature

The atmosphere is a carrier on which some natural and anthropogenic organic and inorganic chemicals are transported, and the wet and dry deposition events are the most important processes that remove those chemicals, depositing it on soil and water. A wide variety of different collectors were tested to evaluate site-specificity, seasonality and daily variability of settleable particle concentrations. Deposition fluxes of POPs showed spatial and seasonal variations, diagnostic ratios of PAHs on deposited particles, allowed the discrimination between pyrolytic or petrogenic sources. Congener pattern analysis and bulk deposition fluxes in rural sites confirmed long-range atmospheric transport of PCDDs/Fs. More and more sophisticated and newly designed deposition samplers have being used for characterization of deposited mercury, demonstrating the importance of rain scavenging and the relatively higher magnitude of Hg deposition from Chinese anthropogenic sources. Recently biological monitors demonstrated that PAH concentrations in lichens were comparable with concentrations measured in a conventional active sampler in an outdoor environment. In this review the authors explore the methodological approaches used for the assessment of atmospheric deposition, from the analysis of the sampling methods, the analytical procedures for chemical characterization of pollutants and the main results from the scientific literature.

An integrated approach to identify the origin of PM10 exceedances

PurposeThis study was aimed to the development of an integrated approach for the characterization of particulate matter (PM) pollution events in the South of Italy.MethodsPM10 and PM2.5 daily samples were collected from June to November 2008 at an urban background site located in Bari (Puglia Region, South of Italy). Meteorological data, particle size distributions and atmospheric dispersion conditions were also monitored in order to provide information concerning the different features of PM sources.ResultsThe collected data allowed suggesting four indicators to characterize different PM10 exceedances. PM2.5/PM10 ratio, natural radioactivity, aerosol maps and back-trajectory analysis and particle distributions were considered in order to evaluate the contribution of local anthropogenic sources and to determine the different origins of intrusive air mass coming from long-range transport, such as African dust outbreaks and aerosol particles from Central and Eastern Europe. The obtained results were confirmed by applying principal component analysis to the number particle concentration dataset and by the chemical characterization of the samples (PM10 and PM2.5).ConclusionsThe integrated approach for PM study suggested in this paper can be useful to support the air quality managers for the development of cost-effective control strategies and the application of more suitable risk management approaches.

Analysis of heavy metals in atmospheric particulate by ion chromatography

Cu, Ni, Zn, Co, Fe+2, Mn, Cd, Fe+3 and Pb are easily separated and detected in isocratic mode by ion chromatography with post-column derivatization using a bifunctional ion-exchange column and an eluent formed by oxalic acid (28 mM) and sodium nitrate (250 mM). The separation is optimised by using a suggested sample solution containing a given concentration of chloride. Detection limits were 10-15 ppb for all the metals except for cadmium and lead, for which detection limits of 30 and 60 ppb were found, respectively. The method was tested on an atmospheric particulate certified sample. The measured values were in good agreement with certified values. Real samples of atmospheric particulate from industrial and urban sites were analysed and the results are discussed.

An integrated approach using high time-resolved tools to study the origin of aerosols

Long-range transport of natural and/or anthropogenic particles can contribute significantly to PM10 and PM2.5 concentrations and some European cities often fail to comply with PM daily limit values due to the additional impact of particles from remote sources. For this reason, reliable methodologies to identify long-range transport (LRT) events would be useful to better understand air pollution phenomena and support proper decision-making. This study explores the potential of an integrated and high time-resolved monitoring approach for the identification and characterization of local, regional and long-range transport events of high PM. In particular, the goal of this work was also the identification of time-limited event. For this purpose, a high time-resolved monitoring campaign was carried out at an urban background site in Bari (southern Italy) for about 20 days (1st-20th October 2011). The integration of collected data as the hourly measurements of inorganic ions in PM2.5 and their gas precursors and of the natural radioactivity, in addition to the analyses of aerosol maps and hourly back trajectories (BT), provided useful information for the identification and chemical characterization of local sources and trans-boundary intrusions. Non-sea salt (nss) sulfate levels were found to increase when air masses came from northeastern Europe and higher dispersive conditions of the atmosphere were detected. Instead, higher nitrate and lower nss-sulfate concentrations were registered in correspondence with air mass stagnation and attributed to local traffic source. In some cases, combinations of local and trans-boundary sources were observed. Finally, statistical investigations such as the principal component analysis (PCA) applied on hourly ion concentrations and the cluster analyses, the Potential Source Contribution Function (PSCF) and the Concentration Weighted Trajectory (CWT) models computed on hourly back-trajectories enabled to complete a cognitive framework and confirm the influence of aerosol transported from heavily polluted areas on the receptor site.

Monitoring of the Deposition of PAHs and Metals Produced by a Steel Plant in Taranto (Italy)

A high time-resolved monitoring campaign of bulk deposition of PAHs and metals was conducted near the industrial area and at an urban background site in province of Taranto (Italy) in order to evaluate the impact of the biggest European steel plant. The deposition fluxes of the sum of detected PAHs at the industrial area ranged from 92 to 2432 ng m−2d−1. In particular the deposition fluxes of BaP, BaA, and BkF were, on average, 10, 14, and 8 times higher than those detected at the urban background site, respectively. The same finding was for metals. The deposition fluxes of Ni (19.8 µg m−2 d−1) and As (2.2 µg m−2 d−1) at the industrial site were about 5 times higher than those at the urban background site, while the deposition fluxes of Fe (57 mg m−2d−1) and Mn (1.02 mg m−2d−1) about 31 times higher. Precipitation and wind speed played an important role in PAH deposition fluxes. Fe and Mn fluxes at the industrial site resulted high when wind direction favored the transport of air masses from the steel plant to the receptor site. The impact of the industrial area was also confirmed by IP/(IP

Application of Artificial Neural Networks to a Gas Sensor-Array Database for Environmental Monitoring

A sensors array based on two different types of chemical sensors such as tin dioxide commercial sensors and carbon nanotubes innovative sensors developed in the ENEA laboratories to monitor gases (e.g., CO, NO2, SO2, H2S and CO2) of relevance in polluted air has been analyzed. Measurements of chemical sensing of the sensors array have been performed in laboratory to create a database for applying artificial neural networks (ANNs) algorithms to quantify gas concentration of individual air pollutants and binary gas-mixture. A total number of 3,875 data-samples based on 413 distinct gas concentrations measured by 14 gas sensors has been used in the database. The ANN performance has been assessed for each targeted air-pollutant. The lowest normalized mean square error (NMSE) of 6%, 9% and 11% has been achieved for NO2, SO2 and CO2, respectively. In the contrast, NMSE as high as 28% and 39% has been measured for CO and H2S, respectively. The aim of this study is the selection of an optimal set of gas sensors in the array for enhanced environmental measurements of gas concentration in real-scenario.

A Portable Sensor System for Air Pollution Monitoring and Malodours Olfactometric Control

A portable sensor-system based on solid-state gas sensors has been designed and implemented as proof-of-concept for environmental air-monitoring applications and malodours olfactometric control. Commercial gas sensors (metal-oxides, n-type) and nanotechnology sensors (carbon nanotubes, p-type) are arranged in a configuration of array for multisensing and multiparameter devices. Wireless sensors at low-cost are integrated to implement a portable and mobile node, that can be used as early-detection system in a distributed sensor network. Real-time and continuous monitoring of hazardous air-contaminants (e.g., NO2, CO, SO2, BTEX, etc.) has been performed by in-field measurements. Moreover, monitoring of landfill gas generated by fermentation of wastes in a municipal site has been carried out by the portable sensor-system. Also, it was demonstrated that the sensor-system is able to assess the malodours emitted from a municipal waste site and remarkably compared to the olfactometry method based on a trained test panel.