assessment and comparison of multi annual size profiles of particulate matter monitored at an urban industrial site by an optical particle counter by a chemometric approach

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Development and Technology Assessment of the Analytical Performance of an Eight Position Dynamic Olfactometer

The European technical standard \u201cAir Quality\u2014Determination of Odour Concentration by Dynamic Olfactometry\u201d adopts dynamic olfactometry, a sensorial methodology based on the employment of a panel of human assessors, as the official methodology for the measurement of odour concentration in gas samples. The olfactometer is the device, useful to dilute the odor sample with neutral air, according to precise ratios and to present it to the panel for the analysis. The present paper describes the development of an Italian olfactometer, able to host eight assessors, designed to improve the instrumental performance of the devices actually present on the market, and to increase the accuracy and repeatability of the olfactometric measurement. In particular, in the paper the principal features of the instrumental device and the results of calibrations of dilution valves will be shown

Studi di metodi analitici e modellistici per la valutazione del rischio chimico ed impatti ambientali per impianti costieri di stoccaggio e pompaggio di idrocarburi

2008/2009I consumi energetici europei si basano per oltre un terzo su prodotti petroliferi, di cui circa il 60% viene importato1. Trieste è tra i primi porti petroliferi italiani ed i petroli rappresentano oltre l’80 % dei circa 46 milioni di tonnellate di merci sbarcati annualmente. Le operazioni di sbarco, stoccaggio e pompaggio dei greggi nell’oleodotto transalpino TAL vengono effettuate nel rispetto delle normative nazionali e di standard internazionali di sicurezza, che hanno fatto sì che dal 1967 ad oggi, a fronte di una movimentazione di oltre un miliardo e 200 milioni di tonnellate di greggio, non si siano verificati incidenti rilevanti con l’eccezione dell’attentato terroristico del 4 Agosto 1972. Una gestione attenta di impianti e processi di queste dimensioni richiede tuttavia continui adattamenti ed indirizzi rispetto alle evoluzioni normative, tecniche e del contesto sociale in cui gli impianti sono inseriti. Risulta indubbio in questo senso evidenziare come la sensibilità nei confronti degli impatti reali o percepiti delle attività produttive sull’ambiente sia aumentata nelle società europee proprio a partire dagli anni settanta del secolo scorso. Il presente lavoro di tesi di dottorato mira a proporre metodi analitici e modellistici per la caratterizzazione degli impatti associati alle emissioni nell’ambiente originate da impianti di stoccaggio/pompaggio di idrocarburi, nel caso di rilasci di lieve entità; i metodi risultano indispensabili anche per l’ottimizzazione di soluzioni tecnologiche volte a rimuovere o minimizzare gli impatti ambientali. Bisogna ricordare come la composizione chimica e le proprietà chimico fisiche dei petroli greggi, miscele naturali, siano variabili e dipendano dai giacimenti d’origine degli stessi, comportando mobilità, persistenza, tossicità e rilevabilità diverse per eventuali rilasci nell’ambiente. In alcuni casi i greggi sono presenti come blend provenienti da giacimenti diversi e quindi a composizione non strettamente definita. Le attività intraprese si articolano in studi (capitolo 1) di caratterizzazione analitica dei petroli, volte a determinare componenti alifatiche ed aromatiche che li caratterizzano come contaminanti, e composti particolarmente persistenti come gli opani spesso impiegati come marker di contaminazione ed indicatori per seguire processi di degradazione. Si sono quindi impostati e condotti esperimenti in condizioni controllate, allestendo microcosmi costituiti da suoli contaminati artificialmente, in presenza ed assenza di fenomeni di biodegradazione. 1 European Commission’s Market Observatory for Energy (2009) Europe’s energy position, markets and supply (http://ec.europa.eu/energy/observatory/annual_reports/doc/2009_annual_report.pdf) L’obiettivo è quello di raccogliere indicazioni e parametri utili per la realizzazione di interventi di bonifica con approcci di attenuazione naturale monitorata, land farming o di allestimento di biopile nel caso di contaminazioni accidentali che si dovessero verificare. Un’ulteriore tipologia emissiva da considerare nell’esercizio di impianti di questa natura è quella che riguarda i composti organici volatili (COV) che possono evolvere dai serbatoi durante le operazioni di riempimento, svuotamento e manutenzione o dalle navi cisterna che alimentano il tankfarm. Si sono messi a punto (capitolo 2) metodi per il campionamento passivo ed attivo di COV, includendo sia composti normati quali benzene, toluene, etilbenzene e xileni (BTEX), quanto idrocarburi alifatici volatili, che possono evolvere in atmosfera durante le operazioni di movimentazione dei greggi o di trattamento suoli. I campionatori passivi consentono di ottenere, a costi contenuti, informazioni su concentrazioni medie di BTEX nell’aria ambiente, mentre i campionatori attivi si prestano a campionamenti di breve durata. In considerazione delle segnalazioni di molestie olfattive in prossimità del tankfarm si è affrontato uno studio(capitolo 3) di correlazione tra la concentrazione di odore associata a una serie di campioni di greggi e la loro composizione chimica, con particolare riferimento alla presenza di composti solforati. La natura transitoria delle emissioni di COV in atmosfera e dei fenomeni di molestia olfattiva rende i campionamenti discreti (non continui) dell’aria relativamente poco efficaci, per cui le simulazioni modellistiche possono fornire un valido complemento alle valutazioni ambientali ed all’ottimizzazione delle strategie di controllo. Si è quindi affrontato (capitolo 4)l’allestimento di catene modellistiche che valutano le emissioni dai serbatoi, anche grazie ai dati sperimentali raccolti negli studi precedenti, e la loro dispersione sul territorio. Tali valutazioni possono consentire di posizionare in maniera ragionata centraline di monitoraggio o nasi elettronici sul territorio, tenendo conto quantitativamente dei dati meteorologici e della specifica orografia. Nel caso di emissioni di origine sconosciuta che giungano ad un sito recettore, i modelli possono essere impiegati per valutare la provenienza delle masse d’aria, ricostruendo i campi meteorologici nel dominio spaziale d’interesse e trovando eventuali correlazioni sorgente/recettore. Gli strumenti individuati e sviluppati costituiscono gli elementi che possono essere integrati in un sistema di monitoraggio e retroazione, utile per una gestione ambientale basata su dati quantitativi, comunicabili e su un approccio razionale.XXII Ciclo197

Sustainable domestic burning of residual biomasses from the Friuli Venezia Giulia region

The implementation of short supply chain of available biomass from forest and agriculture residues locally available aims to gain environmental benefits deriving from reduced transportation, avoided abiotic depletion of resources and reduced net emissions of green-house gases. The main objective of the present study was to analyze possible environmental impacts arising from domestic burning of residual biomasses, in terms air pollution. Three different types of woody residual biomasses (Robinia pseudoacacia, Picea abies and Vitis vinifera) were collected within the Friuli Venezia Giulia region in the form of wood chips, converted into pellets and used in controlled combustion tests in a domestic stove. The efficiency of the combustion process and the amount of selected emitted pollutants (carbon monoxide, organic gaseous carbon, nitrogen oxides, benzene, polycyclic aromatic hydrocarbons and total suspended particulate matter) were evaluated. Moreover, the same analysis and combustion tests were carried out on three commercially available pellets (Abies alba, Fagus sylvatica and softwood mix) to achieve a better interpretation and contextualization of the results obtained. Picea abies developed significantly high concentrations of organic gaseous carbon, benzene and polycyclic aromatic hydrocarbons and rather high carbon monoxide emissions. Vitis vinifera was characterized by the highest total suspended particulate matter and carbon monoxide emissions. Robinia pseudoacacia was a very promising fuel showing both combustion and emission properties similar to the commercial pellets. Thus, with the outcomes of our work we highlighted that possible environmental drawbacks due to air pollution arising from residual biomass burning should be evaluated. Moreover, the scientific community of life cycle assessment scientists may benefit from having updated experimental measurements of air pollutants emitted by a domestic stove loaded with different locally available residual biomasses

Advances in TD/GC-MS untargeted compound analysis on particulate matter beyond PAHs routine monitoring

The monitoring of some micro-pollutants is routinary because of their potential toxic activity and of normative regulation, but focusing only on some targeted compounds can divert analysts and researchers from identifying pollution macro-events associated to untargeted compounds. Routine analysis of micro-pollutants, as PAHs, in fast scan GC-MS produces Single Ion Monitoring (SIM) chromatograms used for quantitative determination of target compounds but also a Total Ion Current (TIC) signal which can potentially contain interesting unrevealed information. This is specially true when thermal desorption from solid samples as air particulate matter filters is used as pretreatment method; TD/GC-MS transfers analytes to the separation column without discarding some/part of the compounds. The aim of this study is to report the setup of an experimental and data analysis procedure adequate for disclosing interesting data from raw GCMS data collections acquired during routine monitoring. In this communication we present a 3 month daily PAHs routine monitoring near an incinerator in a Friuli Venezia Giulia chair production district in which we collected 120 samples of PM10 by quartz filter sampling accordingly to EN12341. A series of raw data (retention time, peak area, peak height, peak width, MW, CAS number) were acquired directly from the data analysis software (meanwhile quantifying PAHs) using the \u201cautointegration\u201d and \u201cMS library search\u201d functions. These data were handled within R free statistical computing environment (http://cran.rproject. org), using a home-made script to filter and intercomparing chromatograms by peak properties. In this way we were able, starting from over 5000 peaks to discriminate, beyond PAHs, 21 relevant peaks present in a great number of samples. Using MS library search reports we were able to identify three molecules with high correspondence to the MS database, which can be related to activities in the sampling site: a plasticizer, a phtalate and an erbicide. These compounds were quantified using corresponding commercial standards

Non-invasive assessment of exhaled breath pattern in patients with multiple chemical sensibility disorder

Multiple chemical sensitivity (MCS) is a complex disorder initiated by chemical exposure, particularly through the airways. MCS patients report sensitivity or intolerance to low levels of a wide spectrum of chemicals. Symptoms could include asthma-like signs, rhinitis, fatigue, cognitive dysfunction, psycho-physiological alteration, and other specific tissue reactions resembling hypoxic and oxidative stress effects. To recognize physiological signs that would allow the diagnosis of MCS in a non-invasive way we investigated the potential application of a new sensor system. In healthy volunteers, we measured exhaled breath content in the control condition and under exposure to olfactory stressors that mimic hypoxic or pollutant stressors playing a potential role in the generation of the MCS disorder. The recording system used is based on metal oxide semiconductor (MOS) sensor having a sensing range of 450-2,000 ppm CO2 equivalents, which is able to detect a broad range of compounds playing a potential role in the generation of the MCS disorder, while correlating directly with the CO2 levels. The results indicate that the recording system employed was suitable for the analysis of exhaled breath content in humans. Interestingly, the system was able to detect and discriminate between the exhaled breath content taken from the control condition and those from conditions under stress that mimicked exposures to pollutant or hypoxia. The results suggest that chronic hypoxia could be involved in the MCS disorder

Urban BTEX spatiotemporal exposure assessment by chemometric expertise

6Normative regulations on benzene in fuels and urban management strategies are expected to improve air quality. The present study deals with the application of self-organizing maps (SOMs) in order to explore the spatiotemporal variations of benzene, toluene, ethylbenzene, and xylene levels in an urban atmosphere. Temperature, wind speed, and concentration values of these four volatile organic compounds were measured after passive sampling at 21 different sampling sites located in the city of Trieste (Italy) in the framework of a multi-year long-term monitoring program. SOM helps in defining pollution patterns and changes in the urban context, showing clear improvements for what concerns benzene, toluene, ethylbenzene, and xylene concentrations in air for the 2001–2008 timeframe.nonemixedA. M. Astel; L. Giorgini; A. Mistaro; I. Pellegrini; S. Cozzutto; P. BarbieriA. M., Astel; L., Giorgini; A., Mistaro; I., Pellegrini; Cozzutto, Sergio; Barbieri, Pierluig

Seasonal apportionment of the sources of ambient air particulates in the city of Trieste

A PCA/APCS model was applied to PM2.5 data, which were collected for the Svevo and Muggia districts of the City of Trieste. The sampling campaigns covered the winter and summer periods of 2006. The set of investigated species comprised major inorganic ions, organic and elemental carbon and several Polyaromatic Hydrocarbons (PAHs) that were considered as probable or possible carcinogens by internationally recognised health and environmental agencies. Identified pollution sources included vehicle engine combustion (\u2018traffic\u2019), \u2018secondary emission\u2019, \u2018domestic combustion processes\u2019 and \u2018sea spray\u2019. \u2018Secondary emission and combustion\u2019 dominated, with a total contribution over 74%. The traffic contribution was quantified as 2\u201316%, while sea spray was 4\u201313%. In general, possible or probable carcinogenic PAHs were related to the \u2018traffic\u2019 source. The high correlation coefficient (R2 > 0.90) between the measured and predicted values proves that the PCA/APCS modelling is an efficient tool for the estimation of pollution sources\u2019 contribution to PM2.5 composition