Browsing by Author "Sprovieri, Francesca"

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Air pollution across the mediterranean basin:modelling,measurements and policy implications
(2010-12-02) Bencardino, Mariantonia; Iorio, G.; Pirrone, Nicola; Sprovieri, Francesca
Chemical characterization of atmospheric aerosols from natural and anthropogenic sources in the Mediterranean area
(Università della Calabria, 2019-10-14) Moretti, Sacha; Carbone, Vincenzo; Sprovieri, Francesca; Naccarato, Attilio
The Mediterranean Sea basin constitutes a semi-enclosed area where atmospheric particles originating from natural and anthropogenic continental sources and gas-to-particle conversion processes are present at all times. The area is, in fact, located to the south of highly populated European countries characterized by industrial, semi-industrial, and rural economies, and to the north of Africa, which includes the Sahara desert. Detailed wind trajectory analysis reported in previous research studies show that more than 60% of air masses crossing the Mediterranean originate from the north-northwest sector, containing particles emitted or derived from industrial and urban sources, whereas 13–16% of air masses coming from the Sahara region carrying predominantly mineral dust. The transport of Saharan dust occurs mostly during the spring and summer seasons and causes sporadic crustal aerosol pulses to the Mediterranean area. On the other hand, aerosol scavenging by precipitation during the rainy season (from October to May) reduces aerosol concentrations. Summer is also characterized by low inversion layers and strong sunlight conditions, causing photochemical smog. Moreover, forest fires, which occur during the summer months in the Mediterranean region and in North Africa, increase black carbon and fine particle emissions. In this frame, it is clear enough that specific meteorological conditions result in high temporal variability of aerosol concentrations. There is strong evidence on the relationship between short-term and long-term exposure to atmospheric particles, with adverse health effects. Therefore, the study on atmospheric Particulate Matter (PM) (solid or liquid particles dispersed in the atmosphere which may persist for long times to undergo transport and diffusion phenomena), and the relative chemical composition of the two particle size fractions PM2.5, (aerodynamic diameter ≤ 2.5 μm) and PM10 (aerodynamic diameter ≤ 10 μm), is essential to evaluate the effect of the PM on human health and environment. The present work of thesis developed during the Ph.D. is focused on the chemical characterization of aerosol in the Mediterranean area through a monitoring program which has foreseen a number of oceanographic campaigns performed in the Mediterranean sea onboard the CNR-research vessel in the framework of the ongoing MEDOCEANOR measurements program as well as long-term measurements carried out on-land, specifically at the high altitude GAW observatory “Monte Curcio” of the CNR-IIA (1780 m a.s.l.), located on the Sila massif, Southern Italy, and thus able to intercept long-range transport air masses and across a number of monitoring sites (i.e., coastal, urban, rural sites etc.) distributed in the south of Italy as part of the I-AMICA regional network. The concentration of aerosol size fractions and its chemical composition performed at permanent ground-based stations as well as during oceanographic measurement campaigns have been analyzed in order to assess a spatially and temporally consistent measurement data across Mediterranean basin, and to investigate the main natural and anthropogenic sources affecting the air quality using source apportionment techniques. The seasonal oceanographic campaigns developed along different routes in the western sector of the Mediterranean Sea basin, and aimed to study the influence of natural and anthropogenic sources of PM and associated levels of pollutants. Chemical analysis assisted by the receptor models, identified, in particular, six main sources: crustal, volcanic, biomass burning, marine spray, industrial and vehicular traffic. The carbonaceous content in the PM sampled in Monte Curcio station shows seasonal trends for Organic Carbon (OC) and Elemental Carbon (EC) in both PM size fractions. The concentrations during the warm season are higher than those observed during the cold season and the annual levels of EC and OC were lower than those observed at the other four monitoring sites as part of the regional network “I-AMICA” distributed in southern Italy (Capo Granitola, Lamezia Terme, Lecce; Naples) due to different environmental conditions (eg, coastal/marine, suburban and urban) characterizing these sampling sites compared to “Monte Curcio” remote site. In particular, both OC and EC average concentrations were minimal at Monte Curcio and increased in the following order: remote < coastal/marine < suburban < urban (i.e., Monte Curcio < Capo Granitola < Lamezia Terme < Lecce < Naples). The Secondary Organic Carbon (SOC) was mainly present in PM2.5 at all sites, and higher SOC/OC ratios were observed at the urban and suburban site. Indeed, the yearly average SOC in Monte Curcio station has been estimated as 52% of OC in PM2.5 and representing, on average, the major mass contributes to PM2.5 during the cold season. Furthermore, the receptor models used shown differences among the possible sources of carbonaceous aerosol between different seasons. The cold season was characterized by aerosol mainly coming from the long-range transport, while during the warm season it is influenced by local and regional sources. In the following Chapters, the results have been presented and discussed.
Controllo ambientale. Campagne di monitoraggio atmosferico
(2012-11-29) Gensini, Mario; De Cindio, Bruno; Perrone, Nicola; Sprovieri, Francesca
La normativa ambientale riveste una importanza fondamentale per chi effettua ricerca in campo ambientale poiché, da un lato, definisce lo stato attuale ed i limiti vigenti; dall’altro, evidenzia proprio tali limiti e permette al ricercatore attento di intraprendere le necessarie azioni correttive affinché eventuali vuoti normativi possano essere colmati. L’analisi della normativa, lo studio delle tecniche analitiche per la determinazione degli inquinanti, l’analisi della strumentazione necessaria al monitoraggio dell’inquinamento atmosferico hanno mostrato che la ricerca in questo campo è molto vivace e si ha un continuo aggiornamento sia tecnico che normativo. I dati ambientali devono essere soprattutto dati di qualità ed implementare un processo sistemico di qualità, non può sicuramente essere un fatto episodico o di semplice attuazione. La ricerca di metodiche di analisi dei dati raccolti, di visualizzazione degli stessi dati sono punti fondamentali per una corretta comprensione delle dinamiche ambientali sia per il trasporto degli inquinanti che per la chimica degli stessi
Conventional and innovative technological systems for measuring mercury (Hg) in ambient air: inter-comparison and case-studies to assess variability and Hg seasonal trends within regional and global monitoring networks
(Università della Calabria, 2021-06-17) Martino, Maria; Cipparrone, Gabriella; Sprovieri, Francesca; Bencardino, Mariantonia
Uno dei maggiori rischi ambientali per la salute umana è l’inquinamento atmosferico, un tema che ha acquisito notevole importanza negli ultimi anni a causa degli effetti tossici causati dagli inquinanti sulla salute umana e sui vari ecosistemi. In questo contesto, un ruolo chiave è occupato dal mercurio (Hg) che è un inquinante in grado di causare gravi effetti negativi sulla salute degli ecosistemi e degli esseri viventi in tutto il mondo come evidenziato da noti episodi storici di avvelenamento da mercurio riconosciuti dalla comunità globale come il disastro di Minamata. Gli effetti tossici causati dal Hg costituiscono una grande minaccia ed è questo il motivo principale che identifica il mercurio come inquinante globale da sottoporre a monitoraggio continuo, all’attenzione della comunità scientifica e dell’agenda politica a livello nazionale, regionale e globale. L’impegno da parte della comunità scientifica e politica nell’attivazione di nuovi piani di monitoraggio e miglioramento di quelli esistenti, volti al controllo delle concentrazioni di Hg e delle sue specie ha l’obiettivo di garantire un controllo rigoroso della presenza di questo inquinante nell’ambiente. Oltre all’atmosfera, le attività di monitoraggio del mercurio interessano anche altre matrici ambientali come acqua, suolo e sistemi biologici viventi. A causa del suo ciclo biogeochimico che ne permette un’ampia distribuzione nei diversi comparti ambientali una volta rilasciato in atmosfera da sorgenti naturali e antropiche. La capacità del mercurio di essere trasportato su lunghe distanze, lontano dalla fonte di emissione prima di essere trasformato nelle sue varie forme e raggiungere diversi comparti ambientali, la sua persistenza, la sua capacità di bioaccumulo negli ecosistemi e i suoi impatti considerevolmente negativi, sono le ragioni chiave che hanno evidenziato il mercurio come un problema ambientale rilevante di interesse globale che richiede azioni concertate per una protezione efficace della salute umana e dell'ambiente. Sulla base di tali motivazioni è stata sottolineata la necessità di avere una prospettiva globale nell’affrontare il problema dell'inquinamento da mercurio nell'ambiente guidata da uno strumento legalmente vincolante quale la Convenzione di Minamata sul Mercurio che ha come obiettivo la protezione della salute e dell'ambiente dalle emissioni di mercurio e dei suoi composti, considerando l'intero ciclo di vita del mercurio, dall'estrazione primaria dell’elemento sino alla gestione dei rifiuti che lo contengono. A tal fine, le disposizioni della Convenzione di Minamata evidenziano una crescente richiesta di attività di monitoraggio e il continuo miglioramento delle stesse al fine di arricchire la comprensione dell’impatto dell’inquinamento da mercurio sull’ambiente grazie alla fornitura di dati coerenti ai responsabili politici, oltre che a ricercatori e al pubblico in generale. Inoltre, i requisiti della Convenzione di Minamata identificano l’osservazione e il monitoraggio dei cambiamenti dei livelli di mercurio nell'atmosfera su scala globale come un modo per poter valutare l’efficacia delle azioni volte alla riduzione dei livelli globali del mercurio stesso. È quindi importante essere in grado di definire gli aspetti chiave come la comparabilità dei dati, l'affidabilità e l'accessibilità dei dati e la garanzia della qualità. In questo contesto, all'interno del network GMOS (Global Mercury Observation System), coordinato dall'Istituto di Ricerca sull'Inquinamento Atmosferico del Consiglio Nazionale delle Ricerche (CNR-IIA) di Rende sono stati sviluppati e implementati diversi strumenti quali le SOP (Standard Operational Procedures). Le SOP sono protocolli comuni standardizzati specifici che forniscono sia informazioni sul metodo per valutare le concentrazioni di mercurio in una matrice ambientale specifica, sia le procedure per l'uso e la manutenzione tecnica su campo degli strumenti automatizzati utilizzati nei siti della rete, e il G-DQM (GMOS-Data Quality Management) sistema utile per l'acquisizione e l'elaborazione dei dati raccolti dai vari siti appartenenti alla rete. Lo scopo di tali strumenti è quello di armonizzare le misure ottenute nella rete e garantire un alto grado di comparabilità tra i dati ottenuti da tutti i siti di monitoraggio e la possibilità di scambio e valutazione congiunta dei dati. A supporto di una più efficace azione di monitoraggio negli anni, è emersa la necessità di metodi innovativi di monitoraggio e analisi a basso costo e di facile utilizzo in grado di integrare l'uso ed i limiti dei metodi analitici convenzionali in aree geografiche ampie o remote. Il lavoro di ricerca presentato in questa tesi è stato rivolto al monitoraggio delle concentrazioni di mercurio atmosferico, sfruttando approcci sia convenzionali che innovativi. Riguardo il campionamento con strumentazione tradizionale, sono stati analizzati i dati di misura derivanti dal campionamento di mercurio atmosferico presso tre diverse stazioni di monitoraggio, dislocate su territorio italiano, quali Monte Sant’Angelo, Monte Curcio, Montelibretti. Tutti i dati, a seguito di opportuna trattazione statistica, e con il supporto di mappe satellitari e di simulazioni modellistiche sulle retro-traiettorie delle masse d’aria, sono stati interpretati alla luce della loro variabilità temporale, delle dinamiche meteorologiche e dell’influenza di specifiche sorgenti, di tipo sia naturale che antropico. Il lavoro di ricerca presentato in questa tesi è rivolto al monitoraggio del mercurio anche mediante approcci innovativi. In questo contesto, il campionamento attivo, su cui si basano i comuni analizzatori di mercurio, è stato confrontato con le prestazioni di dispositivi passivi (PASs) di nuova concezione, la cui struttura è stata migliorata durante il mio dottorato di ricerca e testati sul campo attraverso una campagna di intercomparazione. Nell’ambito dell’indagine comparativa, è stato evidenziato come il campionamento passivo possa essere proposto come alternativa praticabile o sistema complementare utile per colmare le lacune del monitoraggio mondiale del mercurio visti i suoi numerosi vantaggi che aumentano la possibilità concreta di una rete globale sostenibile e la disponibilità di misurazioni del mercurio atmosferico a lungo termine che includa aree geografiche attualmente non coperte da sistemi di monitoraggio esistenti Abstract in English One of the greatest environmental risks to human health is atmospheric pollution, an issue that has acquired considerable importance in recent years due to the toxic effects caused by pollutants on human health and various ecosystems. In this context, a key role is played by mercury (Hg) which is a pollutant capable of causing serious negative effects on health ecosystems and living beings around the world as evidenced by known historical episodes of mercury poisoning recognized by the global community like the Minamata disaster. The toxic effects caused by Hg constitute a great threat and this is the main reason that identifies mercury as a global pollutant to be subjected to continuous monitoring, to the attention of the scientific community and of the political agenda at national, regional, and global level. The commitment by the scientific and political community in the activation of new monitoring plans and improvement for the existing ones, aimed at controlling the concentrations of Hg and its species, has the aim of guaranteeing rigorous control of the presence of this pollutant in the environment. In addition to the atmosphere, mercury monitoring activities also affect other environmental matrices such as water, soil, and biological living systems. Due to its biogeochemical cycle mercury can be widely distributed in different environmental compartments once released into the atmosphere from natural and anthropogenic sources. The ability of mercury to be transported over long distances, away from the emission sources before being transformed into its different forms and reaching the various environmental compartments, its persistence its ability to bioaccumulate in ecosystems, and its considerably negative impacts, are the key reasons that have highlighted mercury as a significant environmental problem of global concern that requires concerted action for effective protection of human health and the environment. Based on these reasons, the need to have a global perspective in addressing the problem of mercury pollution in the environment was underlined, guided by a legally binding instrument such as the Minamata Convention on Mercury aims to protect health and the environment from mercury emissions and its compounds, considering the entire life cycle of mercury, from the primary extraction of the element to the management of the waste containing it. For this purpose, the provisions of the Minamata Convention highlight a growing demand for monitoring activities and their continuous improvement in order to enhance the understanding the impact environmental mercury pollution thanks to the provision of consistent data to policy makers as well as researchers and the general public. Furthermore, the requirements of the Minamata Convention identify the observation and monitoring of changes in mercury levels in the atmosphere on global scale to evaluate the effectiveness of actions aimed at reducing global mercury levels. It is therefore important to be able to define key aspects such as data comparability, data reliability and accessibility and quality assurance. In this context, within the GMOS network (Global Mercury Observation System), coordinated by the Institute of Atmospheric Pollution Research of the National Research Council (CNR-IIA) of Rende various tools have been developed and implemented such as SOPs (Standard Operational Procedures). The SOPs are specific standardized common protocols that provide both information on the method for assessing mercury concentrations in a specific environmental matrix, and the procedures for use and technical maintenance in the field of automated tools used across the network sites, and the G-DQM (GMOS-Data Quality Management) system useful for the acquisition and processing of data collected from the various sites belonging to the network. The aim of these tools is to harmonize the measurements obtained within the network and to ensure a high degree of comparability between the data obtained from all the monitoring sites and the possibility of exchanging and jointly evaluating the data. In support of a more efficacy monitoring action over the years, has been emerged the need for innovative monitoring and analytical methods at low cost and easy to use able to integrate the use and limitations of conventional analytical methods in large or remote geographical areas. The research work presented in this thesis was aimed at monitoring atmospheric mercury concentrations, using both conventional and innovative approaches. With regards to the field campaigns carried out through conventional instruments, a specific investigation has been performed over the Hg atmospheric measurements recorded at three monitoring stations, located across the Italian territory, and corresponding to Monte Sant'Angelo, Monte Curcio, Montelibretti sampling sites. All data, after an appropriate statistical treatment, and with the support of satellite maps, as well as modelling simulations providing air mass backward trajectory, have been interpreted in light of their temporal variability, meteorological dynamics and the influence of specific sources, both natural and anthropogenic..
Development of new sensor technologies for ambient Mercury and comparison with conventional methods/systems
(2018-11-22) Castagna, Jessica; Carbone, Vincenzo; Sprovieri, Francesca
In the last decades, the global ecosystem has been increasingly threatened by problems, like as, climate change and air pollution, due to the increasing of pollutant emissions that are altering the balance of atmospheric gases. Among the pollutants, Mercury (Hg) plays a significant role due to its toxicity and negative consequences about the environmental and human health. Hg is released in the atmosphere through punctual or diffuse sources, which could be of natural and/or anthropogenic origins. In the atmosphere, Hg could be redistributed towards terrestrial or aquatic receptors, through a complex biogeochemical cycle that involves all natural areas such as the atmosphere, hydrosphere, and geosphere. Although the Hg’s knowledge is improving, the current comprehension about several processes that influence the Hg cycle in the environment, such as chemical-physical processes that affect the mobility of Hg in soils and sediments, or the exchange of Hg gaseous to the air-water interface, is incomplete for both a quantitative description and a proper modeling. The Hg cycle is cross-border, therefore, in recent years, the need to control its processes persuaded to join efforts at a global level. The principal result of the international policies is represented by the Minamata International Convention, of which, its main objective proposes is to reduce drastically the Hg emissions. In 2010, the European Project GMOS - Global Mercury Observation System (FP7) has been approved, in order to support the Minamata Convention, as well as, to examine in deep the Hg cycle, improving the data coverage around the globe, especially in areas where datasets were absent or scarce. The GMOS-Project, coordinated by the UOS of Rende of the CNR-IIA, supported the development of a monitoring network for Hg, with 40 ground-based stations that have to monitor in continuous Hg in the atmosphere and in depositions. Moreover, within the GMOS-project, oceanographic campaign and aircraft measurements, exploring respectively the open sea and the troposphere, had been performed. In this context, the following work of PhD research had been developed. The first part of this work concerned with the comprehension of some Hg processes through two different case-studies: the first regarding the monitoring station of GMOS-network set in Bariloche (Argentina), while the second one, was about the oceanographic campaign, performed on board the research vessel "Minerva Uno" of the CNR, into the basin of the Mediterranean Sea. In both the case-studies, the conventional systems for Hg measurements were employed, according to the reference instruments used within the global network. However, these instruments require an excessive cost of maintenance, and present difficulties in using, especially in pristine areas. These are the motivations of the need of development of new technologies and systems for Hg, which should be cheaper, robust, transportable, with no energy supply, and user-friendly. For this reasons, the main objective proposal of the second part of this PhD thesis is the development of new sensors for the Hg monitoring in the air and wet deposition. Regard the Hg in air, I was involved into the development of passives samples, tested first into laboratories, and then, on field during two seasonal campaigns, performed in five monitoring GMOS stations, three in the Northern Hemisphere (Italy, Russia, China), and two in the Southern Hemisphere (Argentina and South Africa). The preliminary results of comparison between the new passive system and the active conventional system, although have shown some problems, seem to be very promising. To develop new sensors for Hg in wet deposition, the Electrochemical Impedance Spectroscopy (EIS) of a functionalized gold three-electrode has been investigated. The analysis of this sensor, performed in laboratories, showed a good response. vii The work of research carried out during the PhD has allowed examining in deep the chemical-physical processes for Hg thanks to the results of the two case studies treated. Furthermore, I was involved into the development of new sensors, which could represent a good start point for the Hg monitoring, in both air and wet deposition. The employment of new sensors will allow measuring Hg over the whole globe, including the pristine areas, and will provide an improvement of Hg cycle’s knowledge.
Monitoring of mercury and organic pollutants in differents environmental compartments through traditional and innovative approaches
(Università della Calabria, 2020-10-20) Tassone, Antonella; Cipparrone, Gabriella; Sprovieri, Francesca; Naccarato, Attilio
Negli ultimi decenni il problema dell'inquinamento ambientale ha acquisito notevole importanza su scala globale sia per il continuo aumento dei livelli di inquinanti che per l'introduzione di nuovi contaminanti. Gli effetti tossici sulla salute umana e sugli ecosistemi rappresentano la più grande minaccia di questi inquinanti. Pertanto, negli ultimi anni la comunità scientifica si è impegnata nel monitoraggio questi inquinanti in tutti i settori ambientali, come aria, acqua, suolo e sistemi viventi con lo scopo di garantire un controllo rigoroso della loro presenza nell'ambiente e successivamente regolamentarli. Infatti, le diverse proprietà fisico-chimiche delle varie sostanze fanno sì che siano distribuiti nei vari comparti secondo un preciso ciclo biogeochimico. È per questo motivo che studi di monitoraggio adatti a ciascun comparto ambientale sono necessari. Nella maggior parte dei casi, i metodi analitici impiegati si basano su tecniche obsolete, che non trovano impiego per via dell’uso di sostante nocive o di un grande dispendio di tempo e risorse. In questo contesto, esiste una domanda crescente di metodi analitici innovativi, rapidi, eco-compatibili, a basso costo, semplici da impiegare. Il lavoro di ricerca presentato in questa tesi riguarda il monitoraggio del mercurio e di alcuni inquinanti organici emergenti, quali esteri organofosfati, benzotriazoli, benzotiazoli e benzosulfonammidi, mediante l’impiego di approcci analitici sia tradizionali che innovativi. Lo studio condotto durante il corso del dottorato ha riguardato l’indagine di diversi settori ambientali, come l’ambiente atmosferico di vari siti, interessati da fonti di inquinamento antropiche oltre che naturali. Inoltre, oggetto d’indagine sono stati anche l'ambiente acquatico del Mar Mediterraneo e il biota campionato in terreni agricoli di San Giovanni in Fiore (CS). Inoltre, lo studio del particolato atmosferico è stato condotto attraverso lo sviluppo di nuovi metodi analitici eco-compatibili per la determinazione di esteri organofosfati, benzotriazoli, benzotiazoli e benzosulfonammidi mediante estrazione mediata da microonde seguita da microestrazione in fase solida e quantificazione mediante gascromatografia-spettrometria di massa tandem. In the last decades, the issue of environmental pollution has acquired considerable importance at a global scale due to both the continuous increase in pollutant levels and the introduction of new contaminants. The toxic effects on human health and other ecosystems represent the greatest threat posed by these pollutants. Therefore, with the aim to ensure a strict control of their presence in the environment and subsequently regulate them, in recent years the scientific community has engaged in monitoring these pollutants in all environmental sectors, such as air, water, soil and living systems. Indeed, the different physico-chemical properties of the various substances ensure that they are distributed in the various compartments according to their own biogeochemical cycle. It is for this reason that monitoring studies suitable for each sector are necessary. In most cases, the analytical methods traditionally used are obsolete, relying on techniques that are no longer used. In this context, there is a growing demand for innovative analytical methods, which are fast, environmentally friendly, low cost, simple to use. Among the major ambient pollutants, the research work presented in this thesis is addressed to the monitoring of mercury and some emerging organic pollutants, i.e. organophosphate esters, benzotriazoles, benzothiazoles, and benzenesulfonamides, exploiting both traditional and innovative approaches. The investigation concerned the atmospheric environment of various sites affected by anthropic as well as natural emission sources, the aquatic environment of the Mediterranean Sea and the biota specimen collected in croplands from San Giovanni in Fiore (CS). Furthermore, the airborne particulate matter was monitored as an environmental matrix with the aim to detect organic pollutants through the use of new eco-friendly analytical methods.
Sviluppo di modelli integrati per la qualità dell'aria
(2008-11-25) Algieri, Andrea; Pirrone, Nicola; Sprovieri, Francesca; de Cindio, Bruno