CIRCULATION AND SUSPENDED PARTICULATE MATTER TRANSPORT IN A TIDALLY DOMINATED ESTUARY: CARAVELAS ESTUARY, BAHIA, BRAZIL

The circulation and transport of suspended particulate matter in the Caravelas Estuary are assessed. Nearly-synoptic hourly hydrographic, current (ADCP velocity and volume transport) and suspended particulate matter data were collected during a full semidiurnal spring tide, on the two transects Boca do Tomba and Barra Velha and on longitudinal sections at low and high tide. On the first transect the peak ebb currents (-1.5 ms(-1)) were almost twice as strong as those of the wider and shallow Barra Velha inlet (-0.80 ms(-1)) and the peak flood currents were 0.75 and 0.60 ms(-1), respectively. Due to the strong tidal currents both inlets had weak vertical salinity stratification and were classified with the Stratification-circulation Diagram as Type 2a (partially mixed-weakly stratified) and Type 1a (well mixed). Volume transports were very close, ranging from -3,500 to 3,100 m(3)s(-1) at the ebb and flood, respectively, with a residual -630 m(3)s(-1). The concentration of the suspended particulate matter was closely related to the tidal variation and decreased landwards from 50 mg. L(-1) at the estuary mouth, to 10 mg.L(-1) at distances of 9 and 16 km for the low and high tide experiments, respectively. The total residual SPM transport was out of the estuary at rates of -18 tons per tidal cycle.

The impact of atmospheric particulate matter on cancer incidence and mortality in the city of Sao Paulo, Brazil

This study aimed to verify the impact of inhalable particulate matter (PM10) on cancer incidence and mortality in the city of Sao Paulo, Brazil. Statistical techniques were used to investigate the relationship between PM10 on cancer incidence and mortality in selected districts. For some types of cancer (skin, lung, thyroid, larynx, and bladder) and some periods, the correlation coefficients ranged from 0.60 to 0.80 for incidence. Lung cancer mortality showed more correlations during the overall period. Spatial analysis showed that districts distant from the city center showed higher than expected relative risk, depending on the type of cancer According to the study, urban PM10 can contribute to increased incidence of some cancers and may also contribute to increased cancer mortality. The results highlight the need to adopt measures to reduce atmospheric PM10 levels and the importance of their continuous monitoring.

Endothelial dysfunction in the pulmonary artery induced by concentrated fine particulate matter exposure is associated with local but not systemic inflammation

Clinical evidence has identified the pulmonary circulation as an important target of air pollution. It was previously demonstrated that in vitro exposure to fine particulate matter (aerodynamic diameter <= 2.5 mu m, PM2.5) induces endothelial dysfunction in isolated pulmonary arteries. We aimed to investigate the effects of in vivo exposure to urban concentrated PM2.5 on rat pulmonary artery reactivity and the mechanisms involved. For this, adult Wistar rats were exposed to 2 weeks of concentrated Sao Paulo city air PM2.5 at an accumulated daily dose of approximately 600 mu g/m(3). Pulmonary arteries isolated from PM2.5-exposed animals exhibited impaired endothelium-dependent relaxation to acetylcholine without significant changes in nitric oxide donor response compared to control rats. PM2.5 caused vascular oxidative stress and enhanced protein expression of Cu/Zn- and Mn-superoxide dismutase in the pulmonary artery. Protein expression of endothelial nitric oxide synthase (eNOS) was reduced, while tumor necrosis factor (TNF)-alpha was enhanced by PM2.5 inhalation in pulmonary artery. There was a significant positive correlation between eNOS expression and maximal relaxation response (E-max) to acetylcholine. A negative correlation was found between vascular TNF-alpha expression and E-max to acetylcholine. Plasma cytokine levels, blood cells count and coagulation parameters were similar between control and PM2.5-exposed rats. The present findings showed that in vivo daily exposure to concentrated urban PM2.5 could decrease endothelium-dependent relaxation and eNOS expression on pulmonary arteries associated with local high TNF-alpha level but not systemic pro-inflammatory factors. Taken together, the present results elucidate the mechanisms underlying the trigger of cardiopulmonary diseases induced by urban ambient levels of PM2.5. (C) 2012 Elsevier Ireland Ltd. All rights reserved.

Burnt sugarcane harvesting: Particulate matter exposure and the effects on lung function, oxidative stress, and urinary 1-hydroxypyrene

Non-mechanised sugarcane harvesting preceded by burning exposes workers and the people of neighbouring towns to high concentrations of pollutants. This study was aimed to evaluate the respiratory symptoms, lung function and oxidative stress markers in sugarcane workers and the residents of Mendonca, an agricultural town in Brazil, during the non-harvesting and harvesting periods and to assess the population and individual exposures to fine particulate matter (PM2.5). Sugarcane workers and healthy volunteers were evaluated with two respiratory symptom questionnaires, spirometry, urinary 1-hydroxypyrene levels, and the measurement of antioxidant enzymes and plasma malonaldehyde during the non-harvesting and harvesting periods. The environmental assessment was determined from PM2.5 concentration. PM2.5 level increased from 8 mu g/m(3) during the non-harvesting period to 23.5 mu g/m(3) in the town and 61 mu g/m(3) on the plantations during the harvesting period. Wheezing, coughing, sneezing, and breathlessness increased significantly in both groups during the harvesting period, but more markedly in workers. A decrease in lung function and antioxidant enzyme activity was observed in both populations during harvesting; this decrease was greater among the sugarcane workers. The urinary 1-hydroxypyrene levels only increased in the sugarcane workers during the harvesting period. The malonaldehyde levels were elevated in both groups, with a higher increase observed in the workers. This research demonstrates the exposure of sugarcane workers and the inhabitants of a neighbouring town to high PM2.5 concentrations during the sugarcane harvest period. This exposure was higher among the sugarcane workers, as illustrated by both higher PM2.5 concentrations in the sugarcane fields and higher urinary 1-hydroxypyrene levels in the volunteers in this group. The higher incidence of respiratory symptoms, greater decrease in lung function and more marked elevation of oxidative stress markers among the sugarcane workers during the harvest confirms the greater effect magnitude in this population and a dose-dependent relationship between pollution and the observed effects. (C) 2012 Elsevier B.V. All rights reserved.

Association between particulate matter air pollution and monthly inhalation and nebulization procedures in Ribeirao Preto, Sao Paulo State, Brazil

The study was designed to investigate the impact of air pollution on monthly inhalation/nebulization procedures in Ribeirao Preto, Sao Paulo State, Brazil, from 2004 to 2010. To assess the relationship between the procedures and particulate matter (PM10) a Bayesian Poisson regression model was used, including a random factor that captured extra-Poisson variability between counts. Particulate matter was associated with the monthly number of inhalation/nebulization procedures, but the inclusion of covariates (temperature, precipitation, and season of the year) suggests a possible confounding effect. Although other studies have linked particulate matter to an increasing number of visits due to respiratory morbidity, the results of this study suggest that such associations should be interpreted with caution.

Association between particulate matter air pollution and monthly inhalation and nebulization procedures in Ribeirão Preto, São Paulo State, Brazil

The study was designed to investigate the impact of air pollution on monthly inhalation/nebulization procedures in Ribeirão Preto, São Paulo State, Brazil, from 2004 to 2010. To assess the relationship between the procedures and particulate matter (PM10) a Bayesian Poisson regression model was used, including a random factor that captured extra-Poisson variability between counts. Particulate matter was associated with the monthly number of inhalation/nebulization procedures, but the inclusion of covariates (temperature, precipitation, and season of the year) suggests a possible confounding effect. Although other studies have linked particulate matter to an increasing number of visits due to respiratory morbidity, the results of this study suggest that such associations should be interpreted with caution.

The impact of atmospheric particulate matter on cancer incidence and mortality in the city of São Paulo, Brazil

This study aimed to verify the impact of inhalable particulate matter (PM10) on cancer incidence and mortality in the city of São Paulo, Brazil. Statistical techniques were used to investigate the relationship between PM10 on cancer incidence and mortality in selected districts. For some types of cancer (skin, lung, thyroid, larynx, and bladder) and some periods, the correlation coefficients ranged from 0.60 to 0.80 for incidence. Lung cancer mortality showed more correlations during the overall period. Spatial analysis showed that districts distant from the city center showed higher than expected relative risk, depending on the type of cancer. According to the study, urban PM10 can contribute to increased incidence of some cancers and may also contribute to increased cancer mortality. The results highlight the need to adopt measures to reduce atmospheric PM10 levels and the importance of their continuous monitoring.

Water-soluble organic compounds in air particulate matter analyzed by HPLC-DAD-MS and HPLC-MS/MS: abundance, sources and transformation of carboxylic acids, nitrophenols and nitrated proteins

Wasserlösliche organische Verbindungen (WSOCs) sind Hauptbestandteile atmosphärischer Aerosole, die bis zu ~ 50% und mehr der organischen Aerosolfraktion ausmachen. Sie können die optischen Eigenschaften sowie die Hygroskopizität von Aerosolpartikeln und damit deren Auswirkungen auf das Klima beeinflussen. Darüber hinaus können sie zur Toxizität und Allergenität atmosphärischer Aerosole beitragen.In dieser Studie wurde Hochleistungsflüssigchromatographie gekoppelt mit optischen Diodenarraydetektion und Massenspektrometrie (HPLC-DAD-MS und HPLC-MS/MS) angewandt, um WSOCs zu analysieren, die für verschiedene Aerosolquellen und -prozesse charakteristisch sind. Niedermolekulare Carbonsäuren und Nitrophenole wurden als Indikatoren für die Verbrennung fossiler Brennstoffe und die Entstehung sowie Alterung sekundärer organischer Aerosole (SOA) aus biogenen Vorläufern untersucht. Protein-Makromoleküle wurden mit Blick auf den Einfluss von Luftverschmutzung und Nitrierungsreaktionen auf die Allergenität primärer biologischer Aerosolpartikel – wie Pollen und Pilzsporen – untersucht.rnFilterproben von Grob- und Feinstaubwurden über ein Jahr hinweg gesammelt und auf folgende WSOCs untersucht: die Pinen-Oxidationsprodukte Pinsäure, Pinonsäure und 3-Methyl-1,2,3-Butantricarbonsäure (3-MBTCA) sowie eine Vielzahl anderer Dicarbonsäuren und Nitrophenole. Saisonale Schwankungen und andere charakteristische Merkmale werden mit Blick auf Aerosolquellen und -senken im Vergleich zu Daten anderen Studien und Regionen diskutiert. Die Verhätlnisse von Adipinsäure und Phthalsäure zu Azelainsäure deuten darauf hin, dass die untersuchten Aerosolproben hauptsächlich durch biogene Quellen beeinflusst werden. Eine ausgeprägte Arrhenius-artige Korrelation wurde zwischen der 3-MBTCA-¬Konzentration und der inversen Temperatur beobachtet (R2 = 0.79, Ea = 126±10 kJ mol-1, Temperaturbereich 275–300 K). Modellrechnungen zeigen, dass die Temperaturabhängigkeit auf eine Steigerung der photochemischen Produktionsraten von 3-MBTCA durch erhöhte OH-Radikal-Konzentrationen bei erhöhten Temperaturen zurückgeführt werden kann. Im Vergleich zur chemischen Reaktionskinetik scheint der Einfluss von Gas-Partikel-Partitionierungseffekten nur eine untergeordnete Rolle zu spielen. Die Ergebnisse zeigen, dass die OH-initiierte Oxidation von Pinosäure der geschwindigkeitsbestimmende Schritt der Bildung von 3-MBTCA ist. 3-MBTCA erscheint somit als Indikator für die chemische Alterung von biogener sekundärer organischer Aerosole (SOA) durch OH-Radikale geeignet. Eine Arrhenius-artige Temperaturabhängigkeit wurde auch für Pinäure beobachtet und kann durch die Temperaturabhängigkeit der biogenen Pinen-Emissionen als geschwindigkeitsbestimmender Schritt der Pinsäure-Bildung erklärt werden (R2 = 0.60, Ea = 84±9 kJ mol-1).rn rnFür die Untersuchung von Proteinnitrierungreaktionen wurde nitrierte Protein¬standards durch Flüssigphasenreaktion von Rinderserumalbumin (BSA) und Ovalbumin (OVA) mit Tetranitromethan (TNM) synthetisiert.Proteinnitrierung erfolgt vorrangig an den Resten der aromatischen Aminosäure Tyrosin auf, und mittels UV-Vis-Photometrie wurde der Proteinnnitrierungsgrad (ND) bestimmt. Dieser ist definiert als Verhältnis der mittleren Anzahl von Nitrotyrosinresten zur Tyrosinrest-Gesamtzahl in den Proteinmolekülen. BSA und OVA zeigten verschiedene Relationen zwischen ND und TNM/Tyrosin-Verhältnis im Reaktionsgemisch, was vermutlich auf Unterschiede in den Löslichkeiten und den molekularen Strukturen der beiden Proteine zurück zu führen ist.rnDie Nitrierung von BSA und OVA durch Exposition mit einem Gasgemisch aus Stickstoffdioxid (NO2) und Ozon (O3) wurde mit einer neu entwickelten HPLC-DAD-¬Analysemethode untersucht. Diese einfache und robuste Methode erlaubt die Bestimmung des ND ohne Hydrolyse oder Verdau der untersuchten Proteine und ernöglicht somit eine effiziente Untersuchung der Kinetik von Protein¬nitrierungs-Reaktionen. Für eine detaillierte Produktstudien wurden die nitrierten Proteine enzymatisch verdaut, und die erhaltenen Oligopeptide wurden mittels HPLC-MS/MS und Datenbankabgleich mit hoher Sequenzübereinstimmung analysiert. Die Nitrierungsgrade individueller Nitrotyrosin-Reste (NDY) korrelierten gut mit dem Gesamt-Proteinnitrierungsgrad (ND), und unterschiedliche Verhältnisse von NDY zu ND geben Aufschluss über die Regioselektivität der Reaktion. Die Nitrierungmuster von BSA und OVA nach Beahndlung mit TNM deuten darauf hin, dass die Nachbarschaft eines negativ geladenen Aminosäurerestes die Tyrosinnitrierung fördert. Die Behandlung von BSA durch NO2 und O3 führte zu anderend Nitrierungemustern als die Behandlung mit TNM, was darauf hindeutet, dass die Regioselektivität der Nitrierung vom Nitrierungsmittel abhängt. Es zeigt sich jedoch, dass Tyrosinreste in Loop-Strukturen bevorzugt und unabhängig vom Reagens nitriert werden.Die Methoden und Ergebnisse dieser Studie bilden eine Grundlage für weitere, detaillierte Untersuchungen der Reaktionskinetik sowie der Produkte und Mechanismen von Proteinnitrierungreaktionen. Sie sollen helfen, die Zusammenhänge zwischen verkehrsbedingten Luftschadstoffen wie Stickoxiden und Ozon und der Allergenität von Luftstaub aufzuklären.rn

Aircraft-based in-situ aerosol mass spectrometry: Chemical characterization and source identification of submicron particulate matter in the free and upper troposphere and lower stratosphere

The composition of the atmosphere is frequently perturbed by the emission of gaseous and particulate matter from natural as well as anthropogenic sources. While the impact of trace gases on the radiative forcing of the climate is relatively well understood the role of aerosol is far more uncertain. Therefore, the study of the vertical distribution of particulate matter in the atmosphere and its chemical composition contribute valuable information to bridge this gap of knowledge. The chemical composition of aerosol reveals information on properties such as radiative behavior and hygroscopicity and therefore cloud condensation or ice nucleus potential. rnThis thesis focuses on aerosol pollution plumes observed in 2008 during the POLARCAT (Polar Study using Aircraft, Remote Sensing, Surface Measurements and Models, of Climate, Chemistry, Aerosols, and Transport) campaign over Greenland in June/July and CONCERT (Contrail and Cirrus Experiment) campaign over Central and Western Europe in October/November. Measurements were performed with an Aerodyne compact time-of-flight aerosol mass spectrometer (AMS) capable of online size-resolved chemical characterization of non-refractory submicron particles. In addition, the origins of pollution plumes were determined by means of modeling tools. The characterized pollution episodes originated from a large variety of sources and were encountered at distinct altitudes. They included pure natural emissions from two volcanic eruptions in 2008. By the time of detection over Western Europe between 10 and 12 km altitude the plume was about 3 months old and composed to 71 % of particulate sulfate and 21 % of carbonaceous compounds. Also, biomass burning (BB) plumes were observed over Greenland between 4 and 7 km altitude (free troposphere) originating from Canada and East Siberia. The long-range transport took roughly one and two weeks, respectively. The aerosol was composed of 78 % organic matter and 22 % particulate sulfate. Some Canadian and all Siberian BB plumes were mixed with anthropogenic emissions from fossil fuel combustion (FF) in North America and East Asia. It was found that the contribution of particulate sulfate increased with growing influences from anthropogenic activity and Asia reaching up to 37 % after more than two weeks of transport time. The most exclusively anthropogenic emission source probed in the upper troposphere was engine exhaust from commercial aircraft liners over Germany. However, in-situ characterization of this aerosol type during aircraft chasing was not possible. All long-range transport aerosol was found to have an O:C ratio close to or greater than 1 implying that low-volatility oxygenated organic aerosol was present in each case despite the variety of origins and the large range in age from 3 to 100 days. This leads to the conclusion that organic particulate matter reaches a final and uniform state of oxygenation after at least 3 days in the free troposphere. rnExcept for aircraft exhaust all emission sources mentioned above are surface-bound and thus rely on different types of vertical transport mechanisms, such as direct high altitude injection in the case of a volcanic eruption, or severe BB, or uplift by convection, to reach higher altitudes where particles can travel long distances before removal mainly caused by cloud scavenging. A lifetime for North American mixed BB and FF aerosol of 7 to 11 days was derived. This in consequence means that emission from surface point sources, e.g. volcanoes, or regions, e.g. East Asia, do not only have a relevant impact on the immediate surroundings but rather on a hemispheric scale including such climate sensitive zones as the tropopause or the Arctic.

Characterisation and calibration of optical counters for airborne particulate matter

Gli aerosol, sospensione colloidale in aria di particelle solide o liquide, sono parte integrante dell’atmosfera. Essi interagiscono con la radiazione solare influenzando il clima (effetto primario e secondario) e la visibilità atmosferica. Gli aerosol hanno effetti sulla salute umana con patologie degli apparati cardiovascolare e circolatorio. La presente tesi affronta alcuni aspetti critici dei contatori ottici di particelle (OPC), utilizzati per caratterizzare l’aerosol ambientale. Gli OPC si basano sullo scattering luminoso per fornire la concentrazione in numero e la distribuzione dimensionale degli aerosol in tempo reale. Gli obiettivi di questa tesi sono: 1)caratterizzare e migliorare le prestazioni di un OPC di nuova concezione (CompactOPC N1, Alphasense; in seguito COPC) rispetto a un OPC standard commerciale (Grimm 1.108; in seguito GRM); 2)realizzare un banco di prova per la calibrazione di un OPC utilizzato in camere bianche e ambienti sanitari (Laser Particle Sensor 3715-00, Kanomax; in seguito LPS). Per questa attività ha mostrato interesse un’azienda locale (Pollution Clean Air Systems S.p.A.; Budrio, BO). Le prove sperimentali sono state effettuate con aerosol indoor e con particelle monodisperse di latex polistirene (PSL) di dimensioni differenti campionando in parallelo con i diversi OPC e su filtro per osservazioni al microscopio elettronico a scansione (SEM). In questo modo si è ottenuto un valore assoluto di riferimento per la concentrazione di aerosol. I risultati ottenuti indicano un buon accordo tra le concentrazioni di particelle fornite dal GRM e quelle ottenute al SEM. Il lavoro ha inoltre permesso di migliorare le prestazioni del COPC modificando la versione di base. Inoltre, è stata effettuata la calibrazione del LPS tramite il banco di prova realizzato nella tesi. Il lavoro sperimentale è stato svolto presso il Laboratorio di Aerosol e Fisica delle Nubi dell’Istituto di Scienze dell’Atmosfera e del Clima (ISAC) del Consiglio Nazionale delle Ricerche (CNR) a Bologna.

Fine particulate matter measurements in Swiss restaurants, cafés and bars: what is the effect of spatial separation between smoking and non-smoking areas?

We performed 124 measurements of particulate matter (PM(2.5)) in 95 hospitality venues such as restaurants, bars, cafés, and a disco, which had differing smoking regulations. We evaluated the impact of spatial separation between smoking and non-smoking areas on mean PM(2.5) concentration, taking relevant characteristics of the venue, such as the type of ventilation or the presence of additional PM(2.5) sources, into account. We differentiated five smoking environments: (i) completely smoke-free location, (ii) non-smoking room spatially separated from a smoking room, (iii) non-smoking area with a smoking area located in the same room, (iv) smoking area with a non-smoking area located in the same room, and (v) smoking location which could be either a room where smoking was allowed that was spatially separated from non-smoking room or a hospitality venue without smoking restriction. In these five groups, the geometric mean PM(2.5) levels were (i) 20.4, (ii) 43.9, (iii) 71.9, (iv) 110.4, and (v) 110.3 microg/m(3), respectively. This study showed that even if non-smoking and smoking areas were spatially separated into two rooms, geometric mean PM(2.5) levels in non-smoking rooms were considerably higher than in completely smoke-free hospitality venues. PRACTICAL IMPLICATIONS: PM(2.5) levels are considerably increased in the non-smoking area if smoking is allowed anywhere in the same location. Even locating the smoking area in another room resulted in a more than doubling of the PM(2.5) levels in the non-smoking room compared with venues where smoking was not allowed at all. In practice, spatial separation of rooms where smoking is allowed does not prevent exposure to environmental tobacco smoke in nearby non-smoking areas.

Reduction of Transient Particulate Matter Spikes with Decision Tree Based Control

Decision trees have been proposed as a basis for modifying table based injection to reduce transient particulate spikes during the turbocharger lag period. It has been shown that decision trees can detect particulate spikes in real time. In well calibrated electronically controlled diesel engines these spikes are narrow and are encompassed by a wider NOx spike. Decision trees have been shown to pinpoint the exact location of measured opacity spikes in real time thus enabling targeted PM reduction with near zero NOx penalty. A calibrated dimensional model has been used to demonstrate the possible reduction of particulate matter with targeted injection pressure pulses. Post injection strategy optimized for near stoichiometric combustion has been shown to provide additional benefits. Empirical models have been used to calculate emission tradeoffs over the entire FTP cycle. An empirical model based transient calibration has been used to demonstrate that such targeted transient modifiers are more beneficial at lower engine-out NOx levels.

Fossil versus contemporary sources of fine elemental and organic carbonaceous particulate matter during the DAURE campaign in Northeast Spain

We present results from the international field campaign DAURE (Detn. of the sources of atm. Aerosols in Urban and Rural Environments in the Western Mediterranean), with the objective of apportioning the sources of fine carbonaceous aerosols. Submicron fine particulate matter (PM1) samples were collected during Feb.-March 2009 and July 2009 at an urban background site in Barcelona (BCN) and at a forested regional background site in Montseny (MSY). We present radiocarbon (14C) anal. for elemental and org. carbon (EC and OC) and source apportionment for these data. We combine the results with those from component anal. of aerosol mass spectrometer (AMS) measurements, and compare to levoglucosan-based ests. of biomass burning OC, source apportionment of filter data with inorg. compn. + EC + OC, submicron bulk potassium (K) concns., and gaseous acetonitrile concns. At BCN, 87 % and 91 % of the EC on av., in winter and summer, resp., had a fossil origin, whereas at MSY these fractions were 66 % and 79 %. The contribution of fossil sources to org. carbon (OC) at BCN was 40 % and 48 %, in winter and summer, resp., and 31 % and 25 % at MSY. The combination of results obtained using the 14C technique, AMS data, and the correlations between fossil OC and fossil EC imply that the fossil OC at Barcelona is ∼47 % primary whereas at MSY the fossil OC is mainly secondary (∼85 %). Day-to-day variation in total carbonaceous aerosol loading and the relative contributions of different sources predominantly depended on the meteorol. transport conditions. The estd. biogenic secondary OC at MSY only increased by ∼40 % compared to the order-of-magnitude increase obsd. for biogenic volatile org. compds. (VOCs) between winter and summer, which highlights the uncertainties in the estn. of that component. Biomass burning contributions estd. using the 14C technique ranged from similar to slightly higher than when estd. using other techniques, and the different estns. were highly or moderately correlated. Differences can be explained by the contribution of secondary org. matter (not included in the primary biomass burning source ests.), and/or by an over-estn. of the biomass burning OC contribution by the 14C technique if the estd. biomass burning EC/OC ratio used for the calcns. is too high for this region. Acetonitrile concns. correlate well with the biomass burning EC detd. by 14C. K is a noisy tracer for biomass burning. [on SciFinder(R)]