Historical Changes in Seasonal Aerosol Acidity in the Po Valley (Italy) as Inferred from Fog Water and Aerosol Measurements.

Acidity profoundly affects almost every aspect that shapes the composition of ambient particles and their environmental impact. Thermodynamic analysis of gas-particle composition datasets offers robust estimates of acidity, but they are not available for long periods of time. Fog composition datasets, however, are available for many decades; we develop a thermodynamic analysis to estimate the ammonia in equilibrium with fog water and to infer the pre-fog aerosol pH starting from fog chemical composition and pH. The acidity values from the new method agree with the results of thermodynamic analysis of the available gas-particle composition data. Applying the new method to historical (25 years) fog water composition at the rural station of San Pietro Capofiume (SPC) in the Po Valley (Italy) suggests that the aerosol has been mildly acidic, with its pH decreasing by 0.5-1.5 pH units over the last decades. The observed pH of the fog water also increased 1 unit over the same period. Analysis of the simulated aerosol pH reveals that the aerosol acidity trend is driven by a decrease in aerosol precursor concentrations, and changes in temperature and relative humidity. Currently, NOx controls would be most effective for PM2.5 reduction in the Po valley both during summer and winter. In the future, however, seasonal transitions to the NH3-sensitive region may occur, meaning that the NH3 reduction policy may become increasingly necessary.

Extensive Soot Compaction by Cloud Processing from Laboratory and Field Observations.

Soot particles form during combustion of carbonaceous materials and impact climate and air quality. When freshly emitted, they are typically fractal-like aggregates. After atmospheric aging, they can act as cloud condensation nuclei, and water condensation or evaporation restructure them to more compact aggregates, affecting their optical, aerodynamic, and surface properties. Here we survey the morphology of ambient soot particles from various locations and different environmental and aging conditions. We used electron microscopy and show extensive soot compaction after cloud processing. We further performed laboratory experiments to simulate atmospheric cloud processing under controlled conditions. We find that soot particles sampled after evaporating the cloud droplets, are significantly more compact than freshly emitted and interstitial soot, confirming that cloud processing, not just exposure to high humidity, compacts soot. Our findings have implications for how the radiative, surface, and aerodynamic properties, and the fate of soot particles are represented in numerical models.

Indoor air pollution exposure effects on lung and cardiovascular health in the High Himalayas, Nepal: An observational study.

BACKGROUND: Exposure to indoor biomass fuel smoke is associated with increased morbidity and mortality. The aim of this study is to evaluate the association between exposure to indoor biomass burning and early pulmonary and cardiovascular damage. METHODS: The indoor levels of particulate matter (PM) [PM10, PM2.5] and black carbon (BC) were monitored in 32 houses in a Himalayan village. Seventy-eight subjects were submitted to spirometry and cardiovascular evaluation [carotid to femoral pulse wave velocity (PWV) and echocardiography]. RESULTS: Peak indoor BC concentration up to 100 µg m-3 and PM10 - PM2.5 up to 1945-592 µg m-3 were measured. We found a non-reversible bronchial obstruction in 18% of subjects ≥40 yr; mean forced expiratory flow between 25% and 75% of the forced vital capacity (FEF25-75) <80% in 54% of subjects, suggestive of early respiratory impairment, significantly and inversely related to age. Average BC was correlated with right ventricular-right atrium gradient (R = 0.449,p = .002), total peripheral resistances (TPR) (R = 0.313,p = .029) and PWV (R = 0.589,p < .0001) especially in subjects >30 yr. In multiple variable analysis, BC remained an independent predictor of PWV (ß = 0.556,p = .001), and TPR (ß = 0.366;p = .018). CONCLUSIONS: Indoor pollution exposure is associated to early pulmonary and cardiovascular damages, more evident for longer duration and higher intensity exposure.

Direct observation of aqueous secondary organic aerosol from biomass-burning emissions.

The mechanisms leading to the formation of secondary organic aerosol (SOA) are an important subject of ongoing research for both air quality and climate. Recent laboratory experiments suggest that reactions taking place in the atmospheric liquid phase represent a potentially significant source of SOA mass. Here, we report direct ambient observations of SOA mass formation from processing of biomass-burning emissions in the aqueous phase. Aqueous SOA (aqSOA) formation is observed both in fog water and in wet aerosol. The aqSOA from biomass burning contributes to the "brown" carbon (BrC) budget and exhibits light absorption wavelength dependence close to the upper bound of the values observed in laboratory experiments for fresh and processed biomass-burning emissions. We estimate that the aqSOA from residential wood combustion can account for up to 0.1-0.5 Tg of organic aerosol (OA) per y in Europe, equivalent to 4-20% of the total OA emissions. Our findings highlight the importance of aqSOA from anthropogenic emissions on air quality and climate.

On the water-soluble organic nitrogen concentration and mass size distribution during the fog season in the Po Valley, Italy.

The study of organic nitrogen gained importance in recent decades due to its links with acid rain, pollution, and eutrophication. In this study, aerosol and fog water samples collected from two sites in Italy during November 2011 were analyzed to characterize their organic nitrogen content. Organic nitrogen contributed 19-25% of the total soluble nitrogen in the aerosol and around 13% in fog water. The largest water soluble organic nitrogen concentrations in the PM1.2 fraction occurred during the diurnal period with mean values of 2.03 and 2.16 µg-N m(-3) (154 and 145 nmol-N m(-3)) at Bologna and San Pietro Capofiume (SPC), respectively. The mean PM10 WSON concentration during diurnal periods at SPC was 2.30 µg-N m(-3) (164 nmol-N m(-3)) while it was 1.34 and 0.82 µg-N m(-3) (95.7 and 58.5 nmol-N m(-3)) in the night and fog water samples, respectively. Aerosol mass distribution profiles obtained during fog changed significantly with respect to those estimated in periods without fog periods due to fog scavenging, which proved to be over 80% efficient. Linear correlations suggested secondary processes related to combustion and, to a lesser extent, biomass burning, as plausible sources of WSON. Regarding the inorganic nitrogen fraction, the results showed that ammonium was the largest soluble inorganic nitrogen component in the samples.

Polycyclic aromatic hydrocarbons in the atmosphere: monitoring, sources, sinks and fate. II: Sinks and fate.

This paper reviews the transformation processes that polycyclic aromatic hydrocarbons (PAHs) undergo in the atmosphere. These processes can take place both in the gas phase and in the particulate/aerosol one. Among the gas-phase processes, the most important ones are the daytime reaction with *OH and the nighttime reaction with *NO3. The relative importance of the two processes depends on the particular PAH molecule. For instance, gaseous naphthalene is mainly removed from the atmosphere upon reaction with *OH, while gaseous phenanthrene is mainly removed by reaction with *NO3. Oxy-, hydroxy-, and nitro-PAHs are the main transformation intermediates. Reaction with ozone and photolysis play a secondary role in the transformation of gaseous PAHs. The particle-associated processes are usually slower than the gas-phase ones, thus the gas-phase PAHs usually have shorter atmospheric lifetimes than those found on particulate. Due to the higher residence time on particulate when compared with the gas phase, direct or assisted photolysis plays a relevant role in the transformation of particle-associated PAHs. Among the other processes taking place in the condensed phase, nitration plays a very important role due to the health impact of nitro-PAHs, some of them being the most powerful mutagens found so far in atmospheric particulate extracts.

Polycyclic aromatic hydrocarbons in the atmosphere: monitoring, sources, sinks and fate. I: Monitoring and sources.

This is the first of a series of two papers intended to review the state-of-the-art knowledge on atmospheric PAHs, concerning their monitoring, sources and transformation processes in the atmosphere. The monitoring section briefly introduces this class of compounds, mainly focusing on the 16 PAHs indicated by the US-EPA as priority pollutants. These compounds undergo partitioning between the gas phase and particulate, which has to be considered in the choice of the sampling methodology. Furthermore, sampling artifacts may arise from further phase transfers inside the sampling device. After sampling, extraction, clean up and detection/quantification procedures will follow. They are closely related since the choice of the extraction technique will heavily condition the clean-up step, and both procedures will place demands on the performance of the detection technique (usually GC-MS or HPLC). This is particularly true in the case of complex samples such as those arising from atmospheric sampling. The sources of atmospheric PAHs are then discussed with a particular focus on receptor models, which can allow the apportionment of PAH sources based on concentration data that can be routinely obtained by pollution control networks.

Optimization of an urban particulate matter multi-element analysis method by inductively coupled plasma--atomic emission spectrometry (ICP-AES).

In the present work a method for simultaneous metals determination, in urban air particulate matter by ICP-AES has been set up. A large number of elements (18) has been analyzed, including major (Al, Fe, K, and Mg), minor (Na, Pb and Zn) and trace (As, Cd, Co, Cr, Cu, Hg, Mn, Ni, Sb, Sr and V) elements. The procedure consists of microwave sample acidic total digestion by HNO3/HF mixture and subsequent analysis by ICP-AES, using different assemblies depending on sample treatment procedure: a quartz Meinhard nebulizer/cyclonic chamber, if HF excess was eliminated, or a cross-flow nebulizer/plastic Scott chamber, suitable for application with HF. A cyclonic chamber for hydride generation was used for As, Sb and Hg determination. The procedure was tested with Standard Reference Materials 1648 NIST Urban Particulate Matter and Certified Reference Material No8 NIES "Vehicle Exhaust Particulates". Two sampling supports, quartz fibre and polycarbonate filters, have been examined in order to find the most suitable i.e. the one characterized by less interference. Some real samples of urban air particulate matter, TSP, PM10 and PM2.5 fractions, collected during an intercomparison campaign promoted by Regione Lombardia, have been analyzed with the procedure developed.

Measurement of the carbonaceous component in the Milan urban particulate matter.

The carbonaceous component in the Milan urban particulate matter, i.e. the two components black carbon (BC) and organic carbon (OC), has been measured by means of a thermogravimetric analyzer combined with an infrared spectrophotometer (TGA/FT-IR). While black carbon may be considered a primary pollutant, organic carbon includes both primary emissions and secondary organic aerosols. Since carbonaceous aerosol (including a small quantity of inorganic carbon, too) makes up roughly from 25% to 50% of the average annual PM 2.5 mass concentration, a deeper understanding of this component is required. The TGA/FT-IR technique, employed for the first time to our knowledge for the quantification of the particulate matter carbonaceous component, allows, thought the results here presented are preliminary, to assess the two components BC and OC in a simple way especially if compared with the methods reported in the literature. The total carbon (TC) determinations performed by TGA/FT-IR on Milan urban particulate matter are in good agreement with the results obtained by a total organic carbon (TOC) analyzer operating directly on the solid sample.