M. Rinaldi

Primary submicron marine aerosol dominated by insoluble organic colloids and aggregates

The chemical properties of sea-spray aerosol particles produced by artificially generated bubbles using oceanic waters were investigated during a phytoplankton bloom in the North Atlantic. Spray pa ...

Primary and Secondary Organic Marine Aerosol and Oceanic Biological Activity: Recent Results and New Perspectives for Future Studies

One of the most important natural aerosol systems at the global level is marine aerosol that comprises both organic and inorganic components of primary and secondary origin. The present paper reviews some new results on primary and secondary organic marine aerosol, achieved during the EU project MAP (Marine Aerosol Production), comparing them with those reported in the recent literature. Marine aerosol samples collected at the coastal site of Mace Head, Ireland, show a chemical composition trend that is influenced by the oceanic biological activity cycle, in agreement with other observations. Laboratory experiments show that sea-spray aerosol from biologically active sea water can be highly enriched in organics, and the authors highlight the need for further studies on the atmospheric fate of such primary organics. With regard to the secondary fraction of organic aerosol, the average chemical composition and molecular tracer (methanesulfonic-acid, amines) distribution could be successfully characterized by adopting a multitechnique analytical approach.

Primary and secondary marine organic aerosols over the North Atlantic Ocean during the MAP experiment

[1] The organic chemical composition of atmospheric submicron particles in the marine boundary layer was characterized over the northeast Atlantic Ocean in summer 2006, during the season of phytoplankton blooms, in the frame of the Marine Aerosol Production (MAP) experiment. First measurements of water‐insoluble organic carbon (WIOC) in marine aerosol particles by nuclear magnetic resonance (NMR) spectroscopy showed that it is structurally similar to lipids, resembling the organic fraction of sea spray formed during bubble‐bursting experiments. The composition of the water‐soluble organic carbon (WSOC) fraction was investigated by liquid chromatography – mass spectrometry and by 1D‐ and 2D‐NMR spectroscopy, and showed a less hydrophilic fraction containing traces of fatty acids and rich of alkanoic acids formed by lipid degradation, and a more hydrophilic fraction, containing more functionalized species encompassing short‐chain aliphatic acids and sulfate esters of hydroxyl‐carboxylic acids. The more oxidized fraction of WSOC accounts for the oxidized organic aerosol components, which can form by either gas‐to‐particle conversion or extensive chemical aging of lipid‐containing primary particles, as also suggested by the parallel measurements using online mass spectrometric techniques (presented in a companion paper), showing oxidized organic substances internally mixed with sea salt particles. These measurements are also compared with online measurements using an Aerosol Time‐Of‐Flight Mass Spectrometer (ATOFMS) and Aerodyne Aerosol Mass Spectrometer (AMS). Given the large variability in the chemical composition of marine organic aerosol particles, a multitechnique approach is recommended to reduce method‐dependent categorizations and oversimplifications and to improve the comparability with the results obtained in different oceanic areas.

Global Modeling of the Oceanic Source of Organic Aerosols

The global marine organic aerosol budget is investigated by a 3-dimensional chemistry-transport model considering recently proposed parameterisations of the primary marine organic aerosol (POA) and secondary organic aerosol (SOA) formation from the oxidation of marine volatile organic compounds. MODIS and SeaWiFS satellite data of Chlorophyll-a and ECMWF solar incoming radiation, wind speed, and temperature are driving the oceanic emissions in the model. Based on the adopted parameterisations, the SOA and the submicron POA marine sources are evaluated at about 5 Tg (1.5 Tg C ) and 7 to 8 Tg (4 Tg C ), respectively. The computed marine SOA originates from the dimethylsulfide oxidation (78%), the potentially formed dialkyl amine salts (21%), and marine hydrocarbon oxidation (0.1%). Comparison of calculations with observations indicates an additional marine source of soluble organic carbon that could be partially encountered by marine POA chemical ageing.

Ocean–Atmosphere Interactions of Particles

This chapter provides an overview of the current knowledge on aerosols in the marine atmosphere and the effects of aerosols on climate and on processes in the oceanic surface layer. Aerosol particles in the marine atmosphere originate predominantly from direct production at the sea surface due to the interaction between wind and waves (sea spray aerosol, or SSA) and indirect production by gas to particle conversion. These aerosols are supplemented by aerosols produced over the continents, as well as aerosols emitted by volcanoes and ship traffic, a large part of it being deposited to the ocean surface by dry and wet deposition. The SSA sources, chemical composition and ensuing physical and optical effects, are discussed. An overview is presented of continental sources and their ageing and mixing processes during transport. The current status of our knowledge on effects of marine aerosols on the Earth radiative balance, both direct by their interaction with solar radiation and indirect through their effects on cloud properties, is discussed. The deposition on the ocean surface of some key species, such as nutrients, their bioavailability and how they impact biogeochemical cycles are shown and discussed through different time and space scales approaches.

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.

Preliminary Results Of The Project “Supersito” Concerning The Atmospheric Aerosol Composition In Emilia-Romagna Region, Italy: PM Source Apportionment And Aerosol Size Distribution

The Emilia-Romagna region and its Agency for Prevention and Environment are running a project – called Supersito – the purpose of which is to gain further knowledge about the components of fine and ultrafine particles in the atmosphere. Supersito began the measurements at the end of 2011, in this paper we summarize the preliminary results observed for the aerosol size distribution and source apportionment of PM2.5 in Bologna’s urban background. Results show that nitrates, sulphates and ammonium accounts for more than 40% of the mass of PM2.5 in the cold season and for about 30% in the summer. The carbonaceous fraction (organic aerosol plus elemental carbon) is about 40% in both seasons. PMF analysis of the data coming from the results of the mass composition shows that important fractions of PM2.5 during the cold season come from

Transfer of labile organic matter and microbes from the ocean surface to the marine aerosol: an experimental approach

Surface ocean bubble-bursting generates aerosols composed of microscopic salt-water droplets, enriched in marine organic matter. The organic fraction profoundly influences aerosols’ properties, by scattering solar radiations and nucleating water particles. Still little is known on the biochemical and microbiological composition of these organic particles. In the present study, we experimentally simulated the bursting of bubbles at the seawater surface of the North-Eastern Atlantic Ocean, analysing the organic materials and the diversity of the bacteria in the source-seawaters and in the produced aerosols. We show that, compared with seawater, the sub-micron aerosol particles were highly enriched in organic matter (up to 140,000x for lipids, 120,000x for proteins and 100,000x for carbohydrates). Also DNA, viruses and prokaryotes were significantly enriched (up to 30,000, 250 and 45x, respectively). The relative importance of the organic components in the aerosol did not reflect those in the seawater, suggesting their selective transfer. Molecular analyses indicate the presence of selective transfers also for bacterial genotypes, highlighting higher contribution of less abundant seawater bacterial taxa to the marine aerosol. Overall, our results open new perspectives in the study of microbial dispersal through marine aerosol and provide new insights for a better understanding of climate-regulating processes of global relevance.

Extreme air pollution from residential solid fuel burning

Atmospheric aerosol particles (also known as particulate matter) are central to the cause of the two greatest threats to human security: air pollution (~5 million premature deaths per year) and climate change (~0.5 million per year). Addressing these threats requires an understanding of particulate matter sources responsible for both extreme air pollution immediately affecting human health and less extreme levels affecting climate over longer timescales. Here, extraordinary levels of air pollution, with submicrometre aerosol (PM1) mass concentration surpassing 300 µg m−3, were observed in a moderately sized European city and are attributed to emissions from residential solid fuel—specifically peat and wood, often promoted as ‘slow-renewable’, ‘low-carbon’ or ‘carbon-neutral’ biomass. Using sophisticated fingerprinting techniques, we find that consumption of peat and wood in up to 12% and 1% of households, respectively, contributed up to 70% of PM1. The results from this approach can better inform emissions reduction policies and help to ensure the most appropriate air pollution sources are targeted. Given the far greater abundance of solid fuels and concomitant emissions required to match the calorific benefit of liquid fuels, even modest increases in the consumption of ‘green’-marketed solid fuels will disproportionally increase the frequency of extreme pollution events.Understanding the sources of particulate matter responsible for extreme air pollution and climate change is critical for designing adequate policies to protect the wellbeing of citizens. This study shows that extraordinary levels of particulate matter with diameter smaller than 1 µm were observed in Dublin in November 2016 and January 2017 and can be attributed to emissions from residential burning of peat and wood, often promoted as ‘slow renewables’.

A Comprehensive CTM Assessment Over an Highly Polluted Area

Photochemistry, particles formation and cycling, and aerosol optical properties predicted by a deterministic modeling system have been evaluated through both in-situ and satellite measurements. The three-dimensional air quality modeling system NINFA/AODEM was implemented over the Po valley for the entire year 2012 with the aim to characterize the atmospheric conditions, in terms of meteorological parameters and chemical composition. In addition, NINFA/AODEM has been deeply evaluated by using measurements of size-segregated aerosol samples collected on hourly basis at the 3 different sampling sites representative of urban background (Bologna), rural background (San Pietro Capofiume) and remote high altitude station (Monte Cimone 2165 ma.s.l.).