Elena Barbaro

Molecular Markers of Biomass Burning in Arctic Aerosols

Biomass burning is one of the most important sources of organic matter in the atmosphere as it affects the absorption and scattering of solar radiation, creates cloud condensation nuclei and possibly influences ice and snow albedo. Here we created and validated an analytical method using HPLC/(-)-ESI-MS/MS to determine phenolic compounds (PCLCs): vanillic acid, isovanillic acid, homovanillic acid, syringic acid, syringaldehyde, ferulic acid, p-coumaric acid, and coniferyl aldehyde at trace levels in particulate matter. We analyzed eighteen high-volume air samples from Ny Ålesund (Svalbard) collected during the boreal spring and summer of 2010. Biomass burning molecules including PCLCs (<0.49 μm, mean atmospheric concentration 6 pg m(-3)), levoglucosan (0.004 to 0.682 ng m(-3)) and acrylamide (32 fg m(-3) to 166 fg m(-3)) were present in the sampled aerosols. Levoglucosan concentrations, an unambiguous cellulose combustion tracer, derived from 2010 Russian fires. PCLCs levels in the Ny Alesund atmosphere in different size fractions reflected both long-range transport linked to biomass burning and a terrigenous local source.

Amino acids in Arctic aerosols

Amino acids are significant components of atmospheric aerosols, affecting organic nitrogen input to marine ecosystems, atmospheric radiation balance, and the global water cycle. The wide range of amino acid reactivities suggest that amino acids may serve as markers of atmospheric transport and deposition of particles. Despite this potential, few measurements have been conducted in remote areas to assess amino acid concentrations and potential sources. Polar regions offer a unique opportunity to investigate atmospheric processes and to conduct source apportionment studies of such compounds. In order to better understand the importance of amino acid compounds in the global atmosphere, we determined free amino acids (FAAs) in seventeen size-segregated aerosol samples collected in a polar station in the Svalbard Islands from 19 April until 14 September 2010. We used an HPLC coupled with a tandem mass spectrometer (ESI-MS/MS) to analyze 20 amino acids and quantify compounds at fmol m −3 levels. Mean total FAA concentration was 1070 fmol m −3 where serine and glycine were the most abundant compounds in almost all samples and accounted for 45–60 % of the total amino acid relative abundance. The other eighteen compounds had average concentrations between 0.3 and 98 fmol m −3. The higher amino acid concentrations were present in the ultrafine aerosol fraction (< 0.49 μm) and accounted for the majority of the total amino acid content. Local marine sources dominate the boreal summer amino acid concentrations, with the exception of the regional input from Icelandic volcanic emissions.

Levoglucosan and phenols in Antarctic marine, coastal and plateau aerosols

Due to its isolated location, Antarctica is a natural laboratory for studying atmospheric aerosols and pollution in remote areas. Here, we determined levoglucosan and phenolic compounds (PCs) at diverse Antarctic sites: on the plateau, a coastal station and during an oceanographic cruise. Levoglucosan and PCs reached the Antarctic plateau where they were observed in accumulation mode aerosols (with median levoglucosan concentrations of 6.4 pg m(-3) and 4.1 pg m(-3), and median PC concentrations of 15.0 pg m(-3) and 7.3 pg m(-3)). Aged aerosols arrived at the coastal site through katabatic circulation with the majority of the levoglucosan mass distributed on larger particulates (24.8 pg m(-3)), while PCs were present in fine particles (34.0 pg m(-3)). The low levoglucosan/PC ratios in Antarctic aerosols suggest that biomass burning aerosols only had regional, rather than local, sources. General acid/aldehyde ratios were lower at the coastal site than on the plateau. Levoglucosan and PCs determined during the oceanographic cruise were 37.6 pg m(-3) and 58.5 pg m(-3) respectively. Unlike levoglucosan, which can only be produced by biomass burning, PCs have both biomass burning and other sources. Our comparisons of these two types of compounds across a range of Antarctic marine, coastal, and plateau sites demonstrate that local marine sources dominate Antarctic PC concentrations.

Simultaneous quantification of microcystins and nodularin in aerosol samples using high-performance liquid chromatography/negative electrospray ionization tandem mass spectrometry

RATIONALE Cyanobacteria are a small group of photosynthetic planktonic bacteria, producing a large group of strong hepatotoxins called microcystins (MCs). Many studies have been conducted to evaluate the presence of MCs and nodularin (NOD) in water or in marine organisms, but little research has been done on the atmospheric environment. Waterborne toxins can be found in the aerosol phase due to bubble-bursting processes. METHODS The aim of this study was to obtain a sensitive method for the simultaneous determination of trace concentrations of individual cyanotoxins in aerosol samples, using liquid chromatography coupled with a triple quadrupole (HPLC/MS/MS). During method development improved electrospray ionization was found in negative ion mode. In contrast with other authors, we have developed a chromatographic separation using alkaline conditions, thus achieving good resolution, improved electrospray ionization and therefore better sensitivity. RESULTS A sensitive analytical method was set up to simultaneously measure trace concentrations of cyanotoxins in aerosol samples in a single chromatographic analysis using the internal standard method. The limit of detection for all the toxins was determined to be between 1 fg/μL (MC LA and LF) and 9 fg/μL (NOD). CONCLUSIONS The method was applied to ten aerosol samples from the Venice Lagoon. In these samples, trace concentrations of MC-LA ranging between 90 fg m(-3) and 706 fg m(-3), MC-LF between n.d. and 369 fg m(-3) and MC-LW between n.d. and 262 fg m(-3). This is the first study to quantify the cyanotoxins in Venetian aerosol samples using the HPLC/(-)ESI-MS/MS.

Impact of maritime traffic on polycyclic aromatic hydrocarbons, metals and particulate matter in Venice air.

AbstractHarbours are important hubs for economic growth in both tourism and commercial activities. They are also an environmental burden being a source of atmospheric pollution often localized near cities and industrial complexes. The aim of this study is to quantify the relative contribution of maritime traffic and harbour activities to atmospheric pollutant concentration in the Venice lagoon. The impact of ship traffic was quantified on various pollutants that are not directly included in the current European legislation for shipping emission reduction: (i) gaseous and particulate PAHs; (ii) metals in PM10; and (iii) PM10 and PM2.5. All contributions were correlated with the tonnage of ships during the sampling periods and results were used to evaluate the impact of the European Directive 2005/33/EC on air quality in Venice comparing measurements taken before and after the application of the Directive (year 2010). The outcomes suggest that legislation on ship traffic, which focused on the issue of the emissions of sulphur oxides, could be an efficient method also to reduce the impact of shipping on primary particulate matter concentration; on the other hand, we did not observe a significant reduction in the contribution of ship traffic and harbour activities to particulate PAHs and metals. Graphical abstractImpact of maritime traffic on polycyclic aromatic hydrocarbons, metals and particulate matter and evaluation of the effect of an European Directive on air quality in Venice

Fragrances as new contaminants in the Venice lagoon

Fragrance Materials (FMs) are omnipresent components of household and Personal Care Products (PCPs). In spite of their widespread use, little is known about their environmental occurrence. We selected 17 among the longest-lasting and most stable fragrance ingredients that are commercially available, namely: Amberketal, Ambrofix, Amyl Salicylate, Benzyl Salicylate, Bourgeonal, Dupical, Hexyl Salicylate, Isobutavan, Lemonile, Mefranal, Myraldene, Okoumal, Oranger Crystals, Pelargene, Peonile, Tridecene-2-Nitrile, Ultravanil. A new analytical method was developed to quantify FMs in water samples and it was applied to perform the first study about the distribution of these compounds in the surface waters of the city of Venice and its lagoon. Total FMs concentrations range from about 30ngL(-1) to more than 10μgL(-1) in polluted canals during the low tide. Sewage discharges were supposed to be the main sources of the selected FMs in the environment. Salicylates, oestrogenic and allergenic compounds, were in general the most abundant and widespread components. This study reports for the first time the detection of most of the selected FMs in surface waters and represent the first step to understand their environmental fate.

Five primary sources of organic aerosols in the urban atmosphere of Belgrade (Serbia)

Biomass burning and primary biological aerosol particles (PBAPs) represent important primary sources of organic compounds in the atmosphere. These particles and compounds are able to affect climate and human health. In the present work, using HPLC-orbitrapMS, we determined the atmospheric concentrations of molecular markers such as anhydrosugars and phenolic compounds that are specific for biomass burning, as well as the concentrations of sugars, alcohol sugars and d- and l-amino acids (D-AAs and L-AAs) for studying PBAPs in Belgrade (Serbia) aerosols collected in September-December 2008. In these samples, high levels of all these biomarkers were observed in October. Relative percentages of vanillic (V), syringic compounds (S) and p-coumaric acid (PA), as well as levoglucosan/mannosan (L/M) ratios, helped us discriminate between open fire events and wood combustion for domestic heating during the winter. L-AAs and D-AAs (1% of the total) were observed in Belgrade aerosols mainly in September-October. During open fire events, mean D-AA/L-AA (D/L) ratio values of aspartic acid, threonine, phenylalanine, alanine were significantly higher than mean D/L values of samples unaffected by open fire. High levels of AAs were observed for open biomass burning events. Thanks to four different statistical approaches, we demonstrated that Belgrade aerosols are affected by five sources: a natural source, a source related to fungi spores and degraded material and three other sources linked to biomass burning: biomass combustion in open fields, the combustion of grass and agricultural waste and the combustion of biomass in stoves and industrial plants. The approach employed in this work, involving the determination of specific organic tracers and statistical analysis, proved useful to discriminate among different types of biomass burning events.

An integrated study of the chemical composition of Antarctic aerosol to investigate natural and anthropogenic sources

Environmental context Owing to its remoteness, Antarctica is an excellent natural laboratory for conducting studies on the behavior of marine aerosols and for monitoring the impact of global human activities. The aim of this study is to provide an extensive chemical characterization of Antarctic aerosol and to investigate its sources. A distinction among anthropogenic, crustal, and biogenic sources was defined using several chemical markers. Abstract During the 2010–11 austral summer, an aerosol sampling campaign was carried out at a coastal Antarctic site (Terra Nova Bay, Victoria Land). In this work, previously published data about water-soluble organic compounds and major and trace elements were merged with novel measurements of major ions, carboxylic acids and persistent organic pollutants (polychlorobiphenyls, polycyclic aromatic hydrocarbons, polychlorinated naphthalenes, polybrominated diphenylethers and organochlorine pesticides) in order to provide a chemical characterisation of Antarctic aerosol and to investigate its sources. The persistent organic pollutants were determined using a high-volume sampler, able to collect both particulate and gaseous fractions, whereas remaining compounds were determined by performing an aerosol size fractionation with a PM10 cascade impactor. Ionic species represented 58% (350ng m–3) of the sum of concentrations of all detected compounds (596ng m–3) in our Antarctic PM10 aerosol samples due to natural emission. Trace concentrations of persistent organic pollutants highlighted that the occurrence of these species can be due to long-range atmospheric transport or due to the research base. Factor analysis was applied to the dataset obtained from the samples collected with the PM10 sampler in order to make a distinction between anthropogenic, crustal and biogenic sources using specific chemical markers.

Fast and Sensitive Method for Determination of Domoic Acid in Mussel Tissue

Domoic acid (DA), a neurotoxic amino acid produced by diatoms, is the main cause of amnesic shellfish poisoning (ASP). In this work, we propose a very simple and fast analytical method to determine DA in mussel tissue. The method consists of two consecutive extractions and requires no purification steps, due to a reduction of the extraction of the interfering species and the application of very sensitive and selective HILIC-MS/MS method. The procedural method was validated through the estimation of trueness, extract yield, precision, detection, and quantification limits of analytical method. The sample preparation was also evaluated through qualitative and quantitative evaluations of the matrix effect. These evaluations were conducted both on the DA-free matrix spiked with known DA concentration and on the reference certified material (RCM). We developed a very selective LC-MS/MS method with a very low value of method detection limit (9 ng g−1) without cleanup steps.

Water-soluble trace, rare earth elements and organic compounds in Arctic aerosol

We investigated the elemental composition and water-soluble-organic compounds (WSOC) present in size-segregated airborne particulate matter to better understand: (1) the distribution of the water-soluble fraction of trace elements (TE), rare earth elements (REE) and WSOCs among different particulate sizes, and (2) the transport processes of aerosol towards the Arctic zone. Samples were collected at Ny-Alesund in the Svalbard Islands (78°55′07″N, 11°53′30″E) from 19 April to 14 September 2010. Water-soluble TE and REE were measured with the aim of recognising reliable tracers of specific sources, which may prove crucial in cost-effective strategies of air pollution control. The TE and REE content, especially in the finest fractions of aerosols in remote areas, is primarily due to long-range transport. It gives valuable information on the global circulation and on the contribution of human activities to aerosol composition (Birmili et al. in Environ Sci Technol 40:1144–1153, 2006; Fernández-Espinosa et al. in Atmos Environ 38:873–886, 2004; Song et al. in Atmos Environ 35:5277–5286, 2001). On the same samples, we also determined water-soluble organic tracers as specific source indicators: levoglucosan and methoxyphenols from biomass burning, acrylamide from anthropogenic origin and amino acids from primary production. These results were discussed in previous papers (Scalabrin et al. in Atmos Chem Phys 12:10453–10463, 2012; Zangrando et al. in Environ Sci Technol 47:8565–8574, 2013).