Characterization of Primary Organic Aerosol from Domestic Wood, Peat, and Coal Burning in Ireland.

An aerosol chemical speciation monitor (ACSM) was deployed to study the primary nonrefractory submicron particulate matter emissions from the burning of commercially available solid fuels (peat, coal, and wood) typically used in European domestic fuel stoves. Organic mass spectra (MS) from burning wood, peat, and coal were characterized and intercompared for factor analysis against ambient data. The reference profiles characterized in this study were used to estimate the contribution of solid fuel sources, along with oil combustion, to ambient pollution in Galway, Ireland using the multilinear engine (ME-2). During periods influenced by marine air masses, local source contribution had dominant impact and nonsea-spray primary organic emissions comprised 88% of total organic aerosol mass, with peat burning found to be the greatest contributor (39%), followed by oil (21%), coal (17%), and wood (11%). In contrast, the resolved oxygenated organic aerosol (OOA) dominated the aerosol composition in continental air masses, with contributions of 50%, compared to 12% in marine air masses. The source apportionment results suggest that the use of domestic solid fuels (peat, wood, and coal) for home heating is the major source of evening and night-time particulate pollution events despite their small use.

A new on-line SPE LC-HRMS method for the analysis of Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS) in PM2.5 and its application for screening atmospheric particulates from Dublin and Enniscorthy, Ireland.

A sensitive analytical method has been developed and validated for the determination of 16 polyfluorinated alkyl substances (PFAS) in fine airborne particulate matter (PM2.5) using on-line solid phase extraction (SPE) coupled with liquid chromatography (LC) - negative electrospray ionisation high resolution mass spectrometry (-) ESI-HRMS. On-line SPE allows simultaneous sample clean-up from interfering matrices and lower limits of detection (LODs) by injecting a large volume of sample into the LC system without compromising chromatographic efficiency and resolution. The method provides LODs in the range 0.08-0.5 pg/mL of sample extract allowing detection of selected PFAS in aerosol particles at low fg/m3 level and showed good tolerance to the considered PM matrix. The validated method was applied for analysis of PFAS in ambient PM2.5 samples collected at two urban locations in Ireland, i.e., Enniscorthy and Dublin. Several PFAS were observed above the detection limit, including perfluorobutyrate (PFBA), perfluorooctanoic acid (PFOA), perfluorooctanesulfonic acid (PFOS), perfluorobutanesulfonic acid (L-PFBS) and perfluorononanoic acid (PFNA), as well as fluorotelomer sulfonates: 4:2 FTS, 6:2 FTS and 8:2 FTS. The results indicate that some toxic PFAS, such as PFOS and PFOA, are still detected in the environment despite being phased out from production and subject to restricted use in the EU and USA for more than two decades. Observation of fluorotelomer sulfonates (4:2 FTS, 6:2 FTS and 8:2 FTS, which are used as alternatives for legacy PFOA and PFOS) in ambient PM2.5 samples raises a concern about their persistence in the atmosphere and impact on human health considering emerging evidence that they could have similar health endpoints as PFOA and PFOS. To our knowledge, this is the first study to identify PFAS in ambient PM2.5 at urban locations in Ireland and also the first study to detect 4:2 and 8:2 fluorotelomer sulfonates in atmospheric aerosol particles.

Real-time Monitoring of Aerosol Generating Dental Procedures.

OBJECTIVE: We aimed to quantify aerosol concentrations produced during different dental procedures under different mitigation processes. METHOD: Aerosol concentrations were measured by the Optical Particle Sensor (OPS) and Wideband Integrated Bioaerosol Sensor (WIBS) during routine, time-recorded dental procedures on a manikin head in a partitioned enclosure. Four different, standardised dental procedures were repeated in triplicate for three different mitigation measures. RESULT: Both high-volume evacuation (HVE) and HVE plus local exhaust ventilation (LEV) eradicated all procedure-related aerosols, and the enclosure stopped procedure-related aerosols escaping. Aerosols recorded by the OPS and WIBS were 84 and 16-fold higher than background levels during tooth 16 FDI notation (UR6) drilling, and 11 and 24-fold higher during tooth 46 FDI notation (LR6) drilling, respectively. Ultrasonic scaling around the full lower arch (CL) or the full upper arch (CU) did not generate detectable aerosols with mitigation applied. Without mitigation the largest concentration of inhalable particles during procedures observed by the WIBS and OPS was during LR6 (139/cm3) and UR6 (28/cm3) drilling, respectively. Brief aerosol bursts were recorded during drilling procedures with HVE, these did not occur with LEV, suggesting LEV provides protection against operator errors. Variation was observed in necessary fallow times (49 - 280 minutes) without mitigation, while no particles remained airborne when mitigation was utilised. CONCLUSION: This data demonstrates that correctly positioned HVE or LEV is effective in preventing airborne spread and persistence of inhalable particles originating from dental AGPs. Additionally, a simple enclosure restricts the spread of aerosols outside of the operating area. CLINICAL SIGNIFICANCE: Employing correctly positioned HVE and LEV in non-mechanically ventilated clinics can prevent the dispersal and persistence of inhalable airborne particles during dental AGPs. Moreover, using enclosures have the additive effect of restricting aerosol spread outside of an operating area.

Assessment of Environmental and Occupational Risk Factors for the Mitigation and Containment of a COVID-19 Outbreak in a Meat Processing Plant.

Throughout the COVID-19 pandemic, meat processing plants have been vulnerable to outbreaks of SARS-CoV-2 infection. Transmission of the virus is difficult to control in these settings because of a combination of factors including environmental conditions and the specific nature of the work. This paper describes a retrospective outbreak investigation in a meat processing plant, a description of the measures taken to prevent or contain further outbreaks, and insights on how those with specific knowledge of the working environment of these plants can collaborate with public health authorities to ensure optimal outbreak control. The plant experienced 111 confirmed positive asymptomatic cases in total with an estimated attack rate of 38% during a five-week period. 4 weeks after the first case, mass screening of all workers was conducted by the public health authorities. Thirty-two workers tested positive, of which 16 (50%) worked in one particular area of the plant, the boning hall (n = 60). The research team prepared and carried out semi-structured interviews with the plant personnel who were charged with COVID control within the plant. They carried out assessments of operational risk factors and also undertook air quality monitoring in the boning hall and abattoir. The air quality measurements in the boning hall showed a gradual build-up of carbon dioxide and aerosol particles over the course of a work shift, confirming that this poorly ventilated area of the plant had an environment that was highly favorable for aerosol transmission of SARS-CoV-2. Assessment of operational conditions incorporated visual surveys of the plant during the working day. Prior to and during the first 2 weeks of the outbreak, multiple measures were introduced into the plant by management, including physical distancing, provision of educational material to workers, visitor restrictions, and environmental monitoring. After the implementation of these measures and their progressive refinement by plant management, the factory had no further linked cases (clusters) or outbreaks for the following 198 days. The tailored approach to risk mitigation adopted in this meat processing plant shows that generic risk mitigation measures, as recommended by public health authorities, can be successfully adapted and optimized by designated plant emergency response teams.

Protonated nitrosamide and its potential role in the release of HONO from snow and ice in the dark.

A joint Fourier transform reflection absorption infrared spectroscopy/thermal programmed desorption (RAIRS/TPD) study has provided good evidence for the existence of protonated nitrosamide (NH3NO(+)) on surfaces at cold temperatures. This species has long been proposed to exist in studies of the DeNO(x) process and the decomposition of ammonium nitrite. In the context of the current experiments, performed at low-temperatures in the absence and presence of water-ice, the results provided a firm mechanistic basis for understanding the release of HONO from snowpack in a "dark" mechanism and also under alkaline surface conditions.

Airborne emissions in the harbour and port of Cork.

It is now accepted that the transport sector is responsible for a large and growing share of global emissions affecting both health and climate. The quantification of these effects requires, as an essential first step, a comprehensive analysis and characterization of the contributing subsectors, i.e. road transport, shipping, aviation and rail. The shipping contribution in dock/harbour areas is of particular interest because many vessels use old engines powered with old technology giving rise to high levels of particulate emissions mainly because the fuel employed contains high levels of sulphur, up to 4.5%. Large amounts of polyaromatic hydrocarbons and varying contents of transition metals are also detected. Few studies on the physicochemical composition of direct emissions from ship fuels have been performed; none have been compared to actual contents in local harbour or port atmospheres. The transformation of these ship-related materials to toxicologically active species may be much more efficient than corresponding road emission or domestic sources because of the expected highly acidic nature of the particulates. Surface, toxic material may therefore become readily bioavailable under such conditions but such studies have not been performed hitherto. This mini-review outlines in detail the issues raised above in the context of measurements made in Cork, Ireland.

A comparison of on-line and off-line bioaerosol measurements at a biowaste site.

An air measurement campaign was carried out at a green-waste composting site in the South of Ireland during Spring 2016. The aim was to quantify and identify the levels of Primary Biological Aerosol Particles (PBAP) that were present using the traditional off-line, impaction/optical microscopy method alongside an on-line, spectroscopic approach termed WIBS (Wideband Integrated Bioaerosol Sensor), which can provide number concentrations, sizes and "shapes" of airborne PBAP in real-time by use of Light Induced Fluorescence (LIF). The results from the two techniques were compared in order to validate the use of the spectroscopic method for determining the releases of the wide-range of PBAP present there as a function of site activity and meteorological conditions. The seven-day monitoring period undertaken was much longer than any real-time studies that have been previously performed and allowed due comparison between weekday (working) activities at the site and weekend (closed) releases. The time-span also allowed relationships between site activities like turning, agitation or waste delivery and the WIBS data to be determined in a quantitative manner. This information cannot be obtained with the Andersen Sampling methods generally employed at green-waste management sites. Furthermore, few specific bioaerosol types other than Aspergillus fumigatus, are identified using the traditional protocols employed for site licensing purposes. Here though the co-location of WIBS with the impaction instrument made it possible to identify the real-time release behaviour of a specific plant pathogenic spore, Ustilago maydis, present after green-waste deliveries were made by a local distillery.

Development of an analytical methodology for obtaining quantitative mass concentrations from LAAP-ToF-MS measurements.

Laser ablation aerosol particle-time of flight mass spectrometer (LAAP-ToF-MS) measures the size number of particles, and chemical composition of individual particles in real-time. LAAP-ToF-MS measurements of chemical composition are difficult to quantify, mostly because the instrument sensitivities to various chemical species in the multicomponent atmospheric aerosol particles are unknown. In this study, we investigate a field-based approach for quantitative measurements of ammonium, nitrate, sulfate, OC, and EC, in size-segregated atmospheric aerosols, by LAAP-ToF-MS using concurrent measurements from high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS), and multi-angle absorption photometer (MAAP). An optical particle counter (OPC) and a high-resolution nanoparticle sizer (scanning mobility particle sizer, or SMPS), were used to measure the particle size distributions of the particles in order to correct the number concentrations. The intercomparison reveals that the degree of agreement of the mass concentrations of each compound measured with LAAP-ToF-MS and HR-ToF-AMS/MAAP increases in the following order NH4+ < SO42- < NO3- < EC < OC < Cl- with r2 values in the range of 0.4-0.95 and linear regression slopes ranging between 0.62 and 1.2. The factors that affect the mass concentrations measured by LAAP-ToF-MS are also discussed in details. Yet, the matrix effect remains one of the strongest limiting factor to achieve an absolute quantification of the aerosol chemical composition. In the future we suggest the development of a methodology based on the calculation of the response factors generated by different types of particles, which could possibly resolve certain difficulties associated with the matrix effect.

Apportionment of urban aerosol sources in Cork (Ireland) by synergistic measurement techniques.

The sources of ambient fine particulate matter (PM2.5) during wintertime at a background urban location in Cork city (Ireland) have been determined. Aerosol chemical analyses were performed by multiple techniques including on-line high resolution aerosol time-of-flight mass spectrometry (Aerodyne HR-ToF-AMS), on-line single particle aerosol time-of-flight mass spectrometry (TSI ATOFMS), on-line elemental carbon-organic carbon analysis (Sunset_EC-OC), and off-line gas chromatography/mass spectrometry and ion chromatography analysis of filter samples collected at 6-h resolution. Positive matrix factorization (PMF) has been carried out to better elucidate aerosol sources not clearly identified when analyzing results from individual aerosol techniques on their own. Two datasets have been considered: on-line measurements averaged over 2-h periods, and both on-line and off-line measurements averaged over 6-h periods. Five aerosol sources were identified by PMF in both datasets, with excellent agreement between the two solutions: (1) regional domestic solid fuel burning--"DSF_Regional," 24-27%; (2) local urban domestic solid fuel burning--"DSF_Urban," 22-23%; (3) road vehicle emissions--"Traffic," 15-20%; (4) secondary aerosols from regional anthropogenic sources--"SA_Regional" 9-13%; and (5) secondary aged/processed aerosols related to urban anthropogenic sources--"SA_Urban," 21-26%. The results indicate that, despite regulations for restricting the use of smoky fuels, solid fuel burning is the major source (46-50%) of PM2.5 in wintertime in Cork, and also likely other areas of Ireland. Whilst wood combustion is strongly associated with OC and EC, it was found that peat and coal combustion is linked mainly with OC and the aerosol from these latter sources appears to be more volatile than that produced by wood combustion. Ship emissions from the nearby port were found to be mixed with the SA_Regional factor. The PMF analysis allowed us to link the AMS cooking organic aerosol factor (AMS_PMF_COA) to oxidized organic aerosol, chloride and locally produced nitrate, indicating that AMS_PMF_COA cannot be attributed to primary cooking emissions only. Overall, there are clear benefits from factor analysis applied to results obtained from multiple techniques, which allows better association of aerosols with sources and atmospheric processes.

The use of polar organic compounds to estimate the contribution of domestic solid fuel combustion and biogenic sources to ambient levels of organic carbon and PM2.5 in Cork Harbour, Ireland.

PM(2.5) samples collected at Cork Harbour, Ireland during summer, autumn, late autumn and winter, 2008-2009 were analyzed for polar organic compounds that are useful markers for aerosol source characterization. The determined compounds include tracers for biomass burning primary particles, fungal spores, markers for secondary organic aerosol (SOA) from isoprene, α-/ß-pinene, and d-limonene. Seasonal and temporal variations and other characteristic features of the detected tracers are discussed in terms of aerosol sources and processes. The biogenic species were detected only during the summer period where the contributions of isoprene SOA and fungal spores to the PM(2.5) organic carbon (OC) were estimated to be 1.6% and 1% respectively. The biomass burning markers, and in particular levoglucosan, were present in all samples and attributed to the combustion of cellulose-containing fuels including wood, peat, bituminous and smokeless coal. The contribution of domestic solid fuel (DSF) burning to the measured OC mass concentration was estimated at 10.8, 50, 66.4 and 74.9% for summer, autumn, late autumn and winter periods, respectively, based on factors derived from a series of burning experiments on locally available fuels. Application of an alternative approach, namely principal component analysis-multiple linear regression (PCA-MLR), to the measured concentrations of the polar organic marker compounds used in conjunction with real-time air quality data provided similar trends and estimates for DSF combustion during all seasons except summer. This study clearly demonstrates that, despite the ban on the sale of bituminous coal in Cork and other large urban areas in Ireland, DSF combustion is still the major source of OC during autumn and winter periods and also makes a significant contribution to PM(2.5) levels. The developed marker approach for estimating the contribution of DSF combustion to ambient OC concentrations can, in principle, also be applied to other locations.

Cirrus cloud mimics in the laboratory: an infrared spectroscopy study of thin films of mixed ice of water with organic acids and ammonia.

The structures of formic and acetic acids deposited on a thin gold substrate held in vacuum at low temperatures and their related water-ice promoted chemistry have been investigated. The condensed water/guest films were taken to act as cirrus cloud "mimics." Such laboratory representations provide a necessary prelude to understanding how low temperature surfaces can affect chemical composition changes in the upper atmosphere. The systems were characterized by reflection-absorption infrared spectroscopy and temperature-programmed desorption spectrometry. The interaction behavior of the binary acid ices was compared to that observed when ternary mixtures of water, formic acid, and ammonia were deposited. Differences in the chemistry were observed depending on deposition method: layering or mixing. The more atmospherically relevant codeposition approach showed that at low temperatures, amorphous formic acid can be ionized to its monodentate form by water ice within the bulk rather than on the surface. In contrast, the introduction of ammonia leads to full bidentate ionization on the ice surface. The thermal desorption profiles of codeposited films of water, ammonia, and formic acid indicate that desorption occurs in three stages. The first is a slow release of ammonia between 120 and 160 K, then the main water desorption event occurs with a maximum rate close to 180 K, followed by a final release of ammonia and formic acid at about 230 K originating from nonhydrous ammonium formate on the surface. The behavior of acetic acid is similar to formic acid but shows lesser propensity to ionize in bulk water ice.

Potential role of the nitroacidium ion on HONO emissions from the snowpack.

The effects of photolysis on frozen, thin films of water-ice containing nitrogen dioxide (as its dimer dinitrogen tetroxide) have been investigated using a combination of Fourier transform reflection-absorption infrared (FT-RAIR) spectroscopy and mass spectrometry. The release of HONO is ascribed to a mechanism in which nitrosonium nitrate (NO+NO3-) is formed. Subsequent solvation of the cation leads to the nitroacidium ion, H2ONO+, i.e., protonated nitrous acid. The pathway proposed explains why the field measurement of HONO at different polar sites is often contradictory.