Real time analysis of atmospheric single particles in urban environments using aerosol time of flight mass spectrometry

In order to determine the size-resolved chemical composition of single particles in real-time an ATOFMS was deployed at urban background sites in Paris and Barcelona during the MEGAPOLI and SAPUSS monitoring campaigns respectively. The particle types detected during MEGAPOLI included several carbonaceous species, metal-containing types and sea-salt. Elemental carbon particle types were highly abundant, with 86% due to fossil fuel combustion and 14% attributed to biomass burning. Furthermore, 79% of the EC was apportioned to local emissions and 21% to continental transport. The carbonaceous particle types were compared with quantitative measurements from other instruments, and while direct correlations using particle counts were poor, scaling of the ATOFMS counts greatly improved the relationship. During SAPUSS carbonaceous species, sea-salt, dust, vegetative debris and various metal-containing particle types were identified. Throughout the campaign the site was influenced by air masses altering the composition of particles detected. During North African air masses the city was heavily influenced by Saharan dust. A regional stagnation was also observed leading to a large increase in carbonaceous particle counts. While the ATOFMS provides a list of particle types present during the measurement campaigns, the data presented is not directly quantitative. The quantitative response of the ATOFMS to metals was examined by comparing the ion signals within particle mass spectra and to hourly mass concentrations of; Na, K, Ca, Ti, V, Cr, Mn, Fe, Zn and Pb. The ATOFMS was found to have varying correlations with these metals depending on sampling issues such as matrix effects. The strongest correlations were observed for Al, Fe, Zn, Mn and Pb. Overall the results of this work highlight the excellent ability of the ATOFMS in providing composition and mixing state information on atmospheric particles at high time resolution. However they also show its limitations in delivering quantitative information directly

Tracing sources of natural organic matter, trihalomethanes and metals in groundwater from a karst region

Groundwater offers an important source for drinking water around the world; however, groundwater quality is under increasing pressure and is particularly vulnerable in karst areas. Total organic carbon (TOC) is significantly related to groundwater quality and when not removed by water treatment processes can give rise to the formation of disinfection by-products trihalomethanes (THMs) above the level of compliance. This study investigated the source of organic matter giving rise to the THM exceedances in a groundwater supply in a karst area. Results highlighted that source water for this groundwater supply was prone to surface water infiltration linked to rainfall events; was not accurately captured in the zone of contribution (ZoC); had inadequate treatment of natural organic matter (NOM) and suffered THM exceedances in 45% of sampling events. THMs were mostly represented by chloroform and caused by terrestrial delivered reprocessed organic matter. This work will support water managers tasked with decision-making

Airborne Fungal Spore Review, New Advances and Automatisation

Fungal spores make up a significant portion of Primary Biological Aerosol Particles (PBAPs) with large quantities of such particles noted in the air. Fungal particles are of interest because of their potential to affect the health of both plants and humans. They are omnipresent in the atmosphere year-round, with concentrations varying due to meteorological parameters and location. Equally, differences between indoor and outdoor fungal spore concentrations and dispersal play an important role in occupational health. This review attempts to summarise the different spore sampling methods, identify the most important spore types in terms of negative effects on crops and the public, the factors affecting their growth/dispersal, and different methods of predicting fungal spore concentrations currently in use

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

On the simultaneous deployment of two single-particle mass spectrometers at an urban background and a roadside site during SAPUSS

The aerosol time-of-flight mass spectrometer (ATOFMS) provides size-resolved information on the chemical composition of single particles with high time resolution. Within SAPUSS (Solving Aerosol Problems by Using Synergistic Strategies), continuous ATOFMS measurements of ambient particles were made simultaneously at two urban locations: urban background (UB) site and roadside (RS) site in the city of Barcelona (Spain) from 17 September to 18 October 2010. Two different instrumental configurations were used: ATOFMS (TSI 3800) with a converging nozzle inlet (high efficiency at about 800–2000 nm) at the UB site and ATOFMS (TSI 3800-100) with an aerodynamic lens inlet (high efficiency at about 300–700 nm) at the RS site. This is the first time, to our knowledge, that two ATOFMS instruments have been deployed in the same field study. The different instrument configurations had an impact on the observed particle types at the two sites. Nevertheless, 10 particle types were detected at both locations, including local and regional elemental carbon (22.7–58.9 % of total particles), fresh and aged sea salt (1.0–14.6 %), local and regional nitrate-containing aerosols (3–11.6 %), local lead-containing metallic particles (0.1–0.2 %), and transported Fe-nitrate particles (0.8–2.5 %). The ATOFMS at the UB also characterized four particle types: calcium-containing dust (0.9 %), Saharan dust (1.3 %), vanadium-containing particles (0.9 %), and vegetative debris (1.7 %). By contrast, the high statistical counts of fine particles detected at the RS allowed identification of eight particle types. Four of these contained organic nitrogen of primary and secondary origin, which highlights the complex nature of the sources and processes that contribute to this aerosol chemical component. Aminium salts were found related to coarse sulfate-rich particle types, suggesting heterogeneous reaction mechanisms for their formation. The other four particle types mainly containing organic carbon were found spiking at different types of the day, also showing a complex single-particle mixing state relationship between organic carbon and nitrate. This ATOFMS study clearly shows that the composition of atmospheric fine particles in Barcelona, and likely other Mediterranean urban areas, is complex, with a wide range of local and regional sources combining with chemical processing to produce at least 22 different particle types exhibiting different temporal behaviour. The advantage of using two ATOFMS instruments is also demonstrated, with the nozzle-skimmer configuration enabling detection of coarse dust particles and the aerodynamic lens configuration allowing better identification of particles rich in organic carbon and amines. Overall, we find that organic nitrogen is a considerable fraction of the single particles detected, especially at the traffic-dominated RS site. Further studies are needed, especially at high time resolution, to better understand the sources and properties of particulate organic nitrogen

Sources and mixing state of size-resolved elemental carbon particles in a European megacity: Paris

An Aerosol Time-Of-Flight Mass Spectrometer (ATOFMS) was deployed to investigate the size-resolved chemical composition of single particles at an urban background site in Paris, France, as part of the MEGAPOLI winter campaign in January/February 2010. ATOFMS particle counts were scaled to match coincident Twin Differential Mobility Particle Sizer (TDMPS) data in order to generate hourly size-resolved mass concentrations for the single particle classes observed. The total scaled ATOFMS particle mass concentration in the size range 150–1067 nm was found to agree very well with the sum of concurrent High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) and Multi-Angle Absorption Photometer (MAAP) mass concentration measurements of organic carbon (OC), inorganic ions and black carbon (BC) (R2 = 0.91). Clustering analysis of the ATOFMS single particle mass spectra allowed the separation of elemental carbon (EC) particles into four classes: (i) EC attributed to biomass burning (ECbiomass), (ii) EC attributed to traffic (ECtraffic), (iii) EC internally mixed with OC and ammonium sulfate (ECOCSOx), and (iv) EC internally mixed with OC and ammonium nitrate (ECOCNOx). Average hourly mass concentrations for EC-containing particles detected by the ATOFMS were found to agree reasonably well with semi-continuous quantitative thermal/optical EC and optical BC measurements (r2 = 0.61 and 0.65–0.68 respectively, n = 552). The EC particle mass assigned to fossil fuel and biomass burning sources also agreed reasonably well with BC mass fractions assigned to the same sources using seven-wavelength aethalometer data (r2 = 0.60 and 0.48, respectively, n = 568). Agreement between the ATOFMS and other instrumentation improved noticeably when a period influenced by significantly aged, internally mixed EC particles was removed from the intercomparison. 88% and 12% of EC particle mass was apportioned to fossil fuel and biomass burning respectively using the ATOFMS data compared with 85% and 15% respectively for BC estimated from the aethalometer model. On average, the mass size distribution for EC particles is bimodal; the smaller mode is attributed to locally emitted, mostly externally mixed EC particles, while the larger mode is dominated by aged, internally mixed ECOCNOx particles associated with continental transport events. Periods of continental influence were identified using the Lagrangian Particle Dispersion Model (LPDM) "FLEXPART". A consistent minimum between the two EC mass size modes was observed at approximately 400 nm for the measurement period. EC particles below this size are attributed to local emissions using chemical mixing state information and contribute 79% of the scaled ATOFMS EC particle mass, while particles above this size are attributed to continental transport events and contribute 21% of the EC particle mass. These results clearly demonstrate the potential benefit of monitoring size-resolved mass concentrations for the separation of local and continental EC emissions. Knowledge of the relative input of these emissions is essential for assessing the effectiveness of local abatement strategies

Quantitative determination of carbonaceous particle mixing state in Paris using single-particle mass spectrometer and aerosol mass spectrometer measurements

Single-particle mixing state information can be a powerful tool for assessing the relative impact of local and regional sources of ambient particulate matter in urban environments. However, quantitative mixing state data are challenging to obtain using single-particle mass spectrometers. In this study, the quantitative chemical composition of carbonaceous single particles has been determined using an aerosol time-of-flight mass spectrometer (ATOFMS) as part of the MEGAPOLI 2010 winter campaign in Paris, France. Relative peak areas of marker ions for elemental carbon (EC), organic aerosol (OA), ammonium, nitrate, sulfate and potassium were compared with concurrent measurements from an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS), a thermal-optical OCEC analyser and a particle into liquid sampler coupled with ion chromatography (PILS-IC). ATOFMS-derived estimated mass concentrations reproduced the variability of these species well (R-2 = 0.67-0.78), and 10 discrete mixing states for carbonaceous particles were identified and quantified. The chemical mixing state of HR-ToF-AMS organic aerosol factors, resolved using positive matrix factorisation, was also investigated through comparison with the ATOFMS dataset. The results indicate that hydrocarbon-like OA (HOA) detected in Paris is associated with two EC-rich mixing states which differ in their relative sulfate content, while fresh biomass burning OA (BBOA) is associated with two mixing states which differ significantly in their OA/EC ratios. Aged biomass burning OA (OOA(2)-BBOA) was found to be significantly internally mixed with nitrate, while secondary, oxidised OA (OOA) was associated with five particle mixing states, each exhibiting different relative secondary inorganic ion content. Externally mixed secondary organic aerosol was not observed. These findings demonstrate the range of primary and secondary organic aerosol mixing states in Paris. Examination of the temporal behaviour and chemical composition of the ATOFMS classes also enabled estimation of the relative contribution of transported emissions of each chemical species and total particle mass in the size range investigated. Only 22% of the total ATOFMS-derived particle mass was apportioned to fresh, local emissions, with 78% apportioned to regional/continental-scale emissions. Single-particle mixing state information can be a powerful tool for assessing the relative impact of local and regional sources of ambient particulate matter in urban environments. However, quantitative mixing state data are challenging to obtain using single-particle mass spectrometers. In this study, the quantitative chemical composition of carbonaceous single particles has been determined using an aerosol time-of-flight mass spectrometer (ATOFMS) as part of the MEGAPOLI 2010 winter campaign in Paris, France. Relative peak areas of marker ions for elemental carbon (EC), organic aerosol (OA), ammonium, nitrate, sulfate and potassium were compared with concurrent measurements from an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS), a thermal-optical OCEC analyser and a particle into liquid sampler coupled with ion chromatography (PILS-IC). ATOFMS-derived estimated mass concentrations reproduced the variability of these species well (R-2 = 0.67-0.78), and 10 discrete mixing states for carbonaceous particles were identified and quantified. The chemical mixing state of HR-ToF-AMS organic aerosol factors, resolved using positive matrix factorisation, was also investigated through comparison with the ATOFMS dataset. The results indicate that hydrocarbon-like OA (HOA) detected in Paris is associated with two EC-rich mixing states which differ in their relative sulfate content, while fresh biomass burning OA (BBOA) is associated with two mixing states which differ significantly in their OA/EC ratios. Aged biomass burning OA (OOA(2)-BBOA) was found to be significantly internally mixed with nitrate, while secondary, oxidised OA (OOA) was associated with five particle mixing states, each exhibiting different relative secondary inorganic ion content. Externally mixed secondary organic aerosol was not observed. These findings demonstrate the range of primary and secondary organic aerosol mixing states in Paris. Examination of the temporal behaviour and chemical composition of the ATOFMS classes also enabled estimation of the relative contribution of transported emissions of each chemical species and total particle mass in the size range investigated. Only 22% of the total ATOFMS-derived particle mass was apportioned to fresh, local emissions, with 78% apportioned to regional/continental-scale emissions

Airborne Fungal Spore Review, New Advances and Automatisation

Fungal spores make up a significant portion of Primary Biological Aerosol Particles (PBAPs) with large quantities of such particles noted in the air. Fungal particles are of interest because of their potential to affect the health of both plants and humans. They are omnipresent in the atmosphere year-round, with concentrations varying due to meteorological parameters and location. Equally, differences between indoor and outdoor fungal spore concentrations and dispersal play an important role in occupational health. This review attempts to summarise the different spore sampling methods, identify the most important spore types in terms of negative effects on crops and the public, the factors affecting their growth/dispersal, and different methods of predicting fungal spore concentrations currently in use

Arsenic in groundwater in south west Ireland: Occurrence, controls, and hydrochemistry

Globally numerous regions have been identified with elevated arsenic within groundwater which can result in potential adverse health risks. In Ireland, a previous national-scale research assessment of groundwater identified isolated clusters of elevated arsenic and indicated that lithology was a major controlling factor on arsenic in groundwater. Complementary comparisons of national-scale and regional-scale groundwater assessments of arsenic are lacking in Europe when compared to other global regions. The aims of this study were to demonstrate the value of a regional-scale groundwater hydrochemistry dataset with an existing national-scale approach, describe anomalies that can become the focus of attention for public health and economic reasons, and to provide a wider context for arsenic in groundwater within Ireland and Europe. Regional-scale data using 470 locations comprising 1,493 analyses using several hydrochemical parameters (arsenic, pH, conductivity, iron, manganese, sodium, potassium, calcium, magnesium, and total hardness) in south west Ireland were integrated with geological, hydrogeological, and land use datasets. Statistical analysis was performed using a combination of methods including score tests of geological groups using an empirical cumulative distribution function plot in addition to spatial analysis. Results revealed that hydrochemical parameters exhibited different spatial clusters, which was generally associated with lithology. Arsenic was elevated in sandstone derived bedrock. Weak correlation of arsenic with other hydrochemical parameters were observed and redox-sensitive elements like manganese and iron showed a greater diversity in spatial occurrence. This study has shown that the variation of hydrochemical parameters are controlled by regional geology. Finally, the paper focuses on anomalies identified by concentrations of individual ions or statistical associations in the context of, for example, historical mineral exploration and mining in the area and also discusses whether groundwater chemistry sampling on this scale can assist in future mineral exploration, as well as guiding the future development of high quality public and private water supplies.Funding based on research grant-aided by the Department of Communications, Energy and Natural Resources under the National Geoscience Programme 2007-2013. The views expressed in this study are the author's own and do not necessarily reflect the views and opinions of the Minister for Communications, Energy and Natural Resources. The authors acknowledge support of the HEA under PRTLI4 for licensing OSI Digital Imagery through the Ryan Institute. This work includes Ordnance Survey Ireland data reproduced under OSi License number NUIG220212. Unauthorized reproduction infringes Ordnance Survey Ireland and Government of Ireland copyright. © Ordnance Survey Ireland, 2012. The authors would like to thank the members of local government for data collection (particularly David Lenihan) and David Ball and Taly Hunter Williams for providing invaluable discussions on the manuscript. The authors would also like to thank David Ball for preparation of Figure 2 for this paper.peer-reviewe