Introduction

CHEMBC is a Marie Curie International Outgoing Fellowship awarded to Dr Robert Healy, funded by the European Commission. It is a 3 year project with 2 years spent at University of Toronto, Canada and the third year spent at University College Cork, Ireland. The CHEMBC project is focussed on the simultaneous measurement of the chemical and optical properties of local and regional black carbon particles in Toronto.

Much of the uncertainty surrounding the impact of BC emissions on global climate arises from our relatively poor understanding of the relationship between BC mixing state and climate-relevant physical properties. Single particle mass spectrometry is one of only a handful of techniques that enable us to assess whether or not BC exists in ‘pure’ atmospheric particles as the sole component, or whether other primary and secondary species, for example organic aerosol and inorganic ions, are also internally mixed. As part of the CHEMBC project new data analysis techniques have been developed to answer these questions.

A range of state-of-the-art instruments and analytical techniques will be employed to identify different sources of black carbon detected at a receptor site in Toronto and to investigate the relationship between chemical composition, atmospheric age and optical properties.

Project Details

CHEMBC is a Marie Curie International Outgoing Fellowship, awarded to Dr Robert Healy, funded by the European Commission.

Title: Chemical and Optical Properties of Black Carbon Particles (CHEMBC)
Fellow: Dr Robert Healy
Outgoing host scientist: Professor Greg Evans
Return host scientist: Dr John Wenger
Grant Number: 299755
Start Date: 1st August 2012
Completion Date: 31st July 2015
Amount of Award: €233,922.50
Activities: Training in statistical analysis methods, instrument design and testing, data mining, training in operation of state-of-the-art aerosol instrumentation, field measurements, personal development, outreach.

Scientific Background

Black Carbon (BC) is a term used to describe primary carbonaceous particles formed through incomplete combustion processes, which include vehicular traffic, domestic solid fuel burning and biomass burning. BC influences climate directly through positive radiative forcing by absorbing solar radiation and also indirectly by altering the microphysical properties, amount and lifetime of clouds.

Compared to greenhouse gases, the atmospheric lifetime of black carbon is relatively low, and thus BC emission controls represent the most likely means by which to mitigate climate change quickly and effectively. However, improved scientific knowledge of the atmospheric processing of BC is required to provide policy makers with the relevant information to implement effective legislation.

The Fellow

Dr. Robert Healy

Presentations

Robert Healy. Chemical and optical properties of black carbon particles in Toronto (CHEMBC). Chemistry Department Seminar Series, University College Cork, Ireland, March 2015. Download Talk

Watch on Youtube


Robert Healy, Greg Evans, Michael Murphy, Zsofia Juranyi, TorstenTritscher, Ernest Weingartner, Martin Gysel, Laurent Poulain, Katharina Kamilli, Alfred Wiedensohler, Ian O’Connor, Eoin McGillicuddy, John Sodeau, John Wenger. Estimation of hygroscopic growth for ambient single particles. International Aerosol Conference, Busan, Korea, September 2014. Download Talk (2,918kB)


Robert Healy, Nicole Riemer, John Wenger, Michael Murphy, Matthew West, Laurent Poulain, Alfred Wiedensohler, Ian O’Connor, Eoin McGillicuddy, John Sodeau, Greg Evans. Assessing aerosol mixing state and diversity. International Aerosol Conference, Busan, Korea, September 2014. Download Talk (1,994kB)


Robert M. Healy, Cheol-Heon Jeong, John C. Wenger, Deborah S. Gross, Jovanna Arndt, Ian P. O’Connor, Eoin McGillicuddy, John R. Sodeau, Xin Yang, Hong Chen, Yuanlong Huang, Berko Sierau, Manuel Dall’Osto, Nicole Riemer, Matthew West, Michael Murphy, Greg J. Evans. A Global Library of Single Particle Mass Spectrometer Data. International Aerosol Conference, Busan, Korea, September 2014. Download Poster (1,136kB)


Robert Healy. Identifying sources contributing to poor air quality using aerosol mass spectrometry techniques. Analytica Conference, "Aerosol and Health" Session, Munich, Germany, April 2014Download Talk (2,160kB)


Robert Healy. Assessing aerosol mixing state through single particle mass spectrometry. Department of Atmospheric Sciences Seminar Series, University of Illinois, February 2014. Download Talk (3,027kB)


Robert M. Healy, Jean Sciare, Laurent Poulain, Monica Crippa, Alfred Wiedensohler, André S. H. Prévôt, Urs Baltensperger, Roland Sarda-Estève, Maygan L. McGuire, Cheol-Heon Jeong, Eoin McGillicuddy, Ian P. O’Connor, John R. Sodeau, Alex K. Y. Lee, Megan D. Willis, Jonathan P. D. Abbatt, Greg J. Evans, John C. Wenger. Source apportionment of carbonaceous aerosol in urban environments through single particle mass spectrometry. American Association for Aerosol Research Fall Meeting, Portland, USA, September 2013Download Poster (483kB)


Robert M.Healy. Applications of Single Particle Mass Spectrometry in Urban Environments. Environment Canada Seminar Series, Toronto, Canada, January 2013. Download Talk (2,784kB)


Robert M. Healy. Applications of Single Particle Mass Spectrometry in Urban Environments. Department of Chemical Engineering Seminar Series, University of Toronto, Canada, October 2012Download Talk (855kB)


Robert M. Healy, Jean Sciare, Laurent Poulain, Alfred Wiedensohler, Cheol-Heon Jeong, Maygan McGuire, Greg J. Evans. Determination of mixing state and sources of wintertime organic aerosol in Paris using single particle mass spectrometry. American Geophysical Union Fall Meeting, San Francisco, USA, December 2012. Download Poster (1,069kB)


Robert M. Healy, Peter J. G. Rehbein, Cheol-Heon Cheong, John C. Wenger, Greg J. Evans. Exploring Gas-Particle Partitioning of Trimethylamine using Single Particle Mass Spectrometry. Atmospheric Chemical Mechanisms Meeting, UC Davis, USA, December 2012. Download Talk (1,309kB)


Robert M. Healy, Stig Hellebust, Ian P. O'Connor, John R. Sodeau, John C. Wenger, Greg J. Evans. Estimating the Relative Impact of Shipping, Traffic and Domestic Solid Fuel Combustion upon Air Quality in Cork City, Ireland - A Case Study. Society for Risk Analysis Annual Conference, San Francisco, USA, December 2012. Download Poster (975kB)


Robert M. Healy, Yang Chen, Ivan Kourtchev, Markus Kalberer, John Wenger. Investigation of SOA Composition from the Photolysis of 1-NitroNaphthalene using Single Particle Mass Spectrometry. American Association for Aerosol Research Fall Meeting, Minneapolis, USA, October 2012. Download Poster (1,364kB)

Publications

Peer-reviewed journal articles directly related to CHEMBC

Lee, A. K. Y., Willis, M. D., Healy, R. M., Onasch, T. B., and Abbatt, J. P. D.: Mixing state of carbonaceous aerosol in an urban environment: single particle characterization using the soot particle aerosol mass spectrometer (SP-AMS). Atmospheric Chemistry & Physics, 15, 1823-1841, 2015. DOI


Wang, J. M., Jeong, C. H., Zimmerman, N., Healy, R. M., Wang, D. K., Ke, F., and Evans, G. J.: Plume-based analysis of vehicle fleet air pollutant emissions and the contribution from high emitters. Atmos. Meas. Tech. Discuss., 8, 2881-2912, 2015. DOI


R. M. Healy, J. M. Wang, C.-H. Jeong, A. K. Y. Lee, M. D. Willis, E. Jaroudi, N. Zimmerman, N. Hilker, M. Murphy, S. Eckhardt, A. Stohl, J. P. D. Abbatt, J. C. Wenger and G. J. Evans. Light absorbing properties of ambient black carbon and brown carbon from fossil fuel and biomass burning sources. Journal of Geophysical Research (Atmospheres), 1-11, 2015. DOI


Dall'Osto, M., Hellebust, S. Healy, R. M., O'Connor, I. P., Kourtchev, I., Sodeau, J. R.,  Ovadnevaite, J., Ceburnis, D., O'Dowd, C. D., and Wenger, J. C. Apportionment of urban aerosol sources in Cork (Ireland) by synergistic measurement techniques. Science of The Total Environment, 493(0), 197-208, 2014. DOI


Healy, R. M., Evans, G. J., Murphy, M., Sierau, B., Arndt, J., McGillicuddy, E., O’Connor, I. P., Sodeau, J. R., Wenger, J. C.: Single particle speciation of alkylamines in ambient aerosol at five European sites, Anal. Bioanal. Chem., 1-11, 2014. DOI


Lee, A. K. Y., Willis, M. D., Healy, R. M., Onasch, T. B., and Abbatt, J. P. D.: Single particle characterization using the soot particle aerosol mass spectrometer (SP-AMS), Atmos. Chem. Phys. Discuss., 14, 15323-15361, 2014. DOI


Healy, R. M., Evans, G. J., Murphy, M., Jurányi, Z., Tritscher, T., Laborde, M., Weingartner, E., Gysel, M., Poulain, L., Kamilli, K. A., Wiedensohler, A., O'Connor, I. P., McGillicuddy, E., Sodeau, J. R., and Wenger, J. C.: Predicting hygroscopic growth using single particle chemical composition estimates, Journal of Geophysical Research: Atmospheres, 2014. DOI


McGuire, M. L., Chang, R. Y. W., Slowik, J. G., Jeong, C. H., Healy, R. M., Lu, G., Mihele, C., Abbatt, J. P. D., Brook, J. R., and Evans, G. J.: Enhancing non-refractory aerosol apportionment from an urban industrial site through receptor modelling of complete high time-resolution aerosol mass spectra. Atmospheric Chemistry & Physics, 2014, 14, 8017-8042. DOI


Kourtchev, I., Fuller, S. J., Giorio, C., Healy, R. M., Wilson, E., O'Connor, I. P., Wenger, J. C., McLeod, M., Aalto, J., Ruuskanen, T. M., Maenhaut, W., Jones, R., Venables, D. S., Sodeau, J. R., Kulmala, M., Kalberer M., Molecular composition of biogenic secondary organic aerosols using ultrahigh resolution mass spectrometry: comparing laboratory and field studies. Atmospheric Chemistry & Physics, 14, 2155-2167, 2014. DOI


Healy, R. M., Riemer, N., Wenger, J. C., Murphy, M., West, M., Poulain, L., Wiedensohler, A., O'Connor, I. P., McGillicuddy, E., Sodeau, J. R., and Evans, G. J.: Single particle diversity and mixing state measurements, Atmos. Chem. Phys., 14, 6289-6299, 2014. DOI


Healy, R. M., Sciare, J., Poulain, L., Crippa, M., Wiedensohler, A., Prévôt, A. S. H., Baltensperger, U., Sarda-Estève, R., McGuire, M. L., Jeong, C. H., McGillicuddy, E., O'Connor, I. P., Sodeau, J. R., Evans, G. J., and Wenger, J. C.: Quantitative determination of carbonaceous particle mixing state in Paris using single-particle mass spectrometer and aerosol mass spectrometer measurements. Atmos. Chem. Phys., 13, 9479-9496, 2013. DOI


Hamilton, J., Romero, M. T. B., Finessi, E., Rickard, A. R., Healy, R. M., Peppe, S., Adams, T. J., Daniels, M. J. S., Ball, S. M., Goodall, I. C. A., Monks, P. S., Borras Garcia, E., and Munoz, A.: Online and Offline Mass Spectrometric Study of the Impact of Oxidation and Ageing on Glyoxal Chemistry and Uptake onto Ammonium Sulfate Aerosols. Faraday Discussions, 2013. DOI


Collaborative peer-reviewed journal articles:

Giorio, C., Tapparo, A., Dall’Osto, M., Beddows, D. C. S., Esser-Gietl, J. K., Healy, R. M., and Harrison, R. M.: Local and Regional Components of Aerosol in a Heavily Trafficked Street Canyon in Central London Derived from PMF and Cluster Analysis of Single-Particle ATOFMS Spectra. Environmental Science & Technology, 2015. DOI


Riva, M., Healy, R. M., Flaud, P. M., Perraudin, E., Wenger, J. C. and Villenave, E. Kinetics of the Gas-Phase Reactions of Chlorine Atoms with Naphthalene, Acenaphthene and Acenaphthylene. Journal of Physical Chemistry A, 118, 3535−3540, 2014. DOI


Dall'Osto, M., Ovadnevaite, J., Ceburnis, D., Martin, D., Healy, R. M., O'Connor, I. P., Kourtchev, I., Sodeau, J. R., Wenger, J. C., and O'Dowd, C.: Characterization of urban aerosol in Cork city (Ireland) using aerosol mass spectrometry. Atmos. Chem. Phys., 13, 4997-5015, 2013. DOI


Dall'Osto, M., Querol, X., Alastuey, A., Minguillon, M. C., Alier, M., Amato, F., Brines, M., Cusack, M., Grimalt, J. O., Karanasiou, A., Moreno, T., Pandolfi, M., Pey, J., Reche, C., Ripoll, A., Tauler, R., Van Drooge, B. L., Viana, M., Harrison, R. M., Gietl, J., Beddows, D., Bloss, W., O'Dowd, C., Ceburnis, D., Martucci, G., Ng, N. L., Worsnop, D., Wenger, J., Mc Gillicuddy, E., Sodeau, J., Healy, R. M., Lucarelli, F., Nava, S., Jimenez, J. L., Gomez Moreno, F., Artinano, B., Prévôt, A. S. H., Pfaffenberger, L., Frey, S., Wilsenack, F., Casabona, D., Jiménez-Guerrero, P., Gross, D., and Cots, N.: Presenting SAPUSS: Solving Aerosol Problem by Using Synergistic Strategies in Barcelona, Spain. Atmos. Chem. Phys., 13, 8991-9019, 2013. DOI


Healy, R. M., Chen, Y., Kourtchev, I., Kalberer, M., O’Shea, D., and Wenger, J. C.: Rapid Formation of Secondary Organic Aerosol from the Photolysis of 1-Nitronaphthalene: Role of Naphthoxy Radical Self-reaction. Environmental Science & Technology, 46, 11813-11820, 2012. DOI

Collaborators

Jon Abbatt, University of Toronto
Nicole Riemer, University of Illinois
Jacqui Hamilton, University of York
Ivan Kourtchev, Markus Kalberer, University of Cambridge

Publicity and Outreach

Introduction

The development and application of novel instrumentation to improve our understanding of atmospheric ices, clouds and precipitation.

Dr David O’Connor has been awarded an Irish Research Council Elevate Postdoctoral Fellowship to study at both the Chemistry Department, University of Denver and University College Cork. This prestigious 3-year grant is co-funded by the EU Marie Curie Actions Programme and the Irish Research Council. He will be supervised by Professor Alex Huffman in Denver and by Professor John Sodeau in Cork.

The research itself will involve the development of an entirely new, cheap and robust laser induced fluorescence (LIF) instrument for the detection and characterization of Primary Biological Research Particles (PBAP). Once this task has been completed its integration into a droplet freezing apparatus will be carried out so as to provide a far greater level of characterization for the ice nucleating ability of PBAP to be determined than is currently the case. It will then be deployed back in Ireland at a field site.

The results will be relevant to climate change research because our current knowledge about the composition of airborne ice nuclei distributed on a global basis is poor. For example there are large uncertainties associated with the prediction of any PBAP/ice impacts on important cloud properties, such as precipitation formation or radiative (climate change) forcing potentials.

Project Details

Title: ATMOSICE
Fellow: Dr David O’Connor
Outgoing host scientist: Professor Alex Hufmann
Return host scientist: Professor John Sodeau
Grant Number: IRC Marie Curie ELEVATEPD/2014/73
Start Date: 1st October 2014
Completion Date: 30th September 2017
Amount of Award: €248811
Activities: The development and deployment of an entirely new, cheap and robust laser induced fluorescence (LIF) instrument for the detection and characterization of Primary Biological Research Particles (PBAP) to assess their ice nucleating abilities.

Scientific Background

Atmospheric aerosol particles are very small pieces of condensed material that can remain airborne for days to weeks at a time. They possess a complex range of physical and chemical properties. Primary biological aerosol particles (PBAP) are a subset of coarse-mode (> 1 µm) particles that are derived directly from biological sources, such as pollen, fungal spores, bacteria or fragments of living cells emitted from marine or terrestrial surfaces. PBAP are therefore broadly important because of their potentially deleterious role in human health, for example as allergens or as infectious agents in the cardio-pulmonary system.

They can also play critical, catalytic roles in atmospheric and biogeochemical reactors, influencing processes such as ice cloud and precipitation formation that can have far-reaching ecological and climate effects. They can also harm crops and livestock all over the world. Despite this multi-faceted importance, relatively little has been known about biological particles in the atmosphere until recently. Currently because of the health and climate change concerns mentioned above there is surging global interest in the capability to rapidly detect and characterize PBAP in both outdoor and indoor environments. 

The Fellow

Dr. David O'Connor

Introduction

An inter-comparison field campaign to assess the merits of current real-time bioaerosol instrumentation

The objectives of the UCC team to the BIODETECT2014 study are:

  • To participate in a summer inter-comparison campaign for testing Light/Laser Induced Fluorescence (LIF) methods for the detection and quantification of bioaerosols. Two sites in the Paris area will be used. (CEA Saclay and LHVP Central Paris). The UCC team will be located at LHVP.
  • During this period of the year, high concentrations of pollen and fungal spores are emitted into the air; these emissions have been shown to frequently coincide with pollution events. Accordingly, a key objective of the UCC campaign is to understand how LIF techniques operate in an urban/suburban environment, specifically with respect to their ability to discriminate bioaerosols from high concentrations of non-biological particles.

 The other research groups involved are from France, Finland, UK and USA.

Scientific Background

The need to measure the occurrence and development of aerosols in our atmosphere has increased dramatically in recent years. The necessity is based both on the undesirable effects that they have on our health and the role they play in climate change. The atmospheric aerosol does not, of course, consist of abiotic chemical components alone. Field measurements have shown that Primary Biological Atmospheric Particles (PBAPs) are also present and comprise of materials such as bacteria, bacterial endotoxins, viruses, protozoa, fungal spores, algae, plant fragments, pollen, oocysts and animal fragments (skin in particular). The diameters of these materials range between nanometres and hundreds of microns.

There is a need for rapid, robust and reliable measurements of bioaerosols to directly inform the public about potential bioaerosol overloads (say as precursors to asthma, COPD and hay fever for those at-risk). Fortunately in the last 10 years military-led research efforts have led to the development of real-time bioaerosol detectors and PBAP quantification technique, which are now commercially available. These exploit the fundamental principle that specific organic molecules of biological origin such as proteins, amino acids, cell wall compounds and pigments exhibit intrinsic fluorescence.

There are a number of instruments on the market that have been deployed in a variety of countries but as of yet there have been no systematic comparison campaigns performed to monitor the effectiveness of each method for measuring spores, bacteria and pollen in the air. Hence an inter-comparison study directed toward rapid/traditional bioaerosol detection is being organised in Saclay/Paris, France in July 2014 by Dr Roland Sarde-Esteve, CEA l’orme des merisiers.

Project Team

Co-ordinator – Prof John Sodeau
Co-Principal Investigator – Dr David O’Connor

Funding Details

Funded by – (i) the Irish Environmental Protection Agency (EPA) - Science, Technology, Research & Innovation for the Environment (STRIVE) Programme; (ii) CEA

Research theme - Environment and Human Health: a theme set up to improve knowledge to assist in the development and implementation of effective policy actions to reduce environmental impacts on human health.

Funding period – 2014

Funding cost - €9500

Research Study:

On-line monitoring of pollen and fungal spores in the field: a pilot study for MeteoSwiss,

Project Outline:

A 4.5-months long pilot field campaign was performed at the MeteoSwiss base in Payerne (March-July 2013) in order to compare the relative merits of traditional approaches to pollen/spore monitoring and counting with on-line techniques including the UCC WIBS (Waveband Integrated Bioaerosol Spectrometer).

Scientific Background:

The airborne monitoring of bioaerosols has become a research area attracting significant scientific interest over the last few years because of potential impacts on human health, plant-life and climate forcing. For example so-called Primary Aerosol Biological Particles (PBAP) such as pollen and fungal spores are known to induce allergic responses and thereby exacerbate reactions such as allergenic rhinitis (hay fever) and chronic obstructive pulmonary disease (COPD). These conditions are linked to exposures to certain species of biological particle.

Due to its novelty, methods based on the fluorescence of PBAP have been used only to a small extent for detecting and counting pollen by comparison to the impaction/light microscopy methodology. In fact, the only other studies (two) have been performed by us. Both campaigns were effective but carried out over only short (week-long) periods of time (in Killarney National Park and Munich). However they did act as a proof of principle that the WIBS on-line approach was able to give high correlation with results obtained by the traditional techniques. Hence the CRACLab team were invited to apply their expertise in a pilot study performed for MeteoSwiss at their monitoring station in Payerne during 2013.

The MeteoSwiss Campaign

The campaign focused mainly on the fine through to super coarse fraction of the ambient aerosol (ie particles with aerodynamic diameter between 1.5-22 µm). Increases in fluorescent particles were seen month on month from Spring to Summer and in addition a far greater fraction of the Summer total particles exhibited fluorescence due to their larger sizes. Diurnal trends for each of the months were constructed using both techniques. However more detailed information on the nature of particle fluorescence with regard to size and shape was also obtained.

The highest correlation for the results using the two techniques was in April, which coincided with the Birch pollination season. The reasons for this are that the size of Birch pollen fit exactly into the current WIBS sizing window. Very good correlations were also observed during the summer months, particularly when the largest amount of pollen (grass) were released. Additionally information on the release of fungal spores was obtained by the WIBS, a result that is extremely difficult and laborious to achieve with the traditional techniques because of their relatively small size and, often, hyaline (transluscent) natures. Important trends of pollen and spore release and detection as a function of various meteorological conditions (rainfall, relative humidity, wind direction/speed) were also determined in real-time.

Our initial conclusions were that currently (and mainly because of the lack of WIBS data-bases) that unambiguous identification of ambient bioparticles could not be attained. However the inherent capability of the collected real-time data was able to provide specific, high-risk days and times for analysts, using traditional impaction/light microscopy techniques, to focus on both for pollen and fungal spore identification/quantification. Hence more campaign experience and data-bases are required to help fulfill the obvious potential of WIBS. (A more extensive campaign of this type is to be performed in France during 2014).

Funding Details:

Funded by – MeteoSwiss, Switzerland
Funding period – 2013.
Funding cost - €25,000

Project Team:

Principal Investigators – Professor John Sodeau and Dr Bernard Clot
Post-doctoral Research Assistant – Dr David O’Connor

A project studying fine particles emitted from a metallurgical process (ferromanganese alloy manufacturer, Glencore Manganese France, in Dunkirk), to determine if and how properties of these particles (chemical composition, size, morphology) changed after being emitted. Our (the ATOFMS) role was to identify which ambient particles were produced by the ferromanganese plant, and to provide mixing state information for these particles. We also used the instrument to analyse samples from the plant's chimneys and of the ores used to make the alloy. Comparison between the ambient and sample mass spectra further confirmed sources and showed some differences in composition of particles at various stages of the alloy-making process and the effect ambient transport had

Website Link

Analysis of the Development and Occurence of Biological and Chemical Aerosols


Description

The main aims of this programme were to develop a complementary field monitoring and laboratory programme directed toward the analysis of natural (bioaerosol) components coincident with measurements of anthropogenic materials such as PM 10 and NO x for the Cork Harbour region. Novel instrumentation was used to investigate the Primary Biological Aerosol Particles (PBAP) in real-time and thereby provide key information on levels and identity of important allergens such as fungal spores and pollen. By this means an understanding of the processes by which particulate emissions, from both natural and anthropogenic sources are released to the Urban/Marine atmosphere in the Cork Harbour region will be developed. The EPA will thereby be provided with an assessment of the contribution of PBAP, PM 10 and NO x in both an inventory and source apportionment form.

The main target areas for study are:

- A thirty month continuous NO x (real-time) and PM 10 monitoring programme as a function of meteorological conditions, seasonality and composition within the Cork Harbour region.

- The proposed real-time measurements of PBAP will be the first in the world to use 2-D fluorescence technology developed in the last few years for the identification of airborne biological materials.

- A source apportionment model will be developed to increase our understanding of the way that anthropogenic pollutants interact with natural particulate-forming processes.

Project Team:

Staff: John Sodeau; Pat Whelan; Marcel Jansen
PDRA: Stig Hellebust and David Healy
PhD: EPA Scholarship, David O’Connor
M.Sc: Keith Linehan
PDRA: Crossover from ELIPSE, Ivan Kourtchev

Project Funding:

Period: 2008-2011
Cost: €736,381

Newsletter Download:

Biochea June 2009 Newsletter

Report Download:

EPA CCRP Report No. 18

Environmental Linkages between In-Port Ship Emissions of Particulate Matter, their Chemical Analyses and Effects on Health

Research Study:

Composition and Sources of Particulate Air Pollution in a Port Environment, Cork, Ireland.

Project Outline:

A twenty-eight month air pollution measurement campaign was performed between 2007 and 2009 at two selected sites, Tivoli Docks (upper harbour) and Haulbowline Naval Base (mid-harbour) in Cork Harbour. Off-line chemical analyses of constituents of the particulate matter with particle diameters less 2.5 mm (PM2.5) were complemented by real-time and semi-continuous measurements of particulate-phase elemental carbon, organic carbon and sulfate. These quantitative measurements together with knowledge on the internal mixing state of particles, using single particle mass spectrometry, allowed statistical analyses to be performed in order to estimate both the relative and absolute contributions to ambient PM2.5 mass concentrations of the various sources of airborne pollution in Cork Harbour.

Scientific Background:

The collection of reliable information about source contributions to levels of key chemical species that are known to adversely impact on human health is crucial for devising effective air quality strategies. Also, from a public health perspective, it is very valuable to have detailed datasets regarding the characterisation of air pollution sources particularly when applied to urban, industrialised regions of key national importance.

PM can be emitted directly into the atmosphere from processes such as combustion (primary particles) or they can be produced in the atmosphere as a result of different chemical reactions (secondary particles).  The particles are generally classified by their size rather than composition or shape. Thus “coarse” particles have aerodynamic diameters larger than 2.5 mm and “fine” particles possess diameters lower than 2.5mm. The principal urban source of PM10 is direct from road traffic emissions and contains much dust, coal and oil fly ash. By contrast, analysis of PM2.5 shows it to contain many more secondary species such as sulfate/nitrate ions and organic compounds. Such size and chemical distinctions are important because inhaled particles with diameters greater than 2.5mm are removed in the head or upper respiratory tract, while those smaller than 2.5mm in diameter can reach the lungs thereby representing a potentially major risk for human health.

One relatively ignored source of PM is that derived from world-wide ship emissions. This is because seagoing ships are not subject to the stringent air quality legislation, which is applied to road transport. However various emission estimates (based on engine-type and total/type of fuel consumed) for vessels both in port and in transit have been performed recently on behalf of the EU. They demonstrate the fact that ships make significant contributions to our pollution inventories of NOx, SO2, organic compounds, PM and CO2. For example, the 2002 estimate of PM in-port emissions for Europe was 21 ktonne/annum (excluding fishing vessels) and is calculated to rise to 24-28 ktonne/annum by 2010. These figures are subject to an uncertainty of some ± 45% and clearly require some verification by field measurement programmes. Clearly, acidic sulfate aerosols can be formed from such emissions. Furthermore hazardous constituents from the combustion of marine fuels (“bunker fuels”), including arsenic, cadmium, chromium, lead, nickel, vanadium and polycyclic aromatic hydrocarbons (PAH) can also be released into the air.

There is no information available regarding size distributions of particles emitted from ship engine exhaust although it is expected that, in common with most large diesel engines, >80% of emitted particulate matter will be PM10 or less. Measurement data about the chemical composition is also sparse but some inferences can be drawn from the following facts:

  • It has been calculated that the PAH-emissions from one fairly large vessel entering port will correspond to those from 1200 heavy trucks.
  • Currently, 50,000 ppm maximum sulfur content for ship fuel operates and compares to a 10 ppm maximum for petrol in cars from 2007. The sulfur content of diesel fuel affects PM emissions because some of the sulfur in the fuel is converted to sulfate particles in the exhaust. The fraction converted to PM varies from one engine to another, but reducing sulfur decreases PM linearly in almost all engines. 
  • The average sulfur content of marine heavy fuel oil used in European waters is 27,000 ppm and it is estimated that by 2010 emissions from ships will equal three-quarters of the EU total for sulfur (and nearly two-thirds of that for nitrogen oxides).
    • Ships currently release about twice as much NOx/ton-km than trucks and it is estimated that 22% of the total NOx air-pollution deposition in Ireland comes from ship emissions.
    • SO2 and NOx can become converted into secondary sulfate and nitrate particles. Ship emissions are estimated to contribute between 20 and 30 % to the air concentrations of these particles in most coastal areas.
    • In-port PM emissions differ significantly from average emission values due to the occurrence of cold-start/warm-starts, the use of auxiliary engines and also to manoeuvring procedures because engine loads change rapidly.

Project Team:

Co-ordinator – Professor John Sodeau

Co-Principal Investigator – Dr John Wenger

Post-doctoral Research Assistant – Dr Stig Hellebust, Dr Arnaud Allanic, Dr Ivan Kourtchev

Research Assistant – Ian O’Connor, Jenny Bell

Funding Details:

Funded by - the Irish Environmental Protection Agency (EPA) - Science, Technology, Research & Innovation for the Environment (STRIVE) Programme.

Research theme - Environment and Human Health: a theme set up to improve knowledge to assist in the development and implementation of effective policy actions to reduce environmental impacts on human health.

Funding period – 2007-2011.
Funding cost - €360,000

Report Download:

EPA Strive Report Series No. 71

Environmental Research Institute - Transfer of Atmospheric & Science Knowledge.

Introduction

A full understanding of the impact of atmospheric pollution on human health and the ecology of the Earth System requires a scientific approach, which links laboratory experiments to field measurements to predictive models. The resultant environmental knowledge can then underpin accurate risk assessments, appropriate risk management strategies and effectively define “clean air” to society.

Epidemiological studies especially have emphasised the role played by particulate matter on health. Adverse outcomes include exacerbation of respiratory symptoms, reduced lung function, chronic bronchitis, cardiovascular diseases and mortality. However toxicological studies suggest that the health effect of particles do depend on their chemical composition, which is particle-size dependent.

The Eritask team includes postdoctoral competence in the following four areas in order to make linkages between the field collection of particles, analysis of their chemical composition, sources and their health effects:
  • Field measurement of particulate matter;
  • “Total” chemical analysis of the particulate matter;
  • Source apportionment modelling;
  • Biochemical toxicology of air particulate components.

Further information on

Particulate Matter
Chemical Composition
Environmental Effects

• The Team

Prof. John Sodeau
Prof. James A. Heffron
Prof. John Wenger

Dr. Jose Manuel Lopez Sebastian
Dr. Andrew Whittaker
Dr. Emma Pere Trepat
Dr. Virginia Silvari

Dr. David Healy
Mary Mahony
Dr. Ian O'Connor

• Funding

Marie Curie Actions
EPA
IRCSET

Links
EUROCHAMP Website
EUROCHAMP Database

Project Summary

The project integrates the most important environmental reaction chambers in Europe for studying atmospheric processes into a Europe-wide infrastructure. The consortium of partners provide their expertise and experience in atmospheric chemistry to researchers of different disciplines, policy and industry and offer an infrastructure that can be used by interested parties for solving a large variety of problems related to atmospheric science. The major goals of the project are:

- the initiation of an effective interdisciplinary collaboration between the community of atmospheric scientists and colleagues from other disciplines that are closely related to it. This will be achieved through the three networking activities of EUROCHAMP.

- the optimisation and further development of the infrastructures' performance. In order to meet these goals, two corresponding research activities are defined in the EUROCHAMP work programme, namely the development and refinement of analytical equipment and the development of chemical modelling techniques.

Besides the project partners, a number of selected associated user groups with a high grade of expertise in the different fields of interest provide their experience either as advisers to special topics or as potential users of the infrastructure.

Overall Description & Fundamental Objectives Of EuroChamp

The fundamental objective of the project is the integration of existing European research facilities to a grid of reaction chambers. These facilities were created by multinational initiatives to study the impact of atmospheric processes on regional photochemistry, global change, as well as cultural heritage and human health effects under most realistic conditions.

Although initial advances in the application of large chambers occurred in the United States, Europe now leads the world in the use of large, highly instrumented chambers for atmospheric model development and evaluation. Smaller chambers that were designed for specific purposes and are operated by experts in their fields excellently support such chambers. The integration of all these environmental chamber facilities within the framework of the EUROCHAMP infrastructure promotes retention of Europe's international position of excellence in this area and is unique in its kind worldwide.

The mobilisation of a large number of stakeholders dealing with environmental chamber techniques provides an infrastructure to the research community at a European level that offers a maximum support for a broad community of researchers from different disciplines. The EUROCHAMP project initiates a currently not existing structuring effect of atmospheric chemistry activities performed in European environmental chambers, since it offers the full availability of corresponding facilities for the whole European scientific community.

With respect to the project objectives mentioned above, three network activities and two joint research activities are formulated and cross-linked in the EUROCHAMP project.

Networking activities
The major objective of the networking activities within the EUROCAHMP project is the initiation of an effective interdisciplinary collaboration between the community of atmospheric scientists and colleagues from other disciplines that are closely related to it. This will be achieved through the three networking activities of EUROCHAMP.

Networking activity N1
The objective of networking activity N1 is the generation and application of standardised rules as a method of quality assurance for raw data analyses of the experiments in each facility. For this purpose a number of inter-comparison studies applying analytical devices in reference experiments will be carried in the different chambers, which provides an indirect measure of the infrastructures' excellence.

Networking activity N2
In order to make the results of experiments performed in the partners’ facilities most transparent and accessible to the scientific community, a standardised data protocol for chamber studies will be defined. This standardised form will be the basis for the central database of environmental chamber studies to be constructed within the project. This WWW-based database will be made accessible to the whole scientific community, leading to a most effective dissemination of the results.

Networking activity N3
Within networking activity N3 four larger international conferences / workshops on infrastructure-related topics will be organised. In order to reach a maximum of success, internationally established experts on the corresponding topics will be invited to join these conferences. The results will be published in suitable proceedings for dissemination to the scientific community.

Joint research activities

The major objective of the joint research activities within the EUROCHAMP project is the optimisation andfurther development of the infrastructures' performance. In order to meet these goals, two correspondingresearch activities are defined in the EUROCHAMP work programme, namely the development and refinement of analytical equipment and the development of chemical modelling techniques.

Joint research activity JRA1

The development of novel and the refinement of existing analytical devices of environmental chambers in order to successfully detect atmospheric trace species or to characterise aerosol particles is an essential task to be followed over the whole lifetime of the EUROCHAMP research facilities. The increasing demands for more comprehensive analytical techniques caused by the more and more complex scientific questions to be answered, requires a continuous improvement of the technical possibilities of a chamber.
Accordingly, the project includes a number of research activities focused on this topic:
- characterisation of oxygenated volatile organic compounds (OVOCs),
- radical measurements (OH, HO2, RO2),
- nitric acid measurements,
- characterisation of aerosols.

Besides the optimisation of existing devices (1st objective), a number of analytical devices will be completely new designed and introduced for the first time in an environmental chamber (2nd objective).

The highly specific equipment will be developed in a mobile form, so that such instruments may be transported to a chamber of choice and used in selected experiments independent of localisation. This philosophy strengthens the idea of a real grid of environmental chambers forming a powerful infrastructure. In addition, the instruments to be developed will be of great use for future field campaigns for which sophisticated, improved analytical instrumentation is urgently required.

Joint research activity JRA2

The field of chemical modelling is directly coupled to each type of environmental chamber studies. The analysis of chamber experiments without any model application is mostly not possible. Accordingly, model activities are urgently necessary and a permanent companion of each experimental task.

1. Since the quality of simulation studies strongly depends on the question how exactly the chemical behaviour of the chamber itself is characterised, sensitive parameters urgently required for simulations have to be determined for each facility of the infrastructure (1 st objective). The dissemination of each result from such studies serves for a better interpretability of environmental chamber studies as a whole.

2. The second objective for model applications is the test of complex chemical mechanisms used for multi-phase model applications related to chamber experiments. An established chemical code for interpretation of chamber studies that can be applied to all facilities increases the quality of the whole infrastructure and offers new possibilities for solving open questions of interest for the European researchers’ community.

3. Furthermore, chemical models to be developed can be applied in the EUROCHAMP network for the solution of specific problems in atmospheric chemistry, e.g. development and validation of degradation mechanisms of organic pollutants that are of paramount importance, the investigation of atmospheric reactivity as an overall property under various conditions or the influence of alternative fuels or solvents as well as bio fuels on tropospheric chemistry (3 rd objective).

In conclusion, this philosophy strengthens the idea of a real grid of environmental chambers as powerful tool for system analysis increasing the value of the whole chambers infrastructure for the European research community.

EUROCHAMP Partners

1. Bergische Universität Wuppertal, Wuppertal, Germany.
2. Forschungszentrum Jülich, Jülich, Germany.
3. Fundación Centro de Estudios Ambientales de Mediterráneo, Valencia, Spain.
4. Universität Bayreuth, Bayreuth, Germany.
5. University College Cork, Cork, Ireland.
6. Centre National de la Rechèrche Scientifique (CNRS-LCSR), Orleans, France.
7. Paul-Scherrer-Institute, Villigen, Switzerland.
8. University of Leeds, Leeds, United Kingdom.
9. SP Swedish National Testing and Research Institute, Borås, Sweden.
10. Karlshrue Institute of Technology, Karlshrue, Germany.
11. Université Paris 12, France.
12. Leibniz Institute for Tropospheric Research, Leipzip, Germany.
13. University of Copenhagen, Denmark.
14. University of Manchester, UK.

Research Study:

Studies of the Chemical Composition and Toxicity of Airborne Fine Particles in Cork's Mid-Harbour:
T
oxicological Analysis and Chemical Correlation for Fine PM in transit to Cobh (TACCo)

Project Outline:

Particulate matter (PM) was collected over a period of one year (April 2007 to April 2008) in Cork Harbour, Ireland. A high-volume cascade impactor and polyurethane foam collection substrates were used in the collection process. The inorganic constituents found in the fine fraction of PM obtained at the mid-harbour site (Haulbowline Naval Base) were characterised by inductively coupled plasma - optical emission spectroscopy (ICP-OES) and ion chromatography. The ability of the fine PM collected to induce toxic effects on biological systems was experimentally investigated. Oxidative stress, cytotoxicity and inflammatory responses were measured in an in vitro system using A549 human lung epithelial cells.

Funding Details:

Funded by - the Irish Environmental Protection Agency (EPA) - Science, Technology, Research & Innovation for the Environment (STRIVE) Programme.

Research theme - Environment and Human Health: a theme set up to improve knowledge to assist in the development and implementation of effective policy actions to reduce environmental impacts on human health.

Funding period – 2009-2010.

Funding cost - €80,000

Additional Funding Bodies – IRCSET (PhD Scholarship), Cork City Council.

Scientific Background:

The World Health Organization has estimated that exposure to fine particulate matter (PM) in outdoor air leads to about 100,000 deaths annually in Europe and that the effect of PM on life expectancy may be of the order of one to two years. Causal linkage between atmospheric particles and human health has been proposed to depend on many factors including size, physical state and chemical composition. However exact interpretation of particulate behaviour in this regard is complex because PM sources vary widely and few studies have related their physical and chemical nature to toxicological testing. What is known, from many previous monitoring studies, is that airborne particles may be solid or liquid in nature and can possess diameters that vary between 0.002 and 100μm. However their shapes are rarely spherical and may be rod-like in nature or totally irregular. They are comprised of trace metals and other inorganic materials, elemental carbon, a variety of organic compounds and also water in varying ratios. Furthermore mortality rates, particularly in urban areas, have been statistically linked to levels of atmospheric particulates when acute lower respiratory symptoms have been observed.

Current interest in the health impacts related to chemical composition of the two types of PM are based on two main tenets: (1) the possibility that they contain surface-adsorbed carcinogens such as polyaromatic hydrocarbons (PAH), which can be released into the body; (2) the promotion of oxygen radical reactions by increasing the bio-availability of certain metals in particulate acidic environments. However before real progress is made in confirming the importance of these ideas many more source types of PM must be chemically analysed and physically characterized before being tested for bio-reactivity.

As mentioned above, the acidity of the emitted PM is important because it can control the bio-availability of many trace metals. This phenomenon is crucial because it has been shown in animal studies that the acute toxicity associated with certain atmospheric dusts is most likely the result of the levels of soluble zinc, vanadium, nickel and sulfate ions present. In other words toxicological effects, such as pulmonary hyper-reactivity and lung damage, caused by the deposition of particulate matter in the airways may depend on their aqueous leachable chemical constituents. All of the above materials have been observed in urban field measurements of particulate matter throughout the world because diesel contains many trace elements resulting from the crude oil sources and catalytic processes, which transform diesel distillate to diesel fuel.

Project Team:

Co-ordinator – Professor John Sodeau

Post-doctoral Research Assistant – Dr John Menton, Dr Siobhan Cashman

Research Assistant – Ian O’Connor

Report Download:

EPA Strive Report Series No. 85

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