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Particulate Air pollution

             Prof.
        Pat Goodman
(On Behalf of the Project Team)
Why worry about Particulate air
               pollution?
•   Adverse health effects
•   Death! (Dublin 1982)
•   Harvard 6 cities (Reduced Life expectancy)
•   The Environment itself
Dublin 1982SMOG 1982 Rates
             Dublin Case Fatality
Kelly and Clancy, Irish Medical Journal; 77:10: 322-324. 1984


          10


           9


           8


           7
    CFR




           6


           5


           4


           3


           2

                 J a n '8 0   J a n '8 1     J a n '8 2   J a n '8 3

                                    D a te
Harvard 6 cities study




    Dr Pat Goodman EPA Conference
           Portlaoise Oct 2006
Daytime in Dublin Jan. 1982
Effect of Air Pollution Control on
            Mortality in Dublin
                   Clancy et al, Lancet


• Effect of ban on sale of    • Effect on mortality
  coal on air pollution in       –   7%    Total Mortality
  Dublin                         –   13%   Cardiovascular
  – 36 g/m3 BS (-71%)            –   16%   Respiratory
  – 11 g/m3 SO 2 (-34%)          –   3%    Other
Goodman, Rich, Zeka, Clancy and
                            Dockery. JAWMA 2009
                                                                                 1998 Ban Cities
                      100
                                                     Arklow         Drogheda           Dundalk            Limerick       Wexford

                       90
                                                                                                                          1998 Ban

                       80

                       70
Black Smoke ( g/m3)




                       60

                       50

                       40

                       30

                       20

                       10

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                            1980 1981 1982 1983 1984 1985 1986 1987 1988 1989 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006
Goodman, Rich, Zeka, Clancy and Dockery. JAWMA 2009
                                                                      2000 Ban Cities
                      100
                                            Celbridge        Galway        Leixlip           Naas           waterford
                       90
                                                                                                                     2000 Ban
                       80

                       70
Black Smoke ( g/m3)




                       60

                       50

                       40

                       30

                       20

                       10

                        0
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                            198019811982198319841985198619871988198919901991199219931994199519961997199819992000200120022003200420052006
The Current Study
The Contribution of Solid Fuel
Use to Particulate and PAH Air
     Pollution in Ireland
Collaborative Team Project
• DIT
   – Project lead
   – Literature Review
   – Chemical Analysis

• DCC
   – Site selection
   – Running of monitoring networks (BS and PM)
   – Staff training
• HSE
   – Local management of monitoring networks

   Harvard Advisor
   Prof. Doug Dockery
Study components
• Air pollution monitoring
  – PM10/2.5
  – Black Smoke
• Chemical analysis of samples
  – BaP and PAHs
• Literature review

• Final report
Monitoring site selection and
        Populations (2006 CSO)
• Navan          24,851
  – Has natural gas and no coal ban
• Killarney      14,603
  – No natural gas, no coal ban
• Tralee         22,744
  – Coal ban but no natural gas
• Letterkenny    17,586
  – No coal ban and no natural gas
Site selection
• Have support of local HSE staff

• Local staff have been trained to change filters and
  check on the equipment

• Filters are sent to DCC/DIT for weighing and
  chemical analysis

• Periodic site visits by DCC and DIT staff
Monitoring
• Measurement of Black Smoke throughout 12
  month period
• Dichot Partisols used for measurement of
  PM2.5 and PM10 at chosen sites, each for a
  total of 6 months
• Monitoring split to measure during both
  summer and winter periods
• Chemical analysis of PM filters and a selection
  of Black Smoke filters
Chemical Analysis
• Quantitative Analysis is being undertaken for the 7 USEPA PAH
  ( Benz(a)anthracene, benzo(a)
  pyrene, benzo(b)fluoranthene, benzo(k)fluoranthene, chrysen
  e, dibenz(a,h)fluoranthene, indeno(1,2,3-c,d)pyrene) all of
  which are suspected carcinogens and known products of fossil
  fuel combustion.


• The analysis is being conducted using High Performance
  Liquid Chromatography (HPLC) with diode array and
  programmable fluorescence detectors in series. Fluorescence
  excitation and emission wavelengths will be optimised for
  each PAH using PAH standards.
Site selection Navan
April 1st – June 27th
January 2012–March 2012

3 local staff involved
Site Selection - Tralee
24th March – 26th June
January 2012 – March 2012
1 local staff member involved
Site Selection - Killarney
28th June 2011 – January 2012
1 local staff member involved
Site Selection - Letterkenny
8th July 2011 – January 2012
4 local staff involved
Filter from 5th November - Letterkenny
PAH Analysis


Sample Treatment
•   Extraction: filter sonicated for 60 min in 30 ml acetonitrile

•   Volume Reduction: Turbovap at 40oC to 0.5 ml followed by
    addition of internal standard (B(e)P) and made up to 1 ml.

•   Analysis: HPLC with fluorescence detection
Interim Results
• Monitoring is not completed yet
• Data presented is based on a data gathered to
  date (but not on a full year)
Town                        A     B    C    D     Dublin
Units all μgm-3


PM2.5


                  Average   14    7    14   5      11

                     Max    62    47   51   53     51

PM10


                  Average   46    11   19   22     14

                     Max    313   62   53   203    48

BS


                  Average   15    5    5    4       4

                     Max    32    34   25   21     32
PAH TEF Value in relation
                              to upcoming legislated limit during episodes




                  4.5
                    4
                  3.5
PAH - TEF Value




                    3
    ngm-3




                  2.5
                    2                                                        pm2.5
                  1.5                                                        pm2.5-10
                    1                                                        EU Limit
                  0.5                                                        Linear (EU Limit)
                    0
                        A Annual   B Annual     C Annual   D Annual
                                         Urban Site
PAH                 Toxic Equivalency Factor   Maximum Episodic Concentrations Determined (ngm-3)
                    (unitless)*


                                               Site A                      Site B                      Site C                      Site D

                                               Date of event:              Date of event: 30/03/2011   Date of event: 03/04/2011   Date of event: 15/12/2011

                                               15/07/2011




B(a)P               1.0                        12.8                        1.99                        1.77                        1.72




B(a)Anth            0.1                        ND                          0.20                        ND                          0.86




Chrys               0.01                       ND                          0.59                        ND                          0.42




B(b)Fl              0.1                        12.9                        2.07                        0.21                        3.26




B(k)Fl              0.1                        5.6                         0.33                        0.41                        0.84




Dibenz              1.0                        ND                          ND                          ND                          ND




TEF Value (B(a)P)                              13.49                       2.26                        1.83                        2.22

(ngm-3)
Overlay of Filter Extract and PAH standard




       Letterkenny pm2.5 14/10/2011
                                        B(a)P




50 ppb PAH Standard
Overlay of Filter Extract and PAH standard



                     Letterkenny pm2.5 5/11/2011
                              Estimated at ~350ppb




                                      B(a)P


50 ppb Standard
Issues and Problems
• Initial filters were faulty
• PM2.5-PM10 fraction need to do batch
  analysis to for PAH work
• HPLC is limited, GC mass spec ordered

• Exploring possibility of x-Ray flour with Prof
  Dockery
Discussion and Conclusions
• Work is ongoing, final report due end Nov
  2012
• Some PM levels giving cause for concern
• As data is interim more detailed analysis
  incorporating meteorological data is needed
• Domestic heating is most likely the source of
  the higher levels observed
Any Questions?

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Particulate Air Pollution - Pat Goodman

  • 1. Particulate Air pollution Prof. Pat Goodman (On Behalf of the Project Team)
  • 2. Why worry about Particulate air pollution? • Adverse health effects • Death! (Dublin 1982) • Harvard 6 cities (Reduced Life expectancy) • The Environment itself
  • 3. Dublin 1982SMOG 1982 Rates Dublin Case Fatality Kelly and Clancy, Irish Medical Journal; 77:10: 322-324. 1984 10 9 8 7 CFR 6 5 4 3 2 J a n '8 0 J a n '8 1 J a n '8 2 J a n '8 3 D a te
  • 4. Harvard 6 cities study Dr Pat Goodman EPA Conference Portlaoise Oct 2006
  • 5. Daytime in Dublin Jan. 1982
  • 6. Effect of Air Pollution Control on Mortality in Dublin Clancy et al, Lancet • Effect of ban on sale of • Effect on mortality coal on air pollution in – 7% Total Mortality Dublin – 13% Cardiovascular – 36 g/m3 BS (-71%) – 16% Respiratory – 11 g/m3 SO 2 (-34%) – 3% Other
  • 7. Goodman, Rich, Zeka, Clancy and Dockery. JAWMA 2009 1998 Ban Cities 100 Arklow Drogheda Dundalk Limerick Wexford 90 1998 Ban 80 70 Black Smoke ( g/m3) 60 50 40 30 20 10 0 w w w w w w w w w w w w w w w w w w w w w w w w w w w a v s 1980 1981 1982 1983 1984 1985 1986 1987 1988 1989 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006
  • 8. Goodman, Rich, Zeka, Clancy and Dockery. JAWMA 2009 2000 Ban Cities 100 Celbridge Galway Leixlip Naas waterford 90 2000 Ban 80 70 Black Smoke ( g/m3) 60 50 40 30 20 10 0 w w w w w w w w w w w w w w w w w w w w w w w w w w w s a v 198019811982198319841985198619871988198919901991199219931994199519961997199819992000200120022003200420052006
  • 10. The Contribution of Solid Fuel Use to Particulate and PAH Air Pollution in Ireland
  • 11. Collaborative Team Project • DIT – Project lead – Literature Review – Chemical Analysis • DCC – Site selection – Running of monitoring networks (BS and PM) – Staff training • HSE – Local management of monitoring networks Harvard Advisor Prof. Doug Dockery
  • 12. Study components • Air pollution monitoring – PM10/2.5 – Black Smoke • Chemical analysis of samples – BaP and PAHs • Literature review • Final report
  • 13. Monitoring site selection and Populations (2006 CSO) • Navan 24,851 – Has natural gas and no coal ban • Killarney 14,603 – No natural gas, no coal ban • Tralee 22,744 – Coal ban but no natural gas • Letterkenny 17,586 – No coal ban and no natural gas
  • 14. Site selection • Have support of local HSE staff • Local staff have been trained to change filters and check on the equipment • Filters are sent to DCC/DIT for weighing and chemical analysis • Periodic site visits by DCC and DIT staff
  • 15. Monitoring • Measurement of Black Smoke throughout 12 month period • Dichot Partisols used for measurement of PM2.5 and PM10 at chosen sites, each for a total of 6 months • Monitoring split to measure during both summer and winter periods • Chemical analysis of PM filters and a selection of Black Smoke filters
  • 16. Chemical Analysis • Quantitative Analysis is being undertaken for the 7 USEPA PAH ( Benz(a)anthracene, benzo(a) pyrene, benzo(b)fluoranthene, benzo(k)fluoranthene, chrysen e, dibenz(a,h)fluoranthene, indeno(1,2,3-c,d)pyrene) all of which are suspected carcinogens and known products of fossil fuel combustion. • The analysis is being conducted using High Performance Liquid Chromatography (HPLC) with diode array and programmable fluorescence detectors in series. Fluorescence excitation and emission wavelengths will be optimised for each PAH using PAH standards.
  • 17. Site selection Navan April 1st – June 27th January 2012–March 2012 3 local staff involved
  • 18. Site Selection - Tralee 24th March – 26th June January 2012 – March 2012 1 local staff member involved
  • 19. Site Selection - Killarney 28th June 2011 – January 2012 1 local staff member involved
  • 20. Site Selection - Letterkenny 8th July 2011 – January 2012 4 local staff involved
  • 21. Filter from 5th November - Letterkenny
  • 22. PAH Analysis Sample Treatment • Extraction: filter sonicated for 60 min in 30 ml acetonitrile • Volume Reduction: Turbovap at 40oC to 0.5 ml followed by addition of internal standard (B(e)P) and made up to 1 ml. • Analysis: HPLC with fluorescence detection
  • 23. Interim Results • Monitoring is not completed yet • Data presented is based on a data gathered to date (but not on a full year)
  • 24. Town A B C D Dublin Units all μgm-3 PM2.5 Average 14 7 14 5 11 Max 62 47 51 53 51 PM10 Average 46 11 19 22 14 Max 313 62 53 203 48 BS Average 15 5 5 4 4 Max 32 34 25 21 32
  • 25. PAH TEF Value in relation to upcoming legislated limit during episodes 4.5 4 3.5 PAH - TEF Value 3 ngm-3 2.5 2 pm2.5 1.5 pm2.5-10 1 EU Limit 0.5 Linear (EU Limit) 0 A Annual B Annual C Annual D Annual Urban Site
  • 26. PAH Toxic Equivalency Factor Maximum Episodic Concentrations Determined (ngm-3) (unitless)* Site A Site B Site C Site D Date of event: Date of event: 30/03/2011 Date of event: 03/04/2011 Date of event: 15/12/2011 15/07/2011 B(a)P 1.0 12.8 1.99 1.77 1.72 B(a)Anth 0.1 ND 0.20 ND 0.86 Chrys 0.01 ND 0.59 ND 0.42 B(b)Fl 0.1 12.9 2.07 0.21 3.26 B(k)Fl 0.1 5.6 0.33 0.41 0.84 Dibenz 1.0 ND ND ND ND TEF Value (B(a)P) 13.49 2.26 1.83 2.22 (ngm-3)
  • 27. Overlay of Filter Extract and PAH standard Letterkenny pm2.5 14/10/2011 B(a)P 50 ppb PAH Standard
  • 28. Overlay of Filter Extract and PAH standard Letterkenny pm2.5 5/11/2011 Estimated at ~350ppb B(a)P 50 ppb Standard
  • 29. Issues and Problems • Initial filters were faulty • PM2.5-PM10 fraction need to do batch analysis to for PAH work • HPLC is limited, GC mass spec ordered • Exploring possibility of x-Ray flour with Prof Dockery
  • 30. Discussion and Conclusions • Work is ongoing, final report due end Nov 2012 • Some PM levels giving cause for concern • As data is interim more detailed analysis incorporating meteorological data is needed • Domestic heating is most likely the source of the higher levels observed