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Exposures of Fire Fighters during Training Exercises
Dr. Brian E. McCarry, Lorraine Shaw, Don Shaw and Sujan Fernando
Occupational and Environmental Health Laboratory (OEHL)
McMaster University
Ontario Professional Fire Fighters Association, Health & Safety 2012 Delta Chelsea Hotel, Toronto
February 9, 2012
Fire Fighter Exposure Study: Research Goals
Overall Goal of Study: To assess exposures of fire fighters to chemicals during fires.
Exposures of Concern: Gases: carbon monoxide, aldehydes, hydrocarbons, VOCs, etc.
Volatile Organic Compounds: benzene, methoxyphenols, etc.
Semi-volatile Compounds: polycyclic aromatic hydrocarbons (PAH).
Particulate Material: fine and ultra-fine particles
Exposure Assessments: Air Exposures: monitor using active and passive samplers
Dermal Exposures: monitor by skin sampling
Internal Exposures: analyse chemicals and metabolites in urine.
Routes of Chemical Exposures
• Inhalation Exposures – when not wearing SCBA, e.g., during knockdown and overhaul.
• Ingestion Exposures - should be minimal for fire fighters.
• Dermal (skin) exposures – surprisingly little is known about skin exposures.
Fire Fighter Training Centre, Toronto Fire Department
Burn House Training Exercises conducted at:
Burlington, Hamilton (2x), Ottawa, Toronto
Sampling and Analysis: Air: particulate, gases (12), VOCs (17), PAH (25)
Skin: Different exposures at different sites on body?
Urine: Measures of true exposures
Occupational Exposure Limits: Aldehydes
Contaminant Ontario OEL
8 Hr
Ontario OEL
15 min
ACGIH TLV 8 Hr
ACGIH TLV 15 min
Formaldehyde 1 ppm 0.3 ppm, A2
Acrolein (Skin) 0.1 ppm 0.1 ppm, A4
Crotonaldehyde 0.2 ppm
Furfural (Skin) 2 ppm 2 ppm, A3
Acetaldehyde C 25 ppm, A3
Propionaldehyde 20 ppm 20 ppm
Polycyclic Aromatic Hydrocarbons (PAH) are by-products of incomplete combustion of carbon-based fuels (wood, plastic, coal, gasoline, diesel fuel, etc.). Some PAH are carcinogens*. PAH are metabolized and excreted as hydroxy-PAH. The levels of hydroxy-PAH in urine are considered to be an excellent measure of human PAH exposures whether via inhalation or ingestion (or dermal) routes.
Naphthalene** Anthracene** Chrysene
Benzo[a]pyrene* Coronene
PAH Primer
** indicates compound
exists primarily in gas phase
Satellite photo of wildfires north of Los Angeles, October 13, 2008
Many wildfire fire fighters are
exposed to high levels of smoke when fighting these fires. There
are serious concerns about smoke exposures of these fire fighters.
Exposures of Wildfire Fire Fighters
Simpson C., “Evaluation of Urinary Methoxyphenols as Biomarkers of Wood Smoke Exposure.” Environ. Sci. Technol., 2006, 40, 2163-2170.
Study found methoxyphenols in fire fighter urine and proposed these compounds served as markers of wood smoke exposures. We added 20 of these compounds to our suite of target analytes.
Air Sampling: • Active air samplers: Filters and tubes that use powered pumps
• Passive air samplers: Personal Passive Dosimeters (PPDs)
Twisters
Air Sampling Equipment
Twister® and 3M Personal Passive Dosimeter (PPD)
Gas sampling tube Particulate filter attached to an air pump.
Agilent 6890N Gas Chromatograph coupled to a Agilent 5973N MSD
Analytical Instrumentation
Ideal instrument for separation and analysis of volatile and semi-volatile compounds.
GC-MS Chromatogram of Smoke Extract (Twister)
6.00 7.00 8.00 9.00 10.00 11.00 12.00 13.00 14.00 15.00
50000
100000
150000
200000
250000
300000
350000
400000
450000
500000
550000
600000
650000
700000
Time-->
Abundance
TIC: SF100107F.D
1 2
3 4
5 6
7 8
Identification of Some Major Wood Smoke Components: (1) 2-methoxyphenol
(2) 2-methoxy-4-methylphenol
(3) 4-ethyl-2-methoxyphenol
(4) 2-methoxy-4-vinylphenol
(5) 2,6-dimethoxyphenol
(6) 2-methoxy-4-(1-propenyl)phenol
(7) 1,2,4-trimethoxybenzene
(8) 5-tert-butylpyrogallol
Methoxyphenols are major components of wood smoke, along with 1000’s of
other chemicals including PAH.
Toronto Fire Service Burn House Exercise
Air Sampling Equipment and Skin Sampling Sites
Air filter (particulate) and tube (gases)
Passive air samplers
Air pump for air filter and tube sampler
Skin sampling: back, fingers, forehead, neck, wrist
back
fingers
wrist
forehead
neck
Airborne Particulate Concentrations: 20 Firefighters at 5 Burn House Exercises
0
50
100
150
200
250
300
350
400 AF
D1
AFD
2 AF
D3
AFD
4 AF
D5
BFD
1 B
FD2
BFD
3 B
FD4
CFD
1 C
FD2
CFD
3 C
FD4
CFD
5 C
FD6
CFD
7 C
FD8
DFD
1 D
FD2
(lost
) D
FD3
EFD
1(lo
st)
EFD
2 EF
D3
EFD
4 EF
D5
Tota
l Par
ticul
ate
(mg/
m3 )
Firefighter ID
OEL 10 mg/m3
Formaldehyde Concentrations in Air 20 Fire fighters
0
2
4
6
8
10
12
Form
alde
hyde
(ppm
)
Firefighter ID
OEL 0.3 ppm
Formaldehyde ~ 2.5 % of TVOC
0 100 200 300 400
AFD
1 AF
D2
AFD
3 AF
D4
AFD
5
BFD
1 B
FD2
BFD
3 B
FD4
CFD
1 C
FD2
CFD
3 C
FD4
CFD
5 C
FD6
CFD
7 C
FD8
DFD
1 D
FD2
(lost
) D
FD3
EFD
1(lo
st)
EFD
2 EF
D3
EFD
4 EF
D5
Tota
l Par
ticul
ate
(mg/
m3 )
Firefighter ID
0 100 200 300 400 500 600 700
AFD
1 AF
D2
AFD
3 AF
D4
AFD
5
BFD
1 B
FD2
BFD
3 B
FD4
CFD
1 C
FD2
CFD
3 C
FD4
CFD
5 C
FD6
CFD
7 C
FD8
DFD
1 D
FD2
DFD
3
EFD
1 EF
D2
EFD
3 EF
D4
EFD
5
Firefighter ID
0 20 40 60 80
AFD
1 AF
D2
AFD
3 AF
D4
AFD
5
BFD
1 B
FD2
BFD
3 B
FD4
CFD
1 C
FD2
CFD
3 C
FD4
CFD
5 C
FD6
CFD
7 C
FD8
DFD
1 D
FD2
DFD
3
EFD
1 EF
D2
EFD
3 EF
D4
EFD
5
Firefighter ID
0 2 4 6 8
10 12
AFD
1 AF
D2
AFD
3 AF
D4
AFD
5
BFD
1 B
FD2
BFD
3 B
FD4
CFD
1 C
FD2
CFD
3 C
FD4
CFD
5 C
FD6
CFD
7 C
FD8
DFD
1 D
FD2
DFD
3
EFD
1 EF
D2
EFD
3 EF
D4
EFD
5
Tota
l VO
C
(mg/
m3)
B
TEX
(mg/
m3 )
Sampler lost during exercise
Comparison of Particulate and VOC Profiles
BTEX: ~ 10% of TVOC
Formaldehyde: ~ 2.5% of TVOC
Form
alde
yde
(ppm
)
Gas and Particle Phase Methoxyphenol Concentrations in Air and on Skin
Skin
0
1000
2000
3000
4000
5000
Con
cent
ratio
n (u
g/m
3 )
AFD
1AF
D2
AFD
3AF
D4
AFD
5
BFD
1BF
D2
BFD
3BF
D4
CFD
1C
FD2
CFD
3C
FD4
CFD
5C
FD6
CFD
7C
FD8
DFD
1D
FD2
DFD
3
Gas PhaseParticle Phase
Air
0
5
10
15
20
25
Con
cent
ratio
n (n
g/cm
2 )
AFD
1AF
D2
AFD
3AF
D4
AFD
5
BFD
1BF
D2
BFD
3BF
D4
CFD
1C
FD2
CFD
3C
FD4
CFD
5C
FD6
CFD
7C
FD8
DFD
1D
FD2
DFD
3
Gas Phase Particle Phase
Skin
0
100
200300
400
500
600700
800
900
Con
cent
ratio
n (u
g/m
3 )
AFD
1AF
D2
AFD
3AF
D4
AFD
5
BFD
1BF
D2
BFD
3BF
D4
CFD
1C
FD2
CFD
3C
FD4
CFD
5C
FD6
CFD
7C
FD8
DFD
1D
FD2
DFD
3
Gas PhaseParticle Phase
Gas and Particle Phase PAH in Air and on Skin
Air
0
1
23
4
5
67
8
9
Conc
entra
tion
(ng/
cm2 )
AFD
1AF
D2
AFD
3AF
D4
AFD
5
BFD
1BF
D2
BFD
3BF
D4
CFD
1C
FD2
CFD
3C
FD4
CFD
5C
FD6
CFD
7C
FD8
DFD
1D
FD2
DFD
3
Gas PhaseParticle Phase
Skin
Skin Sampling at Training Exercises:
Evaluation of Dermal Exposures to Smoke
Skin Sampling and Analysis Strategies
Skin Sampling Protocol:
There are no standard methods for sampling chemicals on skin.
We have used a filter paper wipe method with rubbing alcohol (isopropanol).
Fire fighters were sampled before and after exercise in training facility at 5 body sites:
back, fingers, forehead, neck and wrist
Alcohol on Filter Paper Wipe
Skin Sampling of Ottawa Fire Fighters
Methoxyphenol and PAH: Air and FF Skin Profiles
0
1000
2000
3000
4000
5000
Conc
entra
tion
(ug/
m3 )
AFD
1AF
D2
AFD
3AF
D4
AFD
5
BFD
1BF
D2
BFD
3BF
D4
CFD
1C
FD2
CFD
3C
FD4
CFD
5C
FD6
CFD
7C
FD8
DFD
1D
FD2
DFD
3
Methoxyphenols PAH
Air Sampler Profiles
FF Skin Profiles – All Sites
PAH and Methoxyphenol Concentrations at 5 Skin Sites
0
20
40
60
80
100
120
140
160
Con
cent
ratio
n (n
g/cm
2 )
AFD
1A
FD2
AFD
3A
FD4
AFD
5
BFD
1B
FD2
BFD
3B
FD4
CFD
1C
FD2
CFD
3C
FD4
CFD
5C
FD6
CFD
7C
FD8
DFD
1D
FD2
DFD
3
FingersBackForeheadNeckWrist
PAH and Methoxyphenol Percentage Compositions on Skin (n=20)
0
5
10
15
20
25
30
35
40
Wrist Neck Forehead Back Fingers
Perc
ent C
ompo
sitio
n
T-test (p values)
0.05 0.34 0.18 0.02
Conclusion: All skin sites receive identical chemical exposures except for fingers.
Urine Sampling after Training Exercise: Analysis of PAH Metabolites and
Methoxyphenols in Urine
HydroxyPAH and Methoxyphenols as Exposure Indicators
The determination of hydroxyPAH in urine is considered to be the best measure of PAH exposures in humans.
For many years, 1-hydroxypyrene was the only compound used as a PAH exposure marker. Today, a suite of hydroxyPAH is advocated as the new measure of PAH exposure (as used in NHANES Study).
Selected methoxyphenols are good indicators of wood smoke exposures.
Urine Sample
Criteria for Selection of a ‘Good’ Methoxyphenol Smoke Marker
Simpson C., “Evaluation of Urinary Methoxyphenols as Biomarkers of Wood Smoke Exposure.” Environ. Sci. Technol., 2006, 40, 2163-2170.
0
5000
10000
15000
20000
25000
26 07:12 26 12:00 26 16:48 26 21:36 27 02:24 27 07:12 27 12:00
Time (Hrs)
Con
cent
ratio
n (n
g/g
Cre
atin
ine)
BFD4BFD3DFD3AFD5CFD8
1. Low concentration of compound in all volunteers prior to smoke exposure 2. Low concentration in the second next-morning urine (post-exposure)
1 2
05000
1000015000200002500030000350004000045000
Conc
entra
tion
(ng/
g Cr
eatin
ine)
AFD
1AF
D2
AFD
3AF
D4
AFD
5
BFD
1BF
D2
BFD
3BF
D4
CFD
1C
FD2
CFD
3C
FD4
CFD
5C
FD6
CFD
7C
FD8
DFD
1D
FD2
DFD
3
Pre Exposure
Pre Exposure1-23Hrs Net24Hrs
0
500
1000
1500
2000
2500
3000
3500
Conc
entra
tion
(ng/
g Cr
eatin
ine)
AFD1
AFD2
AFD3
AFD4
AFD5
BFD1
BFD2
BFD3
BFD4
CFD1
CFD2
CFD3
CFD4
CFD5
CFD6
CFD7
CFD8
DFD1
DFD2
DFD3
Pre Exposure
Pre Exposure1-23Hrs Net24Hrs
Levels of Methylsyringol in Urine
Levels of 3 Hydroxyfluorenes in Urine
Methylsyringol and Hydroxyfluorene Levels in FF Urine
Good correlation between methylsyringol & hydroxyfluorene profiles in fire fighter urine.
Net Methylsyringol Levels in FF Urine
05000
1000015000200002500030000350004000045000
Co
nce
ntr
atio
n (n
g/g
C
reat
inin
e)
CF
D1
BF
D1
CF
D2
CF
D3
AF
D1
AF
D2
CF
D4
BF
D2
CF
D5
AF
D3
CF
D6
DF
D1
AF
D4
DF
D2
CF
D7
DF
D3
AF
D5
CF
D8
BF
D3
BF
D4
Pre Exposure
Pre Exposure1-23Hrs Net24Hrs
Sorted as lowest to highest methylsyringol levels: top 5 highlighted
24-h Time Profile of Methylsyringol in Urine (Top 5 FF)
Simpson C., “Evaluation of Urinary Methoxyphenols as Biomarkers of Wood Smoke Exposure.” Environ. Sci. Technol., 2006, 40, 2163-2170.
0
5000
10000
15000
20000
25000
26 07:12 26 12:00 26 16:48 26 21:36 27 02:24 27 07:12 27 12:00
Time (Hrs)
Co
nc
en
tra
tio
n (
ng
/g C
rea
tin
ine
)
BFD4BFD3DFD3AFD5CFD8
Post Exposure1
(6000 ± 4000)
Pre Exposure1
(700 ± 700)
Net Methylsyringol Levels in FF Urine
05000
1000015000200002500030000350004000045000
Co
nce
ntr
atio
n (n
g/g
C
reat
inin
e)
CF
D1
BF
D1
CF
D2
CF
D3
AF
D1
AF
D2
CF
D4
BF
D2
CF
D5
AF
D3
CF
D6
DF
D1
AF
D4
DF
D2
CF
D7
DF
D3
AF
D5
CF
D8
BF
D3
BF
D4
Pre Exposure
Pre Exposure1-23Hrs Net24Hrs
Sorted as lowest to highest methylsyringol levels: top 5 highlighted
Time Profile of Methylsyringol in 5 Low Exposure Firefighters
0
200
400
600
800
1000
26 07:12 26 12:00 26 16:48 26 21:36 27 02:24 27 07:12 27 12:00Time (Hrs)
Co
nc
en
tra
tio
n (
ng
/g C
rea
tin
ine
)
BFD2AFD1CFD3CFD4AFD2
Pre Exposure Values of Simpson
(700 ± 700)
Note: Scale on this graph is 25 times less than previous graph; same profiles
Methylsyringol is an excellent marker for wood smoke
Comparison: Methylsyringol Profiles in Air, on Skin and in Urine
0
100
200
300
400
500
Conc
entra
tion (
ug/m
3 )
CFD1
BFD1
CFD2
CFD3
AFD1
AFD2
CFD4
BFD2
CFD5
AFD3
CFD6
DFD1
AFD4
DFD2
CFD7
DFD3
AFD5
CFD8
BFD3
BFD4
0
0.5
1
1.5
2
2.5
3Co
ncen
tratio
n (ng
/cm2 )
CFD1
BFD1
CFD2
CFD3
AFD1
AFD2
CFD4
BFD2
CFD5
AFD3
CFD6
DFD1
AFD4
DFD2
CFD7
DFD3
AFD5
CFD8
BFD3
BFD4
0
5000
10000
15000
20000
25000
30000
35000
40000
45000
Conc
entra
tion
(ng/
g Cr
eatin
ine)
CFD1
BFD1
CFD2
CFD3
AFD1
AFD2
CFD4
BFD2
CFD5
AFD3
CFD6
DFD1
AFD4
DFD2
CFD7
DFD3
AFD5
CFD8
BFD3
BFD4
Air
Skin
Urine
Some correlation between air and skin profiles. Good correlation (13) Poorer correlation (7) No correlation between air and skin profiles to urine profiles.
Fluorene in Air and on Skin; Hydroxyfluorenes in Urine
0
5
10
15
20
25
30
35
Conc
entra
tion
(ug/
m3 )
CFD1
BFD1
CFD2
CFD3
AFD1
AFD2
CFD4
BFD2
CFD5
AFD3
CFD6
DFD1
AFD4
DFD2
CFD7
DFD3
AFD5
CFD8
BFD3
BFD4
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
Conc
entra
tion (
ng/cm
2 )
CFD1
BFD1
CFD2
CFD3
AFD1
AFD2
CFD4
BFD2
CFD5
AFD3
CFD6
DFD1
AFD4
DFD2
CFD7
DFD3
AFD5
CFD8
BFD3
BFD4
0
500
1000
1500
2000
2500
3000
3500
Conc
entra
tion
(ng/
g Cr
eatin
ine)
CFD1
BFD1
CFD2
CFD3
AFD1
AFD2
CFD4
BFD2
CFD5
AFD3
CFD6
DFD1
AFD4
DFD2
CFD7
DFD3
AFD5
CFD8
BFD3
BFD4
Air
Skin
Urine
Modest correlation between air and skin fluorene profiles. No correlation between air/skin fluorene profiles and hydroxyfluorene profiles in urine. There must be other routes of exposure.
Conclusions: Fire Fighter Exposures
Fire fighters training exercises experienced wide range of exposures to fire-generated chemicals (~100-fold range).
Gas-phase chemicals (aldehydes, VOCs, BTEX, PAH and methoxyphenols) showed different levels but similar profiles.
Skin analyses showed 4 sites had statistically identical exposures; fingers received slightly greater exposures. Skin exposures should be viewed as whole body exposures.
Methylsyringol and 3 hydroxyfluorenes are excellent urinary exposure markers and are cleared from the body within 18-20 h.
Reasonable correlation between air exposures and skin loadings.
No correlation between air exposures and skin loadings to levels of markers in urine. These exposures may be due to operational issues with breathing apparatus.
Acknowledgements We would like to thank:
the Ontario WSIB for funding this study.
Fire Services in Burlington, Hamilton, Ottawa and Toronto for all their cooperation and assistance.
the Ontario Professional Fire Fighters Association for their kind invitation to speak at this conference.
Contact Information
For more information about this study, please contact:
Dr. Brian E. McCarry or Lorraine Shaw Department of Chemistry and Chemical Biology
McMaster University 1280 Main St. West
Hamilton, ON L8S 4M1
Phone: 905-525-9140 ext. 24504 e-mail: mccarry@mcmaster.ca or shawl@mcmaster.ca
Methoxyphenol and PAH Concentrations in Air
0
1000
2000
3000
4000
5000
Con
cent
ratio
n (u
g/m
3 )
AFD
1A
FD2
AFD
3A
FD4
AFD
5
BFD
1B
FD2
BFD
3B
FD4
CFD
1C
FD2
CFD
3C
FD4
CFD
5C
FD6
CFD
7C
FD8
DFD
1D
FD2
DFD
3
Methoxyphenols
PAH
Methoxyphenol and PAH Concentrations on FF Skin
0
5
10
15
20
25
Con
cent
ratio
n (n
g/cm
2 )
AFD
1A
FD2
AFD
3A
FD4
AFD
5
BFD
1B
FD2
BFD
3B
FD4
CFD
1C
FD2
CFD
3C
FD4
CFD
5C
FD6
CFD
7C
FD8
DFD
1D
FD2
DFD
3
Methoxyphenols
PAH
Mean value of sum of five skin samples: back, fingers, forehead, neck, wrist
Gas Phase and Particle Phase Distribution of Compounds in Air
Methoxyphenols PAH
0
20
40
60
80
100G
uaia
col
Met
hylG
uaia
col
Ethy
lGua
iaco
l
Euge
nol
Prop
ylG
uaia
col
Syrin
gol
Isoe
ugen
ol
Met
hyls
yrin
gol
Ethy
lsyr
ingo
l
Acet
ovan
illone
Gua
iacy
lace
tone
Acet
osyr
ingo
ne
Buty
lsyr
ingo
ne
Prop
ylsy
ringo
l
Nap
htha
lene
2-m
ethy
lnap
htha
lene
1-m
ethy
lnap
htha
lene
Acen
apht
hyle
ne
Biph
enyl
Acen
apht
hene
Fluo
rene
Phen
enth
rene
Fluo
rant
hene
Pyre
ne
Benz
o[gh
i]flu
oran
then
e
Benz
o[c]
phen
anth
rene
Cyc
lope
nta[
cd]p
yren
e
Benz
[a]a
nthr
acen
e
Chr
ysen
e
Benz
o[b]
fluor
anth
ene
Benz
o[j]f
luor
anth
ene
Benz
o[k]
fluor
anth
ene
Benz
o[a]
fluor
anth
ene
Benz
o[e]
pyre
ne
Benz
o[a]
pyre
ne
Pery
lene
% G
as P
hase
AFDDFDBFDCFD
PM concentration in Air versus Particulate Organics on Skin
Particle Phase Compounds vs Particulate Matter
R2 = 0.6333
0
5
10
15
20
25
30
0 50 100 150 200 250
Particulate Matter in Air (mg/m3)
Sk
in C
on
ce
ntr
ati
on
(n
g/c
m2)
Clean-up of Urine Samples Solid Phase Extraction (SPE):
1. Load the urine sample onto SPE cartridge – many compounds adsorb to cartridge.
2. Rinse off unwanted compounds. Compounds of interest remain on cartridge.
3. Elute compounds of interest from cartridge and collect in tubes.
Various sizes and types of SPE cartridges
available
Urine samples being loaded onto SPE cartridges
Air Samplers on an Ottawa Fire Fighter
Air filter (particulate) and tube (gases)
Passive air samplers
Air pump for air filter and tube sampler
• Water (~95%)
• Expended foods and metabolic wastes (~5%)
• Metabolites consist of organic molecules and salts.
• Organic molecules in urine include urea, creatinine, uric acid and many other chemicals.
• Toxic and unneeded substances are:
1. excreted directly into the urine, or
2. chemically modified in the lung or liver then excreted in the urine.
Major Components of Urine
Urine Sample
5.00 6.00 7.00 8.00 9.0010.0011.0012.0013.0014.0015.0016.0017.0018.000
1e+07
2e+07
3e+07
4e+07
5e+07
6e+07
7e+07
Time-->
Abundance
TIC: SF90723A.D
5.00 6.00 7.00 8.00 9.0010.0011.0012.0013.0014.0015.0016.0017.0018.000
1e+07
2e+07
3e+07
4e+07
5e+07
6e+07
7e+07
Time-->
Abundance
TIC: SF100121B.D
Chromatogram of raw urine: before clean-up on SPE cartridge
Chromatogram of urine after clean-up on SPE cartridge
Analyses Before and After Sample Clean-up
Gas chromatography-mass spectrometry Analysis of Urine
Comparison: Methylsyringol Profiles in Air and on Skin
0
100
200
300
400
500
Conc
entra
tion
(ug/
m3 )
CFD1
BFD1
CFD2
CFD3
AFD1
AFD2
CFD4
BFD2
CFD5
AFD3
CFD6
DFD1
AFD4
DFD2
CFD7
DFD3
AFD5
CFD8
BFD3
BFD4
0
0.5
1
1.5
2
2.5
3
Conc
entra
tion
(ng/
cm2 )
CFD1
BFD1
CFD2
CFD3
AFD1
AFD2
CFD4
BFD2
CFD5
AFD3
CFD6
DFD1
AFD4
DFD2
CFD7
DFD3
AFD5
CFD8
BFD3
BFD4
Air
Skin
Net Methylsyringol Levels in FF Urines
05000
1000015000200002500030000350004000045000
Con
cent
ratio
n (n
g/g
Cre
atin
ine)
CFD
1B
FD1
CFD
2C
FD3
AFD
1A
FD2
CFD
4B
FD2
CFD
5A
FD3
CFD
6D
FD1
AFD
4D
FD2
CFD
7D
FD3
AFD
5C
FD8
BFD
3B
FD4
1-23Hrs Net
Fluorenes Concentration in Air and Skin
0
5
10
15
20
25
30
35
Con
cent
ratio
n (u
g/m
3 )
CFD
1BF
D1
CFD
2C
FD3
AFD
1AF
D2
CFD
4BF
D2
CFD
5AF
D3
CFD
6D
FD1
AFD
4D
FD2
CFD
7D
FD3
AFD
5C
FD8
BFD
3BF
D4
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
Con
cent
ratio
n (n
g/cm
2 )
CFD
1
BFD
1
CFD
2
CFD
3
AFD
1
AFD
2
CFD
4
BFD
2
CFD
5
AFD
3
CFD
6
DFD
1
AFD
4
DFD
2
CFD
7
DFD
3
AFD
5
CFD
8
BFD
3
BFD
4
Air
Skin
Net OH Fluorene levels in Urine
0
500
1000
1500
2000
2500
3000
3500
Con
cent
ratio
n (n
g/g
Cre
atin
ine)
CFD
1B
FD1
CFD
2C
FD3
AFD
1A
FD2
CFD
4B
FD2
CFD
5A
FD3
CFD
6D
FD1
AFD
4D
FD2
CFD
7D
FD3
AFD
5C
FD8
BFD
3B
FD4
1-23Hrs Net
Presentation Outline:
Research Goals
Background: Chemical products of combustion
Health effects of exposures
Occupational Exposure Limits
Sampling and analysis: Air, skin and urine sampling
Pilot Smoke Exposure study
Toronto Fire Service study
Conclusions
Fire Fighter Exposure Study
Particle-phase PAH and Methoxyphenol Concentrations on Skin
0
5
10
15
20
25
Con
cent
ratio
n (n
g/cm
2 )
AFD
1A
FD2
AFD
3A
FD4
AFD
5
BFD
1B
FD2
BFD
3B
FD4
CFD
1C
FD2
CFD
3C
FD4
CFD
5C
FD6
CFD
7C
FD8
DFD
1D
FD2
DFD
3
• The Ontario WSIB has funded a 3-year study titled: “Determination of Ontario Firefighter’s Exposure to
Particulate, Volatile and Semi-Volatile Organics During Fire Fighting Including Measurements of Air Concentrations, Skin Concentrations and PAH Metabolites in Urine.”
• Research work commenced in February, 2009.
• This presentation covers the last year of work.
Fire Fighter Exposure Study
Gases: • Aldehydes (e.g., formaldehyde, acrolein) • Carbon monoxide (CO) and carbon dioxide (CO2) • Oxides of nitrogen (NO, NO2)
Organic Compounds: • Methoxyphenols (products of lignin [wood] breakdown) • Polycyclic Aromatic Hydrocarbons (PAH) • Volatile Organic Compounds (VOCs)
Particulate Material: • Sub-micron particles (fine and ultra-fine particles)
Background – Products of Wood Combustion
Exposure Comparisons to US Population The NHANES Study
• National Health and Nutrition Examination Survey (NHANES) is a US program designed to assess the health and nutritional status of adults and children across the US.
• Annual monitoring of blood serum and urine of approximately 5,000 people from 15 locations across the US; all ages and all major ethnic backgrounds.
• NHANES monitors for >500 chemicals, including bio-monitoring of PAH metabolites in urine for smokers and nonsmokers.
• Fire fighters’ hydroxyPAH metabolite levels can compared to
NHANES values (i.e., average of US population).
Concentrations of Volatile Organics 20 Fire fighters (≈150 compounds detected)
0
100
200
300
400
500
600
700
TVO
C (m
g/m
3 )
Firefighter ID
Concentrations of BTEX in Air 20 Fire fighters (6 compounds)
0
10
20
30
40
50
60
70
BTE
X (m
g/m
3 )
Firefighter ID
BTEX = ~10% of TVOC
Fire Fighter Exposure Study: Methodology
Smoke Sampling: Burn house training exercises: Burlington, Hamilton (2x), Ottawa, Toronto
Sampling Method Development: Gases and VOCs: conventional occupational health sampling equipment
Air Samplers: conventional active samplers and various passive samplers
Skin Samples: new area of research – no ‘standard’ methods
Urine Samples: true measure of exposures to chemicals
Analytical methods have been developed to determine: Chemicals in the smoke
Chemicals on the skin
Chemicals in urine, pre- and post-exposure.
Occupational Exposure Limits: Benzene and Derivatives (BTEX)
Contaminant Ontario OEL
8 Hr Ontario OEL
15 min ACGIH TLV
8 Hr ACGIH TLV
15 min
Benzene (Skin) 0.5 ppm 2.5 ppm 0.5 ppm 2.5 ppm, A1
Ethyl benzene 100 ppm 125 ppm 100 ppm 125 ppm, A3
Toluene 20 ppm 20 ppm, A4
Xylene 100 ppm 150 ppm 100 ppm 150 ppm, A4
ACGIH Categories of Carcinogenicity:
A1 – Confirmed human carcinogen A2 – Suspected human carcinogen A3 – Confirmed animal carcinogen with unknown relevance to humans
Chemical Analysis of Wood Smoke Extract
6.00 7.00 8.00 9.00 10.00 11.00 12.00 13.00 14.00 15.00
50000
100000
150000
200000
250000
300000
350000
400000
450000
500000
550000
600000
650000
700000
Time-->
Abundance
TIC: SF100107F.D
1 2
3 4
5 6
7 8
PAH are minor components in this chromatogram
14.0014.1014.2014.3014.4014.5014.6014.7014.8014.9015.0015.10
10000
15000
20000
25000
30000
35000
40000
45000
50000
55000
60000
65000
70000
75000
80000
Time-->
Abundance
TIC: SF100107F.D
14.36
14.82
Fluoranthene Pyrene
Comparison: Air Particulate and Particle Phase PAH and Methoxyphenols
0
5
10
15
20
25
Concen
tration (
ng/cm2 )
AFD1
AFD2
AFD3
AFD4
AFD5
BFD1
BFD2
BFD3
BFD4
CFD1
CFD2
CFD3
CFD4
CFD5
CFD6
CFD7
CFD8
DFD1
DFD2
DFD3
Profiles of Hydroxyfluorenes in Urine: Before and After Exposures
0
500
1000
1500
2000
2500
3000
3500
Con
cent
ratio
n (n
g/g
Cre
atin
ine)
CFD
1B
FD1
CFD
2C
FD3
AFD
1A
FD2
CFD
4B
FD2
CFD
5A
FD3
CFD
6D
FD1
AFD
4D
FD2
CFD
7D
FD3
AFD
5C
FD8
BFD
3B
FD4
Pre Exposure
Pre Exposure1-23Hrs Net24Hrs
Recommended