on-site real-time air monitoring for chemical emergencies
TRANSCRIPT
Centre d’expertise en analyse environnementale
du Québec
On-Site Real-Time Air Monitoring
for Chemical Emergencies
Dominic Lortie, M.Sc. Chemist
Centre d’expertise en analyse environnementale
du Québec
CEAEQ – The Organization
X
X X
Centre d’expertise en analyse environnementale
du Québec
CEAEQ – The Organization
…is an agency within the Ministry of the
Environment of the Province of Québec…
– Laboratory analyses (chemistry, biology, microbiology)
– Accreditation and proficency testing
– Ecotoxicological studies
– Field studies (emergencies)
Centre d’expertise en analyse environnementale
du Québec
Field Studies – Emergency Team
5 Chemists + 2 technicians
Services supported by mobile laboratories
– Analytical and scientific support
– In-situ sampling and analysis (water, air, soil, etc.)
– Real-time air and water monitoring
– Emission source identification and localization
– Surveillance of decontamination activities
– Calibration and maintenance of field instruments
– Training of emergency responders
Centre d’expertise en analyse environnementale
du Québec
TAGA Mobile Laboratory
TAGA : « Trace Atmospheric Gas Analyzer »
Real-time in-situ analysis
of vapors, gases and
particulate matters using
a tandem mass
spectrometer (MS/MS)
and other instruments
Centre d’expertise en analyse environnementale
du Québec
MS/MS
Thermo Quantum Discovery MAX
Customized source housing
APCI source
APPI capabilities
Syringe system for standard
injection
Spring and air cushion table
Centre d’expertise en analyse environnementale
du Québec
Calibration and QC C:\Xcalibur\...\Cepsa14062013 2013-06-14 07:24:52
RT: 0.00 - 692.05
0 50 100 150 200 250 300 350 400 450 500 550 600 650
Time (min)
0
20
40
60
80
100
Re
lative
Ab
un
da
nce
680.92
650.78
646.4824.99
601.70138.02644.97594.06540.1829.00 131.49 142.84 531.87 611.00280.8869.44 564.14426.45 484.27252.19 412.43369.57294.49 350.40161.27 234.02
NL:
1.12E6
TIC M S
Cepsa140620
13
RT: 0.00 - 692.05
0 50 100 150 200 250 300 350 400 450 500 550 600 650
Time (min)
0
20
40
60
80
100
Re
lative
Ab
un
da
nce
678.24646.27
601.70
644.3020.92 133.34
593.04
588.50 609.17131.55
69.44 517.1622.20 118.43 280.87135.23 529.31510.95196.83 218.07 413.06 445.49357.91306.63
NL: 3.66E5
TIC F: + c APCI
sid=10.00 SRM ms2
[42.500-43.500] MS
Cepsa14062013
RT: 0.00 - 692.05
0 50 100 150 200 250 300 350 400 450 500 550 600 650
Time (min)
0
20
40
60
80
100
Re
lative
Ab
un
da
nce
646.48
20.88
133.38
676.96642.29131.49
640.51118.42 280.8822.21 608.3969.44 412.61 445.85196.88 357.95321.44 555.13266.14 488.83 506.22162.13
NL: 4.07E5
TIC F: + c APCI
sid=10.00 SRM ms2
[60.500-61.500] MS
Cepsa14062013
RT: 0.00 - 692.05
0 50 100 150 200 250 300 350 400 450 500 550 600 650
Time (min)
0
20
40
60
80
100
Re
lative
Ab
un
da
nce
680.92
650.78
24.99138.02
29.00 142.84566.10529.26413.17 506.35445.67357.90 589.51 628.2954.83 233.80217.89 322.42303.4286.60 110.023.89
NL: 1.12E6
TIC F: + c APCI
sid=10.00 SRM ms2
[32.612-33.612] MS
Cepsa14062013
Centre d’expertise en analyse environnementale
du Québec
10 Other Fixed Instruments
Total Polyaromatic Hydrocarbons • Ecochem PAS 1000i
Nitrogen Oxides • Thermo 42i
Particles • GRIMM 180
Centre d’expertise en analyse environnementale
du Québec
10 Other Fixed Instruments
Sulfur Dioxide • API 100E
Total Reduced Sulfurs • CDN-101 thermal oxidizer
Sulfur Compounds • Chromatotec Chroma-S
BTEX and VOCs • Chromatotec AirmoBTX
Centre d’expertise en analyse environnementale
du Québec
10 Other Fixed Instruments
Mercury • Tekran 2537B
Metals • Pall XACT 625
δ13C signature for CO2 and CH4 • Piccaro G2201-i CRDS isotopic carbon
analyzer
Centre d’expertise en analyse environnementale
du Québec
Portable Spectrometers
GC-MS • Inficon Hapsite E/R
FTIR • Gasmet DX-4040
UV • Cerex UV Hound
Centre d’expertise en analyse environnementale
du Québec
Other Portables
O2, LEL, CO,
H2S, Cl2, NH3
4 gases + PID
(MAH, NH3, etc)
FID / PID
Particulate matters
Combustibles
CH4
O2, CO2, CH4
VOC, NH3,
aldehydes, etc.
VOC
Centre d’expertise en analyse environnementale
du Québec
Remote Monitors
Centre d’expertise en analyse environnementale
du Québec
Local Weather Conditions
Centre d’expertise en analyse environnementale
du Québec
TAGA Interventions
Fire Sites
– Forest
– Tires
– Landfills
– Material storage
Real-time measurements of
PAH, particulate matters, SO2,
H2S, NOX and other chemicals
near the fire and in
surrounding residential areas
Centre d’expertise en analyse environnementale
du Québec
TAGA Interventions
Industrial fires
Real-time monitoring of VOCs,
inorganic substances (HCN, HCl,
Cl2, NH3, etc.), aldehydes,
monomers, etc. until reintegration
of evacuated areas
Centre d’expertise en analyse environnementale
du Québec
TAGA Interventions
Chemical spills Real-time monitoring of
chemical substances released
in ambient air
April 2007
Sichem Aneline
(Benzene)
October 2005
Sodium hydrosulfite
(H2S, SOX)
Centre d’expertise en analyse environnementale
du Québec
Recent Emergency Interventions – 2013
July Train accident and explosion BTEX
June Fireworks warehouse explosion SO2
April Home evacuation CO2
March Tire warehouse fire SO2
Centre d’expertise en analyse environnementale
du Québec
Recent Emergency Interventions – 2012
October Massive mining blast NO2
May Dry material landfill fire CO, PM2.5
May Hydrogen cyanide release HCN
May Food-processing plant fire HCN, NH3
Centre d’expertise en analyse environnementale
du Québec
Recent Emergency Interventions – 2011
October Car salvage yard fire Hg, SO2
July Artificial plants fire HCl, Cl2
June Magnesium industry fire NH3, BTEX
April Home evacuations CO
March Abandoned plant fire BTEX
Centre d’expertise en analyse environnementale
du Québec
Results
Case 1
– Petroleum train derailment and explosion
Case 2
– Emission of toxic fumes from an industrial processing plant
Case 3
– Unknown substance odour coming from sewer
Centre d’expertise en analyse environnementale
du Québec
Case 1 – Summary
July 6th 2013
– A stopped train of 72 cars filled with petroleum
starts moving, no-one on board, at around
1:00AM. The train, going downhill, speeds up
rapidly to miss a curve and derails in downtown
Lac-Mégantic at 1:14 AM. Massive explosions
followed by a huge petroleum fire occur. It will
take 36 hours to extinguish the fire.
Centre d’expertise en analyse environnementale
du Québec
Case 1 – Summary
Centre d’expertise en analyse environnementale
du Québec
Case 1 – Summary
Centre d’expertise en analyse environnementale
du Québec
Case 1 – Summary
Centre d’expertise en analyse environnementale
du Québec
Case 1 – Summary
Centre d’expertise en analyse environnementale
du Québec
Case 1 – Summary
TAGA team is reached and starts doing real-time ambient air analysis a few hours later – PAH – NOX
– BTEX – SO2
– Particulate matters – CO
Results from the TAGA are very useful to the first responders, identifying another complete residential area that needs to be evacuated. Around 1000 more people are evacuated based on these results
Centre d’expertise en analyse environnementale
du Québec
Case 1 – Results
0
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23:3
0:0
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23:3
6:0
9
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23:4
8:2
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23:5
4:3
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6
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2:0
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:49
:20
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:55
:20
1
2
3
1
Total PAH (ng/m3)
TSP and PM2.5 (µg/m3)
2 3
Concentration (µg/m3)
B T E X
1 1 1 <1 <1
2 290 120 27 91
3 34 26 11 60
Centre d’expertise en analyse environnementale
du Québec
Case 2 – Summary
July 21st 2011
– Saint-Félix-de-Valois’ Fire Department is
contacted by a citizen not feeling good because
of bad air quality. Firefighters find toxic fumes
coming from a chick hatchery which uses a mix
of formol and potassium permenganate to
sterilize the hatchers. The citizen’s house is
less than 3 meters away from the hatchery
Centre d’expertise en analyse environnementale
du Québec
Case 2 – Summary
Centre d’expertise en analyse environnementale
du Québec
Case 2 – Summary
TAGA team is contacted to identify and
quantify ambient air contaminants in this
area
– Methanol
– Formaldehyde
– Dimethoxymethane
– Formic acid
Centre d’expertise en analyse environnementale
du Québec
Case 2 – Results
Formaldehyde
Average Average Maximum Average Maximum Average Maximum
20 h 35 - 20 h 50 < 19 < 10 < 10 < 10 < 10 < 83 < 83
21 h 26 - 21 h 41 140 96 2530 75 2600 < 83 190
21 h 42 - 21 h 57 190 45 340 50 470 < 83 130
21 h 57 - 22 h 12 < 57 < 10 87 < 10 55 < 83 91
PeriodConcentration (µg/m
3)
Methanol Dimethoxymethane Formic acid
Concentrations are followed in real-time with the
mass spectrometer
Formaldehyde measurements based on TO-11A
method from US EPA
Centre d’expertise en analyse environnementale
du Québec
Case 2 – Results RT: 78.0 - 160.9
80 90 100 110 120 130 140 150 160
Time (min)
20
40
60
80
100
20
40
60
80
100
Re
lative
Ab
un
da
nce
20
40
60
80
100108.2 108.7
108.1
107.5
113.7
115.6 117.5
106.8
121.6124.4
135.3106.5 124.9 135.9 141.1 144.9 152.0 155.586.8 95.383.0 99.790.7
108.2108.7
109.5113.2
107.8
107.6
113.7107.1
114.3
116.1118.4
106.8120.5
124.5106.6 135.3 135.8134.1 142.5 145.4 152.0 157.291.883.6 95.3 104.389.1
108.2108.7
111.1
107.5119.6107.0
113.9 122.6 135.3124.5106.8 135.8 140.499.2
134.196.1 143.2150.4128.6
93.582.8 92.6 158.2
82.5 84.9 85.5
NL: 1.71E4
TIC F: + c APCI sid=10.00 SRM ms2 [email protected] [32.500-33.500] MS 19h32
NL: 1.20E4
TIC F: + c APCI sid=10.00 SRM ms2 [email protected] [44.500-45.500] MS 19h32
NL: 2.70E3
TIC F: + c APCI sid=10.00 SRM ms2 [email protected] [46.500-47.500] MS 19h32
Methanol
Dimethoxymethane
Formic acid
21 h 17 Desinfection begins
Centre d’expertise en analyse environnementale
du Québec
Case 2 – Results
0,0
20,0
40,0
60,0N
NNE
NE
ENE
E
ESE
SE
SSE
S
SSW
SW
WSW
W
WNW
NW
NNW
DISTRIBUTION DE LA VITESSE DU VENT
6 octobre de 20 h 50 à 22 h 14
0
10
20
30
40
50
60
70
80
90
CALME 0,5 À 3,5 3,5 À 7 7 À 15 >15Vitesse (km/h)
Fréq
uen
ce (
%)
0,0
20,0
40,0
60,0N
NNE
NE
ENE
E
ESE
SE
SSE
S
SSW
SW
WSW
W
WNW
NW
NNW
DISTRIBUTION DE LA VITESSE DU VENT
6 octobre de 20 h 50 à 22 h 14
0
10
20
30
40
50
60
70
80
90
CALME 0,5 À 3,5 3,5 À 7 7 À 15 >15Vitesse (km/h)
Fréq
uen
ce (
%)
Station 1 Station 5 Station 6 Station 4
20 h 35 - 20 h 50 < 57 < 19 < 19 < 19
21 h 26 - 21 h 41 5300 140 140 94
21 h 42 - 21 h 57 5400 190 < 57 68
21 h 57 - 22 h 12 5400 < 57 < 57 < 19
PeriodConcentration (µg/m
3)
FORMALDEHYDE
Centre d’expertise en analyse environnementale
du Québec
Case 3 – Summary
September 15th 2009
– The odour of an unknown substance is
detected in the sewer of Sherbrooke City. The
smell forces the evacuation of a few houses.
Odour reaches a long-term care centre, for
which evacuation is very risky given the health
status of patients
Centre d’expertise en analyse environnementale
du Québec
Case 3 – Summary
Centre d’expertise en analyse environnementale
du Québec
Case 3 – Summary
Local authorities ask the TAGA and its
team to determine the product that causes
this smell. Concentrations have to be
determined in the sewer, in evacuated
houses and in the long-term health care
centre
Centre d’expertise en analyse environnementale
du Québec
Case 3 – Results
First analyses
in the sewer
reveal 3
compounds
with higher
concentrations
Diethyl ether
Chloroform
Unknown
Centre d’expertise en analyse environnementale
du Québec
Case 3 – Results
Chloroform and
diethyl ether are
now added to the
MS method to
follow their
concentrations in
real-time
RT: 0.15 - 28.47
2 4 6 8 10 12 14 16 18 20 22 24 26 28
Time (min)
0
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105
Re
lativ
e A
bu
nd
an
ce
NL:6.69E6
m/z= 74.53-75.53 MS 17h38
795 Chapleau St
Sewer
Chapleau St Sewer
Chapleau St
RT: 0.15 - 28.47
2 4 6 8 10 12 14 16 18 20 22 24 26 28
Time (min)
0
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Re
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NL:6.69E6
m/z= 74.53-75.53 MS 17h38
795 Chapleau St
Sewer
Chapleau St Sewer
Chapleau St
MS Diethyl ether signal
Centre d’expertise en analyse environnementale
du Québec
Case 3 – Results
Investigation,
calculations and
deductions lead to
the identification
of the third
product:
Dicyclopentadiene
17h38 #777-854 RT: 6.83-7.51 AV: 78 SB: 241 13.82-15.92 NL: 5.91E5T: + p APCI sid=-10.00 Q1MS [15.070-250.000]
20 40 60 80 100 120 140 160
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
un
da
nce
165
Dicyclopentadiene
Diethyl ether75
47
93
111 129
37
(H3O)+(H2O)n
55
73
91
17h38 #777-854 RT: 6.83-7.51 AV: 78 SB: 241 13.82-15.92 NL: 5.91E5T: + p APCI sid=-10.00 Q1MS [15.070-250.000]
20 40 60 80 100 120 140 160
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
un
da
nce
165
Dicyclopentadiene
Diethyl ether75
47
93
111 129
37
(H3O)+(H2O)n
55
73
91
Sewer Chapleau St
Centre d’expertise en analyse environnementale
du Québec
Case 3 – Results
Diethyl ether Dicyclopentadiene Chloroform
15 h 18 1 < LDM 60 < LDM
16 h 39 2 < LDM < LDM < LDM
18 h 08 3 600 1600 470
21 h 27 4 < LDM 70 < LDM
8 h 57 4 < LDM 32 < LDM
11 h 11 5 5 10 000 310
20 h 13 3 < LDM 480 320
12 h 06 4 < LDM < LDM < LDM
September 15th
September 16th
September 17th
Concentration (µg/m3)
Time Position
Centre d’expertise en analyse environnementale
du Québec
Future
Centre d’expertise en analyse environnementale
du Québec
Questions ? Dominic Lortie, M.Sc. Chemist
TAGA Coordinator
CEAEQ / Field Studies Team
850, Vanier blvd
Laval, Québec
Canada
H7C 2M7