On-Site Real-Time Air Monitoring for Chemical Emergencies

Centre d’expertise en analyse environnementale

du Québec

On-Site Real-Time Air Monitoring

for Chemical Emergencies

Dominic Lortie, M.Sc. Chemist


du Québec

CEAEQ – The Organization

X

X X


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)


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


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


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


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

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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

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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

[email protected]

[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

[email protected]

[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

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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

[email protected]

[32.612-33.612] MS

Cepsa14062013


du Québec

10 Other Fixed Instruments

Total Polyaromatic Hydrocarbons • Ecochem PAS 1000i

Nitrogen Oxides • Thermo 42i

Particles • GRIMM 180


du Québec


Sulfur Dioxide • API 100E

Total Reduced Sulfurs • CDN-101 thermal oxidizer

Sulfur Compounds • Chromatotec Chroma-S

BTEX and VOCs • Chromatotec AirmoBTX


du Québec


Mercury • Tekran 2537B

Metals • Pall XACT 625

δ13C signature for CO2 and CH4 • Piccaro G2201-i CRDS isotopic carbon

analyzer


du Québec

Portable Spectrometers

GC-MS • Inficon Hapsite E/R

FTIR • Gasmet DX-4040

UV • Cerex UV Hound


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


du Québec

Remote Monitors


du Québec

Local Weather Conditions


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


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


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)


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


du Québec


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


du Québec


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


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


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.


du Québec

Case 1 – Summary


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


du Québec

Case 1 – Results

0

2000

4000

6000

8000

10000

12000

14000

16000

18000

23:3

0:0

4

23:3

6:0

9

23:4

2:1

5

23:4

8:2

5

23:5

4:3

1

00:0

1:3

6

00:0

7:4

1

00:1

3:4

6

00:1

9:5

1

00:2

5:5

7

00:3

2:0

2

00:3

8:1

0

00:4

4:2

0

00:5

0:2

5

00:5

6:3

1

0

500

1000

1500

2000

2500

23

:30

:04

23

:36

:04

23

:42

:05

23

:48

:10

23

:54

:11

00

:01

:11

00

:07

:11

00

:13

:11

00

:19

:11

00

:25

:12

00

:31

:12

00

:37

:15

00

:43

:15

00

:49

:20

00

: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


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


du Québec

Case 2 – Summary


du Québec

Case 2 – Summary

TAGA team is contacted to identify and

quantify ambient air contaminants in this

area

– Methanol

– Formaldehyde

– Dimethoxymethane

– Formic acid


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


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


NL: 2.70E3


Methanol

Dimethoxymethane

Formic acid

21 h 17 Desinfection begins


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


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


du Québec

Case 3 – Summary


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


du Québec

Case 3 – Results

First analyses

in the sewer

reveal 3

compounds

with higher

concentrations

Diethyl ether

Chloroform

Unknown


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

5

10

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20

25

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85

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95

100

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

5

10

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20

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Re

lativ

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bu

nd

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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


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

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45

50

55

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Re

lative

Ab

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da

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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


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


du Québec

Future


du Québec

Questions ? Dominic Lortie, M.Sc. Chemist

TAGA Coordinator

CEAEQ / Field Studies Team

850, Vanier blvd

Laval, Québec

Canada

H7C 2M7

[email protected]

mailto:[email protected]

On-Site Real-Time Air Monitoring for Chemical Emergencies

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