open path ftir deployment at fort mckay station in...

Open Path FTIR Deployment at Fort McKay Station in 2014

An AEMERA Funded Project

Dr. Long Fu1, Dr. Quamrul Huda1, Dr. Bonnie Leung1 Longdong Zhang2, Dr. Zaher Hashisho2

1 Alberta Environmental Monitoring, Evaluation and Reporting Agency

2 Department of Civil and Environmental Engineering, University of Alberta

Outline

• Background • Methodology

– Principles of Open Path FTIR (OP-FTIR) – Site description

• Results & Discussion – Hourly results and comparison – Select 5-min Non-Methane-HydroCarbon (NMHC) results and

comparison

• Conclusions

Background

• Under the Joint Oil Sands Monitoring (JOSM) program, AEMERA deployed an OP-FTIR instrument for monitoring Volatile Organic Compounds (VOC) and other gas species simultaneously and continuously in Fort McKay to: – “enhance science-based monitoring for improved characterization of

the state of the environment and collect the information necessary to understand cumulative effects” (JOSM Plan);

– support resolution of odour and air quality concerns in residential communities in the oil sands region;

– and improve the characterization of VOC and Green House Gases (GHG) emissions in the oil sands regions.

Background (cont’d)

• OP-FTIR originated in the 1970s and became mature in the 1990s.

• It has been used by U.S. EPA and other organizations in a variety of areas.

• Advantages:

OP-FTIR Multi-

compounds; Continuous; Automated; Long-term

Fence-line monitoring

Workplace safety

Accidental spills

Loss prevention

Environmental Compliance

Emission Inventories

& others

– Multi-compounds can be measured simultaneously and continuously. – It’s automated, easy to set up and maintain. – Path averaged digital samples allow real-time and also post-measurement data analyses. – Low cost for long term deployment.

(Russwurm et al., 2002) (Hashmonay et al., 2012)

Methodology (cont’d)

Credit: http://www.faceintel.com/ftir.htm

• A monostatic OP-FTIR (RAM2000 G2; KASSAY FSI, ITT Corp.) was used in this project.

• Standard procedures: U.S. EPA Method TO-16 and ASTM E1982-98(2013).

Methodology (cont’d)

• August 22, 2014 – October 15, 2014 (54 days). Round-trip pathlength was 354 m; Sampling frequency was 1-min/sample, continuously; Heights of FTIR and retro-reflector was 3.1 m and 1.5 m, respectively.

OP-FTIR at AMS1 in Fort

McKay

FTIR

Retro-reflector

177 x 2 m

FTIR

Retro-reflector

3.1 m 1.5 m

• Hourly results of CH4 from OP-FTIR were consistent with those from 55i (Thermo Fisher Scientific) at AMS1, with ratios of OP-FTIR/55i ranging from 0.8 to 1.2.

• 1.6 – 2.9 ppm; average and median = 1.9 ppm (same as in Edmonton)

• High (>= 2.4 ppm) CH4 conc. under SSW

Results & Discussion

1.51.71.92.12.32.52.72.9

0822

_012

008

23_1

827

0825

_123

408

27_0

441

0828

_214

808

30_1

500

0901

_070

909

03_0

019

0904

_173

309

06_1

038

0908

_034

309

09_2

050

0911

_135

809

13_0

603

0914

_231

209

16_1

619

0918

_091

409

20_0

221

0921

_192

809

23_1

238

0925

_054

809

26_2

258

0928

_151

709

30_0

828

1002

_014

010

03_1

849

1005

_115

310

07_0

457

1008

_215

010

10_1

503

1012

_071

410

14_0

026

CH4

Conc

. (pp

m)

Date_Time (MMDD_HHMM)

CH4 OP-FTIR CH4 55i

Conc. Rose

Hour Day 1 Day 2 Day 3 Composite Conc. (average) 1 1.9 2.0 2.1 2.0 ... ... ... ... ... 24 2 2.1 2.2 2.1

How are composite concentrations calculated?

e.g., 3 days’ hourly data

• Consistent composite diurnal variation patterns were observed by both OP-FTIR and 55i, with correlation coefficient (R) = 0.94.

• Composite CH4 concentration was reversely (R = -0.92) correlated with composite temperature, indicating that the CH4 source(s) was most likely local, at least for most of the time during the field campaign.

Results & Discussion (cont’d)

0

20

40

60

1.61.71.81.92.02.1

1 3 5 7 9 11131517192123

Coun

t

Com

posi

te C

onc.

(pp

m)

Composite Time (HH)

Count CH4 OP-FTIR CH4 55i

0

5

10

15

20

1.61.71.81.92.02.1

1 3 5 7 9 11 13 15 17 19 21 23

Tem

p. (o C

)

Com

posi

te C

onc.

(ppm

)

Composite Time (HH)

CH4 OP-FTIR Temp. AMS1


020406080

0822

_012

008

23_1

928

0825

_133

408

27_0

641

0828

_234

908

30_1

701

0901

_100

909

03_0

320

0904

_203

309

06_1

339

0908

_064

509

09_2

350

0911

_165

809

13_1

004

0915

_031

209

16_2

020

0918

_131

409

20_0

622

0921

_232

909

23_1

639

0925

_094

809

27_0

300

0928

_201

909

30_1

330

1002

_064

110

03_2

349

1005

_165

110

07_0

955

1009

_025

110

10_1

904

1012

_121

610

14_0

528

Conc

. (pp

b)


n-Butane n-Octane Ammonia Formaldehyde Methanol

Compound n-Butane

(ppb) n-Octane

(ppb) Ammonia

(ppb) Formaldehyde

(ppb) Methanol

(ppb) Min 5.2 2.1 3.8 4.3 6.9 Max 73 44 22 5.7 14

Average 24.1 16.2 10.1 5.1 10.2 Median 19 14 4.5 5.2 10

No. of Hours Quantified 109 192 3 8 4 AAAQOG (1-hour) NA NA 2,000 53 2,000

Total Hours 1300 (54 days) Total Effective Hours 1080 (83% of total hours)


• 5-min results for non-methane-hydrocarbon (NMHC) episodes on 7 select days when both OP-FTIR and 55i detected NMHC will be discussed as follows.

• NMHC is continuously monitored by AMS1 using 55i. It is reported as CH4 equivalent. E.g., 1 ppm propane (C3H8) equals to 3 ppm CH4. 55i does not provide speciation information.

• In contrast, OP-FTIR provides speciation information, but it does not measure NMHC directly.

Results & Discussion (cont’d) • OP-FTIR cannot differentiate alkanes

with very close carbon numbers (e.g., n-butane (C4H10) and n-pentane (C5H12)) due to their closely resembled IR spectra. Therefore, n-butane (C4H10) and n-octane (C8H18) are used as surrogates for alkanes (U.S. EPA 2009).

• Thus, NMHC (OP-FTIR) can be estimated using concentrations of n-butane (C4H10) and n-octane (C8H18) to compare with NMHC (55i).

(U.S. EPA 2009)

• As a result, [NMHC]OP-FTIR (as CH4 equivalent) = 4 x [n-butane, C4H10] + 8 x [n-octane, C8H18], if the alkanes are truly a mixture of n-butane and n-octane.

0200400600800

0903

_163

409

03_1

714

0903

_175

409

06_1

610

0906

_165

009

06_1

730

0906

_181

009

06_1

850

0906

_193

009

06_2

010

0915

_132

509

15_1

405

0915

_144

509

15_1

525

0915

_160

509

16_1

349

0923

_084

709

23_0

927

0923

_100

709

23_1

047

0923

_112

710

08_1

909

1008

_194

910

08_2

029

1010

_151

510

10_1

555

1010

_163

5

Conc

. (pp

b)


NMHC (OP-FTIR, factors 4 and 8) NMHC (55i)

0120240360

0903

_163

409

03_1

714

0903

_175

409

06_1

610

0906

_165

009

06_1

730

0906

_181

009

06_1

850

0906

_193

009

06_2

010

0915

_132

509

15_1

405

0915

_144

509

15_1

525

0915

_160

509

16_1

349

0923

_084

709

23_0

927

0923

_100

709

23_1

047

0923

_112

710

08_1

909

1008

_194

910

08_2

029

1010

_151

510

10_1

555

1010

_163

5

WD

(o )

Date_Time (MMDD_HHMM) Episodes mainly under northerly wind

Calculated Directly measured

• NMHC by OP-FTIR = 3 x [n-butane (propane)] + 0 x [n-octane] (factor 3, propane (C3H8)). OP-FTIR and 55i results were more consistent than the case of using factors 4 and 8 for OP-FTIR NMHC.

• The difference between the results could be due to: – Estimated NMHC using n-butane and n-octane concentrations (OP-FTIR) vs.

directly measured NMHC (55i). – Path averaged (OP-FTIR) vs. point sampling (55i) – Continuous sampling (OP-FTIR) vs. sampling-analysis (70 sec)-sampling (55i) – Close but different locations

-100100300500700900

0903

_163

409

03_1

714

0903

_175

409

06_1

610

0906

_165

009

06_1

730

0906

_181

009

06_1

850

0906

_193

009

06_2

010

0915

_132

509

15_1

405

0915

_144

509

15_1

525

0915

_160

509

16_1

349

0923

_084

709

23_0

927

0923

_100

709

23_1

047

0923

_112

710

08_1

909

1008

_194

910

08_2

029

1010

_151

510

10_1

555

1010

_163

5

Conc

. (pp

b)


NMHC (OP-FTIR, best fit) NMHC (55i)


• NMHC concentration trends were consistent for the major episodes observed.

• OP-FTIR was a compliment to 55i with speciation information.

• 55i could give real-time readings of NMHC at low concentrations (50 ppb level) while OP-FTIR requires post-measurement analysis at this level.

• No odour complaint was recorded in Fort McKay area during the field campaign (almost 2 months).

A closer look at the major NMHC episode on September 6th, 2014: • R = 0.95 between NMHC (OP-FTIR) and NMHC (55i). Highly correlated. • Ratio of NMHC (OP-FTIR)/NMHC (55i) ranged from 1.0 to 1.8 (median =

1.2, for data values > 50 ppb). 55i has a detection limit of 50 ppb. • R = 0.07 between NMHC (OP-FTIR) and CH4 (OP-FTIR). Not correlated. • R = 0.22 between NMHC (55i) and CH4 (55i) results for data from August 1,

2014 to October 31, 2014. – Sources of CH4 and NMHC are probably separate.

1.9

2.0

2.1

2.2

0

200

400

600

15:36 16:48 18:00 19:12 20:24

CH4

Conc

. (pp

m)

NM

HC C

onc.

(ppb

)

Time (HH:MM

NMHC (OP-FTIR) NMHC (55i) CH4 (OP-FTIR)

Conclusions • Average CH4 conc. was 1.9 ppm. High CH4 conc. (>= 2.4 ppm) were

detected under south-south-westerly wind. • VOC detected were dominated by alkanes, with average conc. of 24.1

ppb, 16.2 ppb, 5.1 ppb and 10.2 ppb for n-butane, n-octane, formaldehyde and methanol, respectively. Ammonia average concentration was 10.1 ppb. – These concentrations are well below those in AAAQOG (when

applicable). – High NMHC were detected under northerly wind.

• CH4 and NMHC results were consistent between OP-FTIR and 55i. • OP-FTIR demonstrated its capability in monitoring multi-compounds

simultaneously and continuously in the oil sands region. • More field campaigns for longer time periods in the oil sands region

are necessary to have a better understanding of odour complaints and air emissions from oil sands operations.

Acknowledgement

Our sincere thanks are due to: • AEMERA for the funding support. • WBEA for the field support and data sharing. • AITF for the logistic support.

• Thank you • Questions?

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