open path ftir deployment at fort mckay station in...
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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
Results & Discussion (cont’d)
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)
Date_Time (MMDD_HHMM)
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)
Results & Discussion (cont’d)
• 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)
Date_Time (MMDD_HHMM)
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)
Date_Time (MMDD_HHMM)
NMHC (OP-FTIR, best fit) NMHC (55i)
Results & Discussion (cont’d)
• 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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