Standard method design considerations for semi-quantification of total naphthenic acids in oil sands process affected water by mass spectrometry: A review
Kevin A. Kovalchik1, Matthew S. MacLennan1, Kerry M. Peru2, John V. Headley1,2, David D.Y. Chen1()
1. Department of Chemistry, University of British Columbia, Vancouver, BC, V6T 1Z1, Canada 2. Watershed Hydrology and Ecology Research Division, Water Science and Technology Directorate, Science and Technology Branch, Environment and Climate Change Canada, Saskatoon, SK, S7N 3H5, Canada
Naphthenic acids are a complex class of thousands of naturally occurring aliphatic and alicyclic carboxylic acids found in oil sands bitumen and in the wastewater generated from bitumen processing. Dozens of analytical methods have been developed for the semi-quantification of total naphthenic acids in water samples. However, different methods can give different results, prompting investigation into the comparability of the many methods. A review of important methodological features for analyzing total naphthenic acids is presented and informs the design of future standard methods for the semi-quantification of total naphthenic acids using mass spectrometry. The design considerations presented are a synthesis of discussions from an Environment and Climate Change Canada (ECCC) led taskforce of 10 laboratory experts from government, industry and academia during April 2016 and subsequent discussions between University of British Columbia and ECCC representatives. Matters considered are: extraction method, solvent, pH, and temperature; analysis instrumentation and resolution; choice of calibration standards; use of surrogate and internal standards; and use of online or offline separation prior to analysis. The design considerations are amenable to both time-of-flight and Orbitrap mass spectrometers.
. [J]. Frontiers of Chemical Science and Engineering, 2017, 11(3): 497-507.
Kevin A. Kovalchik, Matthew S. MacLennan, Kerry M. Peru, John V. Headley, David D.Y. Chen. Standard method design considerations for semi-quantification of total naphthenic acids in oil sands process affected water by mass spectrometry: A review. Front. Chem. Sci. Eng., 2017, 11(3): 497-507.
Liquid-liquid extraction at pH 2 and room temperature with DCM as organic phase, or use ENV+ SPE
1) [24,26?28]
3
Use of surrogate standards
Use isotopically labelled model compounds as surrogate standards
[8]
4
Minimum resolving power of instrument
50000 at m/z 200, acknowledging that potential interferences contribute to method uncertainty
[2,6,14,17]
5
Use of derivatization
Do not utilize derivatization
[19,22,23,29]
6
Polarity and mode of ionization
Negative-ion mode ESI
[4,30]
7
Suitable calibration standard and internal standard
Use commercially available Merichem NA mixture and at least one isotopically labelled internal standard
[2,8,14]
8
Use of on-line or off-line fractionation of sample
Employ on-line chromatography prior to MS detection
[8,17,31,32]
Tab.1
Carbon #
Z-value
0
?2
?4
?6
?8
?10
?12
Target ion accurate mass /amu
6
115.07645
113.0608
111.04515
109.0295
107.01385
104.9982
7
129.0921
127.07645
125.0608
123.04515
121.0295
119.01385
116.9982
8
143.10775
141.0921
139.07645
137.0608
135.04515
133.0295
131.01385
9
157.1234
155.10775
153.0921
151.07645
149.0608
147.04515
145.0295
10
171.13905
169.1234
167.10775
165.0921
163.07645
161.0608
159.04515
11
185.1547
183.13905
181.1234
179.10775
177.0921
175.07645
173.0608
12
199.17035
197.1547
195.13905
193.1234
191.10775
189.0921
187.07645
13
213.186
211.17035
209.1547
207.13905
205.1234
203.10775
201.0921
14
227.20165
225.186
223.17035
221.1547
219.13905
217.1234
215.10775
15
241.2173
239.20165
237.186
235.17035
233.1547
231.13905
229.1234
16
255.23295
253.2173
251.20165
249.186
247.17035
245.1547
243.13905
17
269.2486
267.23295
265.2173
263.20165
261.186
259.17035
257.1547
18
283.26425
281.2486
279.23295
277.2173
275.20165
273.186
271.17035
19
297.2799
295.26425
293.2486
291.23295
289.2173
287.20165
285.186
20
311.29555
309.2799
307.26425
305.2486
303.23295
301.2173
299.20165
21
325.3112
323.29555
321.2799
319.26425
317.2486
315.23295
313.2173
22
339.32685
337.3112
335.29555
333.2799
331.26425
329.2486
327.23295
23
353.3425
351.32685
349.3112
347.29555
345.2799
343.26425
341.2486
24
367.35815
365.3425
363.32685
361.3112
359.29555
357.2799
355.26425
25
381.3738
379.35815
377.3425
375.32685
373.3112
371.29555
369.2799
26
395.38945
393.3738
391.35815
389.3425
387.32685
385.3112
383.29555
27
409.4051
407.38945
405.3738
403.35815
401.3425
399.32685
397.3112
28
423.42075
421.4051
419.38945
417.3738
415.35815
413.3425
411.32685
29
437.4364
435.42075
433.4051
431.38945
429.3738
427.35815
425.3425
30
451.45205
449.4364
447.42075
445.4051
443.38945
441.3738
439.35815
31
465.4677
463.45205
461.4364
459.42075
457.4051
455.38945
453.3738
32
479.48335
477.4677
475.45205
473.4364
471.42075
469.4051
467.38945
33
493.499
491.48335
489.4677
487.45205
485.4364
483.42075
481.4051
34
507.51465
505.499
503.48335
501.4677
499.45205
497.4364
495.42075
35
521.5303
519.51465
517.499
515.48335
513.4677
511.45205
509.4364
36
535.54595
533.5303
531.51465
529.499
527.48335
525.4677
523.45205
37
549.5616
547.54595
545.5303
543.51465
541.499
539.48335
537.4677
38
563.57725
561.5616
559.54595
557.5303
555.51465
553.499
551.48335
39
577.5929
575.57725
573.5616
571.54595
569.5303
567.51465
565.499
40
591.60855
589.5929
587.57725
585.5616
583.54595
581.5303
579.51465
Tab.2
Fig.1
Fig.2
Fig.3
Fig.4
Fig.5
Fig.6
Fig.7
1
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