waters corporation - unispraytm ion source …0 1 auc effect of ion source on q1 using uhplc...
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R² = 0.9889
R² = 0.987
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Concentration (ppm)
Effect of ion source on AEEA 1 using UHPSFC
ESI Unispray
R² = 0.9998
R² = 0.9889
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Concentration (ppm)
Effect of chromatography on +ve ion ESI of AEEA 1
UHPLC UHPSFC
R² = 0.9921
R² = 0.9859
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Concentration (ppm)
Effect of ion source on Q1 using UHPSFC
R² = 0.9998
R² = 0.9819
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Concentration (ppm)
Effect of ion source on AEEA 1 using UHPLC
ESI Unispray
R² = 0.9995
R² = 0.9687
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Concentration (ppm)
Effect of ion source on Q1 using UHPLC
Conclusions
UnisprayTM ion source coupled to UHPSFC for the detection of oilfield additives
Efstathios Andreas Elia1, William Durnie2, Ed Sprake3 and G. John Langley1
1Chemistry, Faculty of Natural and Environmental Sciences, University of Southampton; 2BP Exploration, Sunbury-on-Thames, Middlesex; 3Waters Corporation, Wilmslow, UK
Introduction
Experimental
Results and Discussion
Design of UnisprayTM source
Figure 2. Schematic representation and actual photograph of the UnisprayTM source .
Comparison of UHPSFC to UHPLC
Comparison of ESI and UnisprayTM using UHPLC
Comparison of ESI and UnisprayTM using UHPSFC
Results and Discussion
Figure 5. Comparison of the MS response for the two model CIs using UHPLC with UnisprayTM and ESI.
• Chromatographic separation of six CIs used in the oil industry achieved in 6 min. with no
sample preparation required
• UHPSFC provides a 6-fold increase in sensitivity compared to UHPLC2
– Unispray TM ion source introduces a 6 to 10-fold increase when compared to standard ESI
• A combination of UHPSFC and UnisprayTM could provide a 60 fold increase in sensitivity
compared to using UHPLC with ESI
• Experimentation with the UnisprayTM ion source and different chemistries can provide further
insight into the ionisation mechanism of both ESI and UnisprayTM
1. Elia Efstathios, Durnie William, Langley G. John, Determination of oilfield additives using separation science and mass spectrometry, BMSS Annual Meeting, 2015
2. Lucie Nováková, Alexandre Grand-Guillaume Perrenoud, Raul Nicoli, Martial Saugy, Jean-Luc Veuthey, Davy Guillarme, Ultra high performance supercritical fluid chromatography coupled with tandem mass spectrometry for screening of doping agents. I: Investigation of mobile phase and MS conditions, Analytica Chimica Acta, Volume 853, 1 January 2015, Pages 637-646
References
Figure 3. Combined RICCs of a 10 ppm solution of the model CI formulation and analysed using UHPSFC (A) and UHPLC (B).
Figure 1. Positive ion ESI mass spectra and chemical structures for each CI used.
• Quaternary amines readily amenable to (+)ve ion ESI due to permanent charge, M+ ion detected
• AEEA imidazolines also easily protonated through the addition of formic acid, [M + H]+ ion
detected
• Full scan mass spectra acquired for concentrations above 1 ppm, SRM spectra acquired for
concentrations below 1 ppm
UHPLC conditions used
Instrument: Waters Acquity UPLC H-class
Mobile phase A: H2O + 0.2% formic acid Mobile phase B: ACN + 0.2% formic acid
Flow rate: 0.7 mL/min. Column: Acquity BEH C18 (100 mm × 3 mm, 1.7 µm)
• The oil and gas industry relies on the use of carbon steel for transmission pipelines which is
susceptible to corrosion
• Use of corrosion inhibitors is the most cost effective means of corrosion mitigation
• Although beneficial to the industry, these additives are toxic and pose a direct threat to aquatic life
• Ongoing need to accurately quantify such additives in trace concentrations in oilfield fluids
• Quantitation of such CIs has been shown to be achieved by direct analysis of crude oil using
UHPSFC1
• A novel ion source (UnisprayTM) was compared to standard ESI source for the trace level detection
of six corrosion inhibitors in various oilfield fluids
Figure 6. Comparison of the MS response for the two model CIs using UHPLC with UnisprayTM and ESI.
Using UnisprayTM ion source with UHPSF is shown to increase the MS response by a factor of 60-
100 when compared to UHPLC with ESI. This is believed to be due to the formation of smaller
droplets in early stages of ESI or the introduction of the impact pin directs more of spray towards
the MS or even that it produces a finer electrospray plume.
C11H23 C13H27 C15H31
C17H35
C17H33C11H23
Mass spectrometer conditions used
Parameters ESI UnisprayTM
Cone Voltage 20 V 20 V
Capillary Voltage 3.3 kV 1.4 kV
Source temp. 150 oC 150 oC
Desolvation temp. 350 oC 350 °C
Desolvation gas flow 700 L/h 700 L/h
Extractor 3 V 3 V
R² = 0.9995
R² = 0.9921
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70000
0 0.5 1
AU
C
Concentration (ppm)
Effect of chromatography on +ve ion ESI of Q1
Q1 Q2 Q3
Q4 AEEA1
AEEA2
Q1
Q2 Q3
Q4
AEEA2
AEEA1
Figure 4. A comparison of the ESI response of two CIs using UHPSFC and UHPLC.
One quaternary amine and one imidazoline were chosen as model CIs to perform all statistical analyses
on. The observations below are true for all other CIs in the formulation.
Q1
Q2
Q3
Q4
AE
EA
2
AEEA1
A B
UHPSFC conditions used
Instrument: Waters Acquity UPC2
Mobile phase A: scCO2 Mobile phase B: MeOH + 2% H2O + 50 mM NH4OAc
Flow rate: 1.5 mL/min. Column: Acquity HSS C18 (100 mm × 3 mm, 1.8 µm)
Acknowledgements
Q1 Q2 Q3
Q4 AEEA1
AEEA2
Figure 3. Positive ion UnisprayTM mass spectra for each CI used.