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Static Headspace GC/MS Method for Determination of Methanol and Ethanol

Contents, as the Degradation Markers of Solid Insulation Systems of Power
Transformers

Article  in  Chromatographia · May 2017

DOI: 10.1007/s10337-017-3315-1

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Chromatographia
DOI 10.1007/s10337-017-3315-1
SHORT COMMUNICATION
Static Headspace GC/MS Method for Determination of Methanol
and Ethanol Contents, as the Degradation Markers of Solid
Insulation Systems of Power Transformers
Hoda Molavi1 · Abbas Yousefpour1 · Akbar Mirmostafa2 · Ali Sabzi3 ·
Sepideh Hamedi4 · Milad Narimani1 · Nazanin Abdi1 
Received: 22 November 2016 / Revised: 7 April 2017 / Accepted: 19 April 2017
© Springer-Verlag Berlin Heidelberg 2017
Abstract  Methanol in insulating oil has been proposed as
a new marker for condition assessment of the solid insu-
lation system of power transformers. In the current work,
as a first step of using the new marker, an analytical static
headspace gas chromatography/mass spectrometry method
has been developed, optimized, and validated to measure
methanol and ethanol contents in the insulating mineral
oil. The analyzing setup consists of a 6890 N gas chroma-
tograph equipped with a 5973 network mass spectrometer
(MS) in the absence of a costly headspace autosampler,
and the chromatography separation was performed on a
60 m × 320 µm × 0.5 µm VF-WAXms GC column. Cali-
bration curves have been provided using several concen-
trations of the alcohols, and also limit of detection (LOD),
limit of quantification (LOQ), and relative standard devia-
tion percentage (RSD%) have been determined.
Keywords  Gas chromatography · Static headspace · Oil
analysis · Methanol · Insulating paper · Paper degradation ·
Power transformer
Introduction
Power transformers are vital equipment in electrical net-
works, and their health and life expectancy are important
* Hoda Molavi
hmolavi@nri.ac.ir
1
Niroo Research Institute, Tehran, Iran
2
Zangan Industrial Oil Refining Company, Zanjan, Iran
3
Oil and Fuel Laboratory, Niroo Research Institute, Tehran,
Iran
4
Shahid Beheshti University, Tehran, Iran
issues for utilities. Therefore, considering an appropriate
diagnostic method is essential to prevent unexpected fail-
ures and improve the reliability of the equipment.
It is more than a century that cellulose, a natural poly-
mer containing alpha-d-glucose units, together with min-
eral oil is being employed in transformers as the insulating
system [1]. Plenitude in the nature, good mechanical and
electrical characteristics, along with its ease of use in fabri-
cating operation led to cellulose wide application [1].
Due to the fact that the solid insulation system cannot
be easily replaced as the insulating oil, the age of a trans-
former is evaluated by the health of its solid insulation [2,
3]. Indeed, the extent of insulation paper degradation is
determinative of the remaining life of a solid insulation and
subsequently a transformer [4].
A factor to evaluate the age and the quality of the cel-
lulose insulator is degree of polymerization (DP). This
direct technique is one of the most important tools to
evaluate the lifetime of the paper. New paper has a DP
value of about 1200, which would be reduced to 1000
after applying the drying process, while the water content
is about 0.5%. Reaching a DP value of 200 means that
the tensile strength of the paper has decreased to 20% of
its original value and the transformer life is over [5–7].
Although the measurement of paper’s DP (according to
IEC 60450 [8] or ASTM D4243 [9]), as a direct way, pro-
vides useful information, but it is impossible to access
internal insulation for paper sampling during transformer
regular operation [2].
Utilities are interested in indirect and non-destructive
diagnostic methods for determination of the residual life of
their power transformers, which could be applied easily for
an operating transformer. One of the non-destructive diag-
nostic techniques is using chemical markers, such as car-
bon dioxides and furanic derivations, in the oil.
13

Although the sampling process for these chemical mark-
ers is simply as the conventional oil sampling for DGA and
could be performed, while the equipment is operating [10],
but their application for paper condition monitoring is still
questionable.
The evaluation of the aging state of the insulting paper
by use of carbon dioxides was found to be limited, since
they could be produced from both oil and paper degrada-
tion. Furthermore, in case of oil degassing or regenerat-
ing, or even open-breathing equipment, the carbon oxides
would be disappeared or escaped [3, 4, 11]. The family of
furan compounds, that introduced later [12], is more related
to the insulating paper decomposition [13]. Although, sev-
eral correlations were proposed to relate them to the DP
value [13–18], but their application for diagnosis of paper
condition has several drawbacks: their small amount in
case of using thermally upgraded papers, their low thermal
stability, the high yield of production from hemi-cellulose
compared to cellulose, etc. [1].
Recently, methanol has been found to be a new marker
for insulting paper condition assessment [19]. It could be
used for tracking the condition of the paper from the initial
state of aging to the end [20]. On the other hand, the advan-
tages of using methanol and ethanol are the independency
of the markers production from the type of the insulating
paper (Kraft and thermally upgraded papers), their early
detection, and also stability of the markers over the trans-
former operating temperatures [1, 2, 4, 11, 19, 21–24].
Various chromatography methods have been utilized
to detect the alcohols in the insulating oil. Gas chroma-
tography (GC) equipped with mass spectrometer (MS) or
flame ionization detectors (FID), high-performance liquid
chromatography (HPLC), solid-phase micro-extraction
(SPME), and static headspace are some of the main used
methods to evaluate the dissolved gases in oil. Moreover,
the different combinations of the mentioned methods have
been examined to reach an optimal way for a more accurate
detection of the methanol marker [1, 2, 19, 25, 26].
In the current work, as the first step of using methanol
and ethanol markers for insulation paper degradation, it
was tried to develop a static headspace GC/MS method to
detect and measure the mentioned alcohol-based markers
in the insulating mineral oil using a 6890 N gas chromato-
graph (without an expensive dynamic headspace) available
in Niroo research institute (NRI) oil laboratory.
Experimental
Chemicals
Methanol 99.5%, ethanol 99.9%, 2-propanol 99.8%, and
toluene 99.9% (all from Merck, Darmstadt, Germany) were
13
H. Molavi et al.
used in the experiments and fresh oil samples were taken
from Nynas Nytro Libra oil (Stockholm, Sweden).
Sample Preparation
2-Propanol was chosen as an internal standard for ethanol
and methanol measurements in the oil, which was prepared
by adding 100 µL of 2-propanol to 10 mL toluene (because
of lower viscosity of toluene compared to the mineral oil
which makes it possible to take 1 µL of the internal stand-
ard in a syringe) at room temperature. The prepared internal
standard was added in the constant amount of 1 µL–10 mL
to the all oil samples to provide quantitative analysis.
2-Propanol is a good choice as an internal standard due
to its acceptable stability in the mineral oil. In addition, it
is not produced during paper or oil aging [19] and could be
adequately separated from target compounds in the applied
chromatographic conditions.
The calibration procedure requires a series of samples in
different concentrations. The samples have been prepared
using methanol and ethanol in various concentrations and
1 ppm of 2-propanol as an internal standard in all of them.
Following dilutions have been provided for the calibration
curve, which covers a wide range from ppb to ppm extent
that would be occurred in field samples: 10, 5, 2, 1 ppm,
800, 500, 250, 100, 50, 10, 5, and 1 ppb.
Instrumentation
A 6890 N gas chromatograph equipped with a 5973 net-
work mass spectrometer (both from Agilent technologies,
Santa Clara, CA, USA) operating at 70 eV ionization
energy in the electron ionization mode has been utilized in
this study. Mass range 25–550 m/z was scanned in total ion
current count at 2.81 scan/s rate, while the temperature of
the mass spectrometer was adjusted at 270 °C. The quan-
tification is done using integrated peak areas of extracted
ion of mass 31[CH2OH]+ which is specific for methanol
and ethanol fragmentation and also 45[C3H6OH]+ which
is specific to our internal standard.
The chromatography separation has been done on a
60 m × 320 µm × 0.5 µm VF-WAXms GC column (from
Agilent Technologies, The Netherlands) which is appro-
priate for analyzing trace amount of polar compounds. In
the absence of a headspace autosampler on the equipment,
a 5 mL gas-tight syringe (Hamilton 1005 LTN gas-tight
syringe, Hamilton Bonaduz AG, bonaduz, Switzerland),
vial, heater-stirrer, crimper, magnet, and He carrier gas
have been employed to develop a static headspace method.
It is worth noting that the analytical methods for detect-
ing ethanol and methanol in the insulating oil which have
been presented by other researchers need a headspace
Static Headspace GC/MS Method for Determination of Methanol and Ethanol Contents, as the…
autosampler [1, 2] and also two capillary columns [2]
which lead to higher costs.
Analysis Procedure
The static headspace GC is a simple method, applicable for
analysis of volatile organic compounds [27], which is used
for analyzing the oil samples in order to detect and quantify
ethanol and methanol contents in the transformer insulating
oil samples.
The following procedure is a result of the comprehen-
sive analyses done to obtain the best and accurate results.
First, a vial with appropriate volume size has been chosen
and crimped after putting a magnet inside. Subsequently,
oil, ethanol, and methanol were added to the purged vial,
to have 10 mL of calibration samples with desired concen-
trations of the alcohols and also to avoid analytes’ losses
(Fig. 1a). After that, 1 μL of a 10,000 ppm 2-propanol solu-
tion (in toluene) was added to each vial, to have 1 ppm of
2-propanol in oil solution and the sealed vials were put in
the paraffin bath on the heater-stirrer set at 85 °C (Fig. 1b).
Heating and stirring procedure (using a small magnet in
the vials) was continued for 20 min. Following that, a 5 mL
sample of the headspace gas was taken using the gas-tight
syringe (Fig. 1c) and injected to the GC inlet, subsequently.
It should be noted that the purpose of using Hamilton 1005
LTN gas-tight syringe is due to its “point style 5” needle,
which makes it possible to inject without any problem.
Indeed, point style 5 needle, which has a conical shape
with a side port, is able to penetrate the septum, while no
Fig.  1  a Sealed vial contain-
ing oil, alcohols, and magnet; b
heating and stirring the samples;
and c gas sampling from the
vial headspace
pieces of septum are blocking the gas exiting port. This
blockage was a problem in the case of using point style 2
needle which beveled port is just on the needle’s tip.
It is worth noting that the important factors of the spent
time for heating and stirring the sample, the temperature of
heater, the sample volume in the vials, and also the sam-
ple volume injected to the GC were equal in all the experi-
ments, to provide reliable calibration curves.
Results and Discussion
Method Parameters
The utilized volume for injection (5 mL) was required to
have reliable peaks for alcohols with low concentrations
(lower than 500 ppb). On the other hand, due to high vol-
ume of the injected gas (5 mL), the GC’s liner needs to be
evaluated about any saturation. Therefore, various volumes
of Argon (as the dominant component in each test sample)
in a range of 1–10 mL were injected and the obtained peaks
were investigated. The overload leading to the liner satura-
tion occurred in 7 mL volume of injection. As a result, a
5 mL injection volume is trusted in further peak qualifica-
tion and quantification.
Following that, it was tried to optimize the split ratio
using 5:1, 15:1, and 30:1 values, and also splitless mode.
Furthermore, He carrier gas flow rate was optimized con-
sidering 2, 1, and 0.5 mL/min values.
13
 H. Molavi et al.

As reported in Fig. 2, the best results including sharp
symmetrical peaks and also higher peak areas were
achieved using splitless mode.
As presented in Fig. 3, the optimum value for the carrier
gas flow rate was obtained to be 0.5 mL/min. As one can
see in the figure, reducing the carrier gas flow rate led to
appropriate peaks separation.
The optimum instrumental conditions for gas chroma-
tography analysis have been reported in Table 1.
Analytical Performance
Limits of quantification (LOQ) and limits of detection
(LOD) have been calculated according to EPA definitions
in which [28, 29] LOD corresponds to the standard devia-
tion (SD) of the mean analyte concentration multiplied by
the Student’s t value and LOQ defines as SD value multi-
plied by ten. It should be noted that seven replicates of the
samples, with the lowest expected values of methanol and
ethanol concentrations, were analyzed to evaluate the men-
tioned parameters.
In Table 2, the calculated values for LOD and LOQ have
been reported and compared with the obtained values in the
previous studies [1, 2]. The calculated values in the current
work are higher than the presented values in the previous
studies [1, 2], which is expected due to the absence of the
costly autosampler headspace.
The reproducibility of the whole approach has been
evaluated using the following procedure, in which the prep-
aration and analysis of a same sample (spiking, heating and
analysis) have been done by three different operators. The
RSD percentages for methanol and ethanol in 25 replicates
have been calculated to be 11 and 14%, respectively. It
should be noted that a part of this deviation is due to prepa-
ration procedure to reach the desired concentration, which
would be diminished for the samples from real transformer
and also laboratory aged samples, since in those samples,
the complete dissolving of generated alcohols in the oil
happens.
Calibration Curve
After the tests, the obtained curves for the different concen-
trations of methanol, ethanol, and 2-propanol should result
in a calibration curve to gain a comprehensive formula
to apply for the unknown aged samples. The calibration
curves for methanol and ethanol in which peak area has
been plotted against the alcohols concentrations have been
represented in Fig. 4. The curves have been prepared by
choosing seven different concentrations from 12 analyzed
concentrations. Indeed, the concentrations smaller than the
LOQ have been omitted. The correlation coefficients for
calibration curves were obtained to be more than 0.995 for
both alcohols.
Conclusion
Although measuring DP value is the most accurate chemi-
cal method for evolution of insulation paper state, but the
impossibility of paper sampling from an operating trans-
former leads the utilities to use chemical markers in the oil
as indirect and non-destructive diagnosis techniques.

Fig. 2  Optimizing the split

ratio for determination of
methanol and ethanol in
mineral insulating oil. Carrier
gas rate: 0.5 mL/min, injection
temperature: 110 °C, injec-
tion volume: 5 mL, using a
60 m × 320 µm × 0.5 µm VF-
WAXms GC column

13
Static Headspace GC/MS Method for Determination of Methanol and Ethanol Contents, as the…

Fig. 3  Optimizing the carrier

gas flow rate for determina-
tion of methanol and ethanol
in mineral insulating oil.
Splitless mode, injection
temperature: 110 °C, injec-
tion volume: 5 mL, using a
60 m × 320 µm × 0.5 µm VF-
WAXms GC column

13
 H. Molavi et al.

Table 1  Optimized instrumental conditions for GC In this regard, an analytical static headspace gas chro-
Injection condition Oven temperature program matography/mass spectrometry method has been intro-
duced to detect methanol and ethanol in the insulating oil,
Temperature: 110 °C Tin: 34 °C for 2 min which are the products and also the new markers related to
Injection volume: 5 mL 2.5 °C m­ in−1 to 110 °C
Splitless mode 30 °C ­min−1 to 210 °C and hold for 5 min
degradation of transformers’ solid insulation. The analyses
have been carried out using a single GC column and in the

Table 2  Limits of detection Study Method Component LOD LOQ

(LOD) and quantification
(LOQ) Current study GC–MS, one capillary column, absence of autosam- Methanol (µg/kg) 144 458
pler headspace Ethanol (µg/kg) 155 495
[1] GC–MS, one capillary column, using autosampler Methanol (µg/kg) 4 14
headspace Ethanol (µg/kg) 3.6 13
[2] GC–MS, two capillary columns, using autosampler Methanol (µg/kg) 1.3 3.9
headspace Ethanol (µg/kg) 3.1 9.3
[2] GC-FID, two capillary columns, using autosampler Methanol (µg/kg) 12.1 36
headspace Ethanol (µg/kg) 26.8 79.6

Fig. 4  Calibration curves, a
methanol concentration and b
ethanol concentration

13
Static Headspace GC/MS Method for Determination of Methanol and Ethanol Contents, as the…
absence of a headspace autosampler with high price. The
presented method is able to detect and measure the men-
tioned alcohols with an acceptable error and reproducibility
in a wide range of ppb to ppm, which would be found in
the oil samples from field transformers.
Compliance with Ethical Standards  car E (1988) Application of liquid chromatography to analysis of
Conflict of interest  The authors declare that they have no conflict of
interest.
Ethical approval This article does not contain any studies with
human participants or animals performed by any of the authors.
Funding  This study was funded by Niroo Research Institute (NRI).
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