Environmental Forensics, 11:117145, 2010

C Taylor & Francis Group, LLC

Copyright

ISSN: 15275922 print / 15275930 online
DOI: 10.1080/15275920903558760

Chemical Characterization of Transformer Mineral-Insulating

Oils
Isaac R. Kaplan,1 Jimmy Rasco,2 and Shan-Tan Lu3
1
ESS, Earth and Space Sciences, and IGPP, Institute of Geophysics and Planetary Physics, University of California, Los Angeles,
Los Angeles, CA, USA
2
Ergon Refining, Inc., Vicksburg, MS, USA
3
Zymax Forensics, Escondido, CA, USA

The chemical composition of a group of 14 refined naphthenic and paraffinic transformer-insulating oils and refinery-treated oils by
hydrocracking and hydrotreating are compared with the composition of the starting untreated North Sea naphthenic crude oil. The
crude oil has a broad carbon distribution from C7 to C40+ , and the refined oils have a more restricted distribution from approximately
C11 to C30 , optimizing in a range from C16 to C22 . Neither the naphthenic crude oil nor its refined products contain n-alkanes or
alkylcyclohexanes, but they all contain various concentrations of iso-alkanes, bicyclanes (sesquiterpanes), pentacyclic terpanes, and
polycyclic aromatic hydrocarbons (PAHs). The base mineral oil and the inhibited transformer oils also contained a suite of steranes,
similar in distribution to those in the starting crude oil. By contrast, the four samples of paraffinic transformer oils have a very different
distribution. Three of four of the samples analyzed contain n-alkanes, alkyl-cyclohexanes and bicyclanes, but no iso-alkanes, steranes
or PAH. Two of these transformer oils contain pentacyclic terpanes. Two used transformer oils contain all the families of compounds
described previously, but in different proportions. It is apparent from the data, that the chemical properties of transformer insulating
oils are a function of the crude oil chosen for refining as well as the refining practices, such as pressure, temperature, and catalysts,
used in individual refineries.
Keywords: naphthenic and paraffinic hydrocarbons, polycyclic aromatic hydrocarbons, refining procedures, crude oil composition

The chemical composition of transformer mineral oils has been

given sparse attention in the technical literature. Historically,
transformer oils have been primarily manufactured by treatment of petroleum crude oil. However, in the past few decades,
siloxane-based synthetic fluids and C7 -, C8 -based fatty acid ester products, have also been used (McShane 2000) in various
parts of the world. Petroleum-based transformer fluids are normally divided in two categories: 1) paraffin-rich oils, and 2)
naphthene-rich oils. The former are used primarily in Canada,
Japan, and Sweden, whereas the latter is exclusively used in the
United States and most other countries.

Insulating Transformer Oil History

The use of crude mineral oil as an insulating fluid dates back
to 1891(Wilson 1980). The early manufacturing procedures for
refining transformer oil, involving solvent extraction, acid treatment, and clay filtration, were inadequate and resulted in oxidation reactions during use and the subsequent production of
sludge inside the transformers, causing them to overheat and
IGPP publication no. 6457.
Received 5 June 2008; accepted 12 November 2009.
Address correspondence to Isaac R. Kaplan, Earth and Space Sciences and Institute of Geophysics and Planetary Physics, University of
California, Slichter Hall, Los Angeles, Los Angeles, 90095-1567, CA,
USA. E-mail: irkaplan@ucla.edu

fail. Their performance has been improved over the years, both
as a result of development and application of better refining
techniques and by changes in equipment design which were introduced to overcome oil-associated problems (Wilson 1980).
The previously noted methodology, began to be modified after Monsanto (St. Louis, MO) discovered and began to mass
produce polychlorinated biphenyls (PCBs) in 1929, as a substitute for petroleum-based insulating fluid (Johnson et al., 2006).
However, the use of mineral oil insulating fluids continued to be
used (Broadhurst 1972) in addition to the PCB fluids (known as
askarels). As a consequence of resulting health and environmental problems (in particular as a contributing carcinogenic agent)
caused by unintentional escape of PCB from its containers, PCB
manufacture was banned in the United States in 1977.
Subsequent to the PCB ban, the choice of crude base oil
for insulating fluid became naphthene-rich oils, because of
their preferred heat transfer and low temperature characteristics
(Rouse 1998). Over the past three decades, refining technology
has improved greatly and has led to the development of both
uninhibited- and inhibited-type fluids. The former depends on
controlling refining severity to leave the natural organic components of the oil such as non-specific PAH compounds and
sulfur compounds (e.g., benzo-thiophenes) to act as oxidation
stabilizers by serving as proton donors that stop peroxide degradation. Inhibited type oils are more highly refined in a stepwise
fashion. First, the refinery removes natural oxidation inhibiters,
117

118

I. R. Kaplan et al.

then the refinery substitutes synthetic anti-oxidants. The two

synthetic inhibitors approved for use today (and used at least
since 1980) are, 2,6-ditertiary-butyl-para-cresol (DBPC, BHT)
and 2,6-ditertiary-butyl-phenol (DBP).
Uninhibited oils are only used in distribution transformers
that are considered low stress service. Power transformers
and all high stress service use inhibited oil, which is more
effective in producing a cleaner base oil with better anti-oxidant
performance.

Manufacture of Naphthenic Transformer Oil

General Refining Procedures
The first step is to distill the crude oil into fractions, collecting
the boiling point fraction 204 504 C (400 940 F), confirmed
by ASTM D2887 simulated distillation test as the fraction that
best fits the required specifications for becoming a transformer
insulating fluid. The primary process for refining naphthenic
insulating oil is high-pressure hydrotreating. In many instances,
a refiner is able to control the process closely enough to manage
the concentration of constituents that serve as natural oxidation inhibitors, such as PAH and aromatic sulfur compounds.
These natural antioxidant inhibitors prevent the propagation of
sludge and acid formation and produce uninhibited insulating
fluid. Other refiners choose not to apply this control or they may
use other techniques for control of anti-oxidants. These refineries produce only base oils that require a synthetic inhibitor to
become inhibited-insulating fluid.
Currently, refiners do not operate their units for the sole
manufacture of transformer insulating fluid, rather they produce base oil that can serve this role and for the manufacture
of other petroleum-based products (e.g., polymer plasticizers,
metal working fluids, greases, de-dusting aids, auto belts and
hoses, motor oils, inks, refrigeration oils, tires, pigments, and titanium dioxide production). The diversity of these other applications heavily influences the detailed operations of any particular
refinery. The present demands are for cleaner oil that are highly
hydrotreated and contain less sulfur, nitrogen, oxygen, and aromatics (Rouse 1998). This trend is expected to place continuing
demand on refineries to meet ever more stringent environmental requirements. However, by meeting these requirements, the
consequence is for reducing those chemical components that
interfere with the function of the preferred synthetic antioxidant
additives, which prolong the life of oil in transformers under
high-stress use.
Selection and hydrogenation of crude and base oils. The
primary difference in the composition of the naphthenic and
paraffinic insulating oils depends on two processes. The first is
the selection of the original crude oil, and the second is on the
severity of the hydrogenation process.
During storage of crude oil in natural geologic reservoirs,
biodegradation of the oil frequently occurs as a result of it
coming into contact with formation water. The most vulnerable
compounds to microbial metabolism are the n-alkanes, which
are first removed, leaving behind iso-paraffins and naphthenes.
Hence, the selection of a biodegraded crude oil that has been

depleted of normal paraffins and enriched in naphthenes is the

first step in selecting the starting material for the manufacture of
naphthenic transformer oils. By contrast, crude oils to be used in
the manufacture of paraffinic insulating oils, should preferably
not be biodegraded.
The second difference in the manufacture of the two types of
transformer mineral insulating oils is the process used for treating each base oil. Naphthenic insulating oils are produced from
the distillate cut which is subjected to high pressure hydrogenation at highly elevated temperatures, in the presence of metallic
catalysts and hydrogen. The primary objective in this operation
is to saturate the aromatic compounds and to remove nitrogen, oxygen, and sulfur in heteroatomic aromatic compounds as
volatiles, such as ammonia, water, and hydrogen sulfide.
In the case of paraffinic insulating oils, the major objective
is to saturate the aromatic petroleum compounds, such as PAHs
with hydrogen and to convert the long-chain compounds, such
as paraffinic waxes into shorter carbon chain paraffins, by using high temperature, high pressure, and aggressive catalysts.
The aggressive hydrocracking is usually followed by milder hydrotreatment to complete removal of all aromatic compounds
and waxes.
Standards and Specifications
Mineral insulating fluids must certify to many standards, but
not all are applicable in any one country. Some of the major
standards are:
1) International Electrotechnical Commission (IEC) 602962003 (IEC 2003);
2) American Society for Testing and Materials (ASTM) D
3487-00-2006 (ASTM 2006);
3) Canada/Canadian Standards Association (CAN/CSA)-C5097 (CAN/CSA 2006);
4) Doble Engineering Company transformer oil purchase specification (TOPS) (Doble Engineering Company 2006);
5) Australian Standards (AS) 1767.1 (AS 1999); and
6) Japanese Industrial Standard (JIS) C 2320 (JIS 1993).
All the standards listed have acceptance specifications for
uninhibited and inhibited insulating fluid, except the Japanese
Standard. Those most widely used internationally are IEC 60296
(IEC 2003) and ASTM D 3487-00-2006 (ASTM 2006).
IEC-60296-2003 standard. In Figure 1, we present the requirements demanded to be met by this standard. It is broken up into the following four categories: 1) function; 2) refining/stability; 3) performance; and 4) health and safety and
environmental considerations. The standard specifications for
inhibited and uninhibited oil are the same, with the exception
of some guidelines on anti-oxidants. ASTM D 3487-00-2006
is defined by the categories: physical, chemical, and electrical
properties. All of the national specifications are some combination of the IEC 60296 and ASTM D 3487-00-2006.

Samples Selected for Analysis

A total of 15 samples were analyzed. These included a North
Sea naphthenic crude oil (sample 08F2708) and eight samples

Mineral-Insulating Oils

119

Figure 1. Standard testing # IEC 60296-2003 for transformer mineral insulating oils showing type of analyses performed.

(08F2701-08F2707) (Table 1), as well as a distillate cut taken

from the North Sea crude (boiling range 607 F to 817 F) that
had undergone various treatments at a refinery. In addition, four
refined samples from paraffinic transformer oils, labeled isoparaffin were also included, in addition to two used transformer
oils (UTOs) labeled UTO1 and UTO2. The sample names and
identification numbers are shown in Table 1.
Ergon Refining (Vicksburg, MI) manufactured five naphthenic transformer oils plus one base oil; two were manufactured by Nynas (Nynas, Stockholm, Sweden) and Shell
Oil Refinery (Houston, TX). The four transformer oils that
represent the iso-paraffin category are US2, YB3, MS2,
and CS2, and their refining sources are shown in Table 1.
All the refined products were obtained directly from the
respective refineries, whereas the crude oil was obtained
from either Chevron (San Ramon, CA) or British Petroleum

(London, UK), who produce naphthenic crude from the North

Sea.

Simulated Distillation Boiling Point Ranges

Each sample was analyzed by simulated distillation using ASTM
Method D2887XA1.PRC. The computer program used was
able to determine the amount of product distilled for each 5 F
rise in temperature. Table 2 shows the initial boiling points
(IBPs) and final boiling points (FBPs) for each sample as well
as the temperature at which 50% of the product would have
distilled. It is apparent from this Table, that the overall boiling point temperature range is variable among the different
insulating oils analyzed. For the naphthenic transformer oils,
the IBP range is 407 F493 F and the FBP is 727 F940 F,
whereas for the iso-paraffin oils the IBP is 421 F557 F and the

120

I. R. Kaplan et al.

Figure 2. Chemical structures for steranes, terpanes, monoaromatic and triaromatic steranes, and the iso-alkane, pristane, given as mass unit fractions
identified by mass spectrometry.

FBP is 669 F817 F. The 50% BP value also varies for each
oil.

Analytical Procedures and Compound Identification

The naphthenic crude oil and all 14 refined samples were first
diluted by dissolving 40 l of sample in 1 mL of methylene
chloride and then injecting 1 L of the diluted sample into a HP
5890 (Hewlett Packard [HP], San Jose, CA) gas chromatograph
(GC) connected to a HP 5971A mass spectrometer.
The GC contained a 60-m DBI-ms, 0.25-mm fused silica
capillary column and was programmed at 4 C/min, starting at
40 C (isothermal at 40 C for 5 minutes) to 310 C and held at that

temperature for 30 minutes. To identify unknown compounds

in both the unused and UTOs, mass spectrometer scanning was
performed over a mass range of 50550 amu (full scan). Mass
spectral data were stored and processed with an HP ChemStation
data system. In addition, select ion monitoring was applied to
biomarker analyses (terpanes and steranes).
Compounds (Figure 2, Appendix 1) were identified using
computer spectral matching techniques, by comparing unknown
spectra with those published in the National Bureau of Standards (Gaithersburg, MD) library. Additionally, biomarker compounds (e.g., terpanes, steranes, and aromatic steranes) were
identified by comparing their retention times and mass spectra
with published data (Philp 1985; Peters and Moldowan 1993).

Mineral-Insulating Oils
Table 1. Electrical insulating oils samples and manufacturers
ID Number

Sample Type

Material Type

08F1801
08F2701
08F2702
08F2703
08F2704
08F2705
08F2706

Naphthenic Base Stock

Uninhibited A
Uninhibited B
Uninhibited C
Trace Inhibited
Inhibited A-Hyvolt II
Inhibited B-Hyvolt II 60296

08F2707

Inhibited C

08F2708
08i2301
08i2302
08i2303
08i2304
08i2305
08i2306

Mixed crude
US2
YB3
MS2
CS2
UTO1
UTO2

Ergon Refining, Inc.

Ergon Hyvolt I
Nynas Naphthenics
Shell Refining
Ergon BS + 0.08 BHT
Ergon Hyvolt II
Ergon Hyvolt II 60296
IEC
Ergon BS + Isoparaffin
+ BHT
North Sea crude
S-Oil Ultra S-2
SK Oil Base 3
Motiva Star 2
Penreco Conosol 260
Used T-oil 1
Used T-oil 2

PAH analysis was performed using United States Environmental Protection Agency (US EPA) method 8270M. The internal standards used for this procedure are:
1)
2)
3)
4)
5)
6)

2,4-Dichlorobenzene (d4);
Naphthalene (d8);
Acenaphthene (d10);
Phenanthrene (d10);
Chrysene (d12); and
Perylene (d12).

Chemical Identification and Quantitation by Gas

ChromatographyMass Spectrometry

121

parison among the samples, the mass chromatograms of the

following six samples are shown in Figure 3. These are: 1)
crude oil, # 08F2708; 2) naphthenic base stock, # 08F1801;
3) inhibited transformer oil, # 08F2707; 4) US2, # 08i2301;
5) YB3, # 08i2302; and 6) UTO2, # 08i2306. Additional TIC
chromatograms are displayed in Appendix 2, Figure 1.
It is apparent from its distribution pattern, that the crude oil
covers a wide range of compounds from about C7 C32 with a
maximum peak height at around C19 . The distilled C60 stock
shows a removal of the more volatile components with maximum peaks at C18 , and its content of heavy hydrocarbons has
significantly decreased. Inhibited C transformer oil has quite
a different peak shape to the naphthenic base stock oil sample. It displays a large peak at 38 minutes (as does inhibited
B OilHyvolt 11 60296), which was identified as inhibitor
DBP, and peak maxima between C21 C23 . The other samples
in the 08F2701-08F2706 series resemble more the mass chromatogram of the naphthenic base stock sample, but differences
are evident. The 08i2301-08i2306 series of samples display different patterns among the iso-paraffin refined oils (Table 3) and
show a more restricted molecular distribution than the naphthenic oils. An example is shown for sample YB3, with a range
from C16 C25 .
Sample US2, # 08i2301, has a distinctly different shape in
its ascending curve, beginning at C11 to a maximum at approximately C22 and a sharp descent to a terminal C27 .
The used oil UTO2 has a shape closely resembling sample #
08F1801, with a starting point at C13 , a maximum at C17 and an
endpoint at C25 .
N-Alkanes: m/z 85

Molecular Weight Distribution Patterns by Total Ion Current

(TIC)
The TIC patterns display the molecular distribution of all the
identifiable constituents of the sample. Table 3 displays a summary of compound ranges for each sample analyzed. For com-

The naphthenic crude oil sample does not contain detectable

n-alkanes, and only one sample in the 08F2701-08F2706 series
of naphthenic oils (uninhibited A transformer oil, # 08F2701)
contained n-alkanes in the range of C21 C30 (Figure 4), which
had been added at the refinery. By contrast, with the exception

Table 2. Initial and final boiling points of samples analyzed based on simulated distillation curves and equivalent n-alkane carbon numbers
Sample#

Initial BP F

Carbon #

50% BP F

Carbon #

08F2701
08F2702
08F2703
08F2704
08F2705
08F2706
08F2707
08F2708
08F1801
08i2301
08i2302
08i2303
08i2304
08i2305
08i2306

407
465
471
410
448
442
493
215
269
421
557
534
497
425
436

12
13
13
12
11
13
14
7
12
11
16
15
14
11
13

619
606
636
580
606
622
569
769
607
684
724
651
569
613
611

19
18
20
17
18
19
17
26
18
21
23
20
17
18
18

Final BP F
857
753
805
940
817
858
727
>1328
817
801
817
729
669
695
817

Carbon #
30
21
26
37
27
31
24
>40
28
27
25
22
18
24
25

122

12
21
14
nd
14f
21(1)
27(1)
27a
nd
2m-Naphth

Compound Class
TCI
N-alkanes
Iso-alkanes
Alkyl cyclohexanes
Bicyclanes
Terpanes
Steranes
Mono-aromatic steranes
Tri-aromatic steranes
PAH
30
30
20Ph
nd
16r
32(u)
29(20)
29m
nd
C2Pyrene

Cend

17
22
21Pr
nd
16r
29(k)
27(1)
28e
nd
C4Naphth

Cmax

Cstart

11
nd
15
nd
14f
21(1)
27(1)
27a
nd
2mNaphth

Sample Name

Compound Class
TCI
N-alkanes
Iso-alkanes
Alkyl cyclohexanes
Bicyclanes
Terpanes
Steranes
Mono-aromatic steranes
Tri-aromatic steranes
PAH
27
nd
20Ph
nd
16r
30(N)
29(20)
29l
nd
C2Pyrene

Cend

16
nd
19Pr
nd
16r
24(4)
27(1)
28e
bd
C4Naphth

Cmax

Inhibited A Transformer Oil

08F2705

Cstart

Sample Name

Uninhibited A Transormer Oil

08F2701

21
nd
20Ph
nd
16r
24(4)
nd
nd
nd
Fluorene

Cend

16
nd
19Pr
nd
16r
21(1)
nd
nd
nd
C4Naphth

Cmax

13
nd
15
nd
14f
21(1)
27(1)
nd
nd
Biphenyl

Cstart

31
nd
20Ph
nd
16r
26(6a,6b)
29(8D)
nd
nd
C2Pyrene

Cend

17
nd
19Pr
nd
16r
21(1)
27(1)
nd
nd
C4Naphth

Cmax

Inhibited B-Hyvolt 11 60296

08F2706

13
nd
16
nd
14f
21(1)
nd
nd
nd
Biphenyl

Cstart

Uninnibited B Transformer Oil

08F2702

14
nd
15
nd
14f
21(1)
27(1)
27b
nd
C2Naphth

Cstart

26
nd
20Ph
nd
16r
24(4)
nd
nd
nd
C2Pyrene

Cend

17
nd
19pr
nd
16r
21(1)
nd27(1)
nd
nd
C4Naphth

Cmax

24
nd
20Ph
nd
16r
(32(u)
29(20)
29m
nd
C2Pyrene

Cend

21
nd
19Pr
nd
16r
23(3)
27(1)
28e
nd
C4Naphth

Cmax

Inhibited C Transformer Oil

08F2707

13
nd
15
nd
14f
21(1)
nd
nd
nd
Naphth

Cstart

Uninhibited C Transformer Oil

08F2703

12
nd
14
nd
14f
21(1)
27(1)
28e
nd
Biphenyl

Cstart

27
nd
20Ph
nd
16r
30(N)
27(1)
29m
nd
C3Pyrene

Cend

17
nd
19Pr
nd
16r
21(1)
27(!)
28e
nd
C4Naphth

Cmax

28
nd
20Ph
nd
16r
30(N)
29(20)
29m
nd
C3Pyrene

Cend

18
nd
19Pr
nd
16r
23(3)
27(1)
27a
nd
C3Naphth

Cmax

Naphthenic Base Stockl

08F1801

13
nd
15
nd
14f
21(1)
29(20)
27a
nd
2mNaphth

Cstart

Trace Inhibited Transformer Oil

08F2704

TIC
Ion 85
Ion 113
Ion 83
Ion 123
Ion 191
Ion 217
Ion 253
Ion 231
PAH

Table 2

TIC
Ion 85
Ion 113
Ion 83
Ion 123
Ion 191
Ion 217
Ion 253
Ion 231
PAH

Table 3. Summary of starting, ending and dominant peaks in mass chromatograms for each compound class in addition to specific polycyclic aromatic hydrocarbon (PAH) compounds

123

Cstart

11
14
14
CH5
14f
21(1)
27(1)
27a
nd
2mNaphth

Sample Name

Compound Class
TCI
N-alkanes
Iso-alkanes
Alkyl cyclohexanes
Bicyclanes
Terpanes
Steranes
Mono-aromatic steranes
Tri-aromatic steranes
PAH
24
23
20Ph
CH14
16r
25(5)
28(5)
28k
nd
C3Phenenth

Cend

UTO1
08i2305

27
25
nd
CH13
16r
25(5)
nd
nd
nd
nd

17
19
19Pr
CH10
16r
21(1)
21(1)
28e
nd
C3Naphth

Cmax

22
21
nd
CH11
16r
23(3)
nd
nd
nd
nd

13
14
14
CH7
14f
21(1)
27(1)
27a
20T1
2mNaphth

Cstart

16
17
nd
nd
nd
21(1)
nd
nd
nd
nd

25
23
20Ph
CH12
16r
30(N)
29(19)
29m
27T6
C4Naphth

Cend

UTO2
08i2306

25
25
nd
nd
nd
21(1)
nd
nd
nd
nd

nd, not detected; PAH, polycyclic aromatic hydrocarbons; TCI, UTO, used transformer oils.

11
11
nd
CH5
15j
21(1)
nd
nd
nd
nd

Compound Class
TCI
N-alkanes
Iso-alkanes
Alkyl cyclohexanes
Bicyclanes
Terpanes
Steranes
Mono-aromatic steranes
Tri-aromatic steranes
PAH

17
19
19Pr
CH10
16r
23(3)
27(1)
28e
26T4
C3Naphth

Cmax

22
22
nd
nd
nd
21(1)
nd
nd
nd
nd

7
nd
14
CH1
10a
23(3)
27(1)
27a
20T1
Naphth

Cstart

15
nd
nd
CH9
15o
nd
nd
nd
nd
nd
Crude Oil
08F2708

32
nd
20Ph
CH4
16r
35(yr)
29(20)
29m
28T7
Benzo(ghi)perylene

Cend

22
nd
nd
CH14
16r
nd
nd
nd
nd
nd

19
nd
19Pr
CH1
16r
30(N)
27(1)
28e
26T4
C4Naphth

Cmax

19
nd
nd
CH12
16r
nd
nd
nd
nd
nd

TIC
Ion 85
Ion 113
Ion 83
Ion 123
Ion 191
Ion 217
Ion 253
Ion 231
PAH

14
16
nd
CH9
nd
nd
nd
nd
nd
nd

18
18
nd
CH11
nd
nd
nd
nd
nd
nd

16
16
nd
CH9
nd
nd
nd
nd
nd
nd

TIC
Ion 85
Ion 113
Ion 83
Ion 123
Ion 191
Ion 217
Ion 253
Ion 231
PAH

124

I. R. Kaplan et al.

Figure 3. Total ion current mass chromatograms. Number on each figure represents the sample analyzed (Table 1).

of sample MS2 (08i2303) all the other samples in the suite

08i2301-08i2306 contain n-alkanes. The distribution differed in
each sample, except for the two UTO samples, which resemble
each other (Figure 4). For example, US2 has an initial n-alkane
at C11, an ending at C25 , and has a very narrow peak-range
starting at C15 and terminating at C18 .The two UTOs (UTO1,
08i2305 and UTO2, 08i2306) each have a broader distribution
from C14 C23 (Figure 4).

Iso-Alkanes: m/z 113

All the 08F2701-08F2706 samples contain iso-alkanes (or isoparaffins). Their distribution in the crude oil sample is from
i-C14 to i-C20 (same as phytane or the symbol Ph) (Figure 5;
Appendix 1, Table 1). The three dominant hydrocarbons in
this sample are C14 , C19 (same as pristane or the symbol Pr)
(Figure 2) and C20 (same as phytane or the symbol Ph) with Pr

125

Figure 4. N-alkanes at m/z 85.

126

Figure 5. Iso-alkanes at m/z 113.

Mineral-Insulating Oils

dominating (Figure 5). In the naphthenic base stock oil

(08F1801) the low molecular weight compounds are significantly reduced over their relative heights in the crude oil sample, as a result of the selective distillation during refining. However, the relative peak strengths of i-C18 , Pr and Ph remain the
same, with the exception that their peak heights relative to the
crude oil has increased by a factor of approximately four times,
again because of the selective distillation during refining. Sample 08F2702 has a narrower distribution beginning at iC16 and
ending at Ph, with Pr the most abundant peak at approximately
the same relative strength as in the Crude Oil sample, but superimposed on a large unresolved hump. The UTO samples have a
distribution from i-C14 Ph, with Pr the most abundant peak at
approximately 50% of the intensity as that in the crude oil (Figure 5). Additional mass chromatograms for m/z113 are shown in
Appendix 2, Figure 2. None of the iso-paraffin fluids contain
iso-alkanes!

Alkylcyclohexanes: m/z 83
Alkylcyclohexanes (Figure 6; Appendix 1, Table 2) are common
constituents of crude oil. In the naphthenic crude oil sample, the
narrow range extends from CH-1 to CH-4, with CH-1 dominating the other compounds (Figure 6). None of the refined products from this crude oil contain alkylcyclohexanes. However,
in the iso-paraffin transformer oil series (08i2301-08i2304) and
the two UTOs (08i2305 and 08i2306), all samples except YB3
(08i2302) contain alkylcyclohexanes.
The distribution is significantly different for each of the samples identified previously. The widest distribution is in US2
(08i2301), extending from CH5 CH13 (Figure 6), and the used
oil sample UTO1 (08i2305), extending from CH5 CH14 with a
maximum at CH-10. By contrast, the other used oil, 08i2306,
has a narrower range from CH7 CH12 (Appendix 2, Figure 3
shows additional mass chromatograms).

Bicyclanes: m/z 123

Bicyclanes also known as sesquiterpanes, represent fused cyclohexane rings, with different degrees of alkylation. The series
that are conventionally identified in crude oil are shown in Appendix 1, Table 3. All the samples analyzed in this study with
the exception of YB3 and CS2 (08i2302 and 08i2304) contain
bicyclane hydrocarbons (Figure 7; Appendix 2, Figure 4 shows
additional mass chromatograms)). The dominant compound in
all the samples where bicyclanes were identified is 8 (H) homodrimane (r in Appendix 1, Table 3). The crude oil sample
contains a suite of 14 identifiable compounds (Figure 7) ranging
from a with the lowest molecular weight 138 (C10 H18 ) to r
with a molecular weight of 222 (C16 H30 ). The naphthenic base
stock contains all the bicyclanes in the crude oil sample, except
the low boiling components (i.e., components a, b, c), and compounds f, g, and h were significantly reduced in height relative
to the other eight compounds in the mass chromatograms.

127

The distribution patterns of the mass chromatographs for the

transformer oil series (08F2701-08F2707) was approximately
the same, with the exception that the small peaks representing
compounds g and h are not present in some of them. This
pattern is also represented in the mass chromatograms of the
two UTO samples.
Only two samples in the iso-paraffin series 08i2301-08i2304
contained a few peaks representing bicyclanes. These are sample
US2 which demonstrate 5 peaks, j, m, n o and r and
sample MS2 which contained a trace of o and a high r peak.
Terpanes: m/z 191
Geochemists associate tricyclic, tetracyclic, and pentacyclic terpanes commonly found in crude oils with decaying plants and
bacteria (Peters and Maldowan 1993). The distribution in the
naphthenic crude oil sample (08F2708) extends from C24 C35
(Appendix 1, Table 4). The highest peak (Figure 8) is N (1721hopane). Of note is that the naphthenic base stock contains peak
1, or C21 -tricyclic terpane, which is not present in the naphthenic crude oil. The peak distribution of this base stock oil
with the low molecular weight compounds C21 , C23 and C24
dominating (Figure 8), is recognizably different from the starting crude oil. Trace inhibited transformer oil (08F2704) and
Inhibited A transformer oil (08F2705), inhibited C transformer
oil (08F2707) and uninhibited A transformer oil (08F2701) have
a much wider peak distribution pattern than the naphthenic base
stock oil and contain peaks 2 A, B, C, D, P, Q,
T, and U, which are not present in the base stock oil. By
contrast, uninhibited B transformer oil (08F2702) only has four
peaks in the mass chromatogram (Figure 8) displaying the lowest
molecular weight compounds 1, 2, 3, and 4 (Appendix
2, Figure 5, shows additional mass chromatograms).
In the paraffinic series, 08i2301-08i2304, sample YB3 contains a trace of compound 1, whereas sample US2 (08i2301)
contains low peaks representing compounds 1, 3, 4,
and5. The other two samples contain no identifiable peaks.
Used samples UTO1 and UTO2 (Appendix 2) contain strong
peaks 1, 3,4, and 5 as well as minor amounts of 6a,
6b, and N.
Steranes: m/z 217
Unlike many other hydrocarbon families, distribution of steranes (Figure 2), originating from plant and animal sterols, display only minor changes after distillation of the crude oil to
the naphthenic base stock oil (Figure 9). Of the 32 compounds
listed in Appendix 1, Table 5, 24 steranes are present in both
the previously noted samples. All the compounds from C27 C29
are present in the Base Stock sample (08F1801), but quantitatively at 50% below the concentration in the crude oil; only the
heaviest C30 compounds are missing. These distribution patterns
are reflected in the mass chromatograms of samples 08F2701,
082704, 08F2705 and 08F2707. No steranes were detected in
samples 08F2702 and 08F2703, and a restricted distribution of

128

Figure 6. Alkylcyclohexanes at m/z 83.

129

Figure 7. Bicyclanes at m/z 123.

130

I. R. Kaplan et al.

Table 4. Identification and concentration (mg/kg) of polycyclic aromatic hydrocarbon (PAH) compounds present in all samples analyzed
Sample Identification by Numbers
Compound
name

Crude
Oil

08F
1801

08F
2701

08F
2702

08F
2703

08F
2704

08F
2705

08F
2706

08F
2707

08i
2305

08i
2306

Naphthalene
2-methyl naphthalene
1-methyl naphthalene
Biphenyl
C2 naphthalene
Acenaphthene
Fluorene
C3 naphthalene
C4 naphthalene
C1 fluorene
Dibenzothiophene
Phenanthrene
C1 phenanthrene
C2 phenanthrene
C1 dibenzothiophene
C2 fluorene
C2 dibenzothiophene
C3 fluorene
C3 dibenzothiophene
Pyrene
C3 phenanthrene
C1 pyrene
C4 dibenzothiophene
C4 phenanthrene
C2 pyrene
C3 Pyrene
Benz(a)anthracene
Chrysene
C1 chrysene
C2 chrysene
C3 chrysene
Benzo(b)fluoranthene
Benzo(e)pyrene
Benzo(a)pyrene
Perylene
C4 chrysene
Benzo(g,h,i)perylene

129.8
161.9
138.7
26.1
606.1
53.7
26.4
854.3
942.7
73.4
43.8
173.8
481.7
848.2
233.0
67.4
731.1
140.5
300.5
30.4
549.0
218.1
172.9
223.8
284.3
150.5
4.7
62.4
231.2
159.5
54.9
12.4
28.2
7.4
13.0
15.8
6.7

nd
nd
nd
29.0
31.5
nd
nd
61.0
147.6
nd
nd
nd
nd
17.5
nd
8.5
nd
nd
nd
nd
23.1
25.4
nd
nd
32.4
8.0
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd

nd
2.6
2.8
27.2
29.0
nd
nd
65.9
97.3
nd
nd
nd
nd
4.8
nd
7.6
nd
nd
nd
5.2
5.3
6.4
nd
nd
31.3
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd

nd
nd
nd
14.0
13.7
nd
nd
62.9
182.2
nd
nd
nd
nd
nd
nd
13.7
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd

1.6
nd
nd
nd
15.9
nd
nd
37.1
82.8
nd
nd
nd
29.0
21.8
29.0
8.3
55.3
nd
50.2
nd
9.6
4.7
nd
nd
27.5
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd

nd
1.8
2.1
18.7
31.8
nd
nd
55.0
118.6
nd
nd
nd
nd
11.9
nd
12.0
nd
nd
nd
nd
12.9
11.9
nd
4.9
49.9
7.6
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd

nd
3.0
3.2
27.1
30.6
nd
nd
58.6
152.0
nd
nd
nd
nd
12.3
nd
12.0
nd
49.7
nd
5.5
10.2
9.3
nd
nd
37.0
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd

nd
nd
nd
8.9
13.5
nd
nd
26.2
47.2
nd
nd
nd
nd
nd
nd
8.1
nd
nd
nd
nd
nd
nd
nd
nd
12.3
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd

nd
nd
nd
nd
6.7
nd
nd
11.5
40.4
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
3.8
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd

nd
3.3
3.3
nd
70.5
nd
nd
88.7
204.7
nd
nd
nd
nd
66.7
nd
nd
nd
nd
nd
nd
26.9
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd

nd
2.6
2.7
nd
14.4
nd
nd
22.0
18.5
nd
nd
nd
nd
n/
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd

nd, = not detected.

7 compounds (up to 24-ethyl-13, 17dicholobutane (# 20

in Appendix 1, Table 5) was detected in sample 08F2706 (Appendix 2, Figure 6, shows additional mass chromatograms).
By contrast, in the sample series 08i2301-08i2306, sample
08i2305 (UTO1) displays a trace of four compounds (#s 1,
2, 4, and 5) (Appendix 1, Table 5), but contains approximately 65% of their concentration in sample 08F1801. No transformer oils in the iso-paraffin series 08i2301-08i2304 contained
measurable quantities of steranes.

Monoaromatic Steranes: m/z 253

Monoaromatic steranes (Figure 2) are products of alteration
occurring in petroleum during its maturation. They are often
present in crude oil in low concentration, and are relatively stable to both thermal and environmental degradation. In this family (Appendix 1, Table 6) 13 compounds have been commonly
detected by GC-MS using the analytical methods described
in the Analytical Procedures and Compound Identification

Section. Figures 10a and 10b show the distribution patterns

for naphthenic crude oil and the refined naphthenic base stock,
respectively, which differ only in the fact that the base stock
concentration is approximately 50% that in the crude oil.
Table 5. Total concentration (mg/kg) for all samples containing polycyclic
aromatic hydrocarbon (PAH) and concentration ratios to the naphthenic
crude oil
Sample Name/#
or No.
Crude oil
08F1801
08F2701
08F2702
08F2703
08F2704
08F2705
08F2706
08F2707
08i2305
08i2306

Concentration,
mg/kg
7898.3
384.0
376.4
356.8
366.5
339.1
410.5
107.3
53.4
513.4
59.8

% concentration relative to PAH

in crude oil
4.9
4.8
4.4
4.6
4.3
5.2
1.4
0.7
6.5
0.8

131

Figure 8. Terpanes at m/z 191.

132

I. R. Kaplan et al.

Figure 9. Steranes at m/z 217.

Samples 08F2701, 08F2704 and 082705 have approximately the

same concentration as the base stock sample, whereas sample
08F2707 (Appendix 2, Figure 7) has about half the concentration
of the peaks in the base stock sample. No monoaromatic steranes
were detected in samples 08F2702, 08F2703 and 08F2706.
No monoaromatic steranes were detected in the iso-paraffin
series of samples, 08i2301-08i2304. The two UTO contained the
full series of compounds, but with a slightly different relative
distribution of compounds, namely those represented by peaks

h, i, and l (Appendix 1, Table 6). The concentration of

monoaromatic steranes in sample 08i2305 is approximately 20%
of those in sample 08i2306, which is in turn approximately 50%
smaller than the total in the crude oil sample.
Triaromatic Steranes: m/z 231
Triaromatic steranes (Figure 2) are present in some crude oils,
but generally in small concentrations (Peters and Maldowan

Mineral-Insulating Oils

133

Table 6. Ratios of naphthalenic crude oil individual PAH concentrations relative to PAH in naphthenic base stock and insulating oils
Sample identification by numbers
Compound Name

08F1801

08F2701

08F2704

08F2705

08F2706

2-m naphthalene
1-m naphthalene
Biphenyl
C2 naphthalene
C3 naphthalene
C4 naphthalene
C2 phenanthrene
C2 fluorene
C3 fluorene
Pyrene
C3 phenanthrene
C1 pyrene
C4 phenanthrene
C2 pyrene
C3 pyrene

0.90
19.2
14.0
6.4
48.5
7.9

23.8
8.6

8.8
18.8

62.3
49.5
0.96
20.9
13.0
9.7
176.7
8.9

5.8
103.6
34.1

9.1

89.4
66.0
1.4
19.1
15.5
7.9
71.3
5.6

42.6
18.3
98.0
5.7
19.8

54.0
43.3
2.9
20.1
14.6
6.2
69.0
5.6
2.8
5.5
53.8
23.5

7.7

44.9
32.6
20.0

8.3

12.3

1993). They are, however, considered to be among the most stable hydrocarbons and when present in crude oil or refined oil
released in an environment their relative concentration will
increase with time (Kaplan et al., 1997). All seven of the common compounds identified in Appendix 1, Table 7, are present in
the crude oil sample (Figure 11a), but only the used oil (UTO2)
sample 08i2306 of the entire 14 refined samples displayed the
presence of triaromatic steranes (Figure 11b). Their concentration in this sample was <10% of the concentration in the crude
oil sample, but all except peak # T7 (Appendix 1, Table 7)
were present in this sample.
Polycyclic Aromatic Hydrocarbons (PAHs): Numerous m/z
values
No PAHs were detected in the 4 samples classified as originating
from iso-paraffin oils (Table 3). The eight samples, which had
undergone different refining processes at the Ergon refinery,
have PAH concentrations varying from 53.4 mg/kg to 410.5
mg/kg (Table 5). Two extremely different values were detected
in the two used transformer oils: UTO1 (08i2305 with 513.4
mg/kg) and UTO2 (08i2306 with 59.8 mg/kg).
The starting naphthenic crude oil sample (08F2708) contains
a large suite of PAH (Table 4) with a total measured concentration of 7898.3 mg/kg (Table 5). By contrast, the refined oils
contain a fraction of that in the starting crude oil (Table 5), varying from 5.2% in sample 08F2705 to 0.7% in sample 08F2707,
both manufactured by Ergon Refining. The range in the two
UTO samples is from 6.5% to 0.8%.
The distribution of individual PAH compounds is reasonably similar in the starting naphthenic crude oil and in the
refined products. The following compounds are present in all
the 08F series of samples; C2 naphthalene, C3 naphthalene,
and C4 naphthalene. The following compounds are present
in seven samples of the series; biphenyl, C2 fluorene and C2
pyrene, followed in diminishing concentration by C2 phenanthrene, C3 phenanthrene and C2 pyrene. Several other PAH

08F2707

90.5
72.3
23.3

74.8

compounds present in the crude oil at concentrations >100

mg/kg are not present in the refined products (Table 4), indicating that they were destroyed during the refining process. These
are naphthalene, dibenzothiophene and its four alkylated homologs, phenanthrene, chrysene and its alkylated homologs and
the complex benzene addition compounds of fluoranthene and
pyrene.
The distribution patterns and the concentration differences
between the crude oil and the refined products display three
features:
1) The sulfur-containing PAH compounds are quantitatively destroyed by the high pressure hydrogenation process;
2) C1 -C4 alkylated naphthalenes have the highest rate of survival (i.e., 21% for 08F1801 and 20% for 08F2705); and
3) No PAH compounds were detected in paraffinic insulating
oils
For C4 naphthalene, the survival rate is 16% for 08F1801
and 16% for 08F2705. For C1 pyrene, the survival rate is 12%
for 08F1801 and 4.3% for 08F2705; for C2 pyrene it is 11.4%
for 08F1801 and 13% for 08F2705. Table 6 displays the ratio
of a specific PAH in the crude oil and in six Ergon Refinery
products. From these ratios it is apparent that biphenyl, which
was present in low concentrations in the crude oil, is the least
affected by the refining process (at least in the base oil and two
other refined oils), followed by C4 naphthalene and C2 pyrene.
From these partial comparisons it appears that the initial refining
process, which produces the naphthenic base stock, must also
have undergone the high-pressure hydrotreating treatment that
removed all the organic sulfur compounds and most of the PAH
compounds.

Interpretation of Chemical Properties Measured

The analyzed data described display both similarities and differences among and between each group (Table 3), which in

134

I. R. Kaplan et al.

Figure 10. Monoaromatic steranes at m/z 253.

part reflects the composition of the starting crude oil as well as

the refining procedures. With the exception of sample 08F2701,
for which a controlled amount of medium- to high-molecular
weight n-alkanes were added at the refinery, no other n-alkanes
were present, because of the choice of the starting crude oil.
By contrast, n-alkanes were present in three of the four isoparaffin oils. Iso-alkanes (or iso-paraffins) were present in all
the naphthenic oils, but were absent in all the iso-paraffin oils.
The explanation for these features must be in the difference of
the hydrogenation process between refineries producing the dif-

ferent products, with the more aggressive hydro-cracking in the

paraffinic oil process.
Another obvious difference is the absence of alkylcyclohexanes in the naphthenic oils, but their presence in three of four
of the paraffinic oils analyzed. This feature must be the result
of both selection of the starting crude oil as well as the refinery
process. Sample 08F2708, the crude oil, contains low-boiling
(C1 C4 ) alkyl cyclohexanes, which are removed from the distillate in the first refinery operation. Three paraffinic insulating
oils contain alkyl cyclohexanes in the range C5 C14 .

Mineral-Insulating Oils

135

Figure 11. Triaromatic steranes at m/z 231.

All the naphthenic oils contain bicyclanes and terpanes, and

all except one sample contain steranes. In the paraffinic oil suite,
only two samples contain a limited distribution of bicyclanes and
another two samples contain terpanes, but no sample contains
steranes. Sample 08i2301 (US2) contains both bicyclanes and
terpanes with a reasonably wide distribution, indicating that the
hydrocracking process in the refinery that produced it, is less
aggressive than in the other refineries. PAH compounds perform three important functions in insulating oils (Rouse 1998).
One is they act as antioxidants, a second is they adsorb gases

produced by electric discharges. Hence, the higher their composition the more significant is their role in maintaining the initial
composition of the insulating fluid. The third property, referred
to as dielectric impulse strength, is their role in reducing short
electric shocks. It has been demonstrated that the lower the PAH
concentration in an insulating oil, the greater the capacity of the
oil in controlling arcing and rapid changes in power load. Each
refinery must therefore control the PAH concentration according to the specifications of their product. Finally it is apparent
that the hydro-treating process in the paraffinic oil refineries

136

I. R. Kaplan et al.

was significantly more effective in removing the polynuclear

hydrocarbons than that used in the manufacture of naphthenic
transformer oils.
Two used oils, UTO1 and OTO2 (08i2305, 08i2306) from
unknown manufacturing refineries were also analyzed. These
samples contain a full suite of hydrocarbon families present in
crude oil. As the history of these oils is not known, two interpretations can be ascribed to their composition; one is that the
oils represent decomposition products of virgin transformer oils
during many years of use, or alternatively, they were stored in a
waste container, where oils from both naphthenic and paraffinic
type transformer oils were discarded. We suggest that, when
the compositions of these used oils are compared with both the
unused naphthenic and paraffinic oils, they appear to closely
resemble a mixture of the two types of unused transformer insulating mineral oils.

Discussion
This article demonstrates that the chemical compositions of
naphthenic and paraffinic transformer oils can be differentiated.
However, the analytical data also display differences within either one of the two major groups. This is due to two primary factors: crude oil composition and refining technology. First, biodegraded crude oils with depleted normal alkanes are desirable for
the production of naphthenic transformer oils and undesirable
for paraffinic oils. The rate of biodegradation, which removes
n-alkanes depends on many factors, among them, the availability of water containing nutrients and dissolved oxygen within
the storage reservoir. Hence, different locations in a single
petroleum basin may be compartmentalized, so that the availability of nutrients and oxygen could vary significantly. This could
result in insulating oils which over time of exposure to environmental conditions display differences in their chemical composition, even when the refinery procedures have not changed. To
avoid this contingency, crude oils are carefully screened in the
refinery to ensure they have the needed compound distribution
character, prior to initiating refining operations.
The second factor that affects the overall chemistry of manufactured transformer oils is the nature of the refining process
from distillation to hydro-treatment. Distillation controls the
cut-off boiling points, which in turn affects the freezing points
and viscosity of the manufactured product. The refining process depends on such parameters as pressure, temperature and
the nature of the hydro-treating catalysts. These parameters will
control the efficiency of both the hydrogenation and cracking of
large heterocyclic and polynuclear molecules. Very aggressive
reactions will result in finished transformer fluids which have a
relatively narrow distribution of hydrocarbons, as can be seen in
samples YB3 (08i2302), MS2 (08i2303) and CS2 (08i2304), in
contrast to sample US2 (08i2301). Slight or subtle changes in
chemical composition of the refined product may therefore appear if the refinery amends its refining procedures, which are not
reflected in the insulating or stability properties of the mineral
insulating oil.

Conclusions
Transformer mineral insulating oils fall into two categories;
one is naphthenic oil and the other is paraffinic oil. In this
study, fourteen refined oils from seven different refineries were
analyzed. The naphthenic fluids have a starting carbon range
from C11 C14 and an ending carbon range from C24 C37 . The
paraffinic fluids have a starting carbon range from C11 C15 and
an ending carbon range from C18 C28 .
These families can be differentiated by the following properties:
1) All the paraffinic oils contain a series of n-alkanes, but do
not contain iso-alkanes;
2) By contrast all the naphthenic oils contain iso-alkanes but
do not contain n-alkanes;
3) None of the naphthenic oils contain alkycyclohexanes,
whereas three out of the four paraffinic oils analyzed contain
them;
4) Bicyclanes (or sesquiterpanes) are present in all the naphthenic oils analyzed, but in only two of the four paraffinic
oils analyzed;
5) Naphthenic insulating oil contain a limited number of both
terpanes and steranes in concentrations depleted from the
original crude oils, whereas not all the paraffinic insulating
oils analyzed contain terpanes and steranes, and then only in
trace amounts;
6) Paraffinic oils do not contain monosteranes, whereas some
of the naphthenic oils analyzed contain a limited number of
monoaromatic steranes in concentrations either equal to, or
partially depleted relative to the crude oil;
7) Triaromatic steranes are not present in either the naphthenic
or paraffinic oils; and
8) PAH compounds are absent in all the paraffinic insulating
oils, but are present in all the naphthenic insulating oils.
The uninhibited fluids contain a wider distribution of PAH
and a higher concentration than the Inhibited oils. The chemical
properties of the transformer insulating oil families summarized
above, should allow for the differentiation of hydrocarbon fluids
in the environment.

References
American Society for Testing and Materials (ASTM). 2006. ASTM D 348700-2006: Standard Specifications for Mineral Insulating Oil Used in
Electrical Apparatus. West Conshohocken, PA: ASTM International.
ASTM. 1999. AS 1767.1: Specification for Unused Mineral Insulating
Oil for Transformer and Switchgear. West Conshohocken, PA: ASTM
International.
Broadhurst, M. G. 1972. Use and replaceability of polychlorinated
biphenyls. Environmental Health Perspectives October 1972:81102.
Canada/Canadian Standards Association (CAN/CSA). 2006. CAN/CSAC50-97: Insulating Oil, Electrical Applications for Transformers and
Switches.
Doble Engineering Company. 2006. Transformer Oil Purchase Specification (TOPS)-2006. Watertown, MA: Doble Engineering Company.

Mineral-Insulating Oils
International Electrotechnical Commission (IEC). 2003. IEC 60296: International Standard-Fluids for Electrical Application of Unused Mineral
Insulating Oils for Transformers and Switchgears.
Japanese Industrial Standard (JIS). 1993. JIS C 2320: Japanese Industrial
Standard for Electrical Insulating Oils.
Johnson, G. W., Quensea, J. F., Chiarenzelli, J. R., and Hamilton, M. C. 2006.
Polychlorinated biphenyls. In Environmental Forensics, R.D. Morrison
and B. L. Murphy, eds. 187225. San Diego, CA: Elsevier.
Kaplan, I. R., Galperin, Y., Lu, S-T., and Lee, R.-P. 1997. Forensic environmental geochemistry: Differentiation of fuel-types their sources
and release times. Organic Geochemistry 27:289317. San Diego, CA:
Elsevier.
McShane, C. P. 2000. New safety dielectric coolants for distribution and
power transformers. IEEE Industry Applications Magazine, May/June,
2432.
Peters, K. E., and Maldowan, J. M. 1993. The Biomarker Guide: Interpreting
Molecular Fossils in Petroleum and Ancient Sediments. Prentice Hall:
Englewood Cliffs, NJ.
Philp, R. P. 1985. Fossil fuel biomarkers: Applications and spectra. Amsterdam: The Netherlands: Elsevier. Methods in Geochemistry and Geophysics 23.
Rouse, T. O. 1998. Mineral insulating oil in transformers. IEEE Electrical
Insulation Magazine 14:616.
Wilson, A. C. M. 1980. Insulating Liquids: Their Uses, Manufacture and
Properties. London, UK: Institute for Electrical Engineering, Peter Peregrinus Ltd.

Table 3. Key for bicyclanes (mass m/z 123 chromatograms)

Peak No.
a
b
c
d
f
g
h
j
k
l
m
n
o
p
q
r

Table 1. Key to chromatogram symbol identification for m/z 85 and m/z

113 paraffins and isoparaffins
Symbol
i-10
i-15
i-16
Pr
Ph
nC8
nC15
i-8
i-8
i-8
CH-n

Detail
Iso-alkane with 10 carbon atoms
Farnesane (isoprenoid with 15 carbon atoms)
Isoprenoid with 16 carbon atoms
Pristane (isoprenoid with 19 carbon atoms)
Phytane (isoprenoid with 20 carbon atoms)
n-C8 normal alkane
n-C15 normal atkane
2,5-(2,4)-Dimethylhexane
2,3,4-Trimethylpentane
2, 3-Dimethylhexane
Alkylcyclohexane (where n indicates number of carbon
atoms in the side chain)

Table 2. Key for alkylcyclohexanes (mass m/z 83

chromatograms)
Symbol

Detail

CH-1:
CH-2:
CH-3:
CH-4:
CH-5:
CH-6:
CH-7:
CH-8:
CH-9:
CH-10:
CH-11:
CH-12:
CH-13:
CH-14:

Methylcyclohexane
Ethylcyclohexane
Propylcylohexane
Butylcyclohexane
Pentylcyclohexane
Hexylcyclohexane
Heptylcyclohexane
Octylcyclohexane
Nonylcyclohexane
Decylcyclohexane
Undecylcyclohexane
Dodecylcyclohexane
Tridecylcyclohexane
Tetradecylcyclohexane

Formula

M.W.

2,2,3-Trimethylbicyloheptane
C10 bicycloalkane
3,3,7-Trimethylbicycloheptane
C11 decalin
Nordrimane
Nordrimane
Rearranged drimane
Rearranged drimane
Isomer of eudesmane
4(H) Eudesmane
C15 bicyclic sesquiterpane
8 (H) Drimane
C15 bicyclic sesquiterpane
C16 bicyclic sesquiterpane
C16 bicyclic sesquiterpane
8(H) Homodrimane

C10 H18
C10 H18
C10 H18
C11 H20
C14 H26
C14 H26
C15 H28
C15 H28
C15 H28
C15 H28
C15 H28
C15 H28
C15 H28
C16 H30
C16 H30
C16 H30

138
138
138
152
194
194
208
208
208
208
208
208
208
222
222
222

Table 4. Key for tricyclic, tetracyclic, and pentacyclic

terpanes (m/z 191 mass chromatograms)
Code

Appendix 1

Identity

0
1
2
3
4
5
Z4
6a
6b
7
A
B
C
D
E
F
G
H
10a
10b
1
11a
J
11b
K
C29 Ts
C30
L
Ma
Mb
N
O
13a
13b
P
Q
R
14a
S
14b

Identity

Carbon #

C20 -Tricyclic Terpane

20
21
C21 -Tricyclic Terpane
C22 -Tricyclic Terpane
22
C23 -Tricyclic Terpane
23
C24 -Tricyclic Terpane
24
C25 -Tricyclic Terpane
25
24
C24 -Tetracyclic Terpane
C26 -Tricyclic Terpane
26
26
C26 -Tricyclic Terpane
C27 -Tricyclic Terpane
27
C28 -Tricyclic Terpane #1
28
28
C28 -Tricyclic Terpane #2
C29 -Tricyclic Terpane #1
29
29
C29 -Tricyclic Terpane #2
18-22, 29,30-Trisnorneohopane (Ts) 27
17-22,29,30-Trisnorhopane(Tm)
27
17-22,29-30-Trisnorhopane
27
17-23,28-Bisnorlupane
28
C30 -Tricyclic Terpane #1
30
C30 -Tricyclic Terpane #2
30
17-28,30-Bisnorhopane
28
C31 -Tricyclic Terpane #1
31
17-25-Norhopane
29
C31 -Tricyclic Terpane #2
31
17,21-30-Norhopane
29
18-30-Norneohopane
29
17-Diahopane
30
17-21-30-Normoretane
29
18-Oleanane
30
18-Oleanane
30
17,21-Hopane
30
17,21-Moratane
30
C33 -Tricyclic Terpane #1
33
33
C33 -Tricyclic Terpane #2
22S-17,21-30-Homohopane
31
22R-17,21-30-Homohopane
31
Gammacerane
30
C34 -Tricyclic Terpane #1
34
17,21-Homomoretane
31
C34 -Tricyclic Terpane #2
34
(Continued on next page)

137

138

I. R. Kaplan et al.

Table 4. Key for tricyclic, tetracyclic, and pentacyclic terpanes (m/z 191
mass chromatograms) (Continued)

Table 6. Key for monoaromatic steranes (m/z 253 mass chromatograms)

Code

Identity

Carbon #

Code

T
U
15a
15b
V
WS
WR
16a
16b
XS
XR
YS
YR

22S-17,21-30-Bishomohopane
22R-17,21-30-Bishomohopane
C35 -Tricyclic Terpane #1
C35 -Tricyclic Terpane #2
17,21-C32 -Bishomomoretane
22S-17,21-30,31,32-Trishomohopane
22R-17,21-30,31,32-Trishomohopane
C36 -Tricyclic Terpane #1
C36 -Tricyclic Terpane #2
22S-17,21-30,31,32,33-Tetrahomohopane
22R-17,21-30,31,32,33-Tetrahomohopane
22S-17,21-30,31,32,33,34-Pentahomohopane
22R-17,21-30,31,32,33,34-Pentahomohopane

32
32
35
35
32
33
33
36
36
34
34
35
35

a
b
c
d
e
f
g
h
i
j
k
l
m

Elemental
Composition

Identity
20S, 5 C27 -Monoaromatic sterane
20S, dia C27 -Monoaromatic sterane
20R, 5 C27 -Monoaromatic sterane + 20R C27 dia
MAS
20S, 5 C27 -Monoaromatic sterane
20S, 5 C28 -Monoaromatic sterane + 20S C28 dia
MAS
20R, 5 C27 -Monoaromatic sterane
20S, 5 C28 -Monoaromatic sterane
20R, 5 C28 -Monoaromatic sterane + 20R C28 dia
MAS
20S, 5 C29 -Monoaromatic sterane + 20S C29 dia
MAS
20S, 5 C29 -Monoaromatic sterane
20R, 5 C28 -Monoaromatic sterane
20R, 5 C29 -Monoaromatic sterane + 20R C29 dia
MAS
20R, 5 C29 -Monoaromatic sterane

C27 H42
C27 H42
C27 H42
C27 H42
C28 H44
C27 H42
C28 H4
C28 H44
C29 H46
C29 H46
C28 H44
C29 H46
C29 H46

Table 5. Key for steranes (m/z 217 mass chromatograms)

Code

Identity

1
2
3
4
5
6
7D
7
8D
8
9
9D
10
11
12
13
14D
14
15
16
17
18
19
20
21A
21B
22A
22B
23A
23B
24A
24B

13,17-diacholestane (20S)
13,17-diacholestane (20R)
13,17-diacholestane (20S)
13,17-diacholestane (20R)
24-methyl-13,17-diacholestane (20S)
24-methyl-13, 17-diacholestane (20R)
24-methyl-13, 17-diacholestane (20S)
14,17-cholestane (20S)
24-ethyl-13,17-diacholestane (20S)
14,17-cholestane (20R)
14,17-cholestane (20S)
24-methyl-13,17-diacholestane (20R)
14,17-cholestane (20R)
24-ethyl-13,17-diacholestane (20R)
24-ethyl-13,17-diacholestane (20S)
24-methyl-14,17-cholestane (20S)
24-ethyl-13,17-diacholestane (20R)
24-methyl-14,17-cholestane (20R)
24-methyl-14,17-cholestane (20S)
24-methyl-14,17-cholestane (20R)
24-ethyl-14-cholestane (20S)
24-ethyl-14,17-cholestane (20R)
24-ethyl-14,17-cholestane (20S)
24-ethyl-14,17-cholestane(20R)
24-n-Propylcholestane (20S)
4-methyl-24-ethylcholestane (20S)
4-methyl-24-ethyl-14,17-cholestane (20S)
24-n-propyl-14,17-cholestane (20S)
4-methyl-24-ethyl-14,17-cholestane (20R)
24-n-propyl-l4,17-cholestane (20R)
4-methyl-24-ethylcholestane (20R)
24-n-propylcholestane (20R)

Carbon
27
27
27
27
28
28
28
27
29
27
27
28
27
29
29
28
29
28
28
28
29
29
29
29
30
30
30
30
30
30
30
30

Table 7. Key for tri-aromatic steranes (m/z 231 mass chromatograms)

Code
T1
T2
T3
T4
T5
T6
T7

Identity
C20 Triaromatic sterane
C21 Triaromatic sterane
20S C26 Triaromatic sterane
20R C26 + 20S C27 -Triaromatic
steranes
20S C28 -Triaromatic sterane
20R C27 -Triaromatic sterane
20R C28 -Triaromatic sterane

Elemental Composition
C20 H20
C21 H22
C26 H32
C26 H32 + C27 H34
C28 H36
C27 H34
C28 H36

Mineral-Insulating Oils

Appendix 2

Figure 1. Total ion current (TIC) chromatograms.

139

140

I. R. Kaplan et al.

Figure 2. Iso-alkanes mass chromatograms m/z 113.

Mineral-Insulating Oils

Figure 3. Alkylcyclohexanes mass chromatograms m/z 83.

141

142

I. R. Kaplan et al.

Figure 4. Bicyclanes mass chromatograms m/z 123. (Continued)

Mineral-Insulating Oils

Figure 4. (Continued).

143

144

I. R. Kaplan et al.

Figure 5. Terpanes mass chromatograms m/z 191.

Mineral-Insulating Oils

Figure 6. Steranes mass chromatograms m/z 217.

Figure 7. Mono-aromatic steranes mass chromatograms m/z 253.

145