High Throughput Mineral Oil Analysis
(Hydrocarbon Oil Index) by GC-FID
using the Agilent Low Thermal Mass
(LTM II) System
Application Note
Environmental Analysis
Authors Abstract
Frank David and Karine Jacq Cycle time for GC-FID analysis of mineral oil in environmental samples was dramati-
Research Institute for Chromatography, cally reduced and sensitivity increased by fast oven temperature programming using
Pres. Kennedypark 26, B-8500 Kortrijk, an LTM II oven module. Regulated method requirements for environmental analyses of
Belgium soil and water extracts are met using splitless injection with an analysis time for the
C10-C40 hydrocarbon fraction of less than 3 min. Cool-down time is less than 2 min,
Roger L Firor
resulting in an injection-injection cycle time of 5 min. Method performance criteria,
Agilent Technologies, Inc.
including repeatability, linearity and solute discrimination are presented.
2850 Centerville Road
Wilmington, DE 19808
USA
Introduction Experimental Conditions
Environmental contamination by hydrocarbon fractions, such Solutes and Sample
as diesel or motor oil, is currently measured using GC-FID. This
method, also called hydrocarbon oil index (HOI), mineral oil or An alkane standard containing even numbered n-alkanes from
total petroleum hydrocarbon (TPH) determination is one of the C10 to C40 was purchased from Restek (cat no 31678, Restek,
most important applications in environmental analysis, repre- Bellefonte, USA). The sample was diluted to 5 ng/µL in
senting the highest sample loads in many laboratories. For hexane. Mineral oil calibration was done using a 1:1 mixture
analysis, samples (water, soil, sediment) are extracted by an of diesel and motor oil (cat no 31630, Restek). Calibration
apolar (hydrocarbon) solvent with a boiling point between samples were prepared at concentrations between 40 and
36 °C and 69 °C (for example, hexane). The extract is cleaned 1,000 mg/L in hexane. In addition, a reference sample from
by passing over Florisil (to retain more polar solutes such as RIVM (NMI, the Netherlands) containing diesel and motor oil
lipids), concentrated by N2 blowdown (or Kuderna-Danish) and was used. This sample, was diluted at 1,000 mg/L in hexane.
analyzed by GC-FID [1]. The fraction eluting on an apolar
(HP-1, HP-5) column between decane (C10) and tetracosane (C40) GC-FID Conditions
is defined as mineral oil or HOI, over which the area is Analyses were performed on an Agilent 7890A GC system
summed for quantitation. equipped with a S/Sl inlet, FID and a five inch format LTM II
column module containing a 10 m × 0.32 mm id × 0.1 µm
The ISO 9377 method specifies the use of a column with a
DB-5HT (p/n 123-5701LTM). Non-coated but deactivated
high phase ratio (thin film) to facilitate elution of C40. GC oven
pieces of fused silica (each 0.5 m × 0.32 mm id) were used to
program conditions should, however, also allow the separation
connect the column to SSl inlet and FID.
of the extraction solvent from the first peak (decane) and
therefore low initial temperatures (35 °C–40 °C) are often The fast GC conditions are listed in Table 1. As seen, the LTM
necesssary. An important method requirement is that the column is operated in constant flow mode. The EPC takes into
injection method should minimize solute discrimination. The account the fact that two 50 cm pieces of tubing are connected
method specifies that the relative mass response for tetra- to the column and that these pieces of tubing are at 340 °C
cosane (C40) and eicosane (C20) should be higher than 0.80. isothermal (while the main part of the column is heated by the
Typically, the analysis is performed using a 10–30 m column LTM module). These column and connecting fused silica
using splitless, PTV, or cool on-column injection and oven pro- dimensions are input into column configuration. The overall
gramming from 40 °C to 340 °C at 10–20 °C/min, resulting in result is accurate, constant flow mode.
analyses times in the order of 20–30 min [2]. Oven cool-down
time to the low initial temperature typically requires an addi- Table 1. GC-FID Setpoints for Fast Mineral Oil Analysis Using a Low
tional 5 min or more, resulting in a total cycle time of 30 min or Thermal Mass Oven
longer. Injection 1 µL, splitless (0.4 min purge delay), 350 °C
Currently, environmental laboratories are seeking ways to Inlet liner Split/splitless p/n 5183-4647 (bottom taper, glass
improve throughput and decrease cost per sample. By adding wool near top, 4 mm id )
an LTM II module to an Agilent 7890A GC system with SSl Carrier gas 9 mL/min He constant flow
inlet, Agilent ALS, and FID significantly improved cycle times
Standard oven program 40 °C (0.5 min), & 340 °C (0.5 min) @ 15 °C/min
can be achieved. In this application note, optimized method [total run time = 21 min]
conditions and performance metrics are presented. Cycle GC oven temp when 340 °C isothermal (3 min)
times of 5 min are demonstrated, while still meeting all using LTM II
method requirements. LTM II oven program 40 °C (0.5 min), 200 °C/min & 240 °C,
100 °C/min & 340 °C (0.5 min) [total time = 3 min]
FID 340 °C, H2 = 40 mL/min, Air = 400 mL/min
LTM II System G6680A, 5 inch, with two power supplies
7890A Firmware A.01.12.1 or greater
GC ChemStation B.04.03 DSP 1, includes LTM II control software
2
Results and Discussion This is due to the combination of fast autoinjection (Agilent
7683 or 7693 ALS) and liner selection.
System suitability was checked using a C10–C40 alkane test
Discrimination was checked against requirements by measur-
mixture. The obtained chromatogram is shown in Figure 1.
ing the peak area ratio of C40–C20. In addition, discrimination for
Decane elutes at 0.8 min and is well separated from the sol-
C10–C20 and C40–C10 were also determined and are presented in
vent. Tetracosane elutes at 2.5 min. Retention time repeatability
Table 2. The C40–C20 ratio was 0.92 (± 0.03), well above the
and peak area repeatability were determined for six runs and
method criterion (> 0.80). This provides a nice margin for main-
the results are summarized in Table 2.
taining compliance and demonstrates that the standard SSl
The repeatability of retention times was excellent, with a stan- inlet can meet method requirements. Splitless injection is also
dard deviation < 0.001 min (< 0.03% RSD). This effectively the most robust injection method and applicable to extracts
demonstrates that the LTM oven module reproducibly heats the from both clean samples (surface water) and contaminated
capillary column and that the constant flow mode works prop- samples (soil, sediment,...).
erly. Peak area repeatability was also excellent (~ 1% RSD).
C 20
1600000
C10
1400000
1200000
1000000
C 30
Response
800000
C 40
600000
400000
200000
0
0.00 0.20 0.40 0.60 0.80 1.00 1.20 1.40 1.60 1.80 2.00 2.20 2.40 2.60 2.80
Time (min)
Figure 1. n. Alkane test mixture with fast oven program on LTM II oven module.
3
Table 2. Figures of Merit Next, a calibration mixture of diesel and motor oil was ana-
lyzed. The chromatogram for a 400 mg/L calibration sample is
tR (min) tR Peak area Peak area
Solutes/sample mean (n=6) s (min) (RSD%) mean (n=6) RSD (%) shown in Figure 2. The two humps corresponding to diesel and
C10
motor oil fractions can easily be detected. Calibration is nor-
0.783 0.00015 (0.022%) 61.640 0.70
mally done with a synthetic mineral oil made from a composite
C20 1.450 < 0.0001 (< 0.01%) 65.114 0.67 of diesel and motor oil in the concentration range from 100 and
C40 2.507 0.00073 (0.027%) 60.024 0.77 1,000 mg/L. The linearity of the fast GC-FID LTM method was
Ratio C40–C20 (*) 0.922 0.30
tested from 40 mg/L to 1,000 mg/L. The obtained calibration
curve of the peak area (sum of peak area from end of decane
Ratio C10–C20 0.947 0.19 peak to start of tetracosane peak) in function of concentration
Ratio C40–C10 0.974 0.47 is shown in Figure 3. The linearity was excellent (R2 > 0.999).
Mineral oil (**) 1.293 < 0.0002 (0.011%) 10421.564 0.57 The repeatability of the peak area (sum C10–C40) of the calibra-
tion mixture at 400 mg/L was better than 1% RSD and the limit
RIVM C10–C20 4549.987 1.6
of detection was below 25 mg/L. As an additional benefit of
RIVM C20–C40 5871.667 1.0 fast oven programming, the hydrocarbon fraction is com-
RIVM ratio (***) 1.29 2.4 pressed into a narrower and higher hump. As a result, method
sensitivity is higher than standard methods that use slower
(*) ratio of C40/C20 should be > 0.80
(**) Restek cat. no. 31630, at 400 mg/L temperature programming.
(***) ratio of area sums C20-C40/C10-C40 should be between 1.25 and 1.40
Diesel
4500000
4000000
3500000 Motor oil
3000000
2500000
Response
2000000
1500000
1000000
500000
0
0.00 0.20 0.40 0.60 0.80 1.00 1.20 1.40 1.60 1.80 2.00 2.20 2.40 2.60 2.80
Time (min)
Figure 2. 400 mg/L calibration sample of diesel plus motor oil.
4
30000 Additional discrimination testing was done using a popular ref-
R2 = 0,9997 erence sample (RIVM sample). Peak areas were measured for
25000 the C10–C20 and C20–C40 fractions. The mean peak areas (n = 6)
and corresponding RSDs are included in Table 2. The repeatabil-
20000
ity of peak area was again excellent with a relative standard
deviation < 2%. The ratio of the peak areas of the C20–C40 frac-
Area
15000
tion (motor oil) versus the C10–C20 fraction (“diesel”) was
10000 1.29 (2.4% RSD); within the specifications (methods require a
value be between 1.25 and 1.40). This test also clearly shows
5000
that solute discrimination was minimal using a split/splitless
inlet and fast autoinjection, and that the fast temperature
0
0 200 400 600 800 1000 program easily meets method performance criteria.
mg/L
As can be deduced from the repeatability data, automated inte-
Figure 3. Mineral Oil Calibration: calibration from 40–1000 mg/L; Linearity:
gration of areas (using fixed integration event times) will
R2>0.999; Repeatability at 400 mg/L: RSD on peak area = 0.57 %;
LOD < 0.25 mg/L. remain valid and accurate for the whole C10–C40 range, as well
as for specific regions (smaller fractions, for example, C10–C20,
A comparison of a standard oven program with the fast LTM C20–C30, etc.), reducing or eliminating the need for manual
program (3 min run time) is shown in Figure 4 for a 400 mg/L integration.
calibration sample. The compression and higher signal gained
from the 7X faster LTM run is obvious.
4500000
4000000
3500000
3000000
Response
2500000 LTM, 3 min run
2000000
1500000
1000000
500000
0.00 2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00
Time (min)
4500000
4000000
3500000
3000000 Standard, 21 min run
Response
2500000
2000000
1500000
1000000
500000
0.00 2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00
Time (min)
Figure 4. Comparison of Sensitivity gain from standard oven program to fast LTM program. Diesel plus motor oil standard at 400 mg/L.
5
Conclusion
By adding an LTM II module to a 7890A GC, great improve-
ments can be achieved in the GC-FID analysis of mineral oil in
environmental samples. Analysis time for the separation of C10
to C40 alkanes is below 3 min. Cool-down time to 40 °C was
also very short (2 min), resulting in a total injection-injection
cycle time of 5 min. Excellent repeatability (retention times and
peak areas), linearity and low LOD were achieved. The fast
autoinjection allowed method criteria to be met using a
standard hot SSl inlet.
References
1. International standard ISO 9377-2, Water Quality,
Determination of hydrocarbon oil index, part 2: Method
using solvent extraction and gas chromatography, 2000.
2. B. Wuest, Agilent Technologies publication 5988-0621EN,
2000.
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© Agilent Technologies, Inc., 2011
Printed in the USA
September 23, 2011
5990-9104EN
