2.

2 Gas Chromatography 95

Sharp, slicing tip Sharp pointed tip

Tapered dual gauge 23–26 24 gauge SPME probe

Figure 2.53 Do not use these needle and probe styles with the MicroSeal. Note: Sharp-
edged or sharp-pointed needles can pierce and damage the duckbill seal.

dual gauge tapered needles and 24 gauge SPME probes will not seal properly
in the MicroSeal, (see Figure 2.53). The longer lifetime for many thousands
of injections reduces the chances for septum leaks especially during extended
autosampler runs.

2.2.4
Injection Port Liner

The inlet liners of the injection port are the point of sample evaporation
and determine to a high degree the GC performance in terms of sensitivity,
reproducibility and sample integrity. Inlet liners are retaining nonvolatile matrix
components and protect the analytical column from performance degradation.
They are consumables necessary to be replaced on a regular basis depending
on the sample matrix load on a daily or weekly basis according to a preventive
maintenance plan.
The liner choice need to fit the analytical method setup if split or splitless
injections are planned, or the basic injection techniques hot needle with thermo
spray or the cold needle with liquid band formation are preferred. Different liner
geometries are available to support the individual injection and vaporization
process. There is not a single liner that serves all injection modes. So, a few basic
rules help identifying the liner of choice for the chosen injection technique.

2.2.4.1 Split Injection

Split injections are used to perform a sample ‘dilution’ in the injector with carrier
gas for a reduction of the amount of sample which enters the column. For concen-
trated (undiluted) samples, this is necessary due to the limited sample capacity of
fused silica columns. The amount of sample wasted via the split line relative to the
column carrier gas flow is adjusted by the split flow rate. Split liners provide high
flow speeds inside the liner for a short sample band at the beginning of the column.
Room is required between the needle exit and column entry for the evaporation of
solvent and analytes, and the homogeneous mixing with the carrier gas before the
sample cloud ‘flies’ across the column entry. Straight liners with and without glass
wool are used for split injections (Schomburg et al., 1977). The inside diameter
should be low to guarantee high-split flows through the injector body out to the
split line (see Figure 2.55).
96 2 Fundamentals

The residence times of samples in the liner are short compared to a splitless
injection. With low split ratios labile compounds can also be analysed with good
results, reducing the residence time and degradation in the hot liner significantly.

2.2.4.2 Splitless Injection

Splitless injections are typical for trace analysis with a total sample transfer into
the analytical column. Inlet liners for splitless injection need to provide room for
the solvent cloud to expand during evaporation (see Table 2.21), and typically, lin-
ers with larger inner diameters are used (see Figure 2.55) (Hinshaw, 1992). The
knowledge of liner volume and solvent vapour volume is essential for the opti-
mum parameter setting. Typically, the ‘goose neck’ liners with a tapered bottom
end are preferred for splitless injections preventing analytes getting in touch with
metal surfaces at the bottom of the liner with potential memory and degradation.
Overfilling of the liner need to be avoided by proper selection of the solvent and
the maximum tolerated ‘at once’ injection volume.
A known disadvantage of goose neck liners can be caused by septum particles,
which can get in contact with the sample vapours at the bottom of the tapered
liner. In this case, the use of straight liners for splitless injections can be advan-
tageous as septum particles accumulate at the base of the injector and do less
interfere with the sample.
The transfer time of analytes from injection and evaporation into the analyt-
ical column is the residence time of the solvent/analyte cloud in the inlet liner.
The residence time depends on the flow conditions within the inlet. The sam-
ple vapours are diluted exponentially as they are transferred into the analytical
column increasing the residence time for a certain part of the analytes. Labile com-
pounds require a short residence time in the liner for reduced surface contacts.
Using a surge pressure (pressure pulse) during the transfer phase with a two to
three times higher pressure than the regular column flow head pressure allows
emptying the liner more quickly with shorter splitless times. The surge pressure
needs to be released through the analytical column after switch off for about 2 min
before the split valve can be opened to avoid a back stream and loss of sample from
the analytical column.

2.2.4.3 Liner Activity and Deactivation

The activity of inlet liners can be a number one limitation for the analytical
performance and is still a constant challenge in GC. Liner activity can be caused
by the material itself, an insufficient or degrading deactivation, but is also built
up during regular use by the deposit of nonvolatile matrix components. The liner
activity changes with the first matrix sample injected. While fulfilling a major
task of preventing low or nonvolatile matrix from entering the analytical column,
the matrix deposit in the liner is causing adsorption and decomposition effects
for subsequent injections. A quality control and preventive maintenance plan
is required with regular liner exchange according to the sample matrix burden.
The same applies for glass wool. A glass wool plug can become rapidly active
 2.2 Gas Chromatography 97

and needs to be replaced or even removed with the inlet liner for the analysis of
sensitive compounds.
Significant progress is noticeable in recent years in reducing the liner activ-
ity by chemically modifying the glass surface or applying high temperature coat-
ings. Commercially deactivated liners are available from different manufacturers
using proprietary processes, for instance, with phenylmethyl surface deactiva-
tion. These treatments offer a highly efficient deactivation with stability even to
high temperature ranges above 400 ∘ C, and cover a wide polarity range. While
there is the expectation for a general-purpose liner deactivation, there will be
compromises. Specific deactivations are available, for example, for basic com-
pounds such as amines. The same deactivation procedures are used for the widely
used borosilicate glass liner and wool. It is recommended to test different lin-
ers for a specific application for inertness, recovery and robustness, done with
a typical matrix and analyte concentrations close to the method detection limits
(MDLs).
The liner activity is usually measured and compared by using injections
of endrin and dichloro-diphenyl-trichloroethane (DDT). The breakdown
products are endrin ketone and endrin aldehyde, respectively dichloro-diphenyl-
dichloroethane (DDD). With breakdown percentages less than 15% each, an
insert liner is accepted to be inert (e.g. EPA method 8081b).
Glass wool in the liner, although required for the fast cold needle ‘liquid band’
injection (see 2.2.5.2), can be a root cause of inlet liner activity. Approximately
50 mg of deactivated glass wool is typically used in a liner providing a large sur-
face for interaction with sensitive analytes. There are different types of glass wool:
regular or base-deactivated borosilicate glass wool and also deactivated fused sil-
ica quartz wool with low alkali content. If the glass wool in the liner becomes the
major source of activity by decomposition or analyte absorption due to insufficient
deactivation, the only remedy is to change liners more often, or work, if possible,
using baffled liners without the wool.
Straight liners can be mechanically cleaned with solvents, sonication or a soft
brush (e.g. a pipe cleaner), and reused, but require a new deactivation. Do not
scratch or use acids to leach the liner surface; this will increase the liner activity
significantly. Several liner deactivation methods are reported in the literature typ-
ically offering a gas phase or coated deactivation (Figure 2.54). For a simple and
™
efficient ‘in-house’ coated deactivation, the treatment with Surfasil or Aquasil ™
has proven to be very efficient and durable, and is used and recommended, for
instance, for the multi-residue analysis of pesticides. The immersion procedure
for the precleaned liners is easy to perform with only a few steps (Thermo, 2008).
Liners with a glass wool plug can also be deactivated using the SurfaSil or AquaSil
procedure. Several liners can be treated at once, and stored for later use:

1) Dilute the SurfaSil siliconizing fluid in a non-polar organic solvent such

as acetone, toluene, carbon tetrachloride, methylene chloride, chloroform,
xylene or hexane. Typical working concentrations are 1–10% mass to
volume.
98 2 Fundamentals

100
90 Coated deactivation
80
70 Gas-phase deactivation
% Recovery

60
50
Bare glass
40
30
20
10
0
0 10 20 30 40 50 60 70 80 90 100
Injection number

Figure 2.54 Injection port liner activity dependence from the injection number (Klee,
2013)

2) Completely immerse or flood the dry inlet liner to be coated in the diluted
SurfaSil solution for at least 5–10 s. Agitate the solution to ensure a uniform
coat. A thin film will immediately coat the liner’s surface.
3) Rinse the liner with the same solvent in which the reagent was diluted.
4) Rinse the liner with methanol. This rinse is required to prevent interaction of
the SurfaSil coating with water and thus, reversing siliconization.
5) Air-dry the liner for 24 h or heat at 100 ∘ C for 20–60 min.

Other inlet liner deactivation procedures are using gas phase or solution
silylation procedures. The gas phase silylation provides the more stable liner
deactivation for high temperature use than a liquid process, but is a more
laborious procedure (Rood, 2007):

1) Place the liner in a glass test tube that can be easily flame sealed.
2) Heat the neck of the tube until a 2–3 mm opening remains.
3) Add two to three drops of diphenyltetramethyldisilazane.
4) Immediately flush the tube with a stream of dry nitrogen or argon.
5) Immediately flame seal the glass tube.
6) Heat the test tube at 300 ∘ C for 3 h.
7) Allow to cool to room temperature.
8) Open the tube and rinse the liner with pentane or hexane.
9) Dry the liner at 75–100 ∘ C

2.2.4.4 Liner Geometry

Split liners are typically narrow and straight tubes, while splitless liners are wider
and typically show a tapered end, see Figure 2.55. These bottom tapers keep the
sample cloud in the centre of the liner for an optimized transfer into the column.
Tapers prevent a possible exposure of sample components to the metal (gold) seal
 2.2 Gas Chromatography 99

Straight split liner

Straight splitless liner

Tapered splitless liner

Tapered splitless liner with glasswool

Tapered split liner with glasswool

Tapered split liner for fast GC

Tapered cup liner

Tapered cyclo liner

Laminar split liner

Baffled liner

Figure 2.55 Injection port liner types for split and splitless injections.

at the bottom of the inlet body. With tapered liners, the tip of the column is best
positioned just above of the tapered section. A thin glass or metal rod pushed
upwards in the liner by the column during installation gives valuable assistance in
finding the correct position of the column tip.
Other liner types introduce mechanical obstacles for improved vaporization
and mixing with carrier gas such as the baffled, cup or cyclo liners. Although those
inlet liners offer improved injection conditions, they can hardly be cleaned and
reused; so they are excluded from routine use with matrix samples.
Special liner types are used for headspace applications. In many cases, the
transfer line of a headspace sampler ends in a syringe type needle. Additional
liner dead volume and turbulence must be avoided for the transfer of the sample
plug into the analytical column. Special straight ‘headspace liners’ with narrow
diameters are available for many GC models.
Direct on-column injections can also be done using a regular syringe using a
temperature programmable injector (PTV). This requires a special inlet liner type,
which centres a 0.53 mm ID pre-column in the liner, while the top part of the liner
serves as a needle guide. Regular needle diameters of 0.45 mm OD are used. This
allows the syringe needle to enter, centred and deep enough into the pre-column
for a direct liquid injection into the pre-column. By this way on-column injections
can be automated using regular GC autosampler units.

2.2.5
Vaporizing Sample Injection Techniques

In case liquid samples are applied to GC or GC-MS, the most widely used injec-
tion technique evaporates the liquid sample in the inlet liner of the injector in
order to transfer the analytes into the analytical column. Classical injection tech-
niques involve applying the sample solution in constantly heated injectors. Both
the solvent and the dissolved analytes evaporate in an evaporation tube specially