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Thermal desorption technical Support

Note 32: Analysis of sulphur compounds using TD-GC(MS)
Introduction

Sulphur compounds are probably best associated with their unpleasant, pungent odours, noticeable even
at low concentrations. These compounds, especially when in contact with metals, become increasingly
sensitive to high temperatures. However, despite the limitations this property brings to analysis, the
detection of such compounds is of particular importance to a wide range of industries such as flavour and
fragrance testing, the purification of water and food studies.
The following method was developed to analyse a standard sulphur solution obtained from Chemservice
and consisting of methylmercaptan, methyl sulphide, acetaldehyde, dimethyl-disulphide and styrene (1%
in methanol). The standard solution was introduced onto a Silcosteel® coated stainless steel thermal
desorption tube containing a 40 mm bed of Tenax™ backed up by a 15 mm bed of UniCarb™. Four
different volumes of sample were injected (5 ng, 0.5 µl, 1 µl and 2 µl) respectively, in a flow of inert gas
(helium) at a rate of 50 ml/min and using the calibration standard solution loading rig from Markes
International. The samples were then desorbed using the UNITY™ thermal desorber from Markes
International linked to an Agilent 6890 GC and 5973 MS. The analytical conditions are given below.
The analytical conditions and results obtained from a similar application carried out in the field and using
a UNITY - Air server system from Markes International are also given. On this occasion the calibration
gas used consisted of hydrogen sulphide, methylmercaptan, ethylmercaptan, dimethyl sulphide, carbon
disulphide and dimethyl-disulphide with a concentration of approximately 150-400 ppb. The standard was
sampled for 3 minutes at a rate of 30 ml/min resulting in a total sample volume of 90 ml. Since the
sampling was carried out on-line, no sorbent tube was required - the standard was sampled directly onto
the focusing trap of UNITY.

Analytical Conditions

UNITY: Prepurge time: 0.5 min (split on and trap in line)

Primary desorb: 200°C for 3 mins (split on)
Trap low temp: -10°C
Trap desorb: 200°C for 3 mins (split on)
Trap: U-T6SUL containing Tenax and Unicarb
Flow path temp: 80°C
Carrier gas pressure: 10 psi
Desorb flow: 3 ml/min
Split flow: 45 ml/min
Split ratio: ~ 400:1
GC: Column flow: ~ 2 ml/min
Start temp: 60°C for 0 mins
End temp: 220°C for 6 min
Rate of temp increase: 10°C/min
Column: 30 m, 0.32 mm i.d. with a GS-Gaspro phase

MS: MS Source temp: 230°C MSD transfer line temp: 150°C

MS Quadrupole temp: 150°C Mass Scan Range: 25 to 350 amu
 TDTS 32

Results

Methyl mercaptan Methyl mercaptan

Methyl mercaptan

Methyl sulfide Methyl sulfide

Methyl sulfide
Acetaldehyde Acetaldehyde
Acetaldehyde

Dimethyl disulfide
Dimethyl disulfide
Dimethyl disulfide
February 2003

Styrene
Styrene
Styrene

standard solution

standard solution
standard solution
Page 2 of 4

Figure 2. 1 µl sample of

Figure 3. 2 µl sample of
Figure 1. 0.5 µl sample of
TDTS 32 February 2003 Page 3 of 4

Figure 4. Plot of peak area

against sample volume for
each component

Figure 5. 2 ng sample of
standard solution. This
equates to approximately 2
ppb per litre of air

Analytical Conditions: On-Line Sampling - See figure 6 overleaf

UNITY-Air Sever: GC:
Trap low temp: -15°C Column flow: 0.9 ml/min
Trap desorb: 200°C for 5 mins (split on) Start temp: 40°C for 4 mins
Flow path temp: 80°C End temp: 200°C for 5 min
Carrier gas pressure: 10 psi Rate of temp increase: 10°C/min
Sample flow: 30 ml/min for 3 mins Column:DB-1, 0.32 mm, 4.0 µm thickness
Split flow: 45 ml/min
Trap: H2S Trap containing Tenax and Carboxen 1000
TDTS 32 February 2003 Page 4 of 4

Results

carbon disulphide

dimethyl-disulphide
hydrogen sulphide

ethyl mercaptan

Figure 6. Analysis of a sulphur

compound standard gas mixture using
dimethyl sulphide

UNITY-Air Server-GC.
methyl mercaptan

Summary
Both sets of experiments demonstrated the ability of UNITY to successfully thermally desorb a mixture of
sulphur compounds, despite their sensitivity to heat and reaction with metals. This clearly confirms the
inertness of the flow path in UNITY. From Figure 4 it is evident that there is a linear relationship between
the amount of sample introduced to the tube and the peak area produced. Again this emphasizes the
inertness of the UNITY and UNITY-Air Server flow path since all the sample was desorbed and
subsequently passed onto the GCMS. From the low level standards (Figure 5), it also appears that
quantitation limits in the order of 1 ppb can be readily achieved from as little as 1 L of air.
Sulphur compounds can therefore be analysed successfully using an on-line sampling method via the
UNITY-Air Server system, or the more conventional passive/diffusive method via sorbent tubes and a
UNITY thermal desorber.

Trademarks
UNITY™, Air Server™, UniCarb™ are trademarks of Markes International Ltd., UK
Tenax™ is a trademark of Buchem B.V. The Netherlands
Carboxen 1000™ is a trademark of Supelco Inc., USA
Silcosteel™ is a trademark of RestekInc., USA