Application of GC-MS with a SPME and thermal desorption technique for determination of dimethylamine and trimethylamine in gaseous samples for medical diagnostic purposes.

Biogenic amines are interesting compounds which may be of use for medical diagnosis or therapeutic monitoring. The present paper deals with the problems that occur with concentration determination of dimethylamine (DMA) and trimethylamine (TMA). These occur in the breath of people suffering from renal disease. The measurement of amines present in trace concentrations requires the application of suitable analytical methods during sampling, storage and preconcentration. This is particularly so due to their polar and basic properties. In this paper, the application of solid phase microextraction (SPME) and thermal desorption (TD) with subsequent measurement by GC-MS for the determination of amines is discussed. For DMA, preconcentration by SPME did not give satisfactory results. TMA may be analysed using SPME preconcentration with an LOD of 1.5 ppb. Thermal desorption with Tenax as the adsorbing material allows reliable concentration determination for TMA (LOD = 0.5 ppb) and DMA (LOD = 4.6 ppb). DMA cannot be stored reliably in Tedlar bags and longer storage on Tenax (with subsequent TD) does not give good repeatability of results. For TMA, storage can be done on Tenax or in bags, the best results for the latter being achieved with Flex Foil bags.

Improved pre-concentration and detection methods for volatile sulphur breath constituents.

Suitability of different types of pre-concentration (solid phase microextraction and sorbent trapping) and detection (flame photometric detector (FPD) and mass selective detector (MSD)) for gas chromatographic determination of sulphur-containing compounds (H2S, MeSH, EtSH, DMS, COS and CS2) in breath-gas was assessed in this study. Several factors like influence of humidity, influence of oxygen, or stability of target compounds in extraction vessels (SPME vials and sorbent tubes) were investigated. Despite poor stability of VSCs in SPME vials and matrix effects (unfavorable influence of humidity), SPME was found to be a fast and reliable enrichment method, which coupled with mass selective detector provided satisfactory LODs of target compounds at the ppt level (from 0.15 ppb for CS2 to 2.3 ppb for H2S). Application of sorbent trapping with two-bed sorbent tubes containing Tenax TA and Carboxen 1000 gave excellent LODs (0.03-0.3 ppb for 200 ml sample and MSD). Stability of investigated VSCs in sorbents was found to be very poor (30-40% losses after 2 h). FPD showed satisfactory sensitivity only when it was coupled with sorbent trapping. Breath samples were collected into Tedlar bags in a CO2-controlled manner. Humidity was removed during sampling (permeation dryer--Nafion) to avoid unfavorable water dependent effects during analysis.

Suitability of different polymer bags for storage of volatile sulphur compounds relevant to breath analysis.

Suitability of five polymer sampling containers (Nalophan, transparent Tedlar, black layered Tedlar, Teflon and FlexFoil) for sampling and storage of six relevant to breath analysis volatile sulphur compounds: H(2)S, MeSH, EtSH, COS, DMS and CS(2) was studied using solid phase microextraction (SPME) and gas chromatography coupled with mass spectrometry (GC-MS). Investigations were made with respect to the several factors like: recovery, background, influence of light, ageing effect and matrix effects. Additionally, the optimal reusability conditions were established. Findings suggest analyzing the breath VSCs within 6h after sampling. Flexfoil bags were found to be the best choice for the VSCs storage up to 24h (recovery about 90% with the exception of DMS). For shorter storing times (6-8h) transparent Tedlar is a good alternative for Flexfoil (losses up to 10%).