In situ sensing of volatile organic compounds in groundwater: first field tests of a mid-infrared fiber-optic sensing system.

A prototype mid-infrared sensor system for the determination of volatile organic pollutants in groundwater was developed and tested under real-world conditions. The sensor comprises a portable Fourier transform infrared spectrometer, coupled to the sensor head via mid-infrared transparent silver halide fiber-optic cables. A 10 cm unclad middle section of the 6-m-long fiber is coated with ethylene propylene copolymer in order to enrich the analytes within the penetration depth of the evanescent field protruding from the fiber sensor head. A mixture of tetrachloroethylene, dichlorobenzene, diethyl phthalate, and xylene isomers at concentrations in the low ppm region was investigated qualitatively and quantitatively in an artificial aquifer system filled with Munich gravel. This simulated real-world site at a pilot scale enables in situ studies of the sensor response and spreading of the pollutants injected into the system with controlled groundwater flow. The sensor head was immersed into a monitoring well of the aquifer system at a distance of 1 m downstream of the sample inlet and at a depth of 30 cm. Within one hour, the analytes were clearly identified in the fingerprint region of the IR spectrum (1300 to 700 cm(-1)). The results have been validated by head-space gas chromatography, using samples collected during the field measurement. Five out of six analytes could be discriminated simultaneously; for two of the analytes the quantitative results are in agreement with the reference analysis.

The automated sample preparation system MixMaster for investigation of volatile organic compounds with mid-infrared evanescent wave spectroscopy.

For efficient development assessment, and calibration of new chemical analyzers a large number of independently prepared samples of target analytes is necessary. Whereas mixing units for gas analysis are readily available, there is a lack of instrumentation for accurate preparation of liquid samples containing volatile organic compounds (VOCs). Manual preparation of liquid samples containing VOCs at trace concentration levels is a particularly challenging and time consuming task. Furthermore, regularly scheduled calibration of sensors and analyzer systems demands for computer controlled automated sample preparation systems. In this paper we present a novel liquid mixing device enabling extensive measurement series with focus on volatile organic compounds, facilitating analysis of water polluted by traces of volatile hydrocarbons. After discussing the mixing system and control software, first results obtained by coupling with an FT-IR spectrometer are reported. Properties of the mixing system are assessed by mid-infrared attenuated total reflection (ATR) spectroscopy of methanol-acetone mixtures and by investigation of multicomponent samples containing volatile hydrocarbons such as 1,2,4-trichlorobenzene and tetrachloroethylene. Obtained ATR spectra are evaluated by principal component regression (PCR) algorithms. It is demonstrated that the presented sample mixing device provides reliable multicomponent mixtures with sufficient accuracy and reproducibility at trace concentration levels.

Molecular imprinting and solid phase extraction of flavonoid compounds.

Molecularly imprinted polymers (MIPs) for quercetin have been successfully prepared by a thermal polymerization method using 4-vinylpyridine (4-VP) and ethylene glycol dimethacrylate (EDMA) as functional monomer and cross-linker, respectively. The obtained molecularly imprinted polymers were evaluated by HPLC using organic eluents, with respect to their selective recognition properties for quercetin and related compounds of the flavonoid class. Two equivalent control polymers, a blank polymer and a polymer imprinted with a structural analogous template, were synthesized, in order to confirm the obtained results. Furthermore, preliminary experiments confirm the applicability of the prepared MIPs for solid phase extraction (SPE), as rapid and facile clean-up of wine samples for HPLC analysis is an envisaged field of application. The successful preparation of molecularly imprinted polymers for flavones provides an innovative opportunity for the development of advanced separation materials, with applications in the field of wine and fermentation analysis.