The accurate determination of PAHs at trace levels in environmental matrices is a complex problem and as a result, methods for the preconcentration and determination of PAHs are continuously under investigation. Techniques are required which are sufficiently sensitive and selective to enable the quantitation of PAHs at lower levels than ever before. The importance of trace determination of PAHs in environmental samples is reviewed in chapter 1. Various sample matrices, extractive techniques and analytical methods were examined for the enrichment and determination of PAHs in the environment. The importance of accurate and complete extraction from various matrices is discussed. Particular mention was made to the universal problem of losses of low MW PAHs with the various techniques reviewed. The extraction of five low MW PAHs compounds from aqueous samples is reported on in chapter 2 and chapter 3. Two standard techniques liquid/liquid extraction and solid phase extraction operated in offline mode were reviewed and applied to the first five PAHs recommended as priority pollutants by the USEPA. A more novel extractive procedure was examined in chapter 3 for the same group of compounds. This was online solid phase extraction. In this case the compounds were extracted from the aqueous solution and transferred online to the analytical system by the actuation of a switching valve. This system was then compared and contrasted with extractive systems previously described. The concept of Multi Solid Phase Dispersion was reviewed in Chapter 4. It is a unique system which takes advantage of the physiochemical properties of Cig packing material. These properties allow the material interact with biological matrices in such away as to extract organic material preferentially. This extractive procedure was then applied to the extraction of PAHs from bovine milk samples. The application of ATR/FTIR to the enrichment and detection of compounds is reviewed in chapter 5. A system was developed which allowed the detection of fluoranthene from aqueous samples. The ability of the system to determine PAHs was assessed in chapter 6 . Determination was achieved through the application of various mathematical algorithms and the effectiveness of the algorithms was compared. The system was then used to quantify a number of PAHs simultaneously.