The use of forensic polycyclic aromatic hydrocarbon signatures and Compound Ratio Analysis Techniques (CORAT) for the source characterisation of petrogenic/pyrogenic environmental releases.

This study utilised recent developments in forensic aromatic hydrocarbon fingerprint analysis to characterise and identify specific biogenic, pyrogenic and petrogenic contamination. The fingerprinting and data interpretation techniques discussed include the recognition of: The distribution patterns of hydrocarbons (alkylated naphthalene, phenanthrene, dibenzothiophene, fluorene, chrysene and phenol isomers), • Analysis of “source-specific marker” compounds (individual saturated hydrocarbons, including n-alkanes (n-C5 through 0-C40) • Selected benzene, toluene, ethylbenzene and xylene isomers (BTEX), • The recalcitrant isoprenoids; pristane and phytane and • The determination of diagnostic ratios of specific petroleum / non-petroleum constituents, and the application of various statistical and numerical analysis tools. An unknown sample from the Irish Environmental Protection Agency (EPA) for origin characterisation was subjected to analysis by gas chromatography utilising both flame ionisation and mass spectral detection techniques in comparison to known reference materials. The percentage of the individual Polycyclic Aromatic Hydrocarbons (PAIIs) and biomarker concentrations in the unknown sample were normalised to the sum of the analytes and the results were compared with the corresponding results with a range of reference materials. In addition, to the determination of conventional diagnostic PAH and biomarker ratios, a number of “source-specific markers” isomeric PAHs within the same alkylation levels were determined, and their relative abundance ratios were computed in order to definitively identify and differentiate the various sources. Statistical logarithmic star plots were generated from both sets of data to give a pictorial representation of the comparison between the unknown sample and reference products. The study successfully characterised the unknown sample as being contaminated with a “coal tar” and clearly demonstrates the future role of compound ratio analysis (CORAT) in the identification of possible source contaminants.

Evaluation of the determinism of the actuator sensor interface (ASI) on programmable logic controllers (PLC), personal computers (PC) and real-time operating systems (RTOS)

The purpose of this study was to evaluate the determinism of the AS-lnterface network and the 3 main families of control systems, which may use it, namely PLC, PC and RTOS. During the course of this study the PROFIBUS and Ethernet field level networks were also considered in order to ensure that they would not introduce unacceptable latencies into the overall control system. This research demonstrated that an incorrectly configured Ethernet network introduces unacceptable variable duration latencies into the control system, thus care must be exercised if the determinism of a control system is not to be compromised. This study introduces a new concept of using statistics and process capability metrics in the form of CPk values, to specify how suitable a control system is for a given control task. The PLC systems, which were tested, demonstrated extremely deterministic responses, but when a large number of iterations were introduced in the user program, the mean control system latency was much too great for an AS-I network. Thus the PLC was found to be unsuitable for an AS-I network if a large, complex user program Is required. The PC systems, which were tested were non-deterministic and had latencies of variable duration. These latencies became extremely exaggerated when a graphing ActiveX was included in the control application. These PC systems also exhibited a non-normal frequency distribution of control system latencies, and as such are unsuitable for implementation with an AS-I network. The RTOS system, which was tested, overcame the problems identified with the PLC systems and produced an extremely deterministic response, even when a large number of iterations were introduced in the user program. The RTOS system, which was tested, is capable of providing a suitable deterministic control system response, even when an extremely large, complex user program is required.