Field screening of waterborne petroleum hydrocarbons by thickness shear-mode resonator measurements

An inexpensive, field-portable sensor for direct, aggregate determination of aqueous petroleum hydrocarbons (PH) down to sub-ppm levels was developed. The basis of this sensor was an unusual, highly nongravimetric frequency response of 10 MHz (series fundamental) AT-cut quartz crystals when coated with rubbery silicone films. The response depended linearly and reliably on the total concentration of dissolved hydrocarbons over a range of 0.01-100 mg x L(-1) or up to aqueous solubility limits. Calibration sensitivities were measured individually for laboratory-prepared solutions of BTEX (benzene, toluene, ethylbenzene, and xylene isomers) and C6-C8 aliphatic components. Each component demonstrated a method detection limit (MDL) in the low-to sub-ppm range (benzene 10 mg x L(-1), n-hexane 0.54 mg x L(-1)) for light coatings of a commercially available poly-(dimethylsiloxane) gum (OV-1, > 10(6) g x mol(-1)) and lower MDLs for heavier coatings. Pairwise responses for the aliphatic and benzenoid standards were additive, indicating that aggregate determinations of mixtures (especially light fuels) were possible. Natural matrix interferences caused by sample turbidity and ionic strength were overcome by simple preparative methods. Fuel-spiked natural waters were determined with respect to standards and verified by gas chromatography. A 0.19 mg x L(-1) MDL for gasoline was obtained for heavy OV-1 films. Field determinations of groundwater surrounding a leaking underground fuel tank demonstrated that the sensor and method were useful for on-site PH screening. Large differences between the equilibration times of aliphatic and benzenoid components also indicated one avenue for BTEX speciation with the device.