Most chemical monitoring approaches target a small subset of the pollutants actually present in environmental samples. As a consequence. significant information is routinely overlooked. A program was developed and applied in the southern Chesapeake Bay drainage basin to obtain a more complete picture of the diverse organic contaminants present. Facilities examined included military, water treatment, creosote and fuel handling, shipyard and papermill installations. Matrices analyzed were aqueous discharges, to assess current releases; sediments, for a more synoptic view; and shellfish, to examine bioavailability and bioaccumulation. Tools used included capillary gas chromatography, electron impact and negative chemical ionization mass spectrometry, retention indices, flame ionization and halogen specific detectors. The approach successfully identified a number of sites in the bay drainage impacted by high concentrations of the so-called “priority” pollutants, such as polycyclic aromatic hydrocarbons, PCBs and chlorinated pesticides. In addition, numerous “non-priority” pollutants (e.g. polychlorinated terphenyls, nitrogen and sulfur heterocyclics, phenolics, ketones and ethers) were identified as major contaminants.