EXECUTIVE SUMMARYTrace analysis of signature compounds is usually accomplished by concentrating the target signature compound from a large volume environmental sample on an appropriate sorbent. Unfortunately, the organic matrix components also become concentrated, which necessitates separating the signature compound from this complex mixture in sufficient purity to allow identification and quantification. Due to the complexity of the mixture, sophisticated, laboratory-based multidimensional instrumentation often is required to provide adequate separation.The goal of this research is to develop highly selective sorbents that will enable collection of relatively pure analyte fractions during the sampling step. Due to the high purity of the initial fraction, subsequent analytical steps leading to high-integrity identifications at trace concentrations can be greatly simplified. The required analytical instrumentation can reflect this simplification by being made more compact, lightweight, and field portable. This advancement is made possible by the high degree of matrix discrimination accomplished during the sampling step.Two different selective sorbents were developed and evaluated in this research. Both sorbents must be capable of operation in nonaqueous environments to protect hydrolytically sensitive analytes during analysis. The approaches investigated were nonaqueous immunochromatography featuring the use of stabilized antibody fragments (STABs) and molecularly imprinted polymers (MIPs). Both approaches were pursued in Fiscal Year (FY) 2003, during the course of which it became clear that the MIPs approach had clear advantages over STABs. Further research efforts during FY 2004 and beyond focused exclusively on the development of MIPs.Our MIP studies have had two distinct thrusts: one thrust targeted volatile organic signatures, and the other thrust targeted nonvolatile phosphate or methylphosphonate half-acid esters. The first studies targeted the volatile signatures. By nature these volatile compounds do not contain polar functionalities in their chemical structures. Since most imprinting is based on polar functional group interactions, these compounds proved difficult to imprint. Nonetheless, we were successful in making MIPs that targeted tributyl phosphate (TBP) and diisopropyl methylphosphonate (DIMP). Selective interactions were not pronounced, as expected due to the weak interactions; however, these sorbents were capable of impressive selective capture of the target analyte with near-quantitative recovery from extremely complex environmental samples. These results were summarized in the manuscript submitted to the Journal of Separation Science. During the publication review process, we were asked to provide additional experiments. The experiments demonstrated that 1) our MIP sorbents had the expected cross reactivity toward structurally related analytes and, 2) our MIP selectivity was superior to traditional normal-phase sorbents, e.g., silica or alumina. We also calculated typical matrix discriminatio...