The U.S. EPA has established a National Dioxin Air Monitoring Network (NDAMN) to determine the temporal and geographical variability of atmospheric chlorinated dibenzo-p-dioxins (CDDs), furans (CDFs), and coplanar polychlorinated biphenyls (PCBs) at rural and non-impacted locations throughout the United States. Currently operating at 32 sampling stations, NDAMN has three primary purposes: (1) to determine the atmospheric levels and occurrences of dioxin-like compounds in rural and agricultural areas where livestock, poultry, and animal feed crops are grown; (2) to provide measurements of atmospheric levels in different geographic regions of the U.S.; and (3) to provide information regarding the long-range transport of dioxin-like compounds in air over the U.S. Designed in 1997, NDAMN has been implemented in phases, with the first phase consisting of 9 monitoring stations and is achieving congener-specific detection lmits of 0.1 fg/m3 for 2,3,7,8-TCDD and 10 fg/m3 for OCDD. With respect to coplanar PCBs, the detection limits are generally higher due to the presence of background levels in the air during the preparation and processing of the samples. Achieving these extremely low levels of detection present a host of analytical issues. Among these issues are the methods used to establish ultra-trace detection limits, measures to ensure against and monitor for breakthrough of native analytes when sampling large volumes of air, and procedures for handling and evaluating field blanks. Despite such procedural difficulties, these methods make it possible to measure dioxin-like compounds at extremely low concentrations.