Livestock facilities have historically generated public concerns due to their emissions of odorous air and various chemical pollutants. Odor emission factors and identification of principal odorous chemicals are needed to better understand the problem. Applications of odor emission factors include inputs to odor setback models, while chemical emission factors may be compared with regulation thresholds as a means of demonstrating potential health impacts. A companion study of the National Air Emissions Monitoring Study (NAEMS) included measurements necessary for establishing odor and chemical emission factors for confined animal feeding operations. This additional investigation was conducted by the University of Minnesota, Iowa State University, West Texas A&M Agri-Life Center, and Purdue University. The objectives were to (1) determine odor emission rates across swine and dairy facilities and seasons using common protocols and standardized olfactometry methods, (2) develop a chemical library of the most significant odorants, and (3) correlate the chemical library with the olfactometry results. This document describes the sampling and quality assurance methods used in the measurement and evaluation of odor and chemical samples collected at two freestall dairy farms, one sow (gestation/farrowing) facility, and one finishing pig site. Odor samples were collected in Tedlar bags and chemical samples were collected in sorbent tubes at barn inlet and exhaust locations using the NAEMS multiple-location gas sampling systems. Quality assurance protocols included interlaboratory comparison tests, which were evaluated to identify variations between olfactometry labs. While differences were observed, the variations among the labs and samples appeared random and the collected odor data were considered reliable at a 0.5% level of statistical significance. Overall, the study took advantage of groundbreaking opportunities to collect and associate simultaneous odor and chemical information from swine and dairy buildings while maintaining accordance with standard methods and comparability across laboratories.