Space-faring crews must have safe breathing air throughout their missions to ensure adequate performance and good health. Toxicological assessment of air quality depends on applicable air-quality standards, measurements of pollutant concentrations, and crew reports of air quality. Samples of air were obtained during ingress and egress of the Zarya and Unity modules on missions 2A and 2A.1. The results from 2A suggest that trace pollutants were at safe levels and that there was good air exchange between the modules. Results from the 2A.1 flight also showed that trace pollutants were at acceptable concentrations; however, there was evidence of inadequate mixing between the modules during the hatch-open operations. Furthermore, the 2A.1 crew reported after the flight that the air quality seemed to cause symptoms during their operations in Zarya, particularly when more than one crewmember was working inside open panels for some time. This paper shows that trace contaminants were probably not the cause of these symptoms. The weight of evidence suggests that off-nominal ventilation in the Zarya led to accumulation of crew metabolic products in the crew's microenvironment.