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After several decades of human spaceflight, the community of space-faring nations has accumulated a diverse and sometimes harrowing history of toxicological events that have plagued human space endeavors almost from the very beginning. Some lessons have been learned in ground-based test beds and others were discovered the hard way - when human lives were at stake in space. From such lessons one can build a risk-management framework for toxicological events to minimize the probability of a harmful exposure, while recognizing that we cannot predict all possible events. Space toxicologists have learned that relatively harmless compounds can be converted by air revitalization systems into compounds that cause serious harm to the crew.