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Increase in motorization and densification of populations in cities have led to the use of more resources both for the construction of different objects and for the service and operation of automotive vehicles. As a result, volumes of freight transportation, which are related to the construction and servicing of these objects, increase. New scientifically applied tasks that are related to the safety of freight transportation have emerged. Special attention is being paid to those that are related to dangerous tasks. It is obvious that traffic safety and the quality of the transportation process significantly depend on the behaviors and actions of the driver. The driver, as it is known, is the main chain of the "driver -- automobile -- road -- environment" (DARE) system. With improvements in the technical and operational parameters of vehicles and road characteristics, the study of the functional state (FS) of the driver and the reliability of his skills become more important every time. The specific importance of this becomes clear when drivers operate vehicles that transport dangerous goods. Therefore, research on the interaction of chains of the DARE system (using improved existing and developed methods by the authors) is carried out in this paper, taking into account the indicators of drivers' FS in different situations (stress index, which consists in evaluation of the heart and brain operations). The results obtained provide an opportunity to predict their behavior in different road situations and, as a consequence, to determine possible risks during the transportation of dangerous goods. The authors improved the methodology of determining the levels of possible risks of accidents and assessment of their consequences, taking into account the peculiarities of transportation routes, traffic conditions, and psychophysiological indicators of the driver's body during the transportation of dangerous goods within settlements and on the roads between them. [ABSTRACT FROM AUTHOR]