When transporting hazardous materials by rail, train types (unit train or manifest train) can influence derailment and release risks in several ways. Unit trains only experience risks on mainlines and when arriving at or departing from terminals, while manifest trains experience additional switching risks in yards. A comprehensive risk assessment methodology is needed to quantitively compare shipments with unit trains and manifest trains, considering both mainline and yard operations. To fulfill this research gap, this paper constructs event chains for line-haul risks, arrival/departure risks, and yard switching risks using various probabilistic models and finally determines expected casualties as the consequences of a potential train derailment and release incident. Five illustrative scenarios are designed to analyze the best and worst cases and compare the transportation risk differences between service options using unit trains and manifest trains. The comparison results indicate that placing all tank cars at the positions with the lowest probability of derailing and switching tank cars alone in classification yards could provide the lowest risk estimate given the same transportation demand.