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Converging lines of evidence suggest that individuals with comorbid posttraumatic stress disorder (PTSD) and alcohol use disorder (AUD) may be characterized by heightened defensive reactivity, which serves to maintain drinking behaviors and anxiety/hyperarousal symptoms. However, it is important to note that very few studies have directly tested whether individuals with PTSD and AUD exhibit greater defensive reactivity compared with individuals with PTSD without AUD. Therefore, the aim of the current study was to test this emerging hypothesis by examining individual differences in error-related negativity (ERN), an event-related component that is larger among anxious individuals and is thought to reflect defensive reactivity to errors. Participants were 66 military veterans who completed a well-validated flanker task known to robustly elicit the ERN. Veterans were comprised of 3 groups: controls (i.e., no PTSD or AUD), PTSD-AUD (i.e., current PTSD but no AUD), and PTSD + AUD (i.e., current comorbid PTSD and AUD). Results indicated that individuals with PTSD and controls generally did not differ in ERN amplitude. However, among individuals with PTSD, those with comorbid AUD had significantly larger ERNs than those without AUD. These findings suggest that PTSD + AUD is a neurobiologically unique subtype of PTSD, and the comorbidity of AUD may enhance defensive reactivity to errors in individuals with PTSD.