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To determine whether individuals who use prescribed opioids for chronic noncancer pain have higher rates of any opioid misuse, any problem opioid misuse, nonopioid illicit drug use, nonopioid problem drug use, or any problem alcohol use, compared with those who do not use prescribed opioids.Respondents were from a nationally representative survey (N = 9,279), which contained measures of regular use of prescribed opioids, substance use problems, mental health disorders, physical health, pain, and sociodemographics.In unadjusted models, compared with nonusers of prescription opioids, users of prescription opioids had significantly higher rates of any opioid misuse (odds ratio [OR] = 5.48, P < 0.001), problem opioid misuse (OR = 14.76, P < 0.001), nonopioid illicit drug use (OR = 1.73, P < 0.01), nonopioid problem drug use (OR = 4.48, P < 0.001), and problem alcohol use (OR = 1.89, P = 0.04). In adjusted models, users of prescribed opioids had significantly higher rates of any opioid misuse (OR = 3.07, P < 0.001) and problem opioid misuse (OR = 6.11, P < 0.001) but did not have significantly higher rates of the other outcomes.Users of prescribed opioids had higher rates of opioid and nonopioid abuse problems compared with nonusers of prescribed opioids, but these higher rates appear to be partially mediated by depressive and anxiety disorders. It is not possible to assign causal priority based on our cross-sectional data, but our findings are more compatible with mental disorders leading to substance abuse among prescription opioid users than prescription opioids themselves prompting substance abuse iatrogenically. In patients receiving prescribed opioids, clinicians need to be alert to drug abuse problems and potentially mediating mental health disorders.