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Prenatal polybrominated diphenyl ether (PBDE) exposure has been associated with decrements in IQ and increased attention deficit/hyperactivity disorder related behaviors in children; however, data are limited for the role of postnatal exposures.We investigated the association between a series of childhood PBDE concentrations and Full-Scale Intelligence Quotient (FSIQ) and externalizing problems at 8 years.We used data from 208 children in the Health Outcomes and Measures of the Environment (HOME) Study, a prospective pregnancy and birth cohort. Child serum PBDEs were measured at 1, 2, 3, 5, and 8 years; missing serum PBDE concentrations were estimated via multiple imputation. The Wechsler Intelligence Scales for Children-IV and the Behavior Assessment System for Children-2 was used to assess intelligence and externalizing behavior, respectively, in children at 8 years. We used multiple informant models to estimate associations between repeated lipid-adjusted PBDEs and child neurobehavior and to test for windows of susceptibility.Postnatal exposure to PBDE congeners (− 28, − 47, − 99, − 100, and − 153) at multiple ages was inversely associated with FSIQ at 8 years. For instance, a 10-fold increase in BDE-153 concentrations at 2, 3, 5, and 8 years were all related to lower FSIQ at age 8 (β for 3 years: − 7.7-points, 95% CI − 12.5, − 2.9; β for 8 years: − 5.6-points, 95% CI − 10.8, − 0.4). Multiple PBDE congeners at 8 years were associated with increased hyperactivity and aggressive behaviors at 8 years.Postnatal PBDE exposure was associated with decrements in FSIQ and increases in hyperactivity and aggressive behaviors.Childhood PBDEs are associated with decrements in FSIQ at 8 years.Ten-fold increases in BDE-28 at 3 years and BDE-153 at 2–8 years significantly reduced FSIQ by > 5 points.Several PBDEs at 8 years were positively associated with externalizing behaviors.Concurrent PBDEs were associated with increased hyperactivity and aggression scores.