Nano-scale zerovalent iron (nZVI) has been studied in recent years for environmental remediation applications such as the degradation of chlorinated organic contaminants. To overcome limitations related to the transport of nZVI, it is becoming common to add a polymer stabilizer to limit aggregation and enhance the particle reactivity. Another method investigated to enhance particle reactivity has been to limit particle size through novel synthesis techniques. However, the relative impacts of particle size and interactions of the chemicals with the coatings are not yet well understood. The purpose of this study was to investigate the mechanisms of particle size and polymer coating or polyelectrolyte multilayer (PEM) synthesis conditions on degradation of two common chlorinated contaminants: trichloroethylene (TCE) and polychlorinated biphenyls (PCBs). This was accomplished using two different synthesis techniques, a layer-by-layer approach at different pH values or iron reduction in the presence of varying concentrations of poly(acrylic acid). nZVI produced by both techniques yielded higher degradation rates than a traditional approach. The mechanistic investigation indicated that hydrophobicity and sorption to the multilayer impacts the availability of the hydrophobic compound to the nZVI and that particle size also had a large role with smaller particles having stronger dechlorination rates. (C) 2012 Elsevier B.V. All rights reserved.