The effects of concentration, polar/ionic head group, and structure of surfactants on the biodegradation of polycyclic aromatic hydrocarbons (PAHs) in the aqueous phase, as well as their effects on the bacterial activity were investigated. The toxicity ranking of studied surfactants is: non-ionic surfactants (Tween 80, Brij30, 10LE and Brij35) < anionic surfactants (LAS) < cationic surfactants (TDTMA). For the same head group and similar molecular structure, the toxicity to the bacteria is due to the chain length, in which the toxicity becomes lower as the chain length increases. The bacterial growth increased slightly when phenanthrene and LAS (<= 10 mg L-1) served the sole carbon and energy resource. However, the degradation of C-14-phenanthrene showed either a decrease or no obvious change with the surfactants present at all tested concentrations (5-40 mg L-1). Thus, the surfactant addition is not beneficial to the removal of phenanthrene or other PAH contaminants due presumably to the preferential utilization of surfactants at low levels as the non-toxic nutrient resource and to the high toxicity of the surfactants at high levels to the microorganism activity. Biodegradation of phenanthrene was also influenced by the surfactant concentration, head group type, and structure. Much more research has yet to be completed on the use of surfactants for soil remediation due to the surfactant toxicity or biodegradation effect. (c) 2006 Elsevier B.V. All rights reserved.