Pretreatment zones (PTZs) composed of sand, 10% zero-valent iron [Fe(0)]/sand, and 10% pyrite (FeS2)/sand were examined for their ability to prolong Fe(0) reactivity in above ground column reactors and a subsurface permeable reactive barrier (PRB). The test site had an acidic, oxic aquifer contaminated with tetrachloroethylene (PCE) and trichloroethylene (TCE). The 10% FeS2 and 10% Fe(0) PTZs removed dissolved oxygen and affected the pH and E(h) in the PTZ. None of the PTZs had any effect on pH or E(h) in the 100% Fe(0) zone. Nitrate and sulfate were removed more quickly in the Fe(0) zones preceded by either the 10% Fe(0) PTZ or 10% FeS2. PCE first-order degradation rate constants (k(obs)) decreased significantly (> 80%) with increasing column pore volumes regardless of the PTZ material used. k(obs) finally leveled off after approximately 1 yr of operation. The column results predict that the PRB will experience a breakthrough of PCE in 3-5 yr and illustrate the importance of incorporating temporal variations in degradation rate constants when designing PRBs.