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The rate of 2-chlorobiphenyl dechlorination by palladized iron (Fe/ Pd) decreased with increasing pH until pH > 12.5. Iron corrosion potential (Ec) and current (jc), obtained from polarization curves of a rotating disk electrode of iron, followed the Tafel equation at pH < or = 5.5 and pH > or = 9.5. The pH dependence of the dechlorination rate constant (k1) suggests four pH regimes. In the low pH regime (3-5.5), /Ec/ and je decreased with increasing pH and k1 was linearly correlated to /Ec/ and jc0.5. The correlation between k1 and jc0.5 indicates direct involvement of active hydrogen species (on the Pd surface) in PCB dechlorination. In the mid pH regime (5.5-9.5), no significant effect of pH was evident on the values of k1, je, and Ec, a combined result of limiting anodic oxidation of iron to an intermediate product (iron hydroxide) and a proton-independent overall reaction. Both /Ec/ and jc increased significantly as pH increased from 9.5 to 14. A cleartrough of the k1 values in solutions of pH between 12 and 13 and the mismatch between the kinetic and corrosion data suggest two pH regimes (9.5-12.5 and 12.5-14) of different corrosion mechanisms.

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Partitioning and desorption played specific roles in the dechlorination of 2-chlorobiphenyl (2-CIBP) in sediment slurry supernatants, which are suspensions of dissolved organic matter (DOM). In short-term experiments, the partition coefficient (Kp) was related to the apparent dechlorination rate constant. The Kp value (160 L g(DOC)(-1)), which is independent of the DOM concentration, was determined based on the decrease of the apparent rate constant with the increase of the DOM concentration. In the long-term experiments, the overall rate of dechlorination can be described with a two-compartment model. The time constant for the sediment compartment was related to Kp and the desorption rate constant (k(d)). The k(d) value (0.21 h(-1)) was determined based on the decrease of the time constant values with an increasing DOM concentration. The use of DOM suspensions allowed a short time for equilibrium. Separation of the aqueous and DOM phases was not needed due to the dechlorination of 2-CIBP. The fundamental relationships between overall dechlorination rate constant and properties of the contaminant and sediment were established.