Polychlorinated naphthalenes (PCNs) have been analyzed in archived soil from the U.K. to investigate historical trends. Samples were obtained from the Broadbalk experiment plots (1944−1986) and Luddington experiment station (1968−1990). Luddington samples also include a set of soils that received a one-time sludge treatment in 1968, and duplicate samples of this archived sludge were also analyzed. Peak residues of ΣPCN (sum of all PCN congeners quantified) were 9000 pg g-1 dry weight in 1956, declining to 300 pg g-1 in contemporary soils. The one-time sludge application resulted in elevated soil residues that were 1.5−6 times higher than the control plot over the time series. This increase is consistent with the known application rate and the amount of ΣPCN in the applied sludge (250 000 pg g-1 dry wt). Half-lives for the Luddington control soil and the sludge-amended soil for the period 1972−1990 were 5.3 and 9.9 years, respectively. Investigation of time trends revealed differences between homologue groups with the higher molecular weight congeners peaking earlier in the time series (pre-1950) and the lower molecular weight congeners peaking later, ca. 1970. Time trends of individual congeners were investigated in terms of their relative mass percent contribution to the sum of their homologue group. Significant (p < 0.05) increasing trends were observed for several congeners associated with combustion sources (CN-29, -51, -52/60, -54, and -66/67) suggesting that combustion related sources are more important now than they were in the past. However, no decreasing trend was observed for congeners that were thought to be susceptible to degradation by photolysis suggesting that this may not be a key elimination pathway of PCNs in the environment. A simple calculation of the fugacity status of PCNs in air and soil showed that the tri-CNs are exhibiting net outgassing, while the penta-CNs are still being deposited to soil. Interestingly, the penta-CNs associated with combustion show the largest gradient for air-to-soil transfer, supporting the notion that combustion sources are important contributors to contemporary air burdens of these congeners.