Distinguishing Aroclor and non-Aroclor sources to Chicago Air

Many polychlorinated biphenyl (PCB) congeners are found in both legacy Aroclor mixtures and modern materials, and both contribute to PCBs levels in ambient air. The various sources of PCBs make it difficult to quantify the relative importance of emissions from remaining legacy materials and emissions of PCBs released from production and use of modern products. To address this challenge, we utilized active and passive sampling, analytical methods optimized for PCBs, and Positive Matrix Factorization (PMF) and cos theta to examine the chemical signature of PCBs in Chicago air. Here we report our findings for over 640 samples collected over 7 years and analyzed for all 209 congeners. We conclude that Aroclor sources (1254, 1016/1242, and 1260) are consistent and dominant contributors to Chicago air. However, non-Aroclors sources accounted for 13%-16% of the total PCBs measured. Our analysis indicates non-Aroclor sources explain 99% of PCB11, 90% of PCB 68, and 58-69% of congeners with 8 to 10 chlorines in Chicago air. All of these are known to be emitted from paints or silicone polymers. Additionally, we identified over 20 congeners that have non-Aroclor contributions of more than 50% including PCB 3 (4-monochlorobiphenyl, 83% non-Aroclor) as well as 7 congeners of unknown sources: PCBs 43, 46, 55, 89, 96, 137, and 139 + 140. Non-Aroclor emission sources contribute to the entire range of congeners from mono- to deca-chlorobiphenyls. We found evidence of highly localized non-Aroclor sources including a signature similar to that of green paint. We also found source signals similar to the PCB congeners volatilizing from and absorbing to neighboring Lake Michigan. The measured profiles vary from season to season: lower chlorinated congeners dominate in winter months while higher chlorinated congeners contribute more in summer.