Polychlorinated biphenyl (PCB) concentrations and breakpoint trends across the waters of the Great Lakes by isotope-dilution high-resolution mass spectroscopy.

Water samples were collected during each of the 2012-2019 Cooperative Science and Monitoring Initiative (CSMI) cruises aboard the U.S. EPA R/V Lake Guardian as part of the Great Lakes Fish Monitoring and Surveillance Program (GLFMSP) lower food web contaminant assessment. The CSMI rotates around each of the Great Lakes in a 5-year cycle providing top-to-bottom biological, chemical, and physical environmental assessments, including dissolved-phase surface water studies at two sample locations. Average polychlorinated biphenyl (∑PCB) concentrations across the Great Lakes was 268 pg/L with a station range of 72 pg/L (Keweenaw Point-Lake Superior) to 834 pg/L (Middle Bass Island-Lake Erie). The highest average Great Lakes concentration (pg/L-sample year) were measured in Lake Erie (645 pg/L-2014) and decreased in the order of Lake Huron (378 pg/L-2012) > Lake Erie (364 pg/L-2019) > Lake Ontario (300 pg/L-2013) > Lake Michigan (125 pg/L-2015) > Lake Huron (123 pg/L-2017) > Lake Superior (74 pg/L-2016). Lake Erie registered a 44 % reduction over the 2014-2019 period, attributed to sediment remediation in the late-1990's on the Detroit River, whereas Lake Huron exhibited a 67 % decrease over the 2012-2017 sample period. Our results indicate that dissolved-phase PCB water concentrations in Lake Ontario have significantly increased, rebounding from a low-point in the late-1990's likely due to the bioenergetic diversion of dissolved- and particulate-phase PCBs into the benthic food web by invasive zebra and quagga mussel colonization. Trend analyses uncovered breakpoints in the early 1990's documenting significantly slowing rates of PCB declines for both Lakes Superior and Michigan.