Findings from quality assurance activities in the Integrated Atmospheric Deposition Network.

A series of experiments were conducted among the laboratories participating in the Integrated Atmospheric Deposition Network (IADN) monitoring program to evaluate comparability of the reported persistent organic pollutant concentrations. This quality assurance activity is essential because a variety of methods are currently used for sample collection, extraction, and analysis by the IADN laboratories. The experiments included analyses of a common reference standard (CRS), analyses of split samples, and analyses of samples collected with co-located samplers at the Point Petre IADN measurement station. The analytes included polycyclic aromatic hydrocarbons (PAHs), organochlorine pesticides (OCPs), and polychlorinated biphenyls (PCBs). For virtually all compounds, the laboratories produced generally comparable results for the CRS samples, the split samples and the co-location samples, although some differences were observed. Analysis of the methods may pinpoint areas where variations in the methods will result in the differences observed in the reported data. These differences can be due to the field sampling process, the analytical method, field blank values, or a combination of all these factors. This study points out the importance of QA activities at every step of an environmental monitoring process so that areas where improvements may be needed or where inconsistencies may exist can be identified.

Partial pressures of PCB-11 in air from several Great Lakes sites.

Relatively high concentrations of 3,3'-dichlorobiphenyl (PCB-11) have been reported in water and air, and it has been suggested that this compound did not come from commercial PCB products. We report here data on atmospheric partial pressures of PCB-11 and of total PCBs at five sites around the Great Lakes and demonstrate that both total PCBs and PCB-11 track human population density. In addition, we show that with the exception of Chicago, the PCB congener pattern at our sampling sites is best represented by Aroclor 1242; in Chicago, the pattern is best represented by a 1:1 mixture of Aroclors 1242 and 1254. With the possible exception of Sturgeon Point New York, the levels of PCB-11 in air have not changed between January 2004 and December 2007. The source of PCB-11 may be related to yellow pigments, to the degradation of more highly chlorinated PCB congeners, or to both.

Temporal and spatial trends of atmospheric polychlorinated biphenyl concentrations near the Great Lakes.

Polychlorinated biphenyl (PCB) concentrations were measured in the atmosphere at six regionally representative sites near the five Great Lakes from 1990 to 2003 as part of the Integrated Atmospheric Deposition Network (IADN). Concentration data for several individual PCB congeners and for total PCBs were analyzed for temporal and spatial trends after correcting for the temperature dependency of the partial pressures. Atmospheric PCB concentrations are decreasing relatively slowly for tetra- and pentachlorinated congeners, an observation that is in agreement with primary emissions modeling. Relatively rapid decreases in PCB concentrations at the sites near Lakes Michigan and Ontario may reflect successful reduction efforts in Chicago and Toronto, respectively. Atmospheric PCB concentrations near Lakes Superior and Huron are now so low that the air and water concentrations may be close to equilibrium. Atmospheric PCB concentrations at sites near Lakes Michigan, Erie, and Ontario are relatively higher than those measured at sites near Lakes Superior and Huron. The highest PCB level was observed at the site near Lake Erie, most likely due to nearby urban activity. However, this relatively higher concentration is still 6-10 times lower than that previously reported at the Chicago site. A correlation between average gas-phase PCB concentration with local population indicates a strong urban source of PCBs. The temperature dependence of gas-phase PCB concentrations is similar at most sites except at Burnt Island on Lake Huron, where very low concentrations, approaching virtual elimination, prevent reliable temperature correlation calculations.

Temporal trends of polychlorinated biphenyls in precipitation and air at chicago.

Polychlorinated biphenyl (PCB) concentrations in precipitation (1997-2003) and in the atmospheric gas phase (1996-2003) collected in Chicago, IL, are reported. These data were obtained as part of the Integrated Atmospheric Deposition Network. For comparison, PCB concentrations at a remote site, Sleeping Bear Dunes on the northeastern shore of Lake Michigan, are also reported. Much higher PCB concentrations in both precipitation (7.1 +/- 0.9 ng/L) and the gas phase (1.4 +/- 0.1 ng/m3) at Chicago compared to Sleeping Bear Dunes (1.1 +/- 0.1 ng/L and 0.1 +/- 0.08 ng/m3, respectively) indicate that Chicago is a source of PCBs to the Great Lakes. A long-term decreasing trend of PCB concentrations in precipitation was observed at Chicago with a half-life of 6.8 +/- 3.1 years. The corresponding half-life for PCB concentrations in the gas phase was 7.7 +/- 1.1 years. The significant long-term decrease of PCB concentrations in precipitation and the gas phase in Chicago suggests that regulatory efforts are working, at least in this city.

Annual variations of pesticide concentrations in Great Lakes precipitation.

Twenty pesticides and related analytes were measured in 28-day integrated precipitation samples from five U.S. sites in the Integrated Atmospheric Deposition Network (IADN) between 1997 and 2002. Consistent, significant decreases in concentration as a function of time were observed only for p,p'-DDE and p,p'-DDD, while increases in beta-HCH were observed at all sites. Significant annual variations were observed for most analytes at each site with higher concentrations in the summer for current-use pesticides (endosulfan and gamma-HCH) and peaks in the winter for most others. The increased concentrations in the winter are likely the result of the increased scavenging efficiency of snow compared to rain and, for some analytes, higher concentrations in the particulate phase during winter. These seasonal differences appear to account for a large portion of the observed variability in pesticide concentrations in precipitation samples.

Causes of variability in pesticide and PCB concentrations in air near the Great Lakes.

Data through 2001 from the Integrated Atmospheric Deposition Network (IADN) were used to investigate the causes of variability in gas-phase polychlorinated biphenyl (PCB) and pesticide concentrations measured near Lakes Michigan, Erie, and Superior. A multiple linear regression model that incorporates temperature and time was used explain the variability in the concentrations. Our approach used autocorrelation analyses of the residuals to help us determine the effectiveness of the regression. Autocorrelation plots forthe in-use pesticide lindane indicated that an agricultural application cycle was also present in the regression residual data at all sites. The addition of parameters for this effect to the regression equation accounted for, on average, 16% more of the variability in the data. Similar analyses forthe in-use pesticide endosulfan did not show an agricultural application effect. The banned compounds DDT and chlordane showed that temperature and time correctly accounted for the variability in the atmospheric concentrations of these compounds at all sites. In contrast to the other compounds, PCBs and hexachlorobenzene showed strong residual autocorrelation patterns near Lake Michigan of an unknown origin.

Gas-phase polychlorinated biphenyl and hexachlorocyclohexane concentrations near the Great Lakes: a historical perspective.

The Integrated Atmospheric Deposition Network (IADN) has been measuring gas-phase, polychlorinated biphenyl (PCB) concentrations at sites near Lakes Michigan and Superior for over a decade. Data through 2000 were used in this study to investigate PCB temporal trends in the Great Lakes atmosphere. Decreasing trends were found at both sites, and half-lives of approximately 20 yr were calculated using IADN data. However, when these data were supplemented by historical data for Lakes Michigan and Superior dating back to 1977, half-lives dropped to 10 and 6 yr, respectively. These latter half-lives agreed well with half-lives in other environmental compartments. Exponential curves fitted to the historical and IADN data indicated little decline in PCB concentrations in the basin since the mid-1990s. A similar historical analysis of alpha-and gamma-hexachlorocyclohexane (HCH) data indicated that IADN data were the best predictor of trends, resulting in half-lives of around 4 yr for both compounds. Gamma-HCH concentrations, however, have shown little decline in recent years, most likely because of its continuing use. PCB and alpha-HCH temporal trends indicated that bans on these substances have helped to remove them from the atmosphere. This work also showed that decades of data may be necessary to properly interpret long-term temporal trends in gas-phase organochlorine concentrations.

Ecological monitoring for assessing the state of the nearshore and open waters of the Great Lakes.

The Great Lakes Water Quality Agreement stipulates that the Governments of Canada and the United States are responsible for restoring and maintaining the chemical, physical and biological integrity of the waters of the Great Lakes Basin Ecosystem. Due to varying mandates and areas of expertise, monitoring to assess progress towards this objective is conducted by a multitude of Canadian and U.S. federal and provincial/state agencies, in cooperation with academia and regional authorities. This paper highlights selected long-term monitoring programs and discusses a number of documented ecological changes that indicate the present state of the open and nearshore waters of the Great Lakes.