Current and historical concentrations of poly and perfluorinated compounds in sediments of the northern Great Lakes - Superior, Huron, and Michigan.

Current and historical concentrations of 22 poly- and perfluorinated compounds (PFASs) in sediment collected from Lake Superior and northern Lake Michigan in 2011 and Lake Huron in 2012 are reported. The sampling was performed in two ways, Ponar grabs of surface sediments for current spatial distribution across the lake and dated cores for multi-decadal temporal trends. Mean concentrations of the sum of PFASs (∑PFASs) were 1.5, 4.6 and 3.1 ng g-1 dry mas (dm) in surface sediments for Lakes Superior, Michigan and Huron, respectively. Of the five Laurentian Lakes, the watersheds of Superior and Huron are the less densely populated by humans, and concentrations observed were typically less and from more diffuse sources, due to lesser urbanization and industrialization. However, some regions of greater concentrations were observed and might indicate more local, point sources. In core samples concentrations ranged from 7 that include perfluoro-n-octane sulfonate (PFOS) bind more strongly to sediment, which resulted in more accurate analyses of temporal trends. Shorter-chain PFASs, such as perfluoro-n-butanoic acid which is the primary replacement for C8 PFASs that have been phased out, are more soluble and were identified in some core layers at depths corresponding to pre-production periods. Thus, analyses of temporal trends of these more soluble compounds in cores of sediments were less accurate. Total elemental fluorine (TF) and extractable organic fluorine (EOF) indicated that identified PFASs were not a significant fraction of fluorine containing compounds in sediment (<0.01% in EOF).

Organophosphate Esters in Sediment of the Great Lakes.

This is the first study on organophosphate ester (OPEs) flame retardants and plasticizers in the sediment of the Great Lakes. Concentrations of 14 OPEs were measured in three sediment cores and 88 Ponar surface grabs collected from Lakes Ontario, Michigan, and Superior of North America. The sum of these OPEs (Σ14OPEs) in Ponar grabs averaged 2.2, 4.7, and 16.6 ng g-1 dw in Lakes Superior, Michigan, and Ontario, respectively. Multiple linear regression analyses demonstrated statistically significant associations between logarithm concentrations of Σ14OPEs as well as selected congeners in surface grab samples and sediment organic carbon content as well as a newly developed urban distance factor. Temporal trends observed in dated sediment cores from Lake Michigan demonstrated that the recent increase in depositional flux to sediment is dominated by chlorinated OPEs, particularly tris(2-chloroisopropyl) phosphate (TCPP), which has a doubling time of about 20 years. Downward diffusion within sediment may have caused vertical fractionation of OPEs over time. Two relatively hydrophilic OPEs including TCPP had much higher concentrations in sediment than estimated based on equilibria between water and sediment organic carbon. Approximately a quarter (17 tonnes) of the estimated total OPE burden (63 tonnes) in Lake Michigan resides in sediment, which may act as a secondary source releasing OPEs to the water column for years to come.

Spatial and Temporal Trends of Polyhalogenated Carbazoles in Sediments of Upper Great Lakes: Insights into Their Origin.

Polyhalogenated carbazoles (PHCZs) have been increasingly detected in the environment. Their similarities in chemical structure with legacy pollutants and their potential toxicity have caused increasing concern. In this work, 112 Ponar grab and 28 core sediment samples were collected from Lakes Michigan, Superior, and Huron, and a total of 26 PHCZs were analyzed along with unsubstituted carbazole using gas chromatography coupled with single- or triple-quadrupole mass spectrometry. Our results show that the total accumulation of PHCZs in the sediments of the upper Great Lakes is >3000 tonnes, orders of magnitude greater than those of polychlorinated biphenyls (PCBs) and decabromodiphenyl ether (BDE209). The 27 individual analytes differ in spatial distribution and temporal trend. Our results showed that PHCZs with substitution patterns of -Br2-5, -Cl1-2Br2-4, or having iodine, were more abundant in sediment of Lake Michigan deposited before 1900 than those deposited more recently, implying a natural origin. Some "emerging" PHCZs have been increasingly deposited into the sediment in recent decades, and deserve further environmental monitoring and research. Other PHCZs with low halogen substitution may form from in situ dehalogenation of PHCZs having more halogens. Anthropogenic sources of PHCZs may exist, particularly for the emerging and low molecular mass congeners.

Occurrence of Atrazine and Related Compounds in Sediments of Upper Great Lakes.

Surface grab and core sediment samples were collected from Lakes Michigan, Superior, and Huron from 2010 to 2012, and concentrations of herbicides atrazine, simazine, and alachlor, as well as desethylatrazine (DEA), were determined. Concentrations of atrazine in surface grabs ranged from 0.01 to 1.7 ng/g dry weight and are significantly higher in the southern basin of Lake Michigan (latitude <44°) than other parts of the three lakes. The highest concentration of alachlor was found in sediments of Saginaw Bay in Lake Huron. The inventory and net fluxes of these herbicides were found to decline exponentially from the south to the north. The concentration ratio of DEA to atrazine (DEA/ATZ) increased with latitude, suggesting degradation of atrazine to DEA during atmospheric transport. DEA/ATZ also increased with sediment depth in the sediment cores. Diffusion of deposited herbicides from the upper sediment into deeper sediments has occurred, on the basis of the observed patterns of concentrations in dated sediment cores. Concentrations of atrazine in pore water were estimated and were higher than those reported for the bulk waters, suggesting the occurrence of solid-phase deposition of atrazine through the water column and that contaminated sediments act as a source releasing atrazine to the overlying water.