Laura S. Sherman

Isotopic Composition and Fractionation of Mercury in Great Lakes Precipitation and Ambient Air

Atmospheric deposition is a primary pathway by which mercury (Hg) enters terrestrial and aquatic ecosystems; however, the chemical and meteorological processes that Hg undergoes from emission to deposition are not well understood. Hg stable isotope geochemistry is a growing field used to better understand Hg biogeochemical cycling. To examine the atmospheric Hg isotopic composition in the Great Lakes, precipitation and ambient vapor-phase Hg samples were collected in Chicago, IL, Holland, MI, and Dexter, MI, between April 2007 and September 2009. Precipitation samples were characterized by negative mass-dependent fractionation (MDF) (δ(202)Hg = -0.79‰ to 0.18‰), while most vapor-phase samples displayed positive MDF (δ(202)Hg = -0.59‰ to 0.43‰). Positive mass-independent fractionation (MIF) (Δ(199)Hg = 0.04‰ to 0.52‰) was observed in precipitation, whereas MIF was slightly negative in vapor-phase samples (Δ(199)Hg = -0.21‰ to 0.06‰). Significant positive MIF of (200)Hg up to 0.25‰ was also measured in precipitation. Such MIF of an even-mass Hg isotope has not been previously reported in natural samples. These results contrast with recent predictions of the isotopic composition of atmospheric Hg and suggest that, in addition to aqueous photoreduction, other atmospheric redox reactions and source-related processes may contribute to isotopic fractionation of atmospheric Hg.

Investigation of Local Mercury Deposition from a Coal-Fired Power Plant Using Mercury Isotopes

Coal combustion accounts for approximately two-thirds of global anthropogenic mercury (Hg) emissions. Enhanced deposition of Hg can occur close to coal-fired utility boilers (CFUBs), but it is difficult to link specific point sources with local deposition. Measurement of Hg stable isotope ratios in precipitation holds promise as a tool to assist in the identification of local Hg deposition related to anthropogenic emissions. We collected daily event precipitation samples in close proximity to a large CFUB in Crystal River, Florida. Precipitation samples collected in Crystal River were isotopically distinct and displayed large negative δ(202)Hg values (mean = -2.56‰, 1 SD = 1.10‰, n = 28). In contrast, precipitation samples collected at other sites in FL that were not greatly impacted by local coal combustion were characterized by δ(202)Hg values close to 0‰ (mean = 0.07‰, 1 SD = 0.17‰, n = 13). These results indicate that, depending on factors such as powdered coal isotopic composition and efficiency of Hg removal from flue gas, Hg deposited near CFUBs can be isotopically distinct. As this tool is further refined through future studies, Hg stable isotopes may eventually be used to quantify local deposition of Hg emitted by large CFUBs.

New insight into biomarkers of human mercury exposure using naturally occurring mercury stable isotopes.

Human exposure to methylmercury (MeHg) and elemental mercury vapor (Hg(0)(g)) are often estimated using total Hg concentrations in hair and urine, respectively. We investigated whether Hg stable isotopes could be used to better distinguish between exposure to Hg(0)(g) versus MeHg. We found that hair from North American dental professionals was characterized by high positive Δ(199)Hg values (mean = 1.86‰, 1 SD = 0.12‰, n = 11). This confirms that among people who regularly consume fish, total Hg concentrations in hair reflect exposure to MeHg. In contrast, we found that urine from the same individuals was characterized by a range of Δ(199)Hg values (0.29 to 1.77‰, 2 SD = 0.06‰, n = 12) that were significantly correlated to the number of dental amalgams in each individuals mouth. We hypothesize that fish-derived MeHg is demethylated within the body, causing mass-dependent fractionation and the excretion of inorganic Hg in urine. Mercury in urine therefore represents a mixture of demethylated fish-derived MeHg and amalgam-derived inorganic Hg. We estimate that the majority (>70%) of Hg in urine from individuals with <10 dental amalgams is derived from ingestion of MeHg in fish. These data suggest that within populations that consume fish, urine total Hg concentrations may overestimate Hg exposure from personal dental amalgams.

Mercury stable isotopes in sediments and largemouth bass from Florida lakes, USA

Humans and wildlife can be exposed to mercury (Hg) through the consumption of fish with elevated concentrations of methylmercury (MeHg). Studies have shown that increased atmospheric deposition of Hg often leads to increased MeHg concentrations in aquatic organisms. However, depending on the ecosystem characteristics, reductions in Hg emissions may not always lead to immediate decreases in fish MeHg concentrations. Measurements of natural abundance Hg stable isotope ratios may enable a better understanding of these complex relationships. To gain insight into the sources of Hg to sport fish in central Florida, we measured the Hg isotopic compositions of surface sediments and largemouth bass from freshwater lakes. We found that fish collected from lakes located near the large Crystal River coal-fired power plant did not display evidence of anomalous negative δ(202)Hg values that were observed in nearby precipitation. This suggests that Hg recently deposited from the atmosphere is not preferentially methylated and bioaccumulated in these lakes relative to previously deposited Hg accumulated in the lake sediments. We also observed significant positive Δ(199)Hg values in the fish that were correlated with light penetration depth in the lakes from which they were collected. This indicates that a significant amount of photochemical degradation of MeHg (up to ~40%) occurred prior to uptake of the remaining MeHg into the food webs. These results suggest that depending on physical lake characteristics and biogeochemical factors, decreased atmospheric Hg deposition may not lead to immediate short-term reductions in fish MeHg concentrations. Instead, recovery of some freshwater fish populations to baseline MeHg concentrations may take decades to centuries.

The use of Pb, Sr, and Hg isotopes in Great Lakes precipitation as a tool for pollution source attribution.

The anthropogenic emission and subsequent deposition of heavy metals including mercury (Hg) and lead (Pb) present human health and environmental concerns. Although it is known that local and regional sources of these metals contribute to deposition in the Great Lakes region, it is difficult to trace emissions from point sources to impacted sites. Recent studies suggest that metal isotope ratios may be useful for distinguishing between and tracing source emissions. We measured Pb, strontium (Sr), and Hg isotope ratios in daily precipitation samples that were collected at seven sites across the Great Lakes region between 2003 and 2007. Lead isotope ratios ((207)Pb/(206)Pb=0.8062 to 0.8554) suggest that Pb deposition was influenced by coal combustion and processing of Mississippi Valley-Type Pb ore deposits. Regional differences in Sr isotope ratios ((87)Sr/(86)Sr=0.70859 to 0.71155) are likely related to coal fly ash and soil dust. Mercury isotope ratios (δ(202)Hg=-1.13 to 0.13‰) also varied among the sites, likely due to regional differences in coal isotopic composition, and fractionation occurring within industrial facilities and in the atmosphere. These data represent the first combined characterization of Pb, Sr, and Hg isotope ratios in precipitation collected across the Great Lakes region. We demonstrate the utility of multiple metal isotope ratios in parallel with traditional trace element multivariate statistical modeling to enable more complete pollution source attribution.

Assessing Sources of Human Methylmercury Exposure Using Stable Mercury Isotopes

Seafood consumption is the primary route of methylmercury (MeHg) exposure for most populations. Inherent uncertainties in dietary survey data point to the need for an empirical tool to confirm exposure sources. We therefore explore the utility of Hg stable isotope ratios in human hair as a new method for discerning MeHg exposure sources. We characterized Hg isotope fractionation between humans and their diets using hair samples from Faroese whalers exposed to MeHg predominantly from pilot whales. We observed an increase of 1.75‰ in δ202Hg values between pilot whale muscle tissue and Faroese whalers’ hair but no mass-independent fractionation. We found a similar offset in δ202Hg between consumed seafood and hair samples from Gulf of Mexico recreational anglers who are exposed to lower levels of MeHg from a variety of seafood sources. An isotope mixing model was used to estimate individual MeHg exposure sources and confirmed that both Δ199Hg and δ202Hg values in human hair can help identify dietary MeHg sources. Variability in isotopic signatures among coastal fish consumers in the Gulf of Mexico likely reflects both differences in environmental sources of MeHg to coastal fish and uncertainty in dietary recall data. Additional data are needed to fully refine this approach for individuals with complex seafood consumption patterns.

Coupling atmospheric mercury isotope ratios and meteorology to identify sources of mercury impacting a coastal urban‐industrial region near Pensacola, Florida, USA

Identifying the anthropogenic and natural sources of mercury (Hg) emissions contributing to atmospheric mercury on local, regional, and global scales continues to be a grand challenge. The relative importance of various direct anthropogenic emissions of mercury, in addition to natural geologic sources and reemission of previously released and deposited mercury, differs regionally and temporally. In this study, we used local-scale, mesoscale, and synoptic-scale meteorological analysis to couple the isotopic composition of ambient atmospheric mercury with potential sources of mercury contributing to a coastal urban-industrial setting near a coal-fired power plant in Pensacola, Florida, USA. We were able to broadly discern four influences on the isotopic composition of ambient atmospheric mercury impacting this coastal urban-industrial region: (1) local to regional urban-industrial anthropogenic emissions (mean δ202Hg = 0.44 ± 0.05‰, 1SD, n = 3), (2) marine-influenced sources derived from the Gulf of Mexico (mean δ202Hg = 0.77 ± 0.15‰, 1SD, n = 4), (3) continental sources associated with north-northwesterly flows from within the planetary boundary layer (mean δ202Hg = 0.65 ± 0.04‰, 1SD, n = 3), and (4) continental sources associated with north-northeasterly flows at higher altitudes (i.e., 2000 m above ground level; mean δ202Hg = 1.10 ± 0.21‰, 1SD, n = 8). Overall, these data, in conjunction with previous studies, suggest that the background global atmospheric mercury pool is characterized by moderately positive δ202Hg values; that urban-industrial emissions drive the isotopic composition of ambient atmospheric mercury toward lower δ202Hg values; and that air-surface exchange dynamics across vegetation and soils of terrestrial ecosystems drive the isotopic composition of ambient atmospheric mercury toward higher positive δ202Hg values. The data further suggest that mass-independent fractionation (MIF) of both even-mass- and odd-mass-number isotopes, likely generated by photochemical reactions in the atmosphere or during reemission from terrestrial and aquatic ecosystems, can be obscured by mixing with anthropogenic emissions having different MIF signatures.

Social Justice and Sustainability in Poor Neighborhoods Learning and Living in Southwest Detroit

Sustainability is the new lens that many planning educators and practitioners employ in their efforts. We taught an undergraduate service-learning studio focused on neighborhood sustainability in Detroit, Michigan. To evaluate the course, we identified four desirable learning outcomes based on a modified environmental education framework. Students gained a sense of personal investment in the sustainability challenges faced by the community and developed a more nuanced understanding of the power relationships inherent in these issues. This educational framework can help instructors design and evaluate service-learning studios that highlight the embedded social justice issues in impoverished neighborhoods.