Impacts of Environmental and Engineered Processes on the PFAS Fingerprint of Fluorotelomer-Based AFFF.

Forensic analysis can potentially be used to determine per- and polyfluoroalkyl substance (PFAS) sources at contaminated sites. However, fluorotelomer aqueous film-forming foam (AFFF) sources are difficult to identify because the polyfluorinated active ingredients do not have authentic standards and because the parent compounds can undergo transformation and differential transport, resulting in alteration of the PFAS distribution or fingerprint. In this study, we investigate changes in the PFAS fingerprint of fluorotelomer-derived AFFF due to environmental and engineered processes, including groundwater transport, surface water flow, and land application of contaminated biosolids. Fingerprint analysis supplemented by quantification of precursors and identification of suspected active ingredients shows a clear correlation between a fluorotelomer AFFF manufacturer and surface water of nearby Lake Michigan, demonstrating contamination (>100 ng/L PFOA) of the lake due to migration of an AFFF-impacted groundwater plume. In contrast, extensive processing during wastewater treatment and environmental transport results in large changes to the AFFF fingerprint near agricultural fields where contaminated biosolids were spread. At biosolids-impacted sites, the presence of active ingredients confirms contamination by fluorotelomer AFFF. While sediments can retain longer-chain PFAS, this study demonstrates that aqueous samples are most relevant for PFAS fingerprinting in complex sites, particularly where shorter-chain compounds have been used.

Mercury source changes and food web shifts alter contamination signatures of predatory fish from Lake Michigan.

To understand the impact reduced mercury (Hg) loading and invasive species have had on methylmercury bioaccumulation in predator fish of Lake Michigan, we reconstructed bioaccumulation trends from a fish archive (1978 to 2012). By measuring fish Hg stable isotope ratios, we related temporal changes in Hg concentrations to varying Hg sources. Additionally, dietary tracers were necessary to identify food web influences. Through combined Hg, C, and N stable isotopic analyses, we were able to differentiate between a shift in Hg sources to fish and periods when energetic transitions (from dreissenid mussels) led to the assimilation of contrasting Hg pools (2000 to present). In the late 1980s, lake trout δ202Hg increased (0.4‰) from regulatory reductions in regional Hg emissions. After 2000, C and N isotopes ratios revealed altered food web pathways, resulting in a benthic energetic shift and changes to Hg bioaccumulation. Continued increases in δ202Hg indicate fish are responding to several United States mercury emission mitigation strategies that were initiated circa 1990 and continued through the 2011 promulgation of the Mercury and Air Toxics Standards rule. Unlike archives of sediments, this fish archive tracks Hg sources susceptible to bioaccumulation in Great Lakes fisheries. Analysis reveals that trends in fish Hg concentrations can be substantially affected by shifts in trophic structure and dietary preferences initiated by invasive species in the Great Lakes. This does not diminish the benefits of declining emissions over this period, as fish Hg concentrations would have been higher without these actions.

Modelling the transport of sloughed cladophora in the nearshore zone of Lake Michigan.

The invasion of dreissenid mussels has profoundly altered benthic physical environments and whole-lake nutrient cycling in the Great Lakes over the past several decades. The resurgence of the filamentous green alga Cladophora appears to be one of the consequences of this invasion. Sloughed Cladophora deteriorates water quality, fouls recreational beaches, and may contribute to outbreaks of avian botulism, which have been especially severe in the Sleeping Bear Dunes National Lakeshore (SLBE) region of Lake Michigan. To help determine the fate of sloughed Cladophora, a Lagrangian particle trajectory model was developed to track the transport of Cladophora fragments in the nearshore zone based upon a physical transport-mixing model. The model results demonstrate that the primary deposition sites of sloughed Cladophora within the SLBE region are mid-depth sites not far away from their initial growth area. Because of high algae production in the nearshore waters and limited exchange between the inner and outer bay, the shoreline beach of Platte Bay appears to be particularly vulnerable to fouling, with overall three times as many accumulated particles as those along the Sleeping Bear Bay and Good Harbor Bay. The results of this model may be used to guide regional environmental management initiatives and provide insights into the mechanisms responsible for avian botulism outbreaks. This model may also inform the development of whole-lake ecosystem models that account for nearshore-offshore interactions.

Impacts of lake breeze meteorology on ozone gradient observations along Lake Michigan Shorelines in Wisconsin.

Daytime onshore lake breezes are a critical factor controlling ozone abundance at coastal sites around Lake Michigan. Coastal counties along the western shore of Lake Michigan have historically observed high ozone episodes dating to the 1970s. We classified ozone episode days based on the extent or absence of the lake breeze (i.e., "inland", "near-shore" or "no" lake breeze) to establish a climatology of these events. This work demonstrated variable gradients in ozone abundances based on these different types of meteorology, with the sharpest ozone concentration gradients on days with a near-shore lake breeze. On 76-82% of days in which ozone reached 70 ppb for at least 1 hour, a lake breeze was present. Evidence of ozone gradients from multiple observation platforms during the 2017 Lake Michigan Ozone Study (LMOS 2017) are shown for two days with different depths of lake breezes.

A Comparative Examination of Recent Changes in Nutrients and Lower Food Web Structure in Lake Michigan and Lake Huron.

The lower food webs of Lake Huron and Lake Michigan have experienced similar reductions in the spring phytoplankton bloom and summer populations of Diporeia and cladocerans since the early 2000s. At the same time phosphorus concentrations have decreased and water clarity and silica concentrations have increased. Key periods of change, identified by using a method based on sequential t-tests, were 2003-2005 (Huron) and 2004-2006 (Michigan). Estimated filtration capacity suggests that dreissenid grazing would have been insufficient to directly impact phytoplankton in the deeper waters of either lake by this time (mid 2000s). Despite some evidence of decreased chlorophyll:TP ratios, consistent with grazing limitation of phytoplankton, the main impact of dreissenids on the offshore waters was probably remote, e.g., through interception of nutrients by nearshore populations. A mass balance model indicates that decreased phosphorus loading could not account for observed in-lake phosphorus declines. However, model-inferred internal phosphorus dynamics were strongly correlated between the lakes, with periods of increased internal loading in the 1990s, and increased phosphorus loss starting in 2000 in Lake Michigan and 2003 in Lake Huron, prior to dreissenid expansion into deep water of both lakes. This suggests a limited role for deep populations of dreissenids in the initial phosphorus declines in the lakes, and also suggests a role for meteorological influence on phosphorus dynamics. The high synchrony in lower trophic level changes between Lake Michigan and Lake Huron suggests that both lakes should be considered when investigating underlying causal factors of these changes.

Benthic video image analysis facilitates monitoring of Dreissena populations across spatial scales.

In contrast to marine systems where remote sensing methods in studies of benthic organisms have been widely used for decades, these methods have experienced limited use in studies of freshwater benthos due to the general lack of large epifauna. The situation has changed with the introduction of dreissenid bivalves capable of creating visible aggregations on lake bottoms into North American freshwaters in the 1980s and 1990s. The need for assessment of Dreissena densities prompted exploration of videography as a potentially cost-effective tool. We developed a novel sampling method that analyzes video recorded using a GoPro camera mounted to a benthic sled to estimate Dreissena coverage, density, and biomass over relatively large areas of the lake bed in the Laurentian Great Lakes compared to traditional sampling methods. Using this method, we compared quagga mussel coverage, density, and biomass estimates based on three replicate Ponar grabs vs. 500 m-long video transects across 43 stations sampled in Lake Michigan in 2015. Our results showed that analysis of images from video transects dramatically increased the bottom area surveyed compared to Ponar grabs and increased the precision of Dreissena density and biomass estimations at monitoring stations. By substantially increasing the ability to detect relatively small (<20%) changes between years within a particular station, this method could be a useful and cost-effective addition for monitoring Dreissena populations in the Great Lakes and other freshwater systems where they occur.

Effects of temperature on Renibacterium salmoninarum infection and transmission potential in Chinook salmon, Oncorhynchus tshawytscha (Walbaum).

Renibacterium salmoninarum is a significant pathogen of salmonids and the causative agent of bacterial kidney disease (BKD). Water temperature affects the replication rate of pathogens and the function of the fish immune system to influence the progression of disease. In addition, rapid shifts in temperature may serve as stressors that reduce host resistance. This study evaluated the effect of shifts in water temperature on established R. salmoninarum infections. We challenged Chinook salmon with R. salmoninarum at 12 °C for 2 weeks and then divided the fish into three temperature groups (8, 12 and 15 °C). Fish in the 8 °C group had significantly higher R. salmoninarum-specific mortality, kidney R. salmoninarum loads and bacterial shedding rates relative to the fish held at 12 or 15 °C. There was a trend towards suppressed bacterial load and shedding in the 15 °C group, but the results were not significant. Bacterial load was a significant predictor of shedding for the 8 and 12 °C groups but not for the 15 °C group. Overall, our results showed little effect of temperature stress on the progress of infection, but do support the conclusion that cooler water temperatures contribute to infection progression and increased transmission potential in Chinook salmon infected with R. salmoninarum.

Evolutionary stasis despite selection on a heritable trait in an invasive zooplankton.

Invasive species are one of the greatest threats to ecosystems, and there is evidence that evolution plays an important role in the success or failure of invasions. Yet, few studies have measured natural selection and evolutionary responses to selection in invasive species, particularly invasive animals. We quantified the strength of natural selection on the defensive morphology (distal spine) of an invasive zooplankton, Bythotrephes longimanus, in Lake Michigan across multiple months during three growing seasons. We used multiple lines of evidence, including historic and contemporary wild-captured individuals and palaeoecology of retrieved spines, to assess phenotypic change in distal spine length since invasion. We found evidence of temporally variable selection, with selection for decreased distal spine length early in the growing season and selection for increased distal spine length later in the season. This trend in natural selection is consistent with seasonal changes in the relative strength of non-gape-limited and gape-limited fish predation. Yet, despite net selection for increased distal spine length and a known genetic basis for distal spine length, we observed little evidence of an evolutionary response to selection. Multiple factors likely limit an evolutionary response to selection, including genetic correlations, trade-offs between components of fitness, and phenotypic plasticity.

Demography and threats to population growth of Cirsium pitcheri, a threatened dune plant, in Wisconsin.

Multi-year and multi-site demographic data for rare plants allow researchers to observe threats and project population growth rates and thus long-term persistence of the species, generating knowledge, which allows for effective conservation planning. Demographic studies across more than a decade are extremely rare but allow for the effects of threats to be observed and assessed within the context of interannual environmental variation. We collected demographic data on the Threatened plant Cirsium pitcheri in two sites from 2011-2022. These sites were chosen because one exhibited the presence of non-native seed predators while the other did not, and we hypothesized that we would see declines and potentially extinction of the population threatened by predation. Over the course of our study, we observed additional threats, such as human trampling and high lake levels, which led to significant erosion, sand burial, and storm damage to plants. We find high interannual variation in vital rates and population growth rates for both populations, which mask the overall effects of predation. We observed dramatic declines in plant survivorship and population growth rates in both sites in the years with high lake levels. We conclude that high lake levels, which are expected to become more frequent with climate change, pose a significant threat to all near-shore populations of C. pitcheri.

Aqueous Geochemical Controls on the Sestonic Microbial Community in Lakes Michigan and Superior.

Despite being the largest freshwater lake system in the world, relatively little is known about the sestonic microbial community structure in the Laurentian Great Lakes. The goal of this research was to better understand this ecosystem using high-throughput sequencing of microbial communities as a function of water depth at six locations in the westernmost Great Lakes of Superior and Michigan. The water column was characterized by gradients in temperature, dissolved oxygen (DO), pH, and other physicochemical parameters with depth. Mean nitrate concentrations were 32 µmol/L, with only slight variation within and between the lakes, and with depth. Mean available phosphorus was 0.07 µmol/L, resulting in relatively large N:P ratios (97:1) indicative of P limitation. Abundances of the phyla Actinobacteria, Bacteroidetes, Cyanobacteria, Thaumarchaeota, and Verrucomicrobia differed significantly among the Lakes. Candidatus Nitrosopumilus was present in greater abundance in Lake Superior compared to Lake Michigan, suggesting the importance of ammonia-oxidating archaea in water column N cycling in Lake Superior. The Shannon diversity index was negatively correlated with pH, temperature, and salinity, and positively correlated with DO, latitude, and N2 saturation. Results of this study suggest that DO, pH, temperature, and salinity were major drivers shaping the community composition in the Great Lakes.

The Conservation Genetics of Iris lacustris (Dwarf Lake Iris), a Great Lakes Endemic.

Iris lacustris, a northern Great Lakes endemic, is a rare species known from 165 occurrences across Lakes Michigan and Huron in the United States and Canada. Due to multiple factors, including habitat loss, lack of seed dispersal, patterns of reproduction, and forest succession, the species is threatened. Early population genetic studies using isozymes and allozymes recovered no to limited genetic variation within the species. To better explore genetic variation across the geographic range of I. lacustris and to identify units for conservation, we used tunable Genotyping-by-Sequencing (tGBS) with 171 individuals across 24 populations from Michigan and Wisconsin, and because the species is polyploid, we filtered the single nucleotide polymorphism (SNP) matrices using polyRAD to recognize diploid and tetraploid loci. Based on multiple population genetic approaches, we resolved three to four population clusters that are geographically structured across the range of the species. The species migrated from west to east across its geographic range, and minimal genetic exchange has occurred among populations. Four units for conservation are recognized, but nine adaptive units were identified, providing evidence for local adaptation across the geographic range of the species. Population genetic analyses with all, diploid, and tetraploid loci recovered similar results, which suggests that methods may be robust to variation in ploidy level.

Distinct variations in fluorescent DOM components along a trophic gradient in the lower Fox River-Green Bay as characterized using one-sample PARAFAC approach.

Variations in molecular weight distributions of dissolved organic matter (DOM) and PARAFAC-derived fluorescent components were investigated along a transect in the seasonally hypereutrophic lower Fox River-Green Bay using the one-sample PARAFAC approach coupling flow field-flow fractionation for size-separation with fluorescence excitation-emission matrix (EEM) and PARAFAC analysis. Concentrations of dissolved organic carbon and nitrogen, chromophoric-DOM, specific UV absorbance at 254 nm, and humification index all decreased monotonically from river to open bay, showing a strong river-dominated DOM source and a dynamic change in DOM quality along the river-lake transect. The relative abundance of colloidal DOM (>1 kDa) derived from ultrafiltration exhibited minimal variation, averaging 71 ± 4 % of the bulk DOM, across the entire estuarine transect although the colloidal concentration decreased in general. Using the one-sample EEM-PARAFAC approach, the identified major fluorescent components were distinct between stations along the river-estuary-open bay continuum, with four components in river/upper-estuary but three components in open bay waters. Among the four common fluorescent components (C475, C410, C320 and C290), the most abundant and refractory humic-like component, C475, behaved conservatively and its relative abundance (%ΣFmax) remained fairly constant (50 ± 4 %) along the transect, while the semi-labile humic-like component, C410, consistently decreased from river to estuary and eventually vanished in open Green Bay. In contrast, the two autochthonous protein-like components (C320 and C290) increased from river to open bay along the trophic gradient. The new results presented here provide an improved understanding of the diverse and fluctuating characteristics in DOM composition, lability, and estuarine mixing behavior across the river-lake interface and demonstrate the efficacy of the one-sample PARAFAC approach.

A Hemimysis-driven novel ecosystem at a modified rubble-mound breakwater: An Engineering With Nature® Demonstration Project.

The US Army Corps of Engineers (USACE) repairs aging breakwater structures as part of routine maintenance to maintain safe navigation in Great Lakes commercial ports. A USACE repair to an existing breakwater structure in Milwaukee Harbor (WI) implementing Engineering With Nature (EWN) principles created complex rocky habitat by strategically placing cobble-sized stone over conventional 5.4 to 9.1 metric ton boulders, thus creating "control" (boulder) and "treatment" (cobble) habitats. We evaluated the resultant nature-based breakwater (NBBW) developing food web versus an adjacent reference site on the same breakwater and determined that, unexpectedly, locally abundant Hemimysis anomala were impacting the food-web dynamics and feeding ecology of fishes occupying the structure. Fish and forage communities were sampled using gillnets, night scuba diving surveys, rock collections, and a novel trap to capture invertebrates. The resultant NBBW became home to a prolific population of nonindigenous Hemimysis, with indications that they were more abundant on cobble versus boulders, based on rainbow smelt feeding. This lithophilic/cave swelling mysid provided an important new food resource in Milwaukee Harbor for two introduced pelagic prey fishes: alewife (Alosa pseudoharengus) and rainbow smelt (Osmerus mordax). Gillnetting and night scuba diving surveys confirmed that rainbow smelt preferred to forage on the cobble section (p < 0.05). Hemimysis were also the primary food item consumed by nearshore game fishes such as young-of-the-year (YOY) yellow perch (Perca flavescens), YOY largemouth bass (Micropterus salmoides), and juvenile rock bass (Ambloplites rupestris). We propose that those breakwaters that harbor abundant Hemimysis constitute novel ecosystems (ecosystems that include both native and non-native biota) that might benefit harbor fisheries if well-managed. This project demonstrated how a low-cost design modification could be applied during the repair of rubble-mound, breakwater structures to achieve benefits beyond safe navigation. Integr Environ Assess Manag 2022;18:49-62. Published 2021. This article is a US Government work and is in the public domain in the USA.

Halophilic bacteria in a Lake Michigan drainage basin as potential biological indicators of chloride-impacted freshwaters.

There are few biological indicators for freshwater systems subjected to high chloride levels. Freshwater systems receive many forms of chloride such as road salts (e.g., NaCl, CaCl2, MgCl2), fertilizers (e.g., KCl), and year-round water softener pollution. The goal our study was to investigate Halomonadaceae populations as prospective biological indicators of chloride-impacted freshwaters. The bacterial family Halomonadaceae are halophiles that generally require the presence of salt to survive, which make them an attractive candidate in determining chloride impaired areas. Field sediment surveys assessed how salt tolerant and halophilic bacteria abundance corresponded to chloride and conductivity measurements. Colony forming unit (CFU) counts on modified M9 6% NaCl plates (w/v) at urbanized sites compared to the rural sites had highest counts during winter and spring when chloride concentrations were also highest. Select isolates identified as Halomonadaceae through 16S rRNA sequencing were kept as active cultures to determine the NaCl concentration and temperature preference that resulted in the isolates optimal growth. Isolates tested under 5 °C (cold) grew optimally in 2 % NaCl (w/v), whereas under 18 °C (warm), isolates showed optimal growth at 6 % NaCl. The majority of isolates had maximum growth in the warmer temperature, however, select isolates grew better in the cold temperature. Culture-independent methods were used and identified Halomonadaceae were widespread and permeant members of the microbial community in a Lake Michigan drainage basin. Quantitative polymerase chain reaction (qPCR) targeting Halomonadaceae genera demonstrated that abundance varied by site, but overall were present throughout the year. However, community sequencing revealed there were a large relative proportion of specific Halomonadaceae populations present in winter versus summer. Methods targeting salt tolerant bacteria and specific members of Halomonadaceae appears to be a promising approach to assess chloride-impacted areas to better understand the long-term ecological impacts as we continue to salinize freshwater resources.

High-density genomic data reveal fine-scale population structure and pronounced islands of adaptive divergence in lake whitefish (Coregonus clupeaformis) from Lake Michigan.

Understanding patterns of genetic structure and adaptive variation in natural populations is crucial for informing conservation and management. Past genetic research using 11 microsatellite loci identified six genetic stocks of lake whitefish (Coregonus clupeaformis) within Lake Michigan, USA. However, ambiguity in genetic stock assignments suggested those neutral microsatellite markers did not provide adequate power for delineating lake whitefish stocks in this system, prompting calls for a genomics approach to investigate stock structure. Here, we generated a dense genomic dataset to characterize population structure and investigate patterns of neutral and adaptive genetic diversity among lake whitefish populations in Lake Michigan. Using Rapture sequencing, we genotyped 829 individuals collected from 17 baseline populations at 197,588 SNP markers after quality filtering. Although the overall pattern of genetic structure was similar to the previous microsatellite study, our genomic data provided several novel insights. Our results indicated a large genetic break between the northwestern and eastern sides of Lake Michigan, and we found a much greater level of population structure on the eastern side compared to the northwestern side. Collectively, we observed five genomic islands of adaptive divergence on five different chromosomes. Each island displayed a different pattern of population structure, suggesting that combinations of genotypes at these adaptive regions are facilitating local adaptation to spatially heterogenous selection pressures. Additionally, we identified a large linkage disequilibrium block of ~8.5 Mb on chromosome 20 that is suggestive of a putative inversion but with a low frequency of the minor haplotype. Our study provides a comprehensive assessment of population structure and adaptive variation that can help inform the management of Lake Michigan's lake whitefish fishery and highlights the utility of incorporating adaptive loci into fisheries management.

Drowning incidents and conditions due to hidden flash rips in Lake Michigan.

Flash rips are episodic bursts of water jetting offshore, which can lead to drowning incidents by sweeping swimmers offshore without warning, thus posing a hidden and unrecognized danger to beachgoers. This study reveals hazards of flash rips by investigating a series of drowning incidents along coasts of Lake Michigan during a series of storm events on July 18-21, 2019. Occurrences and causes of flash rips were depicted through webcam image observations, storm features of atmospheric disturbances, hydrodynamic circumstances of wind waves and meteorologically induced water level fluctuations, and model-reconstructed nearshore circulations. Results shows that flash rips were generated during or after storms through nearshore processes of storm-induced wind waves and meteorologically induced water level fluctuations. With small wind waves, low water level fluctuations, and a timing delay of rip occurrences relative to the causative convective storms, flash rips pose a hidden hazard to unaware swimmers. Historical observations for incidents in Lake Michigan between 2002 and 2019 further show that dry conditions or fair weathers and a calm water signature at the beach can likely generate unexpected hidden flash rips, resulting in the highest drowning risks. There is an urgent need for communication, education, and prediction/forecast of hidden flash rips to the Laurentian Great Lakes and worldwide coastal communities.

It's complicated: Heterogeneous patterns of genetic structure in five fish species from a fragmented river suggest multiple processes can drive differentiation.

Fragmentation of river systems by dams can have substantial genetic impacts on fish populations. However, genetic structure can exist naturally at small scales through processes other than isolation by physical barriers. We sampled individuals from five native fish species with varying life histories above and below a dam in the lower Boardman River, Michigan, USA, and used RADseq to investigate processes influencing genetic structure in this system. Species assessed were white sucker Catostomus commersonii, yellow perch Perca flavescens, walleye Sander vitreus, smallmouth bass Micropterus dolomieu, and rock bass Ambloplites rupestris. We detected significant differentiation within each species, but patterns of population structure varied substantially. Interestingly, genetic structure did not appear to be solely the result of fragmentation by the dam. While genetic structure in yellow perch and walleye generally coincided with "above dam" and "below dam" sampling locations, samples from our other three species did not. Specifically, samples from rock bass, smallmouth bass, and, to a much lesser extent, white sucker, aligned with a putative Great Lakes (GL) group that contained mostly individuals sampled below the dam and a putative Boardman River (BR) group that contained individuals sampled both above and below the dam, with some evidence of admixture among groups. We hypothesize that the GL and BR groups formed prior to dam construction and our samples largely represent a mixed stock that was sampled sympatrically outside of the spawning season. Support for this hypothesis is especially strong in smallmouth bass, where GL fish were 151 mm smaller than BR fish on average, suggesting a potential ontogenetic habitat shift of young GL fish into the lower river for feeding and/or refuge. Our study illuminates the complex dynamics shaping genetic structure in fragmented river systems and indicates that conclusions drawn for a single species cannot be generalized.

Incorporation of feeding functional group information informs explanatory patterns of long-term population changes in fish assemblages.

The objective of this study was to evaluate long term trends of fish taxa in southern Lake Michigan while incorporating their functional roles to improve our understanding of ecosystem level changes that have occurred in the system over time. The approach used here highlighted the ease of incorporating ecological mechanisms into population models so researchers can take full advantage of available long-term ecosystem information. Long term studies of fish assemblages can be used to inform changes in community structure resulting from perturbations to aquatic systems and understanding these changes in fish assemblages can be better contextualized by grouping species according to functional groups that are grounded in niche theory. We hypothesized that describing the biological process based on partial pooling of information across functional groups would identify shifts in fish assemblages that coincide with major changes in the ecosystem (e.g., for this study, shifts in zooplankton abundance over time). Herein, we analyzed a long-term Lake Michigan fisheries dataset using a multi-species state space modeling approach within a Bayesian framework. Our results suggested the population growth rates of planktivores and benthic invertivores have been more variable than general invertivores over time and that trends in planktivores can be partially explained by ecosystem changes in zooplankton abundance. Additional work incorporating more ecosystem parameters (e.g., primary production, etc.) should be incorporated into future iterations of this novel modeling concept.

Spatial and temporal variations of persistent organic pollutants impacted by episodic sediment resuspension in southern Lake Michigan.

The impacts of large-scale, episodic sediment resuspension on the cycling of polychlorinated biphenyl congeners (PCBs) were examined using a spatially coordinated air and water sampling strategy conducted in southern Lake Michigan in the late winters of 1998, 1999, and 2000. We found no significant temporal changes in gas phase, dissolved phase, or suspended sediment PCB concentrations despite large-scale seasonal storms occurring before and after sampling campaigns. Only gas phase and suspended sediment PCBs varied spatially. Higher total suspended material (TSM) concentrations and fraction organic carbon (foc ) were measured at sampling stations located in the near-shore region of southern Lake Michigan than at open-water sampling stations. Gas phase concentrations (ΣPCBg) were higher in the west (0.436 ± 0.200 ng/m3, n = 11) and south (0.408 ± 0.286 ng/m3, n = 5) than the east (0.214 ± 0.082 ng/m3, n = 10) and central (0.253 ± 0.145 ng/m3, n = 8) regions of southern Lake Michigan. Dissolved phase concentrations (ΣPCBd) averaged 0.18 ± 0.024 ng/L (n = 52); suspended sediment concentrations (ΣPCBs) accounted for between 4% and 72% (23 ± 4%, n = 52) of the total ΣPCB concentrations (ΣPCBT = ΣPCBd + ΣPCBs). Despite no consistent temporal variations in both dissolved phase or suspended sediment ΣPCB concentrations, there were temporal and spatial variations in the distribution shift between phases that can be linked to sediment resuspension, not a state of equilibrium. Specifically, our analysis suggests sediment resuspension results in preferential sorption of heavier, more chlorinated PCB congeners.

Mercury methylation potential in a sand dune on Lake Michigan's eastern shoreline.

Lake Michigan hosts the largest freshwater sand dune system in the world and is economically important for the fishery industry and tourism. Due to industrial pollution and atmospheric mercury (Hg) deposition, toxic levels of methylmercury (MeHg) have been found in the Lake biota, but little information is known regarding MeHg sources and Hg methylation potential in the shoreline sand dunes. We conducted anaerobic incubation experiments with beach sands collected from Ludington, Michigan, and examined the effects of organic carbon substrate addition, inorganic nitrogen, and mineral magnetite on Hg methylation. Despite nutrient poor and low-organic carbon conditions, appreciable Hg methylation activity coupled with carbon degradation was observed in the sands. Addition of acetate as a carbon source substantially increased MeHg production from 2 to 380 ng/kg sediment while acetate was rapidly degraded in the first 19 days of incubation. Ammonium addition showed little influence on carbon degradation or Hg methylation, whereas iron oxide addition (~1% dry weight) significantly inhibited both carbon degradation and MeHg production (by up to 90%), highlighting strongly coupled interactions between microbes, carbon substrates, and minerals. This research demonstrates the potential of microbial Hg methylation in the sand dunes, which may play a role in MeHg input and bioaccumulation in the Lake Michigan ecosystem.