Butyltin Species and Inorganic Tin in Water and Sediment of the Detroit and St. Clair Rivers

Water and sediment samples from 29 locations in the Detroit and St. Clair rivers were analyzed for the highly toxic tri-n-butyltin (Bu₃Sn⁺) species and for the less toxic di-n-butyltin (Bu₂Sn²⁺) and n-butyltin (BuSn³⁺) species and inorganic tin. In general, locations sampled in the St. Clair River were less contaminated with butyltin species than those in the Detroit River. Inorganic tin and BuSn³⁺ were detected in over 90% of all subsurface water samples, while Bu₂Sn²⁺ and Bu₃Sn⁺ were detected in 45 and 28% of the same samples, respectively. The highest concentration ofBu₃Sn⁺ in subsurface water, 5.9 × 10^?10 mol Sn/L, was at the mouth of the Ecorse River, a tributary of the Detroit River. The three butyltin species and inorganic tin were also detected in 23–46% of all sediment samples. The highest concentrations of Bu₃Sn⁺ in sediment were found close to the mouths of the River Rouge, another tributary of the Detroit River, and the Ecorse River, and were 6.2 × I0^–7 and 1.7 × I0^–7 mol Sn/kg dry weight, respectively, for the top 2 cm of sediment.     

Water Currents in the St. Clair and Detroit Rivers

A 2-D hydrodynamic finite element model (RMA-2V) with mesh generation tools (Fast-TABS) is used to simulate the current velocities in the St. Clair and Detroit rivers. The required shorelines and spot depths were digitized from the bathymetric charts and the NOS (National Ocean Service) hydrographic database using Geographic Information Systems technology. The field data obtained from the tracking of drogues via aerial time-lapse photography were used to calibrate the model. A statistical comparison between field and simulated data revealed a very good agreement between the simulated and observed currents.     

Flow Distribution in Selected Branches of St. Clair and Detroit Rivers

St. Clair and Detroit rivers, which are connecting channels between Lake Huron and Lake Erie in the Great Lakes basin, form part of the boundary between the state of Michigan and the province of Ontario. In 13 reaches, this flow divides locally around islands and dikes to form 31 branches. This study develops a set of simple linear regression equations for computing expected flow proportions in branches, generally as a function of the total flow within the reach. The equations are based on 533 acoustic Doppler current profiler measurements of flow obtained between 1996 and 2000. Root-mean-square errors of these regressions range from 0.00323 to 0.0895. In seven upstream reaches where flow is known because of flow specifications at the boundaries of the waterway and continuity constraints, the uncertainties of the flow proportions can be used to directly infer the uncertainties of the corresponding flows. In six downstream reaches, the uncertainties of flows are determined by both the uncertainties of the flow proportions and the uncertainties of the total flow in the reach. For these reaches, Monte Carlo simulations quantify the ratios of total uncertainty to flow proportion uncertainty, which range from 1.0026 to 13.984. To facilitate routine calculation, polynomial regression equations are developed to approximate these ratios as a function of flow. Results provide a mechanism for computing the magnitudes and uncertainties of steady-state flows within selected branches of the connecting channels by specifying inflows at the headwaters of St. Clair River, seven intervening tributaries, and Lake St. Clair.     

Organochlorine and Mercury Residues in Young-of-the-Year Spottail Shiners from the Detroit River,Lake St. Clair,and Lake Erie

Young-of-the-year spottail shiners (Notropis hudsonius) were used as biomonitors to determine the spatial distribution (1982/83) and assess trend data for organochlorine and mercury residues. Significantly (p < 0.01) higher PCB residues were found in Detroit River spottail shiners than in collections from southwestern Lake St. Clair and northwestern Lake Erie. The highest PCB residues were found in the west bank collections from Michigan waters (912–2,997ng/g) compared to the mid-stream (96–290 ng/g) and east bank collections (153–316 ng/g). Chlordane residues were found to be elevated in all spottail shiner samples from urbanized areas. Octachlorostyrene and ∑ DDT residues were distributed uniformly within the study area, whereas mercury concentrations were found to be lower in spottail shiners from northwestern Lake Erie than in comparable samples from the Detroit River and southwestern Lake St. Clair. Residues for BHC, heptachlor, aldrin, and chlorinated benzenes were near their detection limits; mirex and chlorinated phenols were not detectable. Recent (1982/83) PCB residue levels in spottail shiners exceeded the IJC aquatic life objective (Great Lakes Water Quality Agreement of 1978) at all the sites sampled, except at Pike Creek in Lake St. Clair. PCB residues in spottail shiners from Pike Creek, Big Creek, and Leamington have declined significantly (p < 0.01) since the mid-seventies. Mercury and chlordane residues have decreased in spottail shiner samples from Leamington, but have remained virtually unchanged at Big Creek and Pike Creek.     

Macrozoobenthos of the Detroit and St. Clair Rivers with Comparisons to Neighbouring Waters

A comparison of the results from macrozoobenthic surveys of the Detroit River (1968 and 1980) showed spatial and temporal differences in the types and distribution of organisms recovered. Similar comparisons were also made from studies of the St. Clair River (1968 and 1977) and the western basin of Lake Erie (1967 and 1979). Results are also presented from a 1983 study of Lake St. Clair. These studies indicate a general improvement in the macrozoobenthos of the area, exhibited by a stronger representation of pollution sensitive organisms and an improved community structure. The studies demonstrate both the sensitivity of these large rivers and lakes and their recuperative capabilities following pollution abatement measures. Despite the documented improvements, large areas of impairment still exist, particularly in the St. Clair and Detroit rivers.     

Surface Deposition of Lead and Cadmium from the Atmosphere in the Detroit River—Lake St. Clair Region

The research reported here forms part of a large multidisciplinary study of four toxic contaminants — lead, cadmium, PCBs, and octachlorostyrene in the Essex region of southwestern Ontario. The purpose of this part of the project is to quantify the atmospheric loading of the metallic contaminants. A bulk precipitation sampler, wet-only precipitation sampler, and recording rain gauge were installed at an urban and rural site. Results from 2 years of data indicate that atmospheric loading of lead is 40–50 times that of cadmium in the city and 16–40 times that of cadmium in the rural areas. Lead loadings in the city were found to be 2–4 times higher than in the rural areas, while cadmium loadings appeared to be similar in both areas. Concentrations of the metals are higher in winter than in summer, but because of higher summer precipitation surface loadings are similar in both seasons. Preliminary statistical analysis indicates that concentrations of the metals are related to intensity and amount of precipitation but not usually to wind direction.     

Chlorinated Contaminants in Surficial Sediments of Lakes Huron,St. Clair,and Erie: Implications Regarding Sources Along the St. Clair and Detroit Rivers

Surficial sediments from southern Lake Huron, Lake St. Clair, and Lake Erie have been analyzed for a broad spectrum of chlorinated organics including PCBs, chlorobenzenes, and several pesticides. The differences between sediment contaminant concentrations in Lake Huron and Lake St. Clair indicated sources of hexachlorobenzene, hexachlorobutadiene, octachlorostyrene, and several other chlorinated benzenes along the St. Clair River. Similar differences between sediment PCB concentrations in Lakes Huron/St. Clair and Lake Erie indicated major PCB sources along the Detroit River. Specific PCB congener analysis revealed that PCBs discharged to the Detroit River contained especially high concentrations of highly chlorinated hexa-, hepta-, and octachloro-biphenyls which are major constituents of the industrial mixture Aroclor 1260. The analysis of individual PCB congeners made it possible to trace PCBs of Detroit River origin to the central and eastern basins of Lake Erie, and to estimate the contribution of the Detroit River to the PCB burden in sediments of these basins.     

Biological Monitoring of Organochlorine Contaminants in the St. Clair and Detroit Rivers Using Introduced Clams, Elliptio Complanatus

Introduced clams (in cages) were effective biomonitors in determining the distribution, biological availability, and source areas of a number of chlorinated organic contaminants in the St. Clair River-Detroit River corridor during 1982 and 1983. In the St. Clair River, hexachlorobenzene (HCB), octachlorostyrene (OCS), pentachlorobenzene (QCB), hexachlorobutadiene (HCBD), 2,3,6-trichlorotoluene (TCT), and alpha-BHC were most frequently identified in tissues after 3 weeks’ exposure. When compared to other locations in the St. Clair and Detroit rivers, significantly (p<0.05) higher levels of QCB, HCB, OCS, and HCBD were found in clams exposed along the Sarnia to Corunna, Ontario, shoreline. Elevated concentrations of HCB and OCS were also detected in water samples from this section of the river. TCT was found in clams from most locations, at low levels, with no obvious source area. Low levels of polychlorinated biphenyls (PCBs) were restricted to clams from the Sarnia area. In the Detroit River, PCBs, HCB, and OCS were most frequently detected in clams. PCB levels were significantly (p<0.05) higher along the Michigan shore and the highest concentrations were found in the Rouge River area. PCBs were also detected in some water samples from urbanized areas of the river. HCB and OCS were found at near-detection levels in clams from most stations. Contaminant levels in clams from around Fighting Island were low or non-detectable, indicating an absence of biologically available organochlorine contaminants in this area of the river. In the St. Clair River, p,p-DDE was only detected in the Sarnia area, whereas it was found in clams from both sides of the Detroit River, also at low levels. Aldrin, chlordane, and DDT were only sporadically detected in both rivers.     

Temporal and spatial trends of organochlorines and mercury in fishes from the St. Clair River/Lake St. Clair corridor,Canada

The temporal and spatial relationships of a suite of organochlorine contaminants and mercury were examined in various fish species of the St. Clair River/Lake St. Clair corridor, Canada, in order to evaluate the effectiveness of remediation efforts and to assess the risk to human and wildlife fish consumers. In Lake St. Clair, fish tissue concentrations of mercury, polychlorinated biphenyls (PCBs), octachlorostyrene (OCS), hexachlorobenzene (HCB), and dichlorodiphenyltrichloroethane (DDT) decreased consistently from the 1970s until the 1980s and 1990s, after which the rate of contaminant decline slowed or concentrations stabilized. This trend was consistent in up to 13 species (both young-of-the-year and adult fishes) comprising different trophic positions and dietary habits, suggesting that the changes were reflective of ambient conditions rather than food web processes. Elevated concentrations of mercury, PCBs, OCS, HCB, and DDT were detected in St. Clair River young-of-the-year spottail shiner compared with fish from Lake Huron, indicating that non-atmospheric inputs of these chemicals, likely originating from sediment, remain in the St. Clair River. Current concentrations of mercury and PCBs, and mercury, PCBs, and DDT remain of concern to human and wildlife fish consumers, respectively. Given that contaminant decreases have generally stabilized in fish, we suggest that further natural recovery of contaminants in St. Clair corridor fishes will be slow since contaminants will likely continue to be influenced by sediment levels.     

Geochemistry of the Detroit River Sediments

The objectives of the investigation were to provide information on the concentration and distribution of metals in bottom sediments of the Detroit River and to study the association of metals with various sediment components. Concentrations of major elements (Si, Al, Ca, Mg, Na, K, Fe, Mn, and P) and metals (Co, Cr, Cu, Ni, Pb, and Zn), particle size distribution, and mineralogical composition were determined in 20 surficial sediment samples collected along the Detroit River in 1983. Significantly higher concentrations of metals in the Detroit River sediments than those reported in Lake St. Clair and Lake Erie sediments indicated input from sources in the river's drainage basin. Poor relationships exist between the metals and organic C and the metals and the silt-clay size fraction (< 63 μm). The association of metals with sediment particles was investigated by a separation of sediment into seven size fractions ranging from < 13 to > 63 μm. Zn, Ni, Cr, and Pb were accumulated in the < 13 μm size fraction. However, Cu and Cr concentrations were highest in the < 13 and 48 to 63 μm fractions. Quartz, feldspars, and calcite were found in the > 63 μm fraction. Dolomite, feldspars, and quartz were in the 13 to 63 μm fraction and the clay minerals illite, chlorite, and kaolinite were in the < 13 μm fraction. Concentrations and relationships among major elements reflected the mineralogical composition of different particle size fractions.     

Relationships between wind-driven and hydraulic flow in Lake St. Clair and the St. Clair River Delta

A three-dimensional hydrodynamic forecasting model of the Great Lakes Huron-Erie Corridor is used to investigate mixing and the relationship between hydraulic and wind-induced currents in a shallow lake system in which lake inflows come through several channels of a river delta. The hydrodynamics in Lake St. Clair and the channels of the St. Clair River Delta are evaluated for (1) a one-year simulation from 1985 including water age calculation, (2) 8 different wind direction scenarios, and (3) a storm event. Observations and model simulations show distinct regions in the lake in which currents are forced by either hydraulic flow from the river system or from wind stress over the lake. However, during severe storm events, these regions are found to shift or even disappear due to changes in the delta channel inputs into the lake. These changes underscore the need for realistic, unsteady river flow boundary conditions at interfaces between a shallow lake and river delta. Steady inflow conditions will not allow for potential shifting of these current zones, and will also fail to resolve flow retardation or reversals during storm events.     

Preliminary Assessment of Contaminants in Soft Sediments of the Detroit River

Soft sediments from the Detroit River were analyzed for the USEPA priority pollutants to generally characterize contaminant distribution. Forty-three were detected. Highest heavy metal concentrations were found in the Trenton Channel and immediately downstream of Grosse Ile. They ranged from an area mean (N = 2) of 0.19 mg/kg mercury to 338.7 mg/kg zinc (dry weight). Polynuclear aromatic hydrocarbons ranged from 0.1 mg/kg to 38.8 mg/kg (mean, N = 2) with the highest levels near Grosse Ile. PCBs ranged from 0.015 mg/kg to 1.7 mg/kg (mean, N = 2). Organochlorine pesticides were not detected except for a trace of heptachlor in one sample. Sediment contamination in the Detroit River is widespread with higher concentrations on the U.S. side downstream of the Rouge River and in the Trenton Channel. The significance of these in-place pollutants to biota and as a source to Lake Erie is still unknown.     

Temporal Effects of St. Clair River Dredging on Lakes St. Clair and Erie Water Levels and Connecting Channel Flow

A Great Lakes hydrologic response model was used to study the temporal effects of St. Clair River dredging on Lakes St. Clair and Erie water levels and connecting channel flows. The dredging has had a significant effect on Great Lakes water levels since the mid-1980s. Uncompensated dredging permanently lowers the water levels of Lakes Michigan and Huron and causes a transitory rise in the water levels of Lakes St. Clair and Erie. Two hypothetical dredging projects, each equivalent to a 10 cm lowering of Lakes Michigan and Huron, were investigated. This lowering is approximately half the effect of the 7.6 and 8.2 meter dredging projects. In the first case the dredging was assumed to occur over a single year while in the second it was spread over a 2-year period. The dredging resulted in a maximum rise of 6 cm in the downstream levels of Lakes St. Clair and Erie. The corresponding increase in connecting channel flows was about 150 m³s^?1. The effects were found to decrease over a 10-year period with a half-life of approximately 3 years. The maximum effects on Lake Erie lagged Lake St. Clair by about 1 year.     

Formation of the St. Clair River Delta in the Laurentian Great Lakes System

The St. Clair River delta, the largest in the Laurentian Great Lakes system, is located in Lake St. Clair at the mouth of the St. Clair River. It straddles the border between the state of Michigan in the USA and the province of Ontario in Canada. The current study aims at characterizing and explaining the formation and evolution of the distributary channels in the St. Clair River delta and the delta itself. The delta is classified as a river dominated feature with classic “bird's foot” structure similar to the Mississippi delta model. The delta is composed of two surfaces. The older surface at the delta apex was deposited at a higher lake level some 3,500 to 5,000 years B.P. The current delta started to form following a drop in lake level some 3,500 years B.P. and continues to build to the present day. The delta consists of seven active deep channels averaging 11 m in depth entering a lake with a mean depth of 3 m with much shallower water in the delta front region. The channels are stable and are actively eroding into the sediments of the lake creating both sub-aqueous and sub-aerial levee deposits with crevasses. The interdistributary bays are being filled with sandy deposits created by wave energy and by crevasse deposits. At the erosional front of each distributary a narrow erosional notch “leading channel” is being formed which appears to control the direction of lakeward erosion of each deep distributary channel. The emplacement of the delta body in the shallow receiving water body has been termed “burrowing” delta formation and is the mechanism controlling the formation of this sedimentary feature.     

Effect of Channel Changes in the St. Clair River During the Present Century

Periodic man-made changes in the outlet of Lake Huron through the St. Clair River date back to the middle of the last century. These artificial channel changes have been well documented during the present century. They consist of dredging for commercial gravel removal in the upper river during 1908–25 and uncompensated navigation improvements for the 7.6-m (25-ft) and 8.2-m (27-ft) projects completed in 1933 and 1962, respectively. The total effect of these changes on the levels of Lakes Michigan and Huron (hydraulically one lake) and on the upper St. Clair River profile was determined with dynamic flow models. The ultimate effect of the above dredging was a permanent lowering of the Lake Michigan-Huron levels 0.27 m (0.89 ft), which represents a tremendous loss of freshwater resource [32 km³ (7.7 mi³)].     

Assessment of larval fish assemblages and nursery habitat in the St. Clair River delta

The St. Clair River delta, part of the St. Clair-Detroit River System (SCDRS), is the most fished coastal wetland area in the Laurentian Great Lakes and provides nursery habitat for a variety of fish species; however, few large-scale surveys of larval fish have been performed within the delta since the 1980s. Larval fish, zooplankton, and aquatic plants were sampled at 20 sites from May through July in 2010 and 2011 to characterize shallow channel and backwater delta habitats used by fish. The larval fish assemblage was sampled using active and passive gears (conical nets and light traps) and was dominated by Cyprinidae, Catostomidae, and Gobiidae. The microzooplankton assemblage was composed of rotifers, copepod nauplii, and Dreissena spp. veligers, while the macrozooplankton assemblage was composed of mostly cyclopoids and harpacticoids in May and cladocerans later in the season. Scirpus spp. dominated the plant assemblage in June and was replaced by Chara spp. in July. Seasonal compositional shifts were evident for larval fish, zooplankton, and plant assemblages, and greater densities of microzooplankton and cladocerans were typically found in backwater areas. Assemblage compositions were comparable to those in historical surveys but invasive Gobiidae and Dreissena spp. veligers now represent substantial proportions of the larval fish and zooplankton assemblages, respectively. Due to the high connectivity and advective nature of the SCDRS, understanding the larval fish assemblage dynamics of the delta can help inform estimates of system productivity.     

Spatial Distributions and Temporal Trends in Sediment Contamination in Lake St. Clair

The sediments of Lake St. Clair were surveyed in 2001 for a range of compound classes including metals (such as total mercury and lead), polychlorinated biphenyls, polychlorinated dibenzo-p-dioxins and dibenzofurans, organochlorine pesticides, polycyclic aromatic hydrocarbons, and short- and medium- chain chlorinated paraffins, in order to evaluate the spatial distribution and temporal trends of contamination. Concentrations of contaminants were generally low compared to the lower Great Lakes (Erie and Ontario), and were typically below the Canadian Sediment Quality Probable Effect Level (PEL) guidelines. The only exceptions were for mercury and DDE, where concentrations exceeded their respective PEL at one of the thirty-four sites sampled. With the exception of mercury, it was difficult to interpret spatial trends in contaminant concentrations due to these low levels, although relatively elevated concentrations of several contaminants were found in L’Anse Creuse Bay and at the outflow of the Thames River. In the case of mercury, historically-contaminated sediments in the St. Clair River associated with chlor-alkali production appeared to contribute to loadings to Lake St. Clair. There have been substantial reductions in sediment contamination in Lake St. Clair over the past three decades, as determined through sediment core profiles as well as through comparison of current data to those from historical surveys conducted in the early 1970s. These results indicate that management actions to reduce contaminant loadings to Lake St. Clair have been generally successful.     

Horizontal Distribution and Density of Yeasts and Filamentous Fungi in Lake St. Clair Water

Yeasts and filamentous fungi were collected from 67 stations throughout Lake St. Clair. Organisms from water samples were isolated by filtration through membrane filters and cultured on a selective agar medium. Representative colonies of the predominant types of yeasts and filamentous fungi and certain bacteria were identified. Yeasts and yeast-like fungi, including Rhodotorula, Candida, Cryptococcus, and Aureobasidium species, were widely distributed in densities of 1 to 1,000 colony forming units per 100 mL. The presence of these quantities and types of yeasts in the water may be related to nutrients of municipal and industrial inputs into these waters.     

Distribution and Abundance of Zooplankton in the U.S. Waters of Lake St. Clair, 1973

Zooplankton were obtained in the U.S. waters of Lake St. Clair at 28 stations sampled monthly from July through September 1973. Distribution and abundance of zooplankton were compared with physicochemical data collected concurrently and with previous studies on Lake St. Clair zooplankton.Sixty five species of Rotifera were recorded. Brachionus angularis, Conochilus unicornis and Synchaeta stylata were the three most abundant species. Total rotifers, averaging 47.1 individuals per liter over the study period, were about 30 times more abundant than the micro-crustaceans. The Cladocera were represented by 28 species, while five species of cyclopoids, seven calanoids and four harpacticoids were recorded from the Copepoda. Bosmina longirostris was the predominant micro-crustacean.Spatial distribution of zooplankton was hypothesized to be primarily dependent on current patterns generated by prevailing winds. The Canadian portion of the lake has a persistent eddy structure which apparently allows build-up of nutrient levels encouraging high zooplankton biomass. The U.S. side, however, experiences more rapid flow-through of St. Clair River water which accounts for lower zooplankton abundance. Despite the fast flushing rate on the U.S. side, a localized patch of high zooplankton density and a community structure indicative of eutrophic situations was consistently observed off the Clinton River Cutoff Canal. This is presumably due to nutrient loading from the Clinton River watershed.     

Occurrence of the Odor Compounds, 2-Methylisoborneol and Geosmin in Eastern Lake Ontario and the Upper St. Lawrence River

Unpleasant tastes and odors in drinking water from the upper St. Lawrence River were investigated in the fall of 1996 and 1997 as the result of increasing taste and odor events in recent years. Taste and odor events resulted in widespread public reaction to the earthy/musty tasting water produced and a need for accurate information to assist water treatment efforts. The presence of geosmin, (trans, trans-1,10-dimethyl-9-decalol) and 2-methylisoborneol (MIB2, 1,2,7,7-tetramethyl-exobicyclo[2.2.1]heptan-2-ol), the most common causes worldwide of earthy and musty odors in water, were investigated in eastern Lake Ontario and the upper St. Lawrence River. Gas chromatography-mass spectrometry was used for quantitation and confirmation of the presence of these compounds in water samples. Both geosmin and MIB2 were detected in river water samples at concentrations ranging from 5 to 20 ng/L and 2 to 25 ng/L, respectively. The compounds were also detected in southern coastal lake water which serves as a source to the St. Lawrence River, but not in mid-lake samples. Similar levels of geosmin and MIB2 were detected in untreated Lake St. Lawrence water, in samples taken following pre-chlorination for zebra mussel control, and in samples taken following conventional treatment at a water filtration plant.