Distribution of Major Elements and Metals in Sediment Cores from the Western Basin of Lake Ontario

An investigation was made of the relationship between the changes in metal concentrations in sediments with the distance from the Niagara River mouth and the chemical and physical characteristics of the sediments. Sediment cores were obtained at nine sampling stations in the western basin of Lake Ontario. In addition, surface sediment was collected at three stations on the Niagara Bar. Minerals present at all stations were silica, feldspars, illite/muscovite, chlorite, kaolinite, and calcite. Dolomite was found at some sampling stations as grains of 2 to 63 μm size. Significantly elevated concentrations of calcite (up to 20%) in the surface sediment (about 0 to 10 cm) at four sampling stations in the western basin and in the entire 25-cm sediment column at the Niagara River mouth indicated increased input of this mineral into Lake Ontario during the past 100 years. Furthermore, sediment concentration profiles of Zn, Pb, Cr, Cu, Ni, and especially Hg at all sampling stations indicated major transport of metals associated with the clay- and silt-size particles from the Niagara River into Lake Ontario (especially north-north-east and east of the river mouth). A significant decrease in Hg loading from the Niagara River during the past 20 years was also observed. Although smaller in magnitude, a similar decrease was found for Pb, Zn, Cr, Ni, and Cu loading. However, elevated Hg concentrations (up to 7 μg g～^l above background values) existed in the surface 10 cm of sediment at eight sampling stations.     

Fates of Organic Compounds from Niagara Falls Dumpsites in Lake Ontario

Sediment samples from the western portion of Lake Ontario were analyzed for chlorinated organic compounds using gas chromatography and gas chromatographic mass spectrometry. Both electron impact and negative chemical ionization mass spectrometry were employed. Many of the chlorinated compounds previously found to be leaking into the Niagara River from waste disposal sites in the city of Niagara Falls were identified in the sediments of Lake Ontario. In particular, two unique chlorofluorinated compounds were found in the lake's sediment, showing that stable compounds introduced into the Niagara River accumulate to detectable levels 100 km away in Lake Ontario. Chlorinated styrenes as well as several highly chlorinated poly cyclic aromatic hydrocarbons were also found. Their exact origin is uncertain at this time.     

Compartmental Distribution of Organochlorine Contaminants in the Niagara River and the Western Basin of Lake Ontario

Ten chlorobenzenes, hexachlorobutadiene, and PCBs were measured in Niagara River water and suspended solids, and in western Lake Ontario sediments and benthic fauna. High levels of these contaminants were found on all fractions of the river suspended solids, but the larger particles contained much higher concentrations than the smaller particles. A portion of the CBs, HCBD, and PCBs present in the lake sediments was available to benthic organisms. A trend toward greater bioaccumulation for compounds having higher octanol-water partition coefficients was observed at all trophic levels.     

Trace Organic Contaminants in the Detroit River

Concentrations of polychlorinated biphenyls (PCBs), polynuclear aromatic hydrocarbons (PNAs), chlorobenzenes (CBs), chlorophenols (CPs), and a number of other organochlorine compounds (OCs) have been determined in the surface microlayer, subsurface water, suspended solids, sediments, and in sediment pore water at 20 sampling stations in the Detroit River. The data are discussed in terms of contaminant sources, pathways, and sinks. Spatial trends within the river and relationships of contaminant groups within and between compartments are described. The results indicate a continuing input of all contaminant groups to the river from a variety of sources, particularly from sewage treatment plant effluents and several tributaries. The contaminant distributions and intercorrelations also indicate that major sources of PCBs, PNAs, OCs, and CBs are concentrated on the westerly river shore, while CPs enter the river mainly from the easterly shore.     

Grain Size and Mineralogy of Sediment Cores from Western Lake Huron

Grain size and mineralogical analyses along the lengths of 12 cores recovered from the Alpena and Manitoulin Basins, when combined with ages determined by C-14 dating of surficial and basal sediments, reveal an approximate sedimentary history of this part of Lake Huron. Reddish glaciolacustrine clays, essentially all 10 ?, crop out on the flanks of the sublacustrine basins and underlie gray post-glacial muds in the central basin regions. The post-glacial muds become more coarse in their upper portions where they are very fine silt. Detrital carbonates which comprise approximately 30% of older sediments are reduced in abundance by an order of magnitude in more recent deposits. We interpet these phenomena as recording lowered lake levels and reduced sedimentation rates since the Nipissing high stand which ended about 4,000 years ago.     

Organochlorine Insecticides and PCB in Surficial Sediments (1968) and Sediment Cores (1976) from Lake Ontario

Surficial sediments were collected in 1968 and core sediments in 1976 from Lake Ontario. These were analysed for organochlorine insecticides and PCB. Residues of organochlorine compounds were higher in the three Ontario depositional basins than in sediment in the non-depositional zones. PCB was present at the highest concentration, with mean levels of 57 ppb for the whole lake. Residues of PCB in the three basins exhibited only minimal differences.ΣDDT was the second most frequently found contaminant. Both parent DDT and its two metabolites were present in sediment, giving a mean residue of 42.8 ppb for the whole lake. Differences in residues for the three basins were again minimal. DDT was present in sediments estimated to be deposited between 1958 and 1976. HEOD was present in only 40% of sediments and the mean residue for the whole lake was 0.6 ppb. The Niagara basin contained mean residues (1.4 ppm) of HEOD much above the other basins.Chlordane was virtually absent from the lake in the sediments collected in 1968 but appeared in cores between 1964-1976. Endosulfan appeared in lake sediments as a spill of deck cargo at a location in the Niagara basin. This spill dispersed with the current down the south shore to deposit in the Rochester basin.     

Sedimentology and Geochemistry of Modern Sediments in the Kingston Basin of Lake Ontario

Accumulation of Recent fine sediment is limited to deep water areas in the Kingston basin and thicknesses of more than 50 cm are found only in the St. Lawrence trough; elsewhere, sands and silty sands are largely composed of reworked material. Local sources provide little input of fine sediment to the Kingston basin. Statistical relationships derived from geochemical analyses indicate several forms of association between heavy metals and organic carbon, sulphides, clays, hydrous Fe and Mn oxides, and carbonates. A comparison between Kingston and Niagara sediments shows that the combined effects of riverine and lacustrine erosion have resulted in a generally greater content of carbonates in the Niagara sediments. The content of Fe (which is partly influenced by redox potential) is highest, however, in sediment of the Kingston basin, where higher P values are also associated with an increased clay content. Differences in the concentrations of heavy metals in Lake Ontario, except for Hg, Co, Cu, and Zn, are largely explained by variations in silt and clay contents. Contaminant loadings from the Niagara River are largely responsible for the anomalously high concentrations of Hg and, to a lesser extent, Cu and Zn. Cobalt occurs at higher concentrations in the sediments of eastern Lake Ontario, where its presence is thought to reflect glacial dispersal patterns.     

History of Lake Ontario Contamination from the Niagara River by Sediment Radiodating and Chlorinated Hydrocarbon Analysis

Contamination of Lake Ontario by persistent organic compounds began with the development of the chemical industry along the Niagara River. These compounds are discharged to the river where they are scavenged from the water column by sedimenting particulates which in turn settle out in depositional areas of Lake Ontario. We have determined ²¹⁰Pb, ¹³⁷Cs, and chlorinated hydrocarbon profiles of sediment cores taken about 3 km from the mouth of the Niagara River. Age profiles of the sediments were constructed from the radionuclide measurements and used to determine historic trends of chlorinated hydrocarbon input to Lake Ontario. The historical record found in the sediments for chlorobenzenes, chlorotoluenes, hexachlorobutadiene, octachlorostyrene, mirex, and PCBs is in good agreement with known production and usage patterns of the chemicals. Pollution of Lake Ontario with chlorinated hydrocarbons from the Niagara River is still occurring, but the worst contamination of the lake occurred in the 1960s.     

Downflux of Sediment,Organic Matter,and Phosphorus in the Niagara River Area of Lake Ontario

Vertical arrays of sediment traps were installed near the mouth of the Niagara River and at nearshore and offshore sites. Surveys of temperature, turbidity, and conductivity were used to establish that the traps nearest the river mouth were under the river outflow plume. A single offshore array in 1980 indicated downfluxes of 1-2 g · m^?2 · d^?1 of dry matter in the mid-water column. These fluxes were similar to those of small lakes but much higher fluxes were found near the bottom of Lake Ontario. More extensive work in 1981 confirmed the presence of a near-bottom nepheloid layer and the effect it has on increasing downflux extimates. Sediment traps near shore and at the river mouth caught substantially more material at all depths than did traps at the offshore stations. Downfluxes of phosphorus and sediment were consistent with independent estimates of loading and retention.     

Tetrachloro-9H-Carbazole,a Previously Unrecognized Contaminant in Sediments of the Buffalo River

Three sediment samples taken from the Buffalo River, New York, have been analyzed for polychlorinated planar molecules similar in structure to the highly toxic 2,3,7,8-TCDD. Although no TCDD was found, residues of chlorinated dibenzofuran, fluorene, biphenylene, phenanthrene (anthracene), naphthalene, and 9H-carbazole were identified. l,3,6,8-tetrachloro-9H-carbazole was identified as the major chemical of this type in the sediments, and quantified at levels as high as 25 ng/g at one site.     

Sediment Oxygen Demand in the Central Basin of Lake Erie

Three separate procedures were used to estimate the sediment oxygen demand (SOD) in the central basin of Lake Erie and were compared with other estimates determined previously and with historical data. First, whole core incubations involved sealing sediment cores at 12°C to ensure no interaction between the overlying water and the atmosphere and monitoring continuously to define the linear disappearance of oxygen. Second, sediment plugs were placed inside flow-through reactors and the influent and effluent concentrations were monitored to obtain steady-state reaction rates. Third, an extensive data set for the central basin of Lake Erie was compiled for input into the diagenetic BRNS model, and the SOD was calculated assuming all primary redox reactions, but no secondary reactions. All three procedures produced estimates of SOD that were in reasonable agreement with each other. Whole core incubations yield an average SOD of 7.40 × 10⁻¹² moles/cm²/sec, the flow-through experiments had an average SOD of 4.04 × 10⁻¹² moles/cm²/sec, and the BRNS model predicts an SOD of 7.87 × 10⁻¹² moles/cm²/sec over the top 10 cm of sediment and appears to be calibrated reasonably well to the conditions of the central basin of Lake Erie. These values compare reasonably well with the 8.29 × 10⁻¹² moles/cm²/sec obtained from diffusion modeling of oxygen profiles (Matisoff and Neeson 2005). In contrast, values reported from the 1960s to 1980s ranged from 10.5–32.1 × 10⁻¹² moles/cm²/sec suggesting that the SOD of the central basin has decreased over the last 35 years, presumably, in response to the decrease in phosphorus loadings to Lake Erie. However, since hypoxia in the hypolimnion persists these results suggest that improvement in hypolimnetic oxygen concentrations may lag decreases in loadings or that the hypolimnion in the central basin of Lake Erie is simply too thin to avoid summer hypoxia during most years.     

The Fate of Pentachlorophenol in the Bay of Quinte,Lake Ontario

Unfiltered water, surface film, sediment, and biota samples were collected from the Bay of Quinte between May and September 1978 and analyzed for chlorophenols (CPs). Sectioned sediment cores were dated using ²¹⁰Pb and ¹³⁷Cs analyses. Pentachlorophenol (PCP) was found at high concentrations adjacent to a point source and was detected in all compartments examined throughout the bay (a bioaccumulation factor of 10⁴ was observed for PCP in fish). The ratio of 2,3,4,6- and 2,3,5,6-tetrachlorophenols (TTCPs) to PCP increased with distance from the source in the water column and surface film. Photochemical reduction was proposed to account for the phenomenon. CP concentrations in sectioned cores suggested that settling particles adsorb CPs in similar proportion to that observed in the water column and little further change occurs after burial.     

Recent Changes in the Near-Shore Phytoplankton of Lake Erie's Western Basin at Kingsville,Ontario

A weekly net phytoplankton monitoring programme begun in 1967 at the Union water treatment plant, Kingsville, Ontario, was expanded in 1976 to include weekly chemical analyses of western Lake Erie water samples. Data from the Union intake monitoring programme have been examined in light of the significant reductions, since 1971, in phosphorus loading from the Detroit River. Total phosphorus concentrations in the “raw water” declined to an average of 30-35 μg P/L during 1977-78 from a pre-P control average of 63 μg P/L during 1967-70. Average annual net phytoplankton density during the pre-P control years averaged about 5000 Areal Standard Units per mL (A.S.U./mL), decreased steadily between 1971 and 1976 to a low of 2900 A.S.U./mL, but then increased again to 4490 A.S.U./mL by 1978. The recent increase was attributed almost entirely to massive mid-summer development of Fragilaria crotonensis. Winter densities of net phytoplankton during 1977 and 1978 were the lowest on record for the 12-year period. Similarly, average densities of green and blue-green algae showed a pre-P control density regime which was clearly higher than the post 1971 densities. Annual average diatom density was negatively correlated with annual average lake levels over the 12-year period and recent anomalous increases in Fragilaria may have been related to the observed drop in lake level which influenced turbulence and resuspension of this diatom.     

Anthropogenic,Polyhalogenated, Organic Compounds in Sedentary Fish from Lake Huron and Lake Superior Tributaries and Embayments

Composite samples of fish taken from some of the major tributaries and embayments of Lake Superior and Lake Huron were analyzed for halogenated xenobiotics with the objective of detecting potential environmental problem areas, point source discharges of toxic materials, and previously unrecognized pollutants. The analyses were done by gas chromatographic, methane enhanced, negative ion, mass spectrometry. A variety of halogen-containing organic compounds and pesticides were identified. The highest concentration and variety of compounds were found in the fish from the highly industrialized Saginaw Bay drainage basin; fish from Lake Superior tributaries showed much lower concentrations.     

Sediment Trap Studies in Lake Michigan: Resuspension and Chemical Fluxes in the Southern Basin

The results of 4 years (1977–80) of sediment trap sample collection in the southeastern region of Lake Michigan are summarized and compared with water column and sediment characteristics. Mass flux data indicate strong seasonal patterns, with maximum fluxes recorded during the unstratified period. The large amount of winter resuspension is a mechanism which provides an intimate coupling of recent sediments and the water column. Also these trap study results indicate that there is a near-bottom (10-m-thick) benthic nepheloid layer whose chemical composition approaches that of deep water (fine grain) sediments. The amount of resuspended NaOH extractable phosphorus injected into the euphotic zone is estimated as approximately equal to the load of new phosphorus entering southern Lake Michigan. The role of resuspension in the cycling of organic carbon and contaminants associated with it appears to be important.     

Sedimentology and Geochemistry of Recent Sediments off the Mouth of the Niagara River,Lake Ontario

Sediment thickness and bathymetric characteristics were derived from echo sounding, side scan sonar, and shallow seismic reflection recordings. Sediment samples were analyzed for particle size, major and trace elements, and for benthic organisms. The Niagara Bar has been separated into Inner and Outer Bar deposits and it is proposed that the Outer Bar was formed during an earlier, lower stage of Lake Ontario. Both deposits appear to be largely derived from reworked, local, shoreline materials. Trace element analyses indicate that the surficial sediments (prior to the 1972 Great Lakes Water Quality Agreement) were moderately enriched in Cd, Cr, Cu, Pb, and Zn, and greatly enriched in Hg. Normalized distributions of trace elements in the bar sediments show the presence of distinct dispersal patterns. These dispersals indicate that some of the suspended load passes out of the main outflow channel, across the bar, and toward west and north northwest directions. Particle-size and geochemical characteristics of the off-shore sediments indicate that they differ significantly from marginal facies and imply that local variations in the forms and type of peripheral inputs to the lake have little influence on deep basin deposits.     

Evaluation of adult and offspring thiamine deficiency in salmonine species from Lake Ontario

Thiamine Deficiency Complex (TDC) is an ongoing problem impacting salmonine health in various waterbodies, including Lake Ontario. The prevalence of TDC has been variable and explanations for differences are limited. In the current study, thiamine concentrations were measured in eggs, liver tissue, and muscle tissue sampled from brown trout (Salmo trutta), Chinook salmon (Oncorhynchus tshawytscha), coho salmon (O. kisutch), lake trout (Salvelinus namaycush), and steelhead trout (O. mykiss) that were collected from Lake Ontario and its surrounding tributaries. The occurrence of TDC was measured for each species based on TDC-induced offspring mortality rates under laboratory conditions. TDC-induced offspring mortality was observed for all species except brown trout. For affected species, egg free thiamine (Th) was consistently low compared to lake trout collected from Lake Superior that are considered thiamine replete. In addition, species with the lowest percentages of Th in their eggs were the most susceptible to TDC, suggesting that limited thiamine reserves in the form of Th may cause TDC-induced offspring mortality. Lastly, our results show that egg thiamine concentrations have yearly variation and increased for all species throughout the study. Reasons for such variation are undetermined; but, if egg thiamine concentrations continue to increase, the impacts of TDC on these salmonine species may lessen. Future monitoring is needed for determining if thiamine concentrations are increasing and the potential impacts that may have on the entire Lake Ontario fishery.     

Distribution of Hydrocarbons and Chlorinated Hydrocarbons in Various Phases of the Detroit River

Concentrations of several chlorohydrocarbons, polychlorinated biphenyls, and polynuclear aromatic hydrocarbons in the Detroit River were measured. For purposes of this study, the river ecosystem was divided into six phases or compartments: sediments, pore water in the sediments, suspended solids, subsurface water, surface microlayer, and air. Significant amounts of the above mentioned compounds occur in all of these compartments except air (for which our detection was relatively insensitive). The sediments contained over 99% of the chlorinated compounds. The polynuclear aromatic hydrocarbons were distributed between the subsurface water and the sediments.     

Geochemical Availability of Some Trace and Major Elements in Surficial Sediments of the Detroit River and Western Lake Erie

Surficial bottom sediment from twenty locations in the Detroit River and western Lake Erie has been analyzed for potentially available Ba, Be, Cd, Cr, Co, Cu, Pb, Mn, Mo, Ni, P, V, and Zn. The highest concentrations of all but one of these elements were found at a station at the river-lake interface very close to a dumping ground. The environmental mobility of Cd, Zn, Co, Pb, Cr, Ni, and P is controlled by hydrous iron oxides, whereas V and Mo is controlled by aluminosilicates. The iron oxide phase exhibits a very high sorption capacity for phosphorus (molar adsorption coefficient = .361) which is attributed to the high loadings of Fe and P at the confluence of the Rouge and Detroit rivers as well as continuous inputs along the length of the Detroit River. It is suggested that phosphorus controls instituted in the 1970s will probably result in the iron oxide phase having greater sorption capacity for toxic metals because of the decreasing competition from phosphorus for binding sites.     

Environmental Impact of Two,Adjacent, Hazardous Waste Disposal Sites in the Niagara River Watershed

Sediment core samples were taken from the Niagara River at locations adjacent to the Love Canal and the 102nd Street dumps, two hazardous waste disposal sites in the City of Niagara Falls, New York. The samples were analyzed by capillary gas chromatographic mass spectrometry, and a variety of halogenated organic compounds (including chlorobenzene, -toluene, -naphthalene, -benzyl, and -norbornane derivatives) were identified and quantified. Based on the qualitative and quantitative data obtained, the sources of these pollutants were identified, and the relative migration of chemicals from the two dumps to the Niagara River was established. The impact on the river is localized to the immediate vicinity of the outfall of the sewer draining the Love Canal neighborhood. Remedial action could be as easy as removing 20 truckloads of contaminated sediment from the river.