Chlorinated Organic Contaminants in Water and Suspended Sediments of the Lower Niagara River

Suspended sediment and raw water samples have been collected and analyzed for organochlorines and PCBs from a fixed location in the lower Niagara River at Niagara-on-the-Lake approximately weekly since 1979. Eight of the 19 organochlorine compounds measured were detected in more than 50% of the water samples analyzed, while 11 of the 19 compounds were detected in more than 50% of the suspended sediments collected at Niagara-on-the-Lake. Of the 10 chlorobenzene isomers measured, the one with the greatest usage (1, 4-dichloro) occurs in largest concentrations in the suspended sediments at Niagara-on-the-Lake. Other chlorobenzene isomers commonly occurring in suspended sediments are 1, 2 and 1, 3 dichloro, 1, 2, 4-trichloro, 1,2, 3, 4-tetrachloro, pentachloro, and hexachloro. All isomers of chlorobenzene occurred in more than 70% of the suspended sediment samples collected. Total loadings to Lake Ontario calculated from these data indicate that PCB loadings are about twice as high as previously reported, while mirex and total DDT hate decreased slightly. Although concentrations of contaminants in suspended sediments are usually higher than those measured in water samples, they are responsible for only about 40% of the total loadings for PCBs, DDT, and HCB, and significantly less for other organochlorine contaminants. Therefore, the data indicate that, to estimate total contaminant loadings, the water fraction must be sampled. Lake Erie is not the major source of such organic contaminants as PCBs and chlorobenzenes because contaminant levels in Lake Erie bottom sediments are 10 times lower for PCBs and 20 times lower for chlorobenzenes than in Niagara-on-the-Lake suspended sediments.     

Organochlorine Contaminants of Wintering Ducks Foraging on Detroit River Sediments

Organochlorine analysis was performed on carcasses of 13 diving ducks from a 1981 wintering population that foraged on contaminated sediments in the lower Detroit River. Mean total PCB concentrations were 10 mg/kg for seven lesser scaups (Aythya affinis), 11 mg/kg for three greater scaups (A. marila), and 7.6 mg/kg for three goldeneyes (Bucephala clangula). Highest mean levels of other residues were measured for hexachlorobenzene (1.7 mg/kg) in goldeneyes, and transnonachlor (0.33 mg/kg) and 4,4’-DDE (1.3 mg/kg) in greater scaup. Quantitative analysis of 72 PCB congeners also was applied to water, seston, sediment, benthie oligochaetes, and carp from the same site. Principal congeners in most of the samples included some of the more toxic and persistent PCBs. Results of a multivariate analysis indicated that ratios of more conservative to less conservative PCBs did not vary significantly among ducks (α = .05), but differed from those in carp, oligochaetes, and sediment. For the February through March period of fat mobilization, concentrations of total PCB in lipid were inversely correlated with percent lipid (r = 0.76) in ducks. The percentage of conservative PCBs increased slightly. The distribution and partitioning of organochlorines, including toxic PCB congeners, varied considerably within this water column-sediment-fauna ecosystem. Estimates of toxic exposure based on total PCB values may be unreliable.     

Studies of Trace Contaminants,Nutrients, and Bacteria Levels in the Niagara River

Sediment and water quality of the Niagara River were investigated during 1979 and 1980 to determine spatial and temporal differences in the levels of trace contaminants (heavy metals, phenolics, PCBs, and organochlorine pesticides) as well as nutrients and bacteria. Data from these studies as well as recent biomonitoring studies indicate that the Niagara River continues to be a source of such contaminants as PCBs, BHCs, mirex, and heavy metals to Lake Ontario. The major source of the contaminants is the highly industrialized and urbanized Tonawanda Channel area in the upper section of the river. Although a substantial improvement in phenolics levels was noted in the river since earlier surveys in 1971, bacterial and phosphorus levels show no significant changes, particularly near the U.S. mainland shore of the Tonawanda Channel and near the Buffalo River mouth.     

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.     

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.     

Lake Ontario Sediments as Indicators of the Niagara River as a Primary Source of Contaminants

Past studies on the distribution of mercury, PCB, and mirex in the surficial bottom sediments of Lake Ontario have clearly indicated the significance of the Niagara River as a major source of contaminants to the lake. The distributions have further indicated the net transport of sediment-bound materials in the lake which has assisted in the general understanding of the occurrence of contaminants at many trophic levels in the Lake Ontario ecosystem. Mean concentrations of a number of elements in suspended solids centrifuged from the Niagara River in 1974 further indicated that the river is also a major source for chromium, cadmium, vanadium, and arsenic, and a lesser though significant source of lead, copper, and nickel.     

Volatile Halocarbon Contaminants in the Niagara River and in Lake Ontario

Water samples from 95 stations in Lake Ontario and 16 stations in the lower Niagara River Were analyzed for volatile halocarbons and carbon disulfide. The following contaminants were observed at many stations with their lake-wide means and standard deviations: trichloro-fluoromethane (Freon 11), 249 ± 882 ng · L^?1; methylene chloride, 572 ± 1,826 ng · L^?1; chloroform, 18 ± 92 ng · L^?1; bromodichloromethane, 3 ± 9 ng · L^?1; and tetrachloroethylene, 9 ± 65 ng · L^?1. Eleven other compounds, including carbon disulfide, 1, 1–dichloroethylene, 1,1,1–trichloroethane, carbon tetra-chloride, and tetrachloroethylene were observed at trace levels or absent at most stations. Six compounds were observed in virtually all Niagara River samples and were traceable into the lake. As apparent from the large relative standard deviations for the above, contaminant concentrations varied strongly between stations, indicating areas of contaminant sources. Both industrialized and urban areas, such as Toronto, Hamilton, and the Niagara River, as well as comparatively small tributaries, such as Twelve Mile, Eighteen Mile, and Oak Orchard Creeks, Black River, and the Welland Canal, appear to be sources for several of the observed contaminants.     

Chlorinated Hydrocarbons in the Surface Microlayer of the Niagara River

Concentrations of 18 chlorinated hydrocarbons were determined in the surface microlayer, subsurface water, and suspended solids at five stations along the length of the Niagara River in July 1981. The concentration of heptachlor epoxide in the unfiltered surface microlayer was greater than that in unfiltered subsurface water at all five stations by factors of 138 to 225; alpha-endosulfan and “total PCB” were similarly enriched in the surface microlayer at two stations each, by factors of up to 203 and 32, respectively. In addition, mass balances for the 18 compounds in the three “compartments” sampled showed that (i) at three stations there was more heptachlor epoxide in the unfiltered surface microlayer than associated with those suspended solids which were collected with a continuous flow separator from a depth of 1 to 2 m, and (ii) there was far more alpha- and gamma-BHC, dieldrin, and “total PCB” present in unfiltered subsurface water than associated with the suspended solids. This latter finding in particular necessitates a revision of earlier estimates of loading of at least some chlorinated hydrocarbons to Lake Ontario from the Niagara River, based solely on concentrations in the suspended solids fraction sampled with the same continuous flow separator.     

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.     

Distribution of Mercury,Trace Organics,and Other Heavy Metals in Detroit River Sediments

In 1980 the Ontario Ministry of the Environment carried out a surficial bottom sediment survey of the Detroit River. The survey was designed to update changes in sediment mercury levels from a 1970 study, and to determine the spatial distribution of trace organics and other heavy metals as a baseline for future investigations. The contamination of sediments along the Ontario shoreline of the river was localized near known inputs such as Little River, the West Windsor sewage treatment plant, Turkey Creek, and Riviere aux Canards. Almost the entire U.S. shoreline sediments exhibited elevated levels (above provincial dredging guidelines) of contaminants such as heavy metals and PCBs. Levels of one order of magnitude higher than those on the Canadian shore were prevalent along the U.S. shore. Mercury levels exhibited a substantial decline during the period 1970–1980. Increases in chromium, copper, lead, and zinc in the vicinity of the mouth of the Rouge River along the U.S. shoreline during the same period suggest both recent and continuing inputs from industrial and municipal sources.     

The Influence of the Niagara River on Contaminant Burdens of Lake Ontario Biota

Top predator and forage fish species, netplankton (> 153 μm), zooplankton, and benthic macroinvertebrates from Lake Erie and Lake Ontario were analyzed for whole body levels of trace metals and organic contaminants. Comparison of contaminant concentrations in similar aquatic food chains from both lakes indicated that levels of PCB, DDT, mirex, and mercury are significantly greater (P <0.05) in the biota of Lake Ontario. The Niagara River, the single largest tributary to Lake Ontario, was confirmed as a major source of organic contaminants and trace metals. Organic contaminants are adsorbed to the particulate load of the river and dispersed throughout Lake Ontario by the circulating currents. There was no significant regional difference (P<0.05) in the degree of contaminant accumulation by the pelagic food chain of Lake Ontario. Conversely, both inorganic and organic contaminant levels in the demersal amphipod, Pontoporeia affinis, were significantly different (P<0.05) between the eastern and western basins of Lake Ontario. The uptake and concentration of contaminants at the sediment-water interface is suggested as a possible mechanism to explain this observed difference.     

Tracking River Plumes with Volatile Halocarbon Contaminants: The Niagara River—Lake Ontario Example

The concentrations of six predominant volatile halocarbon contaminants CCl₄, total and industrial CHCl₃, CHBrCl₂, CH₂Cl₂, CFCl₃, and C₂Cl₄ in epi- and hypolimnetic lake waters are used to demonstrate tributary plumes and nearshore currents on the Lake Ontario/Niagara River example. The relative speed and sensitivity of the analysis for volatile halocarbons provides for a synoptic view of the major currents at the time of sampling. For example, the individual distributions of several contaminants indicate the existence of a Niagara River surface water plume in northerly direction for approximately 8 km into the lake. In contrast, the predominantly east-west isostats of the contaminant concentrations in the hypolimnetic water indicate little direct influence by the Niagara River and show the existence of other contaminant sources in these areas.     

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.     

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.     

Organochlorine Contaminant Residues in Spottail Shiners (Notropis Hudsonius) from the Niagara River

Collections of young-of-the-year spottail shiners (Notropis hudsonius) were used to determine spatial distribution (1981) of organochlorine residues and their temporal trends in the Niagara River. PCB and mirex residues in spottail shiners ranged from 164 to 573 ng/g and ND-18 ng/g, respectively. PCB and mirex residues exceeded the aquatic life objectives (Great Lakes Water Quality Agreement of 1978) at all sites except Frenchman's Creek, where mirex was non-detectable. Residues for heptachlor, heptachlor epoxide, aldrin, endrin, chlordane, thiodan, dieldrin, BHC, and DDT were low or non-detectable in Niagara River spottail shiners. Chlorinated benzene and octachlorostyrene residues were also present in most Niagara River spottail shiner samples analyzed. Dioxin (2,3,7,8- TCDD) was present in all Niagara River spottail shiner collections and ranged from 4 to 60 pg/g. The highest dioxin residues were found at Cayuga Creek, N. Y. PCB residues have declined significantly since 1975 in Niagara-on-the-Lake spottail shiners; however, residues increased in 1980 and 1981, although they were below the 1975 concentrations. Mirex residues in spottail shiners from Niagara-on-the-Lake have also declined significantly since 1978, suggesting reduced mirex inputs to Lake Ontario.     

An Introduction to the Niagara River/Lake Ontario Pollution Problem

Considerable public concern about contamination of Lake Ontario has been generated by suspected leakage of toxic chemicals from a multitude of hazardous waste dumps and by the several major chemical outfalls along the United States side of the upstream Niagara River. A cooperative effort by Canadian and United States research scientists has begun to provide the basic information which may be required to enforce controls of loadings of toxic chemicals to this river/lake system. A holistic ecosystem approach, involving analyses of many contaminants in a variety of aquatic media, is necessary to properly manage the problem and assist in setting priorities.     

Identification and Determination of Trace Organic Substances in Sediment Cores from the Western Basin of Lake Ontario

A study was carried out to identify and to determine organic chemicals in sediment from the western basin of Lake Ontario, particularly in the fine-grained sediments near the mouth of the Niagara River. Sediment cores were obtained at five sampling stations, and samples were extracted by the base/neutral and acid method designed by US Environmental Protection Agency for extraction of water samples. The identification of organic compounds in the base/neutral sediment extract was carried out by GC/MS techniques. The major classes of investigated contaminants were aromatics, polynuclear aromatics, alkylated polynuclear aromatics, alkylated benzenes, phthalates, methyl esters of fatty acids, olefins, aldehydes, chlorobenzenes, and benzoates. In addition, all sediment samples were analysed for 2,3,7,8-tetrachloro dibenzo-p-dioxin. In the surface sediments, the abundance of contaminants decreased with the distance from the Niagara River mouth toward the north-west. However, high concentrations of most of the detected organics were present in sediment at the station located east of the River mouth.     

Distribution of Contaminants in Clams and Sediments from the Huron-Erie Corridor. I–PCBs and Octachlorostyrene

Samples of surficial sediments and the clam species Lampsilis radiata siliquoidea were collected from 102 sites covering all of Lake St. Clair and the Canadian shoreline of the St. Clair and Detroit rivers. The distribution patterns of both octachlorostyrene (OCS) and PCBs were mapped throughout this area. The mean level of PCBs in sediments of 3.9 μg kg^?1 (Aroclor 1254) was much lower than values for “total PCBs” reported in studies carried out in the early 1970s. This reduction does not appear to reflect a real decrease in PCB levels in the environment, but rather changes that have been made in sampling procedures and analytical techniques. Highest levels of PCBs in both sample types were found along the western shore of Lake St. Clair. Mean levels of OCS in whole clam tissue and surficial sediment (0–10 cm) were 43.0 and 5.1 μg kg^?1, respectively. The distribution pattern of OCS in the Huron-Erie corridor in both clams and sediments suggests that the primary source is in the St. Clair River. The mean chemical concentration factor was 59 for OCS, indicating considerable bioaccumulation in the biota of Huron-Erie corridor.     

Organochlorine Pesticides,PBBs, And Mercury in Round Whitefish Fillets from Saginaw Bay,Lake Huron, 1977–1978

Successful development of a commercial, small-mesh trap net fishery for round whitefish (Prosopium cylindraceum) in Saginaw Bay, Lake Huron, prompted analysis of round whitefish fillets for selected contaminants [dieldrin, dichlorodiphenyl trichloroethane and metabolites (DDT), polychlorinated biphenyls (PCBs), polybrominated biphenyls (PBBs), chlordane, methyl mercury, and total mercury] to determine the fish's suitability for human consumption. Concentrations of all contaminants measured in 1977–1978 were below U. S. Food and Drug Administration action guidelines for fish; PBBs were below detection limits (0.001 mg/kg) for all fillets analyzed. Only PCBs and total DDT residues displayed a strong direct relationship with fish length. Fillets from males consistently exhibited higher mean concentrations of contaminants than did females. No changes in contaminant levels with season were observed.     

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.