Bioaccumulation of pharmaceuticals and personal care products in the unionid mussel Lasmigona costata in a river receiving wastewater effluent.

Freshwater mussels are frequently found in rivers receiving effluent from wastewater treatment plants (WWTP), and there is strong evidence that poor water quality is deleterious to freshwater mussel populations. WWTPs are among the main sources of pharmaceuticals and personal care products (PPCPs) in surface waters. We monitored 145 PPCPs in wild and caged mussels both upstream and downstream of the Kitchener WWTP in the Grand River, Ontario, as well as 118 PPCPs in water samples. Our objectives were to characterize the seasonal changes in PPCP concentrations in water, to calculate bioaccumulation factors (BAFs) of PPCPs in mussels, and to determine the chemical and physical properties of PPCPs driving the bioaccumulation. Seventy PPCPs were detected in water, and concentrations were highest in the summer or early fall, which corresponded to low river flow. Forty-three PPCPs from many pharmaceutical classes were detected in mussel tissues, including stimulants, a contrasting agent, anti-inflammatory drugs, anti-bacterial agents, antibiotics, antidepressants, antihistamines, progestins, and illicit drugs such as cocaine and amphetamines. The BAFs ranged from 0.66 for metformin to 32,022 for sertraline. Using partial least squares to predict BAFs based upon chemical properties, log KOC, Log KOW, and fugacity ratio (sediment) all had similar and positive loadings with BAFs (R(2)X = 0.70; caged mussels). BAFs of PPCPs in mussels were predictable from fugacity models that estimate bioconcentration factors using log KOW. Our study demonstrated that mussels readily bioaccumulate PPCPs, in a manner consistent with expectations based upon BCF models and the chemical characteristics of each compound.

Sources of aminomethylphosphonic acid (AMPA) in urban and rural catchments in Ontario, Canada: Glyphosate or phosphonates in wastewater?

Correlation analysis suggests that occurrences of AMPA in streams of southern Ontario are linked mainly to glyphosate in both urban and rural settings, rather than to wastewater sources, as some previous studies have suggested. For this analysis the artificial sweetener acesulfame was analyzed as a wastewater indicator in surface water samples collected from urban and rural settings in southern Ontario, Canada. This interpretation is supported by the concurrence of seasonal fluctuations of glyphosate and AMPA concentrations. Herbicide applications in larger urban centres and along major transportation corridors appear to be important sources of glyphosate and AMPA in surface water, in addition to uses of this herbicide in rural and mixed use areas. Fluctuations in concentrations of acesulfame and glyphosate residues were found to be related to hydrologic events.

A pesticide runoff model for simulating runoff losses of pesticides from agricultural lands.

An integrated modeling system was developed to predict runoff losses of pesticides from agricultural lands. The system is an integration of a mathematical model, a database system, and a geographic information system. Information on soil type, land use, land slope, watershed boundaries, precipitation, pesticide usage, as well as physical and chemical properties of pesticides have been input to a GIS, managed through a database, and used for further modeling studies. The modeling outputs were in turn put into the database, such that runoff patterns along with pesticides losses could be further simulated by using a database management system. The final results could then be visualized through GIS. The developed modeling system was applied to the Kintore Creek Watershed, Ontario, Canada, for simulating losses of atrazine from agricultural lands. A water quality monitoring project was carried out from 1988 to 1992 in the watershed to detect conditions of surface water pollution due to the use of pesticides. The modeling outputs were verified through the monitoring data, demonstrating reasonable prediction accuracy. The result indicated that the model provides an effective means for forecasting pesticide runoff from agriculture lands.

Nitrogen pollution: an assessment of its threat to amphibian survival.

The potential for nitrate to affect amphibian survival was evaluated by examining the areas in North America where concentrations of nitrate in water occur above amphibian toxicity thresholds. Nitrogen pollution from anthropogenic sources enters bodies of water through agricultural runoff or percolation associated with nitrogen fertilization, livestock, precipitation, and effluents from industrial and human wastes. Environmental concentrations of nitrate in watersheds throughout North America range from < 1 to > 100 mg/L. Of the 8,545 water quality samples collected from states and provinces bordering the Great Lakes, 19.8% contained nitrate concentrations exceeding those which can cause sublethal effects in amphibians. In the laboratory lethal and sublethal effects in amphibians are detected at nitrate concentrations between 2.5 and 100 mg/L. Furthermore, amphibian prey such as insects and predators of amphibians such as fish are also sensitive to these elevated levels of nitrate. From this we conclude that nitrate concentrations in some watersheds in North America are high enough to cause death and developmental anomalies in amphibians and impact other animals in aquatic ecosystems. In some situations, the use of vegetated buffer strips adjacent to water courses can reduce nitrogen contamination of surface waters. Ultimately, there is a need to reduce runoff, sewage effluent discharge, and the use of fertilizers, and to establish and enforce water quality guidelines for nitrate for the protection of aquatic organisms.

Health of tree swallows (Tachycineta bicolor) nesting in pesticide-sprayed apple orchards in Ontario, Canada. I. Immunological parameters.

The degree of pesticide exposure and its effects on the immune system and its development were determined in 16-d-old tree swallow (Tachycineta bicolor) chicks from 4 sprayed apple orchards and three nonsprayed sites in southern Ontario, Canada, during 1994-1995. Persistent contaminant residues were measured in tree swallow eggs and in each chick hepatic ethoxyresorufin O-deethylase (EROD) activity; body, immune organ, and liver masses; lymphocyte blastogenesis response; respiratory burst and phagocytic responses; hemarological evaluation; and histological development of thymus, bursa of fabricius, and spleen were determined. Chemicals sprayed on apple orchards were mainly ethylene bisdithiocarbamate and myclobutanil fungicides and organophosphorus, carbamate, and synthetic pyrethroid insecticides. During the period between oviposition of the first egg in each nest to d 16 after hatching, individual nests in orchards were exposed to between 4 and 11 individual chemical applications and up to 3 mixtures of pesticide sprays. Concentrations of pesticides, polychlorinated biphenyls (PCBs), and lead and arsenic residues in tree swallow eggs and liver were low and not variable among sites except p,p'-DDE, which was as high as 2.29 microg/g wet weight in eggs. EROD activity was not different among sites. Organochlorine and trace metal residues and EROD activity were not correlated with any immune parameter. In sprayed birds, we found a significantly increased blastogenic response to pokeweed mitogen (12.5 microg/ml). However, nests were initiated over a period of several weeks and we also found changes in other tree swallow immune parameters that were related to the date of chick collection. Hematological parameters, bursal and thymic masses, phagocytic response, and thymic development were all correlated with the day the chicks were 16 d of age. After accounting for the collection date of birds from each nest, we found cell proliferation in the cortex and delayed thymic involution correlated positively with increasing spray exposure. We also found that birds in sprayed orchards were slightly anemic compared to birds from nonsprayed sites, and there were smaller bursal masses and an increase in relative heterophil concentrations in the sprayed orchard birds. The local inflammation may have been caused by trematode parasite infections, although pesticide exposure also correlated positively with these parameters. This is the first study of the immunology and effects of current pesticide exposures in wild passerines; therefore it is difficult to predict the long-term consequences of the apparent stimulated immune systems in sprayed birds. However, some environmental contaminants that overtly stimulate the immune system in mammals have induced hypersensitivity and/or autoimmunity. Therefore we speculate that these effects are possible in tree swallows.

Mercury levels in Great Lakes herring gull (Larus argentatus) eggs, 1972-1992.

Since 1971, the herring gull (Larus argentatus) has been used as a sentinel species for monitoring the levels of persistent contaminants in the Great Lakes ecosystem. In this study, 21 herring gull colonies in the Great Lakes and connecting channels were sampled during 1972-1976, 1981-1983, 1985 and 1992. For each year, 10 eggs (usually) were collected from each colony site and analyzed for total mercury (microg/g, wet wt). Results indicated that eggs from Lake Ontario displayed the highest lake-wide mercury levels (0.28-0.73 microg/g), followed by Lake Superior (0.21-0.50 microg/g). Lake Erie typically displayed the lowest mercury levels (0.18-0.24 microg/g). Overall, mercury levels ranged from 0.12 microg/g in 1985 to 0.88 microg/g in 1982 for Channel Shelter Island (Lake Huron) and Pigeon Island (Lake Ontario), respectively. Generally, all colony sites showed peak egg mercury levels in 1982. A significant decline in egg mercury levels was observed in five colony sites for the period 1972-1992 and in three different colony sites for the period 1981-1992. Mercury levels in the eggs of herring gulls for the period of this study were below levels associated with acute toxic effects in this species but were within a range, for certain years, which potentially reduces hatchability in other avian species.

Geographical distribution of organochlorine contaminants and reproductive parameters in Herring Gulls on Lake Superior in 1983.

As part of the Great Lakes International Surveillance Plan, 1978-83, egg contaminant levels and reproductive output were determined for Herring Gull colonies on Lake Superior in 1983. Since 1974, the Herring Gull has been widely used in the Great Lakes as a spatial and temporal monitor of organochlorine (OC) contaminant levels and associated biological effects. Most eggs contained a wide range of OCs, the main compounds being DDE, polychlorinated biphenyls (PCBs), dieldrin, heptachlor epoxide, oxychlordane, hexachlorobenzene and mirex. Levels of an additional ten OCs and five polychlorinated dibenzo-p-dioxin (PCDD) congeners were also determined for some sites. Overall, levels varied significantly among colonies, but there was no obvious relationship to spatial distribution of contaminants in sediments or fish species. OC levels in eggs had declined by up to 84% since 1974. Eggshells were only 8% thinner than before the introduction of DDT, and shell thinning was not a cause of breeding failure. Average reproductive output varied from 0.15 to 1.57 young per apparently occupied nest in 1983: at 56% of colonies the value was below that thought necessary to maintain stable populations. The main causes of failure were egg disappearence and cannibalism of chicks. Despite this, the population appeared to have been increasing at about 4% per annum. Reduced availability of forage fish during the early 1980s was the most likely reason for the poor reproductive output in 1983.

Enzyme immunoassay based survey of precipitation and surface water for the presence of atrazine, metolachlor and 2,4-D.

The suitability of enzyme immunoassay (EIA) as a method of analysis for 2,4-D, atrazine and metolachlor contamination in water samples was determined by comparing EIA results to gas chromatography (GC) results. The comparison of EIA and GC results yielded a correlation coefficient of 0.92, 0.98 and 0.92 for 2,4-D, atrazine and metolachlor, respectively. EIA was used to monitor seasonal trends in the concentrations of 2,4-D, atrazine and metolachlor in surface water and precipitation throughout the province of Ontario, Canada. 2,4-D was detected in excess of 4 micrograms/L in urban creeks during the period of application. Concentrations of 43 and 9 micrograms/L of atrazine and metolachlor, respectively, were detected during the field application period in surface water samples from the Kintore Creek watershed. The levels of 2,4-D, atrazine and metolachlor detected exceeded the Canadian Water Quality Guidelines for the protection of fresh water aquatic life. Concentrations as high as 445 and 322 ng/L of atrazine and metolachlor, respectively, were detected in precipitation samples collected from 17 locations in Ontario during the herbicide application period. The EIA was shown to be qualitatively and quantitatively comparable to GC analysis.

Geographical distribution of contaminants and productivity measures of herring gulls in the Great Lakes: Lake Erie and connecting channels 1978/79.

The distribution and size of colonies, residue levels of DDE, DDT, HCB, dieldrin, mirex and PCBs in eggs, productivity and eggshell thickness were determined for herring gulls at 14 sites in Lake Erie and connecting channels. The centre of distribution for breeding herring gulls was the Western Basin where approximately 90% of the 6200 nests in the study area were located. Seven of 22 colonies showed an average annual population increase of 48.3%. Most of the increase in breeding herring gulls on Lake Erie is directly associated with sites that have undergone habitat modification by man. Levels of PCBs and DDE ranged from 35 to 140 ppm (wet weight) and from 2.8 to 9.4 ppm, respectively; all other residues were less than 0.49 ppm. Most organochlorine residue levels were highest in eggs from colonies in or near the Niagara or Detroit Rivers. Mirex residues were greatest in the Niagara River and decreased significantly to the west. PCB residues were greatest in the Detroit River and decreased significantly to the east. The lowest levels generally came from colonies in the Sandusky Basin and near Pelee Island in western Lake Erie. Discriminant function analysis of six organochlorine contaminants correctly classified 90% or more of the eggs from up to four colonies in one or more years. Levels of PCBs and HCB appeared to have the greatest discriminating power. Herring gull productivity at all colonies (1-1.7 young gulls/pair) was normal and showed no significant geographical variation. Eggshell thickness was greatest in colonies in the Sandusky Basin and least in colonies in the Detroit River and extreme west end of the lake; mean eggshell thickness was 0.350 +/- 0.02 mm (6.7% thinning), which was weakly, but significantly correlated to DDE concentration. The variation in contaminants in herring gull eggs on a Basin basis (i.e., Western, Eastern, Sandusky, etc.) paralleled those known for sediments, water and fish. Thus, we suggest that in addition to its role as an indicator of lake-wide contamination of the Great Lakes, the herring gull, under some circumstances, may function as an indicator of "regional" contamination. This is an important distinction as it improves the geographical specificity of the herring gull as an indicator species on the Great Lakes, where it is a non-migratory species.