The occurrence of steroidal estrogens in south-eastern Ontario wastewater treatment plants.

We measured steroidal estrogens in wastewater in Ottawa and Cornwall (Ontario, Canada) to determine removal efficiency of these steroids during the treatment process, and whether removal varies during a seasonal cycle. Estrone (E1), 17ß-estradiol (E2) and 17α-ethinylestradiol (EE2) were found at maximum concentrations in raw sewage (RS), at 104, 66.9 and 5.7 ng L(-1), respectively. For the Ottawa wastewater treatment plant (WWTP), there was sufficient data to show that E1 concentrations in RS correlated with both ambient air temperature and mean daily flow of the WWTP (R(2)=0.792, p=0.003 and R(2)=0.757, p=0.005). E1 removal was correlated with the percent difference in cBOD from RS to FE (final effluent) (R(2)=0.435, p=0.075). However estrogenic potency, as determined by a sensitive in vitro reporter gene assay, did not decrease during the water treatment process, suggesting that many estrogenic chemicals are conserved in FE. E1 and EE2 were found in river water, both upstream and downstream of the WWTPs, and at much lower concentrations than in FE. Our study demonstrates the persistence of steroidal estrogens and estrogenic potency in Ontario WWTP effluents and surface waters, and has uncovered temporal patterns of release that may be used to help predict risks to aquatic organisms in these environments.

Historical pesticide applications coincided with an altered diet of aerially foraging insectivorous chimney swifts.

Numerous environmental pressures have precipitated long-term population reductions of many insect species. Population declines in aerially foraging insectivorous birds have also been detected, but the cause remains unknown partly because of a dearth of long-term monitoring data on avian diets. Chimney swifts (Chaetura pelagica) are a model aerial insectivore to fill such information gaps because their roosting behaviour makes them easy to sample in large numbers over long time periods. We report a 48-year-long (1944-1992) dietary record for the chimney swift, determined from a well-preserved deposit of guano and egested insect remains in Ontario (Canada). This unique archive of palaeo-environmental data reflecting past chimney swift diets revealed a steep rise in dichlorodiphenyltrichloroethane (DDT) and metabolites, which were correlated with a decrease in Coleoptera remains and an increase in Hemiptera remains, indicating a significant change in chimney swift prey. We argue that DDT applications decimated Coleoptera populations and dramatically altered insect community structure by the 1960s, triggering nutritional consequences for swifts and other aerial insectivores.

Effects of seabird vectors on the fate, partitioning, and signatures of contaminants in a High Arctic ecosystem.

Seabirds bioaccumulate contaminants from prey, transport them to their nesting sites, and deposit them in their excreta and carcasses, thereby focusing marine-derived contaminants into remote, terrestrial receptor sites. In the case of organochlorine chemicals transported by northern fulmars (Fulmarus glacialis) to a High Arctic seabird colony on Devon Island, Nunavut, Canada (76°13'N, 89°14'W), this contaminant pathway dominates all others. In freshwater ponds below the nesting cliffs, concentrations of organochlorine contaminants characteristic of fulmar input were 2- to 45-fold higher in sediments and water (depending on seabird input to the particular pond) than in ponds remote from the colony. Air-water fugacity quotients for the ponds decreased with seabird input, indicating that fulmar contaminant input shifts air-water partitioning to increasingly favor volatilization to air. Although contaminant evasion from water was favored, direct evidence of it was not detected in air samples. For PCBs, congener profiles of pond sediments or water became more similar to seabird sources as seabird input increased, and less similar to air profiles. Based on measurements of contaminants in fulmars and other local environmental media, this study presents the first application of fugacities and multivariate source apportionment statistics to resolve seabird biological vectors.

Environmental factors affecting ultraviolet photodegradation rates and estrogenicity of estrone and ethinylestradiol in natural waters.

The environmental fate and persistence of steroidal estrogens is influenced by their photodegradation. This can potentially occur both in the presence of the ultraviolet (UV) portion of solar radiation and in tertiary wastewater treatment plants that use UV radiation for disinfection purposes. To determine patterns of UV photodegradation for estrone (E1) and 17α-ethinylestradiol (EE2), water samples containing these compounds were exposed to levels of UVB radiation that would simulate exposure to ambient sunlight. E1 degraded with a pseudo-first-order rate law constant that was directly proportional to UVB radiation intensity (R² = 0.999, P < 0.001) and inversely proportional to dissolved organic carbon (DOC) concentration (R² = 0.812, P = 0.037). DOC acted as a competitive inhibitor to direct photolysis of E1 by UV. In contrast to E1, EE2 was more persistent under similar UVB treatment. A reporter gene assay showed that the estrogenicity of UVB-exposed estrogens did not decrease relative to non-UVB-exposed estrogens, suggesting that some of the photoproducts may also have estrogenic potency. These results show that environmental degradation rates of steroidal estrogens are predictable from the UV intensity reaching surface waters, and the DOC concentrations in these surface waters.

Trophic position influences the efficacy of seabirds as metal biovectors.

Seabirds represent a well documented biological transport pathway of nutrients from the ocean to the land by nesting in colonies and providing organic subsidies (feces, carcasses, dropped food) to these sites. We investigated whether seabirds that feed at different trophic levels vary in their potency as biovectors of metals, which can bioaccumulate through the marine foodweb. Our study site, located on a small island in Arctic Canada, contains the unique scenario of two nearby ponds, one of which receives inputs almost exclusively from upper trophic level piscivores (Arctic terns, Sterna paradisaea) and the other mainly from lower trophic level molluscivores (common eiders, Somateria mollissima). We used dated sediment cores to compare differences in diatoms, metal concentrations and also stable isotopes of nitrogen (delta(15)N), which reflect trophic position. We show that the seabirds carry species-specific mixtures of metals that are ultimately shunted to their nesting sites. For example, sediments from the tern-affected pond recorded the highest levels of delta(15)N and the greatest concentrations of metals that are known to bioaccumulate, including Hg and Cd. In contrast, the core from the eider-affected site registered lower delta(15)N values, but higher concentrations of Pb, Al, and Mn. These metals have been recorded at their greatest concentrations in eiders relative to other seabirds, including Arctic terns. These data indicate that metals may be used to track seabird population dynamics, and that some metal tracers may even be species-specific. The predominance of large seabird colonies on every continent suggests that similar processes are operating along coastlines worldwide.

Accelerated delivery of polychlorinated biphenyls (PCBs) in recent sediments near a large seabird colony in Arctic Canada.

Polychlorinated biphenyls (PCBs) were measured in sediment cores from ponds located near a large seabird colony at Cape Vera, Devon Island, Arctic Canada. Surface sediment PCB concentrations were approximately 5x greater in seabird-affected sites relative to a nearby control pond and were correlated with independent indicators of seabird activity including, sedimentary delta(15)N and lakewater chlorophyll a and cadmium concentrations. PCB fluxes were amongst the highest recorded from the High Arctic, ranging from 290 to 2400 ng m(-2) yr(-1). Despite a widespread ban of PCBs in the mid-1970s, PCB accumulation rates in our cores increased, with the highest values recorded in the most recent sediments. Possible mechanisms for the recent PCB increases include a vertical flux step driven by seabird-delivered nutrients and/or delayed loading of PCBs from the catchment into the ponds. The high PCB levels recorded in the seabird-affected sites suggest that seabird colonies are exposing coastal ecosystems to elevated levels of contaminants.

Historical analysis of salmon-derived polychlorinated biphenyls (PCBs) in lake sediments.

Several recent studies have highlighted the importance of salmon as a means to deliver biomagnifying contaminants to nursery lakes. There is a lack of studies, however, which demonstrate empirically how this source has varied through time. This is of great significance because past salmon-derived contaminant loading was potentially greater than it is today. By analyzing radiometrically dated sediment cores collected from ten lakes in Alaska and British Columbia (B.C.), we relate historical numbers of sockeye salmon spawners to SigmaPCB concentrations and delta(15)N values (a paleolimnological proxy for past salmon-derived nitrogen) in the sediments. The results confirm that sockeye salmon have provided an important route for PCBs to enter the lakes in the past, a finding that is especially evident when the data of all lakes are pooled. Significant relationships between sockeye salmon numbers and delta(15)N, as well as SigmaPCB concentrations and delta(15)N in sediments, were also found. However, it is difficult to establish relationships between salmon numbers, SigmaPCBs and delta(15)N in individual lakes. This may be due to a number of factors which may influence contaminant loadings to the lakes. The factors include: a) changing salmon contaminant loads over time resulting from a lag in the upper ocean reservoir and/or changing salmon feeding locations; b) greater importance of atmospheric transport in lakes with relatively low salmon returns; and c) increased PCB scavenging due to higher algae productivity in the lakes in recent years.

Concentrations and fluxes of salmon-derived polychlorinated biphenyls (PCBs) in lake sediments.

Fourteen sediment cores were collected from 10 lakes spanning a large gradient of sockeye salmon returns (0-40 000 spawners km(-2)) in Alaska and British Columbia in 1995-98 and 2002/03. The cores were analyzed for 210Pb to determine sedimentation rates and focusing factors. Polychlorinated biphenyl (PCBs) concentrations in the surface sediments (0-2 cm) were highly correlated with the number of sockeye salmon returns to each nursery lake. For 2002/03, the correlation between PCB concentration and number of salmon spawners was best with no correction factors applied, but decreased considerably when corrected for sedimentation rates, and was improved again by correcting for sediment focusing. Although sigmaPCB concentrations were similar in 1995-98 and 2002/03, the congener patterns varied. Because salmon are the dominant source of PCBs for most of these lakes, variation in sediment congener pattern likely derives from variation in congener patterns carried by the salmon. Overall, total PCB input by salmon has remained relatively constant since 1995. Unlike temperate Great Lakes contaminant studies, the North American west-coast lakes dominated by salmon bio-transport showed no sign of recent decrease in PCBs.

Arctic seabirds transport marine-derived contaminants.

Long-range atmospheric transport of pollutants is generally assumed to be the main vector for arctic contamination, because local pollution sources are rare. We show that arctic seabirds, which occupy high trophic levels in marine food webs, are the dominant vectors for the transport of marine-derived contaminants to coastal ponds. The sediments of ponds most affected by seabirds had 60 times higher DDT, 25 times higher mercury, and 10 times higher hexachlorobenzene concentrations than nearby control sites. Bird guano greatly stimulates biological productivity in these extreme environments but also serves as a major source of industrial and agricultural pollutants in these remote ecosystems.

Air-water gas exchange of chlorinated pesticides in four lakes spanning a 1,205 meter elevation range in the Canadian Rocky Mountains.

Concentrations of selected persistent organic pollutants (POPs) in air and water were measured from four lakes that transect the Canadian Rocky Mountains. These data were used in combination with wind velocity and temperature-adjusted Henry's law constants to estimate the direction and magnitude of chemical exchange across the air-water interface of these lakes. Bow Lake (1,975 m above sea level [masl]) was studied during the summers of 1998 through 2000; Donald (770 masl) was studied during the summer of 1999; Dixon Dam Lake (946 masl) and Kananaskis Lake (1,667 masl) were studied during the summer of 2000. Hexachlorobenzene (HCB) and dieldrin volatilized from Bow Lake in spring and summer of 1998 to 2000 at a rate of 0.92 +/-1.1 and 0.55+/-0.37 ng m(-2) d(-1), respectively. The alpha-endosulfan deposited to Bow Lake at a rate of 3.4+/-2.2 ng m(-2) d(-1). Direction of gas exchange for gamma-hexachlorocyclohexane (gamma-HCH) changed from net deposition in 1998 to net volatilization in 1999, partly because of a surge in y-HCH concentrations in the water at Bow Lake in 1999. Average gamma-HCH concentrations in air declined steadily over the three-year period, from 0.021 ng m(-3) in 1998, to 0.0023 ng m(-3) in 2000, and to volatilization in 1999 and 2000. Neither the concentrations of organochlorine compounds (OCs) in air and water, nor the direction and rate of air-water gas exchange correlate with temperature or elevation. In general, losses of pesticides by outflow were greater than the amount exchanged across the air-water interface in these lakes.

Persistent organic pollutants in air and vegetation from the Canadian Rocky Mountains.

The exchange of chlorinated organic pollutants between air and vegetation in cold, mountain environments was investigated through the extraction of coniferous vegetation and high-volume air samples collected from the Canadian Rocky Mountains during the summers of 1999 and 2000. Concentrations of several compounds in vegetation increased as temperatures decreased, whereas atmospheric concentrations were not related to temperature. Daily cycling of these compounds between air and vegetation as a result of diurnal temperature changes was not observed. Compared with concentrations in vegetation from the Canadian Rocky Mountains, plant samples from the western valley in British Columbia (Canada) showed higher pollutant levels. Chemical partitioning between vegetation and air was not correlated with temperature, indicating that air contamination is governed by long-range transport and not by local revolatilization events. Based on these observations, we show that both deposition at higher altitudes and long-range atmospheric transport influence chemical accumulation in vegetation from the Canadian Rocky Mountains.

Orographic cold-trapping of persistent organic pollutants by vegetation in mountains of western Canada.

Conifer needles from mountain areas of Alberta and British Columbia, Canada, were collected from sites that ranged in altitude from 770 to 2200 masl and were analyzed for polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCs) to determine if they are progressively concentrated in colder, more elevated mountain areas, where temperatures decrease as elevation increases. Concentrations of OCs in needles ranged from 43 to 2430 pg g(-1), 55-17500 pg g(-1), and 11-2930 pg g(-1) (dry weight), for total hexachlorocyclohexanes (HCHs), PCBs, and endosulfans, respectively. The more volatile OCs, with subcooled liquid vapor pressures (PL) > 0.1 Pa at 25 degrees C, increased at higher altitudes, whereas the less volatile OCs were either unrelated or inversely correlated with altitude. These spatial patterns were similar for species of spruce (Picea engelmannii and glauca) and pine (Pinus contorta and albicaulis). Back trajectories revealed that air masses arriving at these sites traveled over Asia and the Pacific Ocean before reaching the Rocky Mountains. Results from this study demonstrate that alpine ecosystems accumulate these chemicals to the same degree that is observed in polar environments that are known to receive contaminants by long-range transport.

Dichlorodiphenyltrichloroethane in the aquatic ecosystem of the Okavango Delta, Botswana, South Africa.

Concentrations of DDT and its metabolites were measured in water, plants, invertebrates, and fish from lagoons in the Okavango Delta, Botswana (Africa), where DDT has been used for approximately 50 years. The sampling area was sectioned to distinguish spraying for malaria and for African sleeping sickness. Average concentrations of total DDT (sum of DDT and its metabolites) in the Okavango ranged from 0.009 ng/L in water to 18.76 ng/g wet weight in fish. These levels are approximately 1% of those found in piscivorous fish from temperate North America. The dichlorodiphenyl ethylene (DDE) metabolite was the most abundant fraction of total DDT. Although total DDT concentrations were higher in areas treated for malaria than areas treated for sleeping sickness, these concentrations were likely driven by factors other than the historic application of the pesticide. Equilibration with air concentrations is the most likely explanation for these levels. Since the mean annual temperature exceeds the temperature of vaporization of DDT, this research points to the need for reliable transport models. Our results showed that total DDT concentration in fish was best explained by lipid content of the fish and trophic position inferred by delta15N, regardless of DDT application history in those areas. The reservoir above Gaborone Dam, an area downstream of the Okavango but where DDT had not been used, was sampled to compare total DDT levels to the treated areas. The two species (a herbivorous threespot talapia and the omnivorous sharptooth catfish) from Gaborone had levels higher than those found in the Okavango Delta, but these differences can again be explained using trophic position inferred by delta15N rather than by fish size or location.

Assessment and characterization of polychlorinated biphenyls near a hazardous waste incinerator: analysis of vegetation, snow, and sediments.

Samples of spruce needles, snowpack, and sediment were analyzed in the area around the Alberta Special Waste Treatment Centre (ASWTC) near Swan Hills, Canada, in 1997 and 1998, following a major accidental release of polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) in October 1996. The PCB concentrations in spruce needles and snow were mostly elevated to the east of the plant and contained congeners that were not present at upwind or distant sites. Several years of annual vegetation monitoring data indicated that PCB emissions increased prior to the reported accident. Within 3 km of the plant, there was a predominance of higher chlorinated congeners penta-, hexa-, hepta-, and octachlorobiphenyls in white spruce (Picea glauca) needles and snow. Polychlorinated biphenyl congener patterns varied seasonally in spruce needles, likely influenced by temperature effects on the volatilization and of particle-bound and vapor phase PCBs in the forest canopy. The similarity of deposition patterns in snow and needles in 1997 and 1998 suggested the PCBs in the surrounding area were derived by long-term fugitive releases of PCBs rather than an accidental release. In addition, hexachlorobenzene, a combustion by-product of chlorinated organics in waste incinerators, was not measured at elevated concentrations in spruce needles or snow east of the facility and, when detected, was not correlated with PCB concentrations. A radiometrically dated sediment core from nearby Chrystina Lake (AB, Canada) showed a gradual increase in annual PCB flux during the early years of operation of the ASWTC, followed by a higher PCB flux in 1997, indicating that the lake may have been directly contaminated by the accidental release.