Persistent organic pollutants in Detroit River suspended sediments: polychlorinated dibenzo-p-dioxins and dibenzofurans,dioxin-like polychlorinated biphenyls and polychlorinated naphthalenes

Suspended sediments from the Detroit River were collected in 1999 and 2000 using sediment traps at sites ranging from western Lake Erie to southern Lake St. Clair and analyzed to determine the spatial distributions of contaminants including polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/PCDFs), dioxin-like PCBs (DLPCBs) and polychlorinated naphthalenes (PCNs). Concentrations of all three contaminant classes were clearly elevated at sites in the lower reaches of the river in the Trenton Channel. The potential influence of the Trenton Channel as a source of contamination to western Lake Erie was further evidenced by PCDD/PCDF homologue profiles, which indicated a contribution from chemical manufacturing in addition to the normal background combustion profile. Toxic equivalents (TEQs) for PCDDs/PCDFs generally exceeded those for DLPCBs; combined total TEQs in July 2000 for these two compound classes ranged from 2.30 pg/g in southern Lake St. Clair to 306 pg/g at a station just downstream of the outflow of Monguagon Creek in the Trenton Channel. The spatial distribution of PCN contamination was similar to that of PCDDs/PCDFs and DLPCBs, with the highest level of total PCNs (8200 ng/g) detected at a site in the Trenton Channel near Elizabeth Park; TEQs for PCNs in the Trenton Channel ranged from 73 to 3300 pg/g. The data indicate that PCNs represent a significant contribution to dioxin-like biological activity in Detroit River suspended sediments.     

Spatial and temporal trends in surface water and sediment contamination in the Laurentian Great Lakes

Data from recent sediment and surface water surveys have been collated and mapped to illustrate the spatial distribution of contaminants across the entire Great Lakes basin. Information from historical surveys, together with data from surface water monitoring programs in three major connecting channels, has also been collated in order to evaluate temporal trends. In general, Lakes Superior and Michigan exhibited the lowest levels of sediment contamination while Lake Ontario had the highest. Contaminants such as gamma-HCH (lindane) and dieldrin were ubiquitous in surface waters across the entire basin, which was indicative of atmospheric sources. The distribution of other compounds including hexachlorobenzene, octachlorostyrene and mirex indicated the presence of local sources within the watersheds of the connecting channels. Surficial sediment contamination was found to have decreased markedly since the late 1960s and 1970s. Similarly, surface water contamination decreased over the period 1986-1997 with concentrations of dieldrin, hexachlorobenzene, octachlorostyrene and mirex reduced by over 50%. However, the spatial distributions of both sediment and surface water contamination indicate that further effort is warranted in reducing local sources of contaminants, particularly in Lake Ontario.     

Early reproductive success of western bluebirds and ash-throated flycatchers: a landscape-contaminant perspective

Eggshell quality, clutch size, sex ratio, and hatching success of western bluebirds (Sialia mexicana) and ash-throated flycatchers (Myiarchus cinerascens) were studied on a landscape-soil contaminant gradient at Los Alamos National Laboratory (LANL) in New Mexico from 1997 to 1999. A variety of contaminants (heavy metals, chemicals, insecticides, polychlorinated biphenyls (PCBs), organochlorines, and radioactive isotopes) range across different spatial scales and concentrations on LANL land. This study is an example of a monitoring program over a large area with varying degree of contamination that is used to highlight locations of concern for future research. There were two locations where the flycatcher had a lower hatching success. The bluebirds at Sandia wetland, a location of concern for PCBs. had a thinner eggshell thickness index (RATCLIFFE) and the eggs were smaller than at other locations. The flycatcher had thinner eggshells than bluebirds, which could add to sensitivity to exposure to contaminants. There was no variation in clutch size or sex ratio between locations or areas closer to contaminant release sites for both species. Percent females in the clutch ranged from 0 to 100% in the WEBL and from 33 to 67% for ATFL.     

Contamination by polybrominated diphenyl ethers of sediments from the Lake Maggiore basin (Italy and Switzerland)

Polybrominated diphenyl ethers (PBDEs) are characterized by chemical properties and toxicological profiles similar to other POPs (persistent organic pollutants) included in the EU Priority Pollutant List (2455/01/CE). However, limited data have been available for these compounds thus far for Italian freshwater abiotic matrices. Lake Maggiore basin, a heavily industrialized and densely populated area, was selected for studying PBDE contamination in Italy. PBDEs and OCs (organochlorine compounds) in the basin were quantified by analysing both sediment cores collected in 2005 from the lake and grab samples from the main tributaries and the emissary. Fourteen PBDEs, from tri-BDE to hepta-BDE congeners and BDE209, were compared with some organochlorine POPs (PCBs and DDTs) characterizing Lake Maggiore basin contamination. Analyses of tri-to hepta-BDEs, PCBs and DDTs were undertaken by GC-MS/MS, while BDE-209 was analysed by GC/ECD. Results showed a dominant presence of BDE-209 (>95% of SigmaBDE) and limited amounts of BDE-47, BDE-99, BDE-100, BDE-153 and BDE-154. Lake core profiles highlighted a decreasing trend in PCB concentrations starting from the year 2000, while PBDEs showed greater concentrations after the beginning of the 1990s (up to 30 ng g(-1)d.w.). Among the tributaries, the Bardello and Boesio rivers were the most PBDE-contaminated (up to 290 ng g(-1)d.w.).     

Determination of potential sources of PCBs and PBDEs in sediments of the Niagara River

Sediments from Niagara River, an important waterway connecting two of the Great Lakes (Lake Erie to Lake Ontario), were analyzed for 14 congeners of polychlorinated biphenyls (PCBs) and 9 congeners of polybrominated diphenyl ethers (PBDEs) using accelerated solvent extraction and gas chromatography/mass spectrometry. Total concentrations of PCBs ranged from 1.7 to 124.6 ng/g were PCBs 138 and 153 were found in all samples. All sites but one showed PBDE in sediments with total concentrations as high as 148 ng/g, suggesting that PBDE is becoming an important class of POP. A land-use and coverage map was used to trace potential localized sources of PCB and PBDE contamination. Results indicate that the highest levels of PCBs and PBDEs were found in sediments collected from areas closest to the discharge locations of municipal wastewater treatment plants (WWTP) and local industries. This is the first study that suggests the importance of WWTP discharges as a potential source of PBDE contamination in the Great Lakes.     

Patterns and sources of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans in surficial sediments of Lakes Erie and Ontario

This study determines spatial trends and congener patterns of 2378-substituted polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in surficial sediments of Lakes Erie and Ontario. Sediments are enriched in 2378-PCDFs in Lake Ontario, and the PCDD/F concentrations increased from shallow near-shore sediments towards deep-water depositional zone sediments. In Lake Erie, sediments were dominated by octachlorodibenzo-p-dioxin, and the highest PCDD/F concentrations were observed in the western basin and the southern shoreline of the central basin with a decrease towards the eastern basin and the northern shoreline of the central basin. Principal components analysis revealed that chemical manufacture and disposal of chemical waste along the Niagara River has been a major PCDD/F source to Lake Ontario; while PCDD/Fs in Lake Erie are from multiple sources including industrial sources along the Detroit River, major tributaries along the southern shoreline of the lake, and atmospherically-derived material from the upper lakes and connecting channels.     

Sexual difference in PCB congener distributions of burbot (Lota lota) from Lake Erie

Concentrations of 86 congeners of polychlorinated biphenyls (PCBs) were determined for 25 adult female and 25 adult male burbot (Lota lota) from Lake Erie. Significant differences in mean proportions of total PCB concentration between males and females ages 14–17 were found for 26 congeners. Males generally had higher mean proportions of hexachloro congeners, whereas females had higher mean proportions of more highly chlorinated congeners. In contrast, only four congeners exhibited differences between males and females ages 6–13 in mean proportions of total PCB. Therefore, the sexual difference in PCB congener distribution widened for older burbot. Males ages 14–17 also had higher proportions of certain hexachloro congeners than the other three demographic groups (males ages 6–13, females ages 6–13, and females ages 14–17) we examined. The reverse was true for more highly chlorinated congeners. The results supported a previous hypothesis that older male burbot spent a substantial amount of time feeding in the vicinity of mouths of rivers with sediment contaminated with PCBs. However, additional studies are needed to clarify and corroborate this apparent “hot spot” effect, such as seasonal movements, spatial distributions, and diet of burbot; and PCB congener distributions of various species of prey fishes captured at various locations throughout the eastern basin of Lake Erie and at different locations in the contaminated rivers.     

The assimilation of contaminants from suspended sediment and algae by the zebra mussel, Dreissena polymorpha

Since their invasion into the Great Lakes, zebra mussels, Dreissena polymorpha, have increased the water clarity in Lake St. Clair and Lake Erie due to their extensive particle filtration. Because these particles contain sorbed contaminants, the potential for contaminant accumulation from both suspended sediment and algae were examined. Sediment or algae were dosed with selected radiolabeled polycyclic aromatic hydrocarbon congeners and/or hexachlorobiphenyl (HCBP). Assimilation efficiencies were measured and depended on food quality. Zebra mussels, 17 ± 2 mm long, assimilated 58.3 ± 13.5% of the pyrene and 44.7 ± 5.8% of the benzo(a)pyrene (BaP) from sediment particles with a particle clearance rate of 493 – 897 ml/g tissue/h. However, assimilation efficiencies were 91.7 ± 3.7% for pyrene, 91.9 ± 1.4% for BaP, 96.6 ± 1.4% for chrysene, and 97.7 ± 0.5% for HCBP from suspended algae. Algal particle clearance rates for the mussels ranged from 47 – 143 ml/g tissue/h. Thus, zebra mussels efficiently accumulated non-polar contaminants sorbed to algae, while a smaller fraction of the sediment-associated contaminant was bioavailable. Furthermore, the contaminants sorbed onto suspended sediment particles were quickly removed from the water and deposited as pseudofeces. The pseudofeces production was positively correlated with filtration rate and suspended particle concentrations.     

A spatial temporal assessment of pollution from PCBs in China

This research represents an assessment of the current state of pollution from polychlorinated biphenyls (PCBs) in China. Various environmental media including sediment, water, organism and soil were analyzed and the spatial character of PCB pollution in each environmental medium was determined. On a national basis, PCB levels in all environmental media were relatively low, with little evidence of major contamination in China's main regions and rivers. However, there were some locations with high PCB concentrations. Sediments in Pearl River (83.1 ng/g) and its estuary (58.9 ng/g), Dalian Bay (58.1 ng/g) and Songhua River (36.8 ng/g) had relatively high level of PCBs. There were also some areas, which were mainly the industrial pollution sites or PCB equipment storage locations, remained seriously polluted with the highest PCB residue level of 150,000 ng/g. In addition, Minjiang Estuary (985.2 ng/g) and Taihu Lake (631 ng/g) had high levels of water pollution, while Pearl Estuary (635.7 ng/g) and Jiaozhou Bay (273.3 ng/g) had relatively high PCB levels in organisms. PCB pollution in soil was limited to a few special pollution areas with the highest PCB level of 4.5448 x 10(6) ng/g. Point source pollution was the common pattern of contamination, influenced primarily by local geographic, economic and historical factors. Analysis of PCB concentrations from the 1980s to 1990s shows an increasing trend, possibly due to the improper disposal of and leakage from PCB containers, chemical transfers, and the general rise of industrial pollution.     

Levels and distributions of polybrominated diphenyl ethers,hexabromocyclododecane, and tetrabromobisphenol A in sediments from Taihu Lake,China

The concentrations and distribution of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCD), and tetrabromobisphenol A (TBBPA) were investigated in 28 sediment samples collected from Taihu Lake, Eastern China. The results showed that all three classes of compounds were detected in 28 sediment samples but that PBDEs were the main contaminants in the study area. The total PBDE concentrations ranged from 3.77 to 347 ng/g dry weight (dw) with a mean value of 72.8 ng/g dw, whereas the concentrations ranged from 0.168 to 2.66 and from 0.012 to 1.30 ng/g dw for HBCD and TBBPA, respectively. In all of the sediment samples, BDE-209 was the predominant congener, accounting for 95.9 to 98.6 % of the total PBDEs, which indicated that commercial mixtures of deca-BDEs were the main sources of PBDE contamination. Higher concentrations of PBDEs were found in samples collected from Meiliang Bay and Gonghu Bay near the inflow river, which suggested that inflow runoff might play an important role in the PBDE levels in Taihu Lake sediments.     

Historical trends in persistent organic pollutants and metals recorded in sediment from Lake Ellasjøen, Bjørnøya, Norwegian Arctic

Ellasj?en receives contaminants from both atmospheric and biological transport (seabird guano). Historical trends of selected persistent organic pollutants and metals were determined by interpretation of down-core contaminant profiles in conjunction with sediment layer ages, determined by the (210)Pb method. Polychlorinated biphenyls (PCBs) and dichloro-diphenyl-trichloroethane and metabolites (DDTs) increased from about 1930 until 1970 (max. sum PCBs 71.8 ng/g dry weight (dw), max sum DDTs 4.0 ng/g dw), declining afterwards to 46.4 ng/g dw and 1.6 ng/g dw, respectively. Polybrominated diphenylethers (PBDEs) concentrations are increasing in Ellasj?en, reaching 0.73 ng/g dw in 2001. Hexabromocyclododekane (HBCD) was measured only in sediment from 1-2 cm depth (0.43 and 3.88 ng/g dw of alpha- and gamma-HBCD, respectively). Most metals (As, Cd, Co, Ni and Zn) showed a similar pattern as PCBs. No clear trends were observed for Cr, Pb or V. Mercury (Hg) has increased gradually since the beginning of the industrial era.     

Organic contaminant loads into the Western Mediterranean Sea: estimate of Ebro River inputs

Annual input estimates for several organic contaminants from the Ebro River into the Northwestern Mediterranean Sea were carried out on the basis of monthly sampling from November 2002 to October 2003. Some organochlorine compounds (DDT and its degradation products, DDD and DDE, PCBs (9 congeners), HCB and gamma-HCH) were selected due to their reported occurrence in the river. Furthermore, some polar pesticides used in the Ebro Delta were also determined (atrazine, simazine, diazinon, fenitrothion and molinate). Concentrations ranged from 0.4 to 19.5 ng l(-1) for the organochlorine compounds (sum of particulate and dissolved phases) and from not detected (ND) to 170 ng l(-1) for the more polar pesticides, which were only found in the dissolved phase. The sum of PCB congeners (mean 8.9 ng l(-1)) showed the highest concentrations among the organochlorine compounds and atrazine (mean 82 ng l(-1)) among the polar pesticides. Based on the contaminant concentrations and on hydrological data, contaminant discharges into the sea were estimated amounting in total to 167 and 1,258 kg year(-1) of organochlorine compounds and polar pesticides, respectively. Furthermore, it was observed that PCBs, DDTs and HCB inputs were basically influenced by spate periods due to an increase in suspended particulate matter associated to runoff and sediment resuspension. Whereas for more water soluble contaminants, such as the agrochemicals, their seasonal use had a higher incidence in contaminant fluxes. Bulk chemical parameters such as SPM, DOC, POC, %OC, %ON and C/N ratio provided additional information on the organic matter sources. This provides a better understanding of the temporal variability of the contaminant concentrations.     

Environmental PCBs in Guánica Bay,Puerto Rico: implications for community health

Guánica Bay, located in southwestern Puerto Rico, has suffered oil spills and other pollution discharges since the 1960s. Previous research showed elevated concentrations of polychlorinated biphenyls (PCBs) in coral reef and sediment. This research examined PCB concentrations in sediment and fish. Sediment and fish sampling in the bay was facilitated by community members. This study identified the second highest reported PCB level (129,300 ng/g) in sediment in the USA. Fish samples also showed elevated concentrations (1623 to 3768 ng/g), which were higher than the thresholds of safe levels of PCBs in fish for human consumption. The alarmingly high concentration of PCBs calls for proactive community engagement to bring awareness about contamination of the bay and more extensive sampling to test for the concentration of PCBs in seafood and the people of Guánica. This study also underscores the value of the involvement of local communities during sampling design aimed at identifying hot spots of contaminants.     

Characterization of contaminants in snapping turtles (Chelydra serpentina) from Canadian Lake Erie Areas of Concern: St. Clair River, Detroit River, and Wheatley Harbour

PCBs, organochlorine pesticides and dioxins/furans in snapping turtle eggs and plasma (Chelydra serpentina) were evaluated at three Areas of Concern (AOCs) on Lake Erie and its connecting channels (St. Clair River, Detroit River, and Wheatley Harbour), as well as two inland reference sites (Algonquin Provincial Park and Tiny Marsh) in 2001-2002. Eggs from the Detroit River and Wheatley Harbour AOCs had the highest levels of p,p'-DDE (24.4 and 57.9 ng/g) and sum PCBs (928.6 and 491.0 ng/g) wet weight, respectively. Contaminant levels in eggs from St. Clair River AOC were generally higher than those from Algonquin Park, but similar to those from Tiny Marsh. Dioxins appeared highest from the Detroit River. The PCB congener pattern in eggs suggested that turtles from the Detroit River and Wheatley Harbour AOCs were exposed to Aroclor 1260. TEQs of sum PCBs in eggs from all AOCs and p,p'-DDE levels in eggs from the Wheatley Harbour and the Detroit River AOCs exceeded the Canadian Environmental Quality Guidelines. Furthermore, sum PCBs in eggs from Detroit River and Wheatley Harbour exceeded partial restriction guidelines for consumption. Although estimated PCB body burdens in muscle tissue of females were well below consumption guidelines, estimated residues in liver and adipose were above guidelines for most sites.     

Levels,congener profile and inventory of polychlorinated biphenyls in sediment from the Songhua River in the vicinity of cement plant,China: a case study

This study investigated the contamination levels, homologue, and congener profiles and evaluated the residue inventory of polychlorinated biphenyls (PCBs) in sediment of the Songhua River in the vicinity of cement plant. The total concentration of detected 35 PCB congeners ranged from 1.12 to 2.19 ng/g dry weight (dw) in sediment, with a mean value of 1.56 ng/g dw, and the concentration of PCBs decreased in the following order: the downstream?>?cement plant?>?upstream. The results of total organic carbon (TOC)-normalized PCB concentrations indicate that the sediments have low potential ecological risk in this area. The study results on homologue and congener of PCBs show that the emissions from cement production could be the major sources of PCBs in sediment, and the low-chlorinated PCBs will be exchanged among air, water, and sediment with increasing temperature during summer and flow to downstream with water during the wet season. The spatial density and total burden of PCBs in the surface sediments were 17.2 ng/cm² and 1.2 kg, respectively. To our knowledge, this study is the first to explore the pollution characteristics of unintentionally produced PCB emissions from cement industry by means of monitoring sediment samples.     

Sediment pollution and dynamic in the Mar Piccolo of Taranto (southern Italy): insights from bottom sediment traps and surficial sediments

Major and trace element, PAH, and PCB concentrations were measured in surface sediments and particles from sediment traps collected in the First and Second Basin of the Mar Piccolo (Gulf of Taranto) in two periods (June–July and August–September, 2013). The aim of the study was to evaluate pollution degree, sediment transport and particle redistribution dynamic within the area. Results confirm the higher contamination of sediments from the First Basin observed by previous researches, particularly for Cu, Hg, Pb, total PAHs, and total PCBs. Advective transport from the First to the Second Basin appears to be the leading transfer mechanism of particles and adsorbed contaminants, as evidenced by measured fluxes and statistical analyses of contaminant concentrations in surficial sediments and particles from sediment traps. Long-range selective transports of PAHs and microbial anaerobic degradation processes for PCBs have been also observed. These results are limited to a restricted time window but are consistent with the presence of transport fluxes at the bottom of the water column. This mechanism deserves further investigation and monitoring activities, potentially being the main responsible of pollutant delivering to the less contaminated sectors of the Mar Piccolo.     

Assessment of decadal changes in sediment contamination in a large connecting channel (Detroit River,North America)

Concentrations of selected heavy metals (Cd, Cu, Hg, Pb, Zn) and organic contaminants (PCBs, PAHs) were investigated in samples from the Detroit River (Great Lakes, North America) in 1999 and 2008/09 collected using a stratified random sampling design. Getis–Ord geospatial analysis was used to further establish locations of areas demonstrating significantly high and low contaminant concentrations in the river. Based on the stratified random sampling design, a majority of the examined metals and organic contaminants demonstrated little or no trends with respect to regional sediment concentrations and river-wide mass balances over the investigated time interval. The Getis–Ord analysis revealed local scales of contaminated and clean areas which did not conform to the original strata used in the geostatistical sampling design. It is suggested that geospatial analyses such as Getis–Ord be used in the design of future sediment quality surveys to refine locations of strata that can simultaneously address sediment recovery over system-wide, regional and local spatial scales.     

Within- and among-clutch variation of organohalogenated contaminants in eggs of great tits (Parus major)

In this study we investigated the variation of organohalogenated compounds, such as polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), and organochlorine pesticides (OCPs), within and among clutches of a small insectivorous songbird, the great tit (Parus major), and determined whether egg laying order affects the concentrations of these compounds. PCBs were the major organohalogenated contaminants in the eggs of great tits (mean 4778 ng/g lipid weight), while PBDEs (mean 204 ng/g lipid weight) and DDTs (mean 601 ng/g lipid weight) were found at much lower concentrations. Within-clutch variability of PCBs, PBDEs, and DDTs residues in the egg samples was small (7%, 3%, and 22%, respectively) compared to among-clutch variability (93%, 97%, and 78%, respectively). The small within-clutch variability may be in part related to the small home range of great tits and low spatial heterogeneity of the contaminants. We found no laying order effects on the concentrations of PCBs, PBDEs, and DDTs. Our results show that random egg samples of great tits are suitable as a biomonitoring tool for contamination with persistent organohalogenated pollutants in terrestrial environments.     

Halogenated organic contaminants (HOCs) in sediment from a highly eutrophicated lake, China: Occurrence, distribution and mass inventories

Halogenated organic contaminants (HOCs) including 16 polybrominated diphenyl ethers (PBDEs) and 37 polychlorinated biphenyls (PCBs) were determined in 49 surfacial sediments from Chaohu Lake, a highly eutrophicated lake, China. PBDEs were detected in almost samples with the range of the total concentration (defined as Σ₁₆PBDEs) from 0.84 to 86.6 ng g⁻¹. Compared with the occurrence of PBDEs in Pearl River Delta and Yangtze River Delta in China, lower percentage of BDE-209 over the concentration of Σ₁₆PBDEs was inferred by the high-volume application of penta-BDE mixture product for local domestic furniture purpose. The total concentration of 37 PCBs (Σ₃₇PCBs) ranged from 0.05 to 3.36 ng g⁻¹ with the most detection of PCB-1, -4, -52 and -71. Both the concentrations of Σ₁₆PBDE and Σ₃₇PCB poorly correlated with total organic carbon (TOC), suggesting the significant contribution of phytoplankton organic carbons to sediment TOC. The contamination by PBDEs and PCBs in western region of the lake was significantly more serious than in eastern lake. Our findings about the higher residues of PBDEs and PCBs in sediments at the estuary of Nanfei River compared to the other estuaries also supported the conclusion that urban area (Hefei city) was the main source of PBDEs and PCBs. The comparison with the concentration of HOC in the present study with those in other lacustrine sediments around the world suggested the contamination by PBDEs in Chaohu Lake is at middle of the global concentration range, whereas PCBs is at low end of the global range which could be elucidated by local economic development and historical usage of PBDEs and PCBs. The mass inventories of HOCs in the lake were estimated at 561 and 38 kg, which corresponds to only 0.000006% and 0.0001% of these global historical produce volumes, respectively.     

The chemical response of particle-associated contaminants in aquatic sediments to urbanization in New England, U.S.A

Relations between urbanization and particle-associated contaminants in New England were evaluated using a combination of samples from sediment cores, streambed sediments, and suspended stream sediments. Concentrations of PAHs, PCBs, DDT, and seven trace metals (Cd, Cr, Cu, Hg, Ni, Pb, Zn) were correlated strongly with urbanization, with the strongest relations to percentage commercial, industrial, and transportation (CIT) land use. Average PAH and metal concentrations in the most urbanized watersheds were approximately 30 and 6 times the reference concentrations, respectively, in remote, undeveloped watersheds. One-quarter to one-half of sampling sites had concentrations of PAHs, Cu, Pb, or Zn above the probable effects concentration, a set of sediment quality guidelines for adverse effects to aquatic biota, and sediments were predicted to be toxic, on average, when CIT land use exceeded about 10%. Trends in metals in cores from urban watersheds were dominantly downward, whereas trends in PAHs in a suburban watershed were upward. A regional atmospheric-fallout gradient was indicated by as much as order-of-magnitude-greater concentrations and accumulation rates of contaminants in cores from an undeveloped reference lake in Boston compared to those from remote reference watersheds. Contaminant accumulation rates in the lakes with urbanization in their watersheds, however, were 1-3 orders of magnitude greater than those of reference lakes, which indicate the dominance of local sources and fluvial transport of contaminants to urban lakes. These analyses demonstrate the magnitude of urban contamination of aquatic systems and air sheds, and suggest that, despite reductions in contaminant emissions in urban settings, streams and lakes will decline in quality as urbanization of their watersheds takes place.