Chapter 3
Persistent Organic Pollutants in the Coastal Atmosphere of the Mid-Atlantic States of the United States of America Downloaded via UNIV OF CALIFORNIA SANTA BARBARA on July 10, 2018 at 05:07:03 (UTC). See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.
Steven J . Eisenreich, Cari L. Gigliotti, Paul A. Brunciak, Jordi Dachs, Thomas R. Glenn IV, Eric D. Nelson, Lisa A. Totten, and Daryl A. Van Ry Department of Environmental Sciences, Rutgers, The State University of New Jersey, 14 College Farm Road, New Brunswick, NJ 08901 (E-mail:
[email protected])
Abstract The concentrations of polychlorinated biphenyls (PCBs; ~ 60 congeners), chlordanes (cis, trans chlordane; cis, trans nonachlor), polycyclic aromatic hydrocarbons (PAHs; 36 compounds), and nonylphenols (NPs; 11 isomers) were measured in the urban, suburban and coastal atmosphere of the N Y - N J area near the lower Hudson River Estuary (HRE). Concentrations exhibited significant seasonal and directional variability and were driven by local and regional emissions from combustion sources (PAHs), surface exchange at the atmosphere-land and atmosphere-water interfaces sub-regionally (PCBs, NPs) and long range transport from areas to the south and west (chlordanes). P C B concentrations in the region are typically higher than observed elsewhere reflecting the mix of historical uses and urban/industrial density plus volatilization from estuarine waters. P A H concentrations are high and reflect the mix of strong combustion sources in the region, especially vehicular and heating emissions. NPs in the atmosphere are reported for the first time and their source is dominated by volatilization from the H R E . Chlordanes exhibit low concentrations except when warm air masses transport volatilized pesticides from the S/SE United States.
I. Introduction Wet deposition via rain and snow, dry deposition of fine/coarse particles, and gaseous air-water exchange are the major atmospheric pathways for persistent organic pollutant (POP) input to the Great Waters such as the Great Lakes and Chesapeake Bay (1-3). The Integrated Atmospheric Deposition Network (IADN) operating in the Great Lakes (4, 5) and the Chesapeake Bay Atmospheric Deposition Study (CBADS)
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© 2001 American Chemical Society Lipnick et al.; Persistent, Bioaccumulative, and Toxic Chemicals I ACS Symposium Series; American Chemical Society: Washington, DC, 2000.
29 (6) were designed to capture the regional atmospheric signal, and thus sites were located in background areas away from local sources. However, many urban/industrial centers are located on or near coastal estuaries (e.g., Hudson River Estuary and N Y Bight) and the Great Lakes. Emissions of pollutants into the urban atmosphere are reflected in elevated local and regional pollutant concentrations and localized intense atmospheric deposition that is not observed in the regional signal (4, 5). The southern basin of Lake Michigan as one such location is subject to contamination by air pollutants such as PCBs and PAHs, Hg and trace metals (1-3) because of its proximity to industrialized and urbanized Chicago, IL and Gary, IN. Concentrations of PCBs and PAHs are significantly elevated in the Chicago and coastal lake offshore as compared to the regional signal (7-10). Higher atmospheric concentrations are ultimately reflected in increased precipitation (11) and dry particle fluxes of PCBs and PAHs (12) and trace metals (13, 14) to the coastal waters as well as enhanced air-water exchange fluxes of PCBs (15). The story is similar in the Chesapeake Bay (16, 17). The Hudson River Estuary is bordered by the densely urbanized and industrialized area of New York City, Connecticut, and northern New Jersey and in a prevailing transport regime downwind of other large atmospheric emission sources: Philadelphia, PA, Wilmington, DE, the Baltimore-Washington complex, and the Ohio River Valley. Except for Chesapeake Bay (1), there is little information on atmospheric concentrations and deposition and fate of persistent organic pollutants (POPs) in the Mid-Atlantic States. Our goal was to perform long-term spatially targeted measurements of atmospheric POPs such as PCBs, chlorinated pesticides, PAHs, and emerging chemicals near the Hudson River Estuary (HRE). Here we report the first year of atmospheric concentrations including seasonal and spatial trends for PCBs, chlordanes, PAHs and nonylphenols (NPs) as an example of emerging chemicals.
II. Setting and Brief Experimental Description Atmospheric research and monitoring stations were established at three locations surrounding the Hudson River Estuary (HRE) (Figure 1). The first site was established at the Rutgers Gardens Meteorological Station in August 1997 in a suburban area outside of New Brunswick, New Jersey (NB) about 1.5 km both from US Highway 1 and the N J Turnpike (suburban site). The second site was established at Sandy Hook, N J in February 1998 on a sandy spit reef extending into the N Y Bight and serving as the boundary between Raritan Bay/Hudson River Estuary and the Atlantic Ocean (marine/coastal site). The third site was established at the Liberty Science Center (LSC) in Jersey City, Ν J in July 1998 in the heart of the urban/industrial complex, on the H R E and across the Hudson River from Manhattan and the Statue of Liberty (urban-industrial site). Each site is equipped with a modified organics Hi-volume air sampler with a quartz fibre filter (QFF) and polyurethane foam (PUF) adsorbent operating at a calibrated flow rate of -0.5 nvVmin. At each site, 24-hour integrated air samples were collected every 6 days for
Lipnick et al.; Persistent, Bioaccumulative, and Toxic Chemicals I ACS Symposium Series; American Chemical Society: Washington, DC, 2000.
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Figure L Map of land and water sampling sites as part of the measurement of POPs in the NY-NJ area and the lower Hudson River Estuary.
Lipnick et al.; Persistent, Bioaccumulative, and Toxic Chemicals I ACS Symposium Series; American Chemical Society: Washington, DC, 2000.
31 the first year. The sampling frequency was changed to once in 12 days to match the I A D N as well as other long term monitoring programs. Integrated, wet-only precipitation samples were also collected every 12 (or 18) days using MIC collectors with 0.21 m stainless steel collection funnels and attached glass columns filled with X A D 2 resin. Additionally, an intensive sampling campaign was undertaken in the summer of 1998 that included air and water sampling from the Raritan Bay and lower HRE. Samples were extracted with petroleum ether (PUF), dichloromethane (QFF) and acetone/hexane (XAD), and cleaned up and fractionated on 3% H 0-deactivated alumina columns. The PCB fraction was analyzed on a HP 5890 G C equipped with a 60m high resolution glass capillary column (DB-5) and a Ni-63 electron capture detector. Samples were analyzed for chlordane (cis/trans), M C 5 , nonachlor (cis/trans), oxychlordane and PAHs using a HP 6890 Gas Chromatograph/5973 Mass Selective Detector in EI mode and selective ion monitoring. Nonylphenols and octylphenol were analyzed in the third fraction on a HP 5890 GC/5972 M S . Correlative measurements of total suspended particulate matter (TSP), particulate matter < 2.5 μηι in aerodynamic diameter (PM2.5) and particulate organic carbon (OC) and elemental carbon (EC) with supporting meteorological measurements (wind speed and direction, rainfall intensity, temperature) were also made but will not be reported extensively here. Back trajectories were obtained for each sampling interval using the N O A A H Y S P L I T model. A complete quality assurance protocol was established and followed on all analytes and media. 2
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III. Atmospheric Concentrations and Behavior
Polychlorinated Biphenyls (PCBs)
Urban/industrial areas are major sources of atmospheric polychlorinated biphenyls (PCBs) to surrounding waters (7, 11, 14, 15). Atmospheric transport from major urban/industrial areas can lead to significant loadings of PCBs to surrounding terrestrial and aquatic ecosystems (11, 18-22). Pathways for atmospheric P C B deposition to environmental surfaces include air-water exchange, air-vegetation exchange, wet deposition, and dry deposition. Once these aquatic and terrestrial surfaces have been loaded with PCBs, they may also act as a source to the regional atmosphere. Measurements of atmospheric PCBs in the New Jersey/New York area are few although the Chesapeake Bay has been extensively studied (15, 16, 21, 23). Analysis of sediment and water from wastewater treatment systems reveals an extensive impact in the New Jersey/New York area (17, 24-27). For example, Durrell and Lizotte (24) found total P C B influent concentrations in wastewater treatment facilities ranging
Lipnick et al.; Persistent, Bioaccumulative, and Toxic Chemicals I ACS Symposium Series; American Chemical Society: Washington, DC, 2000.
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from 31 to 625 ng L" during normal flow (110 ng L" average). The other major source of PCBs to the Hudson River Estuary (HRE) derive from upstream loading of PCBs resulting from historical industrial releases and the continuing release from contaminated sediments (28). With elevated concentrations in water and sediments, and based on the vapor pressures of these compounds, atmospheric transport must play a key role in the cycling of PCBs. . High concentrations of PCBs in water and sediments have been well-documented for several rivers in the New Jersey/New York metropolitan area (17, 25). In contrast, little is known about atmospheric concentrations of PCBs in this area. Atmospheric PCBs derive from historical uses in the urban/industrial setting, surface to air exchange from local waters and terrestrial areas, emissions from landfills, and from sub-regional and long-range transport into the metropolitan area. Table I shows the atmospheric P C B concentrations at the New Brunswick suburban, Sandy Hook coastal and Liberty Science Center urban/industrial sites. Concentrations of the gas (G) + particle (P) phase in air and in precipitation were highest at the LSC site. In comparison to other studies, the Z P C B concentrations (-60 congeners) at the Sandy Hook coastal site are approximately 2 X those reported at Sturgeon Point, N Y , an Integrated Atmospheric Deposition Network (IADN) site (4, 5), but similar to reported values in the Chesapeake Bay, M D (15, 21). Although S H is a marine/coastal site, P C B concentrations are sufficiently high to suggest that "local" sources impact this site. Precipitation volume-weighted mean concentrations are higher at New Brunswick than at both the Sandy Hook site and Chesapeake Bay. The P C B concentrations measured in precipitation at the Sandy Hook site are comparable to those reported in Chesapeake Bay (21). Figure 2 shows a comparison of L P C B concentrations (G+P) at the N B , S H , and L S C sites plotted with a temperature profile from N B . Average concentrations over the sampling period from October 1997 through November 1998 were higher at N B (560 pg m" ) than at Sandy Hook (457 pg m' ) from the commencement of sampling in February 1998 through November 1998. A comparison of the average I P C B concentrations over the same sampling period (February through November 1998) showed an even greater difference in concentration between the N B (605 pg m* ) and SH (457 pg m" ) sites. The patterns of I P C B s between the two sites are statistically different (p
