Polychlorinated Dioxins and Furans from the World Trade Center

View Sections. ACS2GO © 2018. ← → → ←. loading. To add this web app to the home screen open the browser option menu and tap on Add to hom...
0 downloads 0 Views 666KB Size
Download PDF
Environ. Sci. Technol. 2005, 39, 1995-2003

Polychlorinated Dioxins and Furans from the World Trade Center Attacks in Exterior Window Films from Lower Manhattan in New York City SIERRA RAYNE Department of Chemistry, University of Victoria, P.O. Box 3065, Victoria, BC, Canada, V8W 3V6 MICHAEL G. IKONOMOU* Institute of Ocean Sciences, Fisheries and Oceans Canada, 9860 West Saanich Road, Sidney, BC, Canada V8L 4B2 CRAIG M. BUTT, MIRIAM L. DIAMOND, AND JENNIFER TRUONG Department of Geography, University of Toronto, 45 St. George Street, Toronto, ON, Canada, M5S 3G3

Samples of ambient organic films deposited on exterior window surfaces from lower Manhattan and Brooklyn in New York City were collected six weeks after the terrorist attacks at the World Trade Center (WTC) on September 11, 2001 and analyzed for polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). Total tetra- through octaCDD/F concentrations in window films within 1 km of the WTC site in lower Manhattan ranged up to 630 000 pg/m2 (estimated as a mass concentration of ca. 1 300 000 pg/ g) and a maximum toxic equivalent (TEQ) concentration of 4700 TEQ/m2 (ca. 10 000 pg TEQ/g). Measurements at a background site 3.5 km away in Brooklyn showed lower concentrations at 130 pg TEQ/m2 (260 pg TEQ/g). Ambient gasphase PCDD/F concentrations estimated for each site using an equilibrium partitioning model suggested concentrations ranging from ca. 2700 fg-TEQ/m3 near the WTC site to the more typical urban concentration of 20 fgTEQ/m3 at the Brooklyn site. Multivariate analyses of 2,3,7,8substitued congeners and homologue group profiles suggested unique patterns in films near the WTC site compared to that observed at background sites in the study area and in other literature-derived combustion source profiles. Homologue profiles near the WTC site were dominated by tetra-, penta-, and Hexa-CDD/Fs, and 2,3,7,8substituted profiles contained mostly octa- and hexachlorinated congeners. In comparison, profiles in Brooklyn and near mid-Manhattan exhibited congener and homologue patterns comprised mainly of hepta- and octa-CDDs, similar to that commonly reported in background air and soil.

Introduction The terrorist attacks at the World Trade Center (WTC) complex in New York City on September 11, 2001 resulted * Corresponding author phone: (250)363-6804; fax: (250)363-6807 e-mail: [email protected]. 10.1021/es049211k CCC: $30.25 Published on Web 02/15/2005

 2005 American Chemical Society

in the immediate loss of life of nearly 3000 persons. Each of the twin towers at the WTC site was attacked by a hijacked commercial airplane and destroyed by the combined effects of the plane impacts and the fires ignited by the jet fuel carried by the planes. These events marked the first time high-rise buildings have been destroyed by such tactics (1). Before the attacks, the north and south towers of the WTC were the tallest buildings in New York City (NYC) at 110 stories each, with respective heights of 417 and 415 m. The hijacked planes collided with the north and south towers at 8:46 AM EST and 9:03 AM EST, each carrying an estimated 34 000 L and 31 000 L of jet fuel, respectively (2). The initial building fires weakened the steel floor joists, causing the eventual collapse of the north and south towers within 104 and 62 min after being hit, respectively. WTC-7, a 47-story office building, was also damaged by the collapsing towers, subsequently caught fire, and collapsed later in the afternoon of September 11, 2001. The terrorist attacks on the WTC resulted in a single-day death toll greater than at any other time in American history except the Civil War battle of Antietam (3). When the WTC towers collapsed, more than 1.2 million tons of building material came down in the core of lower Manhattan (4). The resulting fires caused by the nearly full airline fuel tanks at the times of the impacts were estimated to range from 750 °C (5-7) up to 2500 °C (8). Following the collapse of the towers, fires continued to burn at the site for several months at lower temperatures. The large quantities of plastics in building materials (e.g., PVC piping and coated copper wire), consumer and office goods present in each tower, and ∼130 000 gallons of PCB contaminated transformer oil (4) stored below ground level represented a potential store of halogenated organic contaminants arising from subsequent processes of combustion and pyrolysis. In the present study, we investigated concentrations and patterns of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in exterior surface films obtained from windows in Lower Manhattan and Brooklyn six weeks after the WTC attacks. Surface films such as these accumulate on impervious surfaces that are characteristic of urban areas (e.g., windows, building exteriors, asphalt). The films are derived from the deposition of numerous organic and inorganic compounds present in ambient urban air (9, 10). As such, the films provide a sample of the complex mixture of semivolatile organic compounds (SVOCs) to which humans and biota are exposed through inhalation of urban air and ingestion of, and contact with, urban soils and vegetation. Furthermore, exterior surfaces of windows were chosen as convenient impervious surfaces because of their ubiquity, ease of sampling, relatively inert nature, and absence of inherent contamination (10). Material accumulated on the exterior of windows has also proven to be a convenient and reproducible means of obtaining an integrated sample of atmospherically deposited chemicals. Particles and particlesorbed chemicals are efficiently captured on such surface films (9) that are presumed to initially accumulate because of the condensation of gas-phase compounds, followed by the deposition of particulate matter. As the film continues to grow and develop, gas-phase compounds may partition between the air and the organic phase of the film (10, 11). The primary objectives of this study were to use window films as (a) indicators of the potential degree of contamination by PCDD/Fs in lower Manhattan and surrounding regions from the WTC attacks on September 11, 2001 and subsequent fires and (b) to explore previously unreported unique PCDD/ Fs congener patterns that resulted from the WTC fires. VOL. 39, NO. 7, 2005 / ENVIRONMENTAL SCIENCE & TECHNOLOGY

9

1995

FIGURE 1. Sampling locations for window films in New York City. Sampling site labels and superscripts correspond with site descriptions in other figures and tables. The height of the vertical bars in (a) and (b) correspond with relative ΣPCDD/F and ΣPCDD/F-TEQ concentrations between sites as given in Table 1, respectively. The base of each bar indicates the geographical location of the sampling site.

TABLE 1. Concentrations (in pg/m2) of 2,3,7,8-Substituted PCDD/Fs, ΣP4-8CDD/F, and TEQs in Window Films from New York City

latitude (°N) longitude (°W) date sampled (dd/mmm/yy) date of last cleaning (dd/mmm/yy) window area (m2) 2,3,7,8-D F 1,2,3,7,8-DF 2,3,4,7,8-DF 1,2,3,4,7, 8-DF 1,2,3,6,7, 8-DF 2,3,4,6,7, 8-DF 1,2,3,7,8, 9-DF 1,2,3,4,6, 7,8-DF 1,2,3,4,7, 8,9-DF OCDF 2,3,7,8-D D 1,2,3,7,8-DD 1,2,3,4,7, 8-DD 1,2,3,6,7, 8-DD 1,2,3,7,8, 9-DD 1,2,3,4,6, 7,8-DD OCDD ΣPCDD/F TEQ

Brooklyn

Manhattan (Church & Warren)

Manhattan (Broadway & Worth)

Manhattan (Museum)

40.69205 -73.9883 3 28/Oct/01 unknown

40.71486 -74.0082 8 27/Oct/01 26-31/Aug/01

40.71677 -74.0043 5 28/Oct/01 unknown

40.70510 -74.0140 9 29/Oct/01 Jul/00

40.72190 -74.0044 2 27/Oct/01 25/Oct/01

3.091 12 1.5 24 27 1.0 18 1.0 166 12 198 1.9 7.1 15 24 18 268 2037 5465 126

0.600 3948 9.7 10 2463 4.8 1250 207 4300 560 1635 455 1505 1082 1525 1807 4295 14978 626 472 978

2.477 865 1.8 1.8 1376 1.7 853 112 2491 392 555 131 798 758 1031 872 2066 1703 224 849 4680

1.053 1042 16.5 16 902 3.2 602 79 1759 229 721 128 482 387 585 564 1801 6454 153 475 1166

4.291 299 1.2 1.2 515 0.9 335 42 962 156 247 41 269 249 361 413 818 768 74 599 3090

Further, window films have been used to examine the extent and magnitude of September 11th contamination with respect to polycyclic aromatic hydrocarbons (PAH), polychlorinated biphenyls (PCB), polybrominated diphenyl ethers (PBDE), polychlorinated naphthalenes (PCN), and organochlorinated pesticides (12).

Experimental Section Sample Collection. Organic film samples were collected from the outside of windows at eight sites in lower Manhattan and Brooklyn, New York City (Figure 1) by scrubbing the surfaces with precleaned laboratory Kimwipes soaked in HPLC grade 2-propanol. All sampling locations were on window surfaces facing the WTC site. Between 0.6 and 5.6 m2 of window surface area was cleaned at each site depending on the apparent quantity of organic film (Table 1). Kimwipes were precleaned by extracting with CH2Cl2, air-drying, and storing in precleaned clear glass jars. Field blanks were 1996

9

ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 39, NO. 7, 2005

Manhattan Manhattan (Broadway & (Park Row/ Canal) Spruce)

Manhattan (Union Square)

Manhattan (NYU)

40.71240 -74.0059 2 27/Oct/01 unknown

40.73491 -73.9864 5 28/Oct/01 3.5-4.0 km from the WTC site that are representative of background conditions in Brooklyn and northern lower Manhattan. ΣP4-8CDD/F concentrations in window films decreased rapidly as a function of distance from the WTC site (Figure 1). Concentrations of all 135 congeners in the three blank samples taken in Brooklyn and in lower Manhattan (at the Church & Warren and NYU) were below the method detection limits for P4-8CDDs (3.3-14.2 pg per congener) and P4-8CDFs (1.8-12.1 pg per congener), respectively. These results suggest negligible PCDD/F contamination of Kimwipe window film samples during exposure to the ambient atmosphere at each site, even those closest to the WTC (e.g., Church & Warren). In lower Manhattan, window films appeared to have greater mass than those found in other urban areas (∼100-200 mg/m2) (10), possibly up to 400-500 mg/m2. Using an upper estimate of 500 mg/m2 window film in lower Manhattan, P4-8CDD/F concentrations are conservatively estimated at 1 300 000 pg/g (pg analyte per gram of surface film) in window films near the WTC. Similar spatial patterns were also observed for the 17 individual 2,3,7,8-substituted PCDD/Fs. For all 2,3,7,8substituted PCDD/F congeners except 2,3,4,7,8-PeCDF, the highest concentrations were observed nearest the WTC site and decreasing levels were found moving north into midManhattan and southeast into Brooklyn. The anomalous spatial pattern for 2,3,4,7,8-PeCDF (exhibiting a maximum of 330 pg/m2 at the Union Square site, with all other concentrations in the range 0.9-24 pg/m2) may be a result of its coelution with 1,2,4,8,9-, 1,3,4,8,9-, and 1,2,3,6,9-PeCDF, making the reported values subject to background regional PCDD/F patterns. In other words, there may be a regional background PCDD/F pattern with localized PCDD/F “hot spots” for certain congeners in Manhattan superimposed on VOL. 39, NO. 7, 2005 / ENVIRONMENTAL SCIENCE & TECHNOLOGY

9

1997

TABLE 2. Predicted Gas-Phase Air Concentrations (in fg/m3) of 2,3,7,8-Substituted PCDD/Fs and TEQs in New York City Back-Calculated from Window Films, on the Basis of an Equilibrium Partitioning Approach

2,3,7,8-DF 1,2,3,7,8-DF 2,3,4,7,8-DF 1,2,3,4,7,8-DF 1,2,3,6,7,8-DF 2,3,4,6,7,8-DF 1,2,3,7,8,9-DF 1,2,3,4,6,7,8 -DF 1,2,3,4,7,8,9 -DF OCDF 2,3,7,8-DD 1,2,3,7,8-D D 1,2,3,4,7,8-DD 1,2,3,6,7,8-DD 1,2,3,7,8,9-DD 1,2,3,4,6,7,8 -DD OCDD TEQ

Brooklyn

Manhattan (Church & Warren)

Manhattan (Broadway & Worth)

Manhattan (Musuem)

Manhattan (Broadway & Canal)

Manhattan (Park Row/ Spruce)

Manhattan (Union Square)

Manhattan (NYU)

30 1.3 15.6 6.6 0.2 3.4 0.2 21.5 0.8 4.5 3.4 3.7 2.3 3.6 2.5 17.8 33.0 20

9604 8.3 6.5 605 1.1 240 34.2 556 39.3 37.5 822 783 169 228 248 285 243 2730

2111 1.5 1.2 338 0.4 164 18.5 322 27.5 12.7 237 415 118 154 120 137 27.6 951

2538 14.1 10.4 222 0.8 115 13.0 228 16.1 16.5 231 251 61 87.5 77.3 120 105 804

732 1.0 0.8 127 0.2 64.2 6.9 124 10.9 5.7 74.1 140 38.9 54.0 56.6 54.3 12.5 320

605 2.3 1.8 99.7 0.6 51.0 4.8 102 8.4 4.7 4.9 121 36.1 49.5 49.1 53.6 14.6 219

352 3.6 213 71.5 0.9 35.8 2.8 68.4 0.3 3.9 13.9 65.5 22.5 31.1 22.8 43.8 29.0 241

11 0.8 0.6 2.0 0.1 1.3 0.1 3.6 0.0 0.3 1.3 2.4 1.1 1.5 0.1 2.9 2.9 6

the PCDD/F signature produced by the WTC attacks. Full congener concentrations of the 135 individual P4-8CDD/Fs analyzed in this study at each site are provided in Supporting Information Table S2. Concentrations of the 118 non-2,3,7,8substituted P4-8CDD/Fs followed a similar spatial pattern to the 2,3,7,8-subsituted congeners discussed above. The highest concentrations for 134 of 135 congeners (except for 2,3,4,7,8pentaCDF as discussed above) were observed nearest the WTC site. This attests to the WTC attacks as the dominant source of all tetra- through octa-CDD/F congeners in lower Manhattan. Calculated Equilibrium Air Concentrations of PCDD/ Fs. Surface films also play an important role in mediating chemical transport among environmental compartments (15, 16). These films act as transient sinks for chemicals whereby low vapor pressure compounds are transferred to surface waters via precipitation and subsequent runoff, and higher vapor pressure compounds may volatilize into the atmosphere (16). The rapid response time of the mass of chemicals in the film (days to weeks) contrasts sharply with that of soil (years) (15). Within the atmosphere, SVOCs (such as PCDD/ Fs) sorbed to particulate matter are assumed to be at equilibrium with the gas phase (17). This equilibrium partitioning can also be extended to surface films (18), and gas-phase concentrations can thus be calculated as Cg-air ) Cfilm/(foc × KOA), where Cg-air is the concentration of a particular analyte in the atmospheric gas phase, Cfilm is the analyte concentration in the surface film, foc is organic carbon content of the surface film (on a mass basis; typically 0.2 for exterior surface films (10)), and KOA is the octanol-air partition coefficient (15). This technique has been successfully used to estimate gas-phase air concentrations of polybrominated diphenyl ethers in Southern Ontario, Canada (19). For PCDD/ Fs at approximately 17 °C, values of log KOA range from 10.90 for 2,3,7,8-TeCDF to 13.00 for octa-CDD (20). Previous work has reinforced the validity of assuming equilibrium between the atmospheric gas phase and surface films for persistent SVOCs (i.e., those with minimal degradation within the film such as PCBs) (18). The potential to reconstruct gas-phase PCDD/F air concentrations using this equilibrium partitioning approach in NYC is complicated by the reported rapid decrease in total atmospheric (i.e., gas + particle phase) PCDD/F concentrations following the WTC attacks (21). On the basis of previous studies of air particles, the kinetics of sorption-desorption are not assumed to be rate-limiting, and that diffusion, which is presumed to be 1998

9

ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 39, NO. 7, 2005

the rate-limiting step, is rapid and occurs within a time scale of hours to days. Given this potential for rapid air-film exchange, chemical concentrations in surface films are likely representative of atmospheric conditions at the time of sampling, although it must be remembered that the surface film material itself, and hence the mass of contaminants within the film, accumulates over time. Using this equilibrium partitioning approach under changing atmospheric contaminant levels (conditions were observed to occur after the WTC attacks), back-calculated gas-phase air concentrations of SVOCs can provide order-of-magnitude estimates. Predicted PCDD/F-TEQ gas-phase air concentrations (Table 2) ranged from 6 to 20 fg-TEQ/m3 at sites most remote from the WTC (NYU and Brooklyn, respectively) and up to 2730 fg-TEQ/m3 near the former site of the WTC (Church & Warren) in a pattern analogous to ΣPCDD/F concentrations in window films. These predicted PCDD/F-TEQ concentrations are within the range reported for air samples taken at the same time by the U.S. EPA in lower Manhattan (100010 000 fg-TEQ/m3 throughout most of lower Manhattan and increasing up to 175 pg-TEQ/m3 at the WTC site) (21). The U.S. EPA data are gas + particle-phase PCDD/Fs and are expected to exceed our estimated gas-phase only concentrations by severalfold since most PCDD/F are found in the particle phase. The estimated gas-phase PCDD/F-TEQs near the former WTC site are up to 2.5 orders of magnitude higher than at background sites in Brooklyn and closer to midManhattan. By comparison, atmospheric gas + particle-phase PCDD/F-TEQ concentrations reported in the literature can typically be divided into the following three groups on the basis of proximity to human activities: remote regions ( P6CDF > P7CDF ≈ P8CDF. At these other two sites, P4CDF was the dominant PCDF homologue group with a consistent pattern of decreasing contribution with increasing chlorination. The slightly higher contribution of P5CDF than P4CDF at some sites in lower Manhattan is also similar to other reported PCDF combustion signatures (24, 31). The fires resulting from the WTC attacks also produced unusual 2,3,7,8-substituted PCDD/F congener patterns (Figure 3). Here, we use the congener data from the DB225 column that separates 2,3,7,8-TeCDF from the other TeCDF congeners. The seven sites in lower Manhattan exhibit a VOL. 39, NO. 7, 2005 / ENVIRONMENTAL SCIENCE & TECHNOLOGY

9

1999

FIGURE 3. 2,3,7,8-Substituted PCDD/F congener profiles for window films in New York City. Contributions of 2,3,7,8-DF at each sampling site shown above are those obtained from use of the DB225 analytical column which resolves 2,3,7,8-DF from its coeluting tetra-CDF congeners. significantly lower proportion of octa-CDD (0.7-12% of ΣP4-8CDD/F) than in Brooklyn (37%). The second most abundant 2,3,7,8-substituted congener was 1,2,3,4,6,7,8-HpCDF which comprised 98% by mass) that would have preferentially captured particle associated PCDD/Fs, such as penta- through octa-CDD/Fs, which have decreasing proportions in the gas phase with increasing chlorination (e.g., minimum gas-phase fractions for octa-CDD/F of 1.3% and 1.9%, respectively (20)). Furthermore, the high organic content of window films (38) versus the largely inorganic and ionic content of the dust further favors partitioning of PCDD/Fs into these surface films. Finally, the differences could be due to different combustion conditions that contributed to the PCDD/F profiles sampled immediately after the WTC attacks versus the smoldering conditions that prevailed in the ensuing wreckage.

FIGURE 4. Cluster analysis plot of 2,3,7,8-substituted PCDD/F congener patterns in window films from lower Manhattan and Brooklyn in New York City and samples from other combustion processes known to produce PCDD/Fs. The cluster analysis was performed using the contributions of 2,3,7,8-DF, including those reported both in the literature references and in the current study, determined on DB5 or SP2331 columns which are unable to resolve 2,3,7,8-DF from its other coeluting tetra-CDF congeners.

Cluster analysis (CA; Figure 4) and principal components analysis (PCA; Figure 5) were used to further interpret 2,3,7,8substituted PCDD/F film profiles relative to source profiles (as percent in total 2,3,7,8-substituted PCDD/Fs, see Supporting Information Tables S4 and S5 for published congener patterns corresponding references). These multivariate analyses were performed using the contributions of 2,3,7,8DF, including those reported both in the literature references and in the current study, determined on DB5 or SP2331 columns which are unable to resolve 2,3,7,8DF from its other coeluting tetra-CDF congeners. The analyses show that the samples from lower Manhattan group together (suggesting similar congener patterns and a common source) and apart from the Brooklyn sample, which is more remote from the WTC site. In the CA plot, a close correlation is observed between the Brooklyn window sample and other normal urban and rural air samples, suggesting that the Brooklyn site was largely unaffected by the WTC PCDD/F plume. The lower Manhattan samples are also distinct from, but most closely related to, other combustion and pyrolysis samples, including those from various types of incinerators, hydrocarbon combustion (e.g., heavy oil, diesel fuel, paper), PVC combustion, and combinations of these processes and materials (e.g., PVC + paper combustion). Similar results were observed for the PCA plot, whereby the lower Manhattan

FIGURE 5. Principal component analysis plot of 2,3,7,8-substituted PCDD/F congener patterns in window films from lower Manhattan and Brooklyn in New York City and samples from other combustion processes known to produce PCDD/Fs. This was performed using the contributions of 2,3,7,8-DF, including those reported both in the literature references and in the current study, determined on DB5 or SP2331 columns which are unable to resolve 2,3,7,8-DF from its other coeluting tetra-CDF congeners. VOL. 39, NO. 7, 2005 / ENVIRONMENTAL SCIENCE & TECHNOLOGY

9

2001

window film samples grouped separately from other known combustion sources and the Brooklyn window film, which grouped with other normal urban and rural air samples.

Acknowledgments We thank the building owners and managers of New York City who granted permission for sample collection. J. Archbold, K. Tsoi, and H. Jones of University of Toronto assisted with sampling. Funding was provided by Environment Canada. We thank the analysts of the Regional Dioxin Laboratory at the Institute of Ocean Sciences for their assistance with sample analyses. We are also grateful to the Department of Fisheries and Oceans for supporting us with our collaborative research.

Supporting Information Available Additional tables as noted in the text. This material is available free of charge via the Internet at http://pubs.acs.org.

Literature Cited (1) Rehm, R. G.; Pitts, W. M.; Baum, H. R.; Evans, D. D.; Prasad, K.; McGrattan, K. B.; Forney, G. P. Initial Model for Fires in the World Trade Center Towers; Building and Fire Research Laboratory, National Institute of Standards and Technology: Gaithersburg, MD, 2002. (2) World Trade Center Building Performance Study: Data Collection, Preliminary Observations, and Recommendations; Federal Emergency Management Agency, Federal Insurance and Mitigation Administration: Washington, DC, 2002. (3) Lipton, E. A New Count of the Dead, but Little Sense of Relief. New York Times, Dec 2, 2001, 41. (4) Nordgren, M. D.; Goldstein, E. A.; Izeman, M. A. The Environmental Impacts of the World Trade Center Attacks: A Preliminary Assessment; Natural Resources Defense Council: Washington, DC, 2002. (5) Eagar, T. W.; Musso, C. Why did the World Trade Center Collapse? Science, engineering, and speculation. JOM-J. Min. Met. Mater. Soc. 2001, 53, 8-11. (6) Bazant, Z. P.; Zhou, Y. Why did the World Trade Center collapse? Simple analysis. J. Engr. Mech.-ASCE 2002, 128, 2-6. (7) Ashley, S. When the Twin Towers Fell. Sci. Am. [Online] http:// www.sciam.com/explorations/2001/100901wtc/ (accessed Dec 9, 2001). (8) Investigative Reports. Anatomy of September 11th, Broadcast September 9, 2002 (Arts & Entertainment Network). (9) Liu, Q. T.; Diamond, M. L.; Gingrich, S. E.; Ondov, J. M.; Maciejczyk, P.; Stern, G. A. Accumulation of metals, trace elements and semi-volatile organic compounds on exterior window surfaces in Baltimore. Environ. Pollut. 2003, 122, 5161. (10) Diamond, M. L.; Gingrich, S. E.; Fertuck, K.; McCarry, B. E.; Stern, G. A.; Billeck, B.; Grift, B.; Brooker, D.; Yager, T. D. Evidence for organic film on an impervious urban surface: characterization and potential teratogenic effects. Environ. Sci. Technol. 2000, 34, 2900-2908. (11) Gingrich, S. E.; Diamond, M. L. Atmospherically derived organic surface films along an urban-rural gradient. Environ. Sci. Technol. 2001, 35, 4031-4037. (12) Butt, C. M.; Diamond, M. L.; Truong, J.; Ikonomou, M. G.; Helm, P. A.; Stern, G. A. Semivolatile organic compounds in window films from lower Manhattan after the September 11th World Trade Center attacks. Environ. Sci. Technol. 2004, 38, 35143524. (13) Ikonomou, M. G.; Fraser, T. L.; Crewe, N. F.; Fischer, M. B.; Rogers, I. H.; He, T.; Sather, P. J.; Lamb, R. F. A comprehensive multi-residue ultra-trace analytical method, based on HRGC/ HRMS, for the determination of PCDDs, PCDFs, PCBs, PBDEs, PCDEs, and organohalogen pesticides in six different environmental matrices. Can. Technol. Rep. Fish. Aquat. Sci. 2001, 2389, 1-95. (14) Van den Berg, M.; Birnbaum, L.; Bosveld, A. T. C.; Brunstrom, B.; Cook, P.; Feeley, M.; Giesy, J. P.; Hanberg, A.; Hasegawa, R.; Kennedy, S. W.; Kubiak, T.; Larsen, J. C.; van Leeuwen, F. X. R.; Liem, A. K. D.; Nolt, C.; Peterson, R. E.; Poellinger, L.; Safe, S.; Schrenk, D.; Tillitt, D.; Tysklind, M.; Younes, M.; Waern, F.; Zacharewski, T. Toxic equivalency factors (TEFs) for PCBs, PCDDs, PCDFs for humans and wildlife. Environ. Health Perspect. 1998, 106, 775-792. 2002

9

ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 39, NO. 7, 2005

(15) Diamond, M. L.; Priemer, D. A.; Law, N. L. Developing a multimedia model of chemical dynamics in an urban area. Chemosphere 2001, 44, 1655-1667. (16) Priemer, D. A.; Diamond, M. L. Application of the multimedia urban model to compare the fate of SOCs in an urban forested watershed. Environ. Sci. Technol. 2002, 36, 1004-1013. (17) Harnly, M.; Stephens, R.; Mclaughlin, C.; Marcotte, J.; Petreas, M.; Goldman, L. Polychlorinated dibenzo-p-dioxin and dibenzofuran contamination at metal recovery facilities, open burn sites, and a railroad car incineration facility. Environ. Sci. Technol. 1995, 29, 677-684. (18) Butt, C. M. Chemical and Physical Characterization of Organic Films on an Impervious Surface. M. Sc. Thesis, Department of Geography, University of Toronto, Toronto, ON, Canada, 2003. (19) Butt, C. M.; Diamond, M. L.; Truong, J.; Ikonomou, M. G.; ter Shure, A. F. H. Spatial distribution of polybrominated diphenyl ethers in southern Ontario as measured in indoor and outdoor window organic films. Environ. Sci. Technol. 2004, 38, 724731. (20) Harner, T.; Green, N. J. L.; Jones, K. C. Measurements of octanolair partition coefficients for PCDD/Fs: a tool in assessing airsoil equilibrium status. Environ. Sci. Technol. 2000, 34, 31093114. (21) U.S. EPA. Exposure and Human Health Evaluation of Airborne Pollution from the World Trade Center Disaster; EPA/600/P2/002A(External Review Draft); United States Environmental Protection Agency, Office of Research and Development, National Center for Environmental Assessment: Washington, DC, 2002. (22) Lohmann, R.; Jones, K. C. Dioxins and furans in air and deposition: a review of levels, behaviour and processes. Sci. Total Environ. 1998, 219, 53-81. (23) Anthony, E. J.; Jia, L.; Granatstein, D. L. Dioxin and furan formation in FBC boilers. Environ. Sci. Technol. 2001, 35, 30023007. (24) Lugar, R. M.; Harless, R. L.; Dupuy, A. E.; McDaniel, D. D. Results of monitoring for polychlorinated dibenzo-p-dioxins and dibenzofurans in ambient air at McMurdo Station, Antarctica. Environ. Sci. Technol. 1996, 30, 555-561. (25) Pandompatam, B.; Kumar, Y.; Guo, I.; Liem, A. J. Comparison of PCDD and PCDF emissions from hog fuel boilers and hospital waste incinerators. Chemosphere 1997, 34, 1065-1073. (26) Katami, T.; Ohno, N.; Yasuhara, A.; Shibamoto, T. Formation of dioxins from sodium chloride-impregnated newspapers by combustion. Bull. Environ. Contam. Toxicol. 2000, 64, 372376. (27) Yasuhara, A.; Katami, T.; Okuda, T.; Ohno, N.; Shibamoto, T. Formation of dioxins during the combustion of newspapers in the presence of sodium chloride and poly(vinyl chloride). Environ. Sci. Technol. 2001, 35, 1373-1378. (28) Lorber, M.; Pinsky, P.; Gehring, P.; Braverman, C.; Winters, D.; Sovocool, W. Relationships between dioxins in soil, air, ash, and emissions from a municipal solid waste incinerator emitting large amounts and dioxins. Chemosphere 1998, 37, 2173-2197. (29) Duarte-Davidson, R.; Sewart, A.; Alcock, R. E.; Cousins, I. T.; Jones, K. C. Exploring the balance between sources, deposition, and the environmental burden of PCDD/Fs in the UK terrestrial environment: an aid to identifying uncertainties and research needs. Environ. Sci. Technol. 1997, 31, 1-11. (30) Lee, R. G. M.; Green, N. J. L.; Lohmann, R.; Jones, K. C. Seasonal, anthropogenic air mass, and meteorological influences on the atmospheric concentrations of polychlorinated dibenzo-pdioxins and dibenzofurans (PCDD/Fs): evidence for the importance of diffuse combustion sources. Environ. Sci. Technol. 1999, 33, 2864-2871. (31) Brzuzy, L. P.; Hites, R. A. Global mass balance for polychlorinated dibenzo-p-dioxins and dibenzofurans. Environ. Sci. Technol. 1996, 30, 1797-1804. (32) Sakai, S. I.; Hayakawa, K.; Takatsuki, H.; Kawakami, I. Dioxinlike PCBs released from waste incineration and their deposition flux. Environ. Sci. Technol. 2001, 35, 3601-3607. (33) Ryan, J. V.; Gullett, B. K. On-road emission sampling of a heavyduty diesel vehicle for polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans. Environ. Sci. Technol. 2000, 34, 4483-4489. (34) Berlincioni, M.; Didomenico, A. Polychlorodibenzo-para-dioxins and polychlorodibenzofurans in the soil near the municipal incinerator of Florence, Italy. Environ. Sci. Technol. 1987, 21, 1063-1069. (35) Safe, S.; Brown, K. W.; Donnelly, K. C.; Anderson, C. S.; Markiewicz, K. V.; Mclachlan, M. S.; Reischl, A.; Hutzinger, O. Polychlorinated dibenzo-para-dioxins and dibenzofurans as-

sociated with wood-preserving chemical sites - biomonitoring with pine needles. Environ. Sci. Technol. 1992, 26, 394-396. (36) Eitzer, B. D.; Hites, R. A. Polychlorinated dibenzo-para-dioxins and dibenzofurans in the ambient atmosphere of Bloomington, Indiana. Environ. Sci. Technol. 1989, 23, 1396-1401. (37) Lioy, P. J.; Weisel, C. P.; Millette, J. R.; Eisenreich, S.; Vallero, D.; Offenberg, J.; Buckley, B.; Turpin, B.; Zhong, M. H.; Cohen, M. D.; Prophete, C.; Yang, I.; Stiles, R.; Chee, G.; Johnson, W.; Porcja, R.; Alimokhtari, S.; Hale, R. C.; Weschler, C.; Chen, L. C. Characterization of the dust/smoke aerosol that settled east of the World Trade Center (WTC) in lower Manhattan after the

collapse of the WTC 11 September 2001. Environ. Health Perspect. 2002, 110, 703-714. (38) Liu, Q. T.; Chen, R.; McCarry, B. E.; Diamond, M. L.; Bahavar, B. Characterization of polar organic compounds in the organic film on indoor and outdoor glass windows. Environ. Sci. Technol. 2003, 37, 2340-2349.

Received for review May 27, 2004. Revised manuscript received December 16, 2004. Accepted December 20, 2004. ES049211K

VOL. 39, NO. 7, 2005 / ENVIRONMENTAL SCIENCE & TECHNOLOGY

9

2003