Research Communications Occurrence of Estrogenic Nonylphenols in the Urban and Coastal Atmosphere of the Lower Hudson River Estuary JORDI DACHS, DARYL A. VAN RY, AND STEVEN J. EISENREICH* Department of Environmental Sciences, Rutgers-The State University of New Jersey, 14 College Farm Road, New Brunswick, New Jersey 08901
Nonylphenol polyethoxylates (NPEOs) have been widely used as surfactants in many industrial and household applications. However, NPEOs biodegradation in water leads to the formation of estrogenic nonylphenols (NPs). To date, NPs have only been reported in aquatic environments. In this paper, the occurrence of NPs in coastal and urban atmospheres is reported for the first time. Water-toair volatilization of NPs from estuarine waters is a source of NPs to the estuarine atmosphere. Furthermore, the high concentrations found in the coastal atmosphere of the New York-New Jersey Bight (2.2-70 ng m-3) suggests that the NPs occurrence in the atmosphere may be an important human and ecosystem health issue in urban, industrial, and coastal-impacted areas receiving treated sewage effluents.
Introduction The environmental fate of surfactants has been an issue of concern due to potential adverse impact on ecosystems (13). Nonylphenol polyethoxylates (NPEOs) have been widely used as nonionic surfactants in many industrial and household applications. Either aerobic or anaerobic biotransformation of NPEOs leads to the formation of nonylphenols (NPs) in water (4). Both NPEOs and NPs are introduced to the environment through wastewater discharges (4-6). However, NPs are persistent, bioaccumulative, toxic to aquatic organisms, and estrogenic (7-12). To date, NPs have been reported only in aquatic environments (13, 14). Here we report for the first time the occurrence of NPs in the atmosphere. The objectives of this paper are to document the occurrence of NPs in the atmosphere, to determine the range of air concentrations in the atmosphere of the lower Hudson River Estuary, and to assess the potential role of the estuarine waters as a source of NPs to the regional atmosphere.
Methods Atmospheric particulate and gas-phase samples were obtained with modified Hi-Vols (flow rate of ∼0.5 m3 min-1) using quartz fiber filters and Polyurethane Foam (PUF), respectively. Water dissolved and particulate samples were obtained using an Infiltrex 100 in-situ sampler with a glass * Corresponding author phone: 732-932-9588; fax: 732-932-3562; e-mail:
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fiber filter and XAD-2 adsorbent as generally described elsewhere (15). PUFs and quartz fiber filters were extracted in a Soxhlet apparatus with petroleum ether and dichloromethane, respectively. The extracts were concentrated down to 0.5 mL and fractionated on a 3% H2O-deactivated alumina (4 g) column. The third fraction containing the nonylphenols was obtained by eluting with 15 mL of dichloromethane:methanol (1:2). Nonylphenols were identified and quantified by GC-MSD-EI in SIM mode using the ions 135 and 149 as reported by Kannan et al. (16). The identification of nonylphenols in atmospheric samples was shown unequivocally by the complete match of the 11 isomers in chromatographic profiles between samples and the NPs technical mixture (Figure 1). Quantification was performed using the internal standard 1-phenyldodecane, whereas 2,4,6trimethylphenol or 4-n-hepthylphenol were used as surrogate compounds. Matrix spikes for all the matrixes were processed together with the field samples. Matrix spike recoveries were from 72 to 90%, and sample concentrations were not corrected for surrogate recovery. Detection limits were 4 and 3 ng for aerosol and PUF samples, respectively. Nonylphenol concentrations were above detection limits in all the samples analyzed (n ) 112). The NPs concentrations reported are the sum of 11 isomers. Procedural and field blanks were processed for all the sampling sites and all the matrixes. The mass of NPs recovered from field blanks ranged between 0 and 84 ng, while the mass recovered from samples ranged from 670 to 32 300 ng. Blanks were always below 5% of field values.
Results and Discussion Gas and aerosol phase samples were obtained at two sampling sites located in the urban-industrial (Liberty Science Center, LSC) and coastal (Sandy Hook, SH) zones of the Lower Hudson River Estuary (HRE; Figure 2). A 24-h sample was taken at these sites every 6 or 9 days from June 28 to October 30, 1998. Furthermore, during an intensive sampling campaign from July 5 to July 11, 1998, water samples (dissolved + particulate) were taken simultaneously with overwater atmospheric samples (gas + aerosol) in two locations in the Lower Hudson River Estuary (Figure 2). Consecutive 12-h air samples were also taken concurrently during the intensive sampling period at the land-based sites (LSC and SH). Concentrations of NPs in water from the lower HRE ranged from 11.6 to 94.5 ng L-1 in the dissolved phase and from 2.6 to 21.6 ng L-1 in total suspended matter (Table 1). These concentrations are 10 to 100× higher than water concentrations of priority pollutants such as polychlorinated biphenyls (PCBs) and DDTs found in this and other urban-impacted estuaries, rivers, and coastal waters (15, 17-19). It is wellknown that water bodies can be an important source of semivolatile organic pollutants to the atmosphere (15, 18, 20). The Henry’s Law constants (H) for the NPs, estimated as the ratio of the subcooled liquid vapor pressure and aqueous solubility, were 3 to 4 × 10-5 atm m3 mol-1 (21, 22). These values of H are sufficient to support gaseous airwater exchange of NPs to the atmosphere. Nonylphenols were detected in all atmospheric samples analyzed (n ) 112). Table 1 shows the average and range of NPs concentrations in the air phases (gas and particulate) for each of the sampling sites. Atmospheric NPs concentrations range from 0.2 to 68.6 ng m-3 for the gas phase and 10.1021/es990253w CCC: $18.00
1999 American Chemical Society Published on Web 06/22/1999
FIGURE 1. Chromatographic profiles obtained by GC-MS in the EI/SIM mode (ions 135-149) of nonylphenols from a representative atmospheric particulate sample and the nonylphenol technical mixture.
TABLE 1: Concentrations of Nonylphenols in the New Jersey-New York Urban and Coastal Atmosphere and Watera air samples (ng m-3)
Hudson River Estuary (n ) 5) Sandy Hook (n ) 30) Liberty Science Center (n ) 21)
water samples (ng L-1)
air-water exchange
gas
aerosol
dissolved
particulate
fW /fG
19.2 (1.5-69)
6.1 (0.1-14)
48.0 (12-95)
7.9 (2.6-22)
18.3 (1.3-69)
10.2 (0.9-56)
9.8 (0.3-51)
2.5 (0.2-8.1)
5.6 (1.8-23)
a NPs concentrations are reported as the sum of 11 isomers. The average and ranges were calculated taking into account all the samples analyzed from the regular and intensive sampling campaigns.
from 0.1 to 51.4 ng m-3 for the aerosol phase. These concentrations are surprisingly high for a pollutant whose occurrence in the atmosphere has never been previously reported. For example, NPs concentrations are even higher than those of polycyclic aromatic hydrocarbons (PAHs) and up to 2 orders of magnitude higher than PCB concentrations in impacted urban-industrial areas (18, 23). Figure 3 shows the NPs concentrations in the gas and aerosol phases at the LSC, SH, and overwater sites in the lower HRE corresponding to the intensive sampling period of July 1998. The aerosolphase concentrations of NPs that were measured at the LSC site were usually higher than those in the gas phase, but the
gas phase is more enriched in NPs (Table 1 and Figure 3) for the other two water-dominated sites (Sandy Hook and lower HRE). The relative contributions of the gaseous and aerosol phases to the total concentrations of NPs in the atmosphere are explained by the greater influence of direct water-to-air exchange from surrounding water bodies at SH and over the estuary than at LSC. Indeed, even though the SH site is on land, it is located on a narrow peninsula surrounded by the Atlantic Ocean and the Hudson-Raritan Bay (Figure 2). Direct evidence of volatilization of NPs from the lower HRE was obtained by calculating their fugacities in the water (fW) and gas phase (fG) for which the ratio is indicative of the VOL. 33, NO. 15, 1999 / ENVIRONMENTAL SCIENCE & TECHNOLOGY
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FIGURE 2. Map of the New Jersey-New York urban and coastal area and the lower Hudson River Estuary with the sampling site locations. Shadow zones indicate the location of urban and suburban areas. Map adapted from the USGS Web atlas. net direction of transfer
fW ) CWH
(1)
fG ) CGRT
(2)
where CW (mol L-1) and CG (mol L-1) are the NPs concentrations in the water (dissolved) and atmospheric gas phases, respectively; R is the gas constant (atm L mol-1 K-1); and T is the temperature (K) (24). Henry’s Law constants were not corrected for temperature since the surface water temperatures ranged only from 20 to 23 °C, and the H value above was reported at 25 °C. Due to the proximity of water temperatures to 298 K, this assumption exerts a negligible effect on the calculated fugacities. The water/air fugacity ratios (fW/fG) ranged from 1.3 to 69 with an average value of 18 (Table 1). These ratios are higher than unity in all cases and provide conclusive evidence that net volatilization from the estuarine waters is a source of NPs to the regional atmosphere. Therefore, the scenario that explains the NPs occurrence and trends observed in the New York-New Jersey urban and coastal atmosphere is that the moderately high NPs concentrations in the estuarine waters drive water to air fluxes. Indeed, over the estuary and at SH, the gas phase is enriched in NPs due to direct NPs volatilization from the water. Once NPs are emitted into the atmospheric gas phase, they quickly sorb to the atmospheric aerosols (TSP ∼30-50 µg m-3), thus increasing the relative proportion of NPs in the aerosol phase as observed at the LSC. Furthermore, aerosol-associated NPs are subject to removal processes such as dry deposition, reducing their residence time in the atmosphere but still loaded to proximate aquatic and terrestrial ecosystems. The NPs water concentrations reported in other rivers, estuaries, and coastal zones of the world are often much higher than in the Hudson River estuary. For example, NPs concentrations reported for the Glatt River in Switzerland or the Krka River Estuary in Croatia are 1-2 orders of magnitude higher than in the Hudson River estuary (13, 25). Therefore, the occurrence of NPs in the air must be ubiquitous and perhaps even more important in other urban, industrial, and coastal regions of the world where NPEOs and NPs are discharged to surface waters. The atmospheric occurrence of NPs in highly populated areas raises concern regarding new routes of exposure to NPs and the extent of exposure to humans of NPs in the gas and aerosol phases. A corollary 2678
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FIGURE 3. Time series of gaseous and aerosol-phase concentrations of NPs at the Liberty Science Center (urban-industrial), Sandy Hook (marine), and the Lower Hudson River Estuary for the samples corresponding to the intensive sampling period July 1998. to this study is that rivers and estuaries containing high concentrations of organic chemicals with appropriate Henry’s Law constants will contribute to the contamination of the local and regional atmosphere.
Acknowledgments C. Lavorgna, P. Brunciak, T. Glenn, R. Pelleriti, and E. Nelson are kindly acknowledged for field and laboratory assistance. J. Dachs acknowledges a postdoctoral fellowship from the Spanish Ministry of Education and Culture. This research was funded in part by the Hudson River Foundation (Project Officer, D. Suszkowski) and New Jersey Sea Grant College (NOAA) (Project Officer, M. Weinstein).
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Received for review March 5, 1999. Revised manuscript received May 12, 1999. Accepted May 18, 1999. ES990253W
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