Environ. Sci. Technol. 2010, 44, 2816–2821 the production and use in commerce of PCBs was banned Evidence for Unique and Ubiquitous by a series of legislative acts, including the 1973 act that prohibited the use of PCBs in open applications. These open Environmental Sources of applications included the use of PCBs as a transfer agent in 3,3′-Dichlorobiphenyl (PCB 11) carbonless copy paper. An important and often overlooked loophole in the various laws regulating PCB use was that the ,† † inadvertent production of PCBs was allowed to continue as LISA A. RODENBURG,* JIA GUO, long as monitoring requirements were met. Despite this SONGYAN DU,† AND exclusion, PCBs in the United States and in many other GREGORY J. CAVALLO‡ countries are regulated as the sum of all 209 congeners Department of Environmental Sciences, Rutgers University, (∑PCBs). In the United States, the Clean Water Act requires 14 College Farm, Road, New Brunswick, New Jersey 08901, that waterways in which ∑PCBs exceed the applicable water and Delaware River Basin Commission, 25 State Police Drive, quality standard must be subjected to a process in which a West Trenton, New Jersey 08628 total maximum daily load (TMDL) is calculated, promulgated, and implemented. Thus, although inadvertent production Received April 16, 2009. Revised manuscript received July of PCBs is not banned in the United States, it will increasingly 29, 2009. Accepted August 7, 2009. be subject to regulation via the Clean Water Act and the TMDL process. The dichloro congener 3,3′dichlorobiphenyl (PCB 11) is produced inadvertently during the production of diarylide The non-Aroclor congener 3,3 -dichlorobiphenyl (PCB 11) has ′ yellow pigments, which are the most common yellow been recently detected in air, water, biota, sediment, and pigments used in printing as well as a wide variety of other suspended sediment. Although it has been known since at applications (2). The original 1979 Code of Federal Regula- least the 1970s that this congener is produced inadvertently tions (3) specifically states that “after July 1, 1979, processing during the production of diarylide yellow pigments, this work and distribution in commerce of diarylide or phthalocyanin presents the first evidence that the use of these pigments in pigments that contain 50 ppm or greater PCBs is permitted consumer goods results in the dispersion of PCB 11 throughout only for persons who are granted an exemption.” Worldwide the environment at levels that are problematic in terms of production of color organic pigments was estimated to be achieving water quality standards for the sum of polychlorinated about 250 million metric tons in 2006, with about 25% of the biphenyls (PCBs). In this work, PCB 11 is measured at ppb market being diarylide yellow pigments (4). About 65% of the total production of color organic pigments is used in levels in consumer goods that are likely to be discarded in ways printing (4). PCB 11 concentrations in printing inks with that allow them to enter wastewater treatment plants and yellow pigments have been measured to be on the order of combined sewer overflows, including newspapers, magazines, 15 ppb (5). Given that an average of 40% composition in cardboard boxes used for food packaging, and plastic bags. printing inks are pigments (6), PCB 11 concentrations in Also, using data sets acquired for the purpose of calculating total diarylide yellow pigments are roughly 38 ppb. Therefore, maximum daily loads (TMDLs) for PCBs, PCB 11 loads to the worldwide production of PCB 11 via the manufacture of New York/New Jersey Harbor and Delaware River are calculated. diarylide yellow pigments is estimated to be 1.5 t in 2006. Despite the fact that there are no known manufacturers of The recent development of a reference method for PCB diarylide yellow pigments in the Delaware River watershed, the analysis in environmental samples based on high resolution loads of PCB 11 to the Delaware River exceed the TMDL for mass spectrometry (Environmental Protection Agency, EPA, the sum of PCBs by nearly a factor of 2. The ratio of PCB 11 to method 1668A) has enabled researchers to measure PCB 11 routinely. In 2002, Litten (7) reported concentrations of PCB acharacteristicdechlorinationendproduct,PCB4(2,2′- 11 as high as 225 ng L-1 in the effluents from two wastewater dichlorobiphenyl), in these data sets indicates that dechlorination treatment plants in the New York/New Jersey Harbor area. is not a significant source of PCB 11 in these systems. In the These two plants received waste from pigment manufactur- upper Hudson River, where extensive dechlorination of heavy ers. The load of PCB 11 to the harbor from these two plants PCB congeners occurs, the ratio is just 0.012. In contrast, was estimated to be about 100 kg y-1 at the time these samples downstream in the NY/NJ Harbor as well as in the Delaware were collected (8). That same year, King et al. (9) reported River the ratio is much higher and more variable. Pigment PCB 11 as a dominant PCB congener in water, suspended use therefore appears to be the main source of PCB 11 in these particulate material, and mussel tissues in Halifax Harbour. systems, and this congener is likely to present a significant They noted the connection between PCB 11 and pigment obstacle to achieving PCB water quality standards throughout production, and hypothesized that intermittent discharges from one or more unidentified industrial sources were the the United States. most likely source of PCB 11. Since that time, PCB 11 has been reported in the water column and in air at many Introduction locations (10-12). In recent work (13), we reported that PCB 11 is ubiquitous in the tidal Delaware River, and that it can Polychlorinated biphenyls (PCBs) are a class of persistent be used as a tracer for wastewater and combined sewer organic pollutants (POPs) that have been targeted for overflows (CSOs), even in watersheds where there are no elimination by the United Nations Environment Programme known manufacturers of diarylide yellow pigments. as one of the “dirty dozen” POPs (1). In the United States, Here, we provide evidence that the widespread use of diarylide yellow pigments is a significant source of PCB 11 * Corresponding author phone 732-932-9800 extension 6218; fax 732-932-8644; e-mail [email protected]. to urban waterways, and that this source is likely to be large † Rutgers University. enough that it must be addressed in order to implement ‡ Delaware River Basin Commission. TMDLs for PCBs nationwide. The goals of this work are (1) 2816 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 44, NO. 8, 2009 10.1021/es901155h CCC: $40.75 © 2010 American Chemical Society Published on Web 08/24/2009 TABLE 1. Concentrations of PCB 11 in Consumer Goods TABLE 2. Loads of Dichloro PCBs to the NY/NJ Harbor during Collected in 2008a 1998-2001 PCB 11 concentration flow (L y-1) loads (mg d-1) material (ng g-1 ) ppb) ( 1010) PCB 4 PCB 11 × black and white printed newspaper (A) 0.85 CSOs 12 74 68 black and white printed newspaper (B) 0.45 stormwater 71 93 470 brown (unprinted) cardboard (A) 3.0 wastewater effluents 319 1300 1200 brown (unprinted) cardboard (B) 2.8 tributaries (New York) color glossy magazine (A) 4.5 Hudson 742 41000 710 color glossy magazine (B) 3.3 Mohawk 527 440 99 color newspaper (A) 6.6 Wallkill 101 41 49 color newspaper (B) 5.7 tributaries (New Jersey) plain white copy paper (A) ND Elizabeth 2 66 8 plain white copy paper (B) ND Hackensack 5 3 3 manila envelope (A) ND Passaic 96 300 150 manila envelope (B) 0.11 Rahway 5 5 5 yellow cereal box (A) 3.0 Raritan 105 96 120 yellow cereal box (B) 2.9 total 43000 2900 yellow plastic bag (A) 3.4 yellow plastic bag (B) 38 yellow sticky note (A) 0.82 yellow sticky note (B) 0.11 TABLE 3. Estimated Loads of Dichloro PCBs to the Tidal lab blank (GFF) (A) ND Delaware River during 2001-2003 lab blank (GFF) (B) ND a ND ) not detected. flow (L y-1) loads (mg d-1) ( 1012) PCB 4 PCB 11 × to provide evidence that PCB 11 can enter urban waterways tributaries via the use of diarylide yellow in consumer goods including Delaware at Trenton 8.8 430 350 printed paper and cardboard packaging, (2) to provide Schuylkill 2.1 240 110 minor tributaries 1.6 130 91 evidence that the dominant source of PCB 11 in urban top 12 dischargers watersheds is not dechlorination of heavier PCB congeners, (wastewater treatment plants) and (3) to provide a preliminary assessment of the magnitude municipal 0.83 740 170 of these nonpoint PCB 11 sources in two urban watersheds. industrial 0.11 25 21 These goals are addressed by measuring PCB 11 in a variety sum 1600 740 of consumer goods and by using existing data sets from the NY/NJ Harbor-Hudson River and the Delaware River to yellow is reported to be able to withstand temperatures of assess the loading profile of PCB 11 in these two systems up to 180-200 °C(2), breakdown of diarylide yellow to form (maps are provided in the Supporting Information). These PCB 11 during the extraction process is unlikely. Extracts two water bodies are excellent test beds for examining the were then reduced in volume by rotary evaporation and sources of PCB 11 because in both systems large, high-quality separated into two fractions on a column of 3% water- data sets on PCB concentrations are available. Sediments in deactivated alumina. The fraction containing PCBs was the upper Hudson River are highly contaminated with PCBs concentrated under a gentle stream of nitrogen gas to about (14), and this is the site of arguably the most extensive 0.5 mL and injected with internal standard PCBs 30 and 204 documented in situ dechlorination of PCBs in the world prior to analysis.