Paul A. Brunciak

Evidence for destruction of PCBs by the OH radical in urban atmospheres

Evidence for reaction of polychlorinated biphenyl (PCB) congeners with the hydroxyl (OH) radical in the troposphere was observed in diurnal variations in ambient gas-phase PCB concentrations at three urban sampling sites located in the Chicago, IL; Baltimore, MD; and Jersey City, NJ urban/industrial areas. The magnitude of the depletion of individual PCB congeners decreased by about 10-20% for each additional chlorine substituent, reflecting slower reaction rates for higher MW congeners with the OH radical. Octa- and nonachlorobiphenyls, which are largely unreactive with the OH radical, were used as tracers to investigate the effects of dilution on diurnal variation. The environmental rate constants for disappearance of the PCBs range from about 1.0 day(-1) for trichlorobiphenyls to about 0.3 day(-1) for hexachlorobiphenyls. Assuming a OH radical concentration of 3 x 10(6) molecules cm (-3), the second-order rate constants for reaction of specific congeners with the OH radical are consistent with laboratory measurements. More importantly, the relative reactivity of PCB homologues agrees well with the relationship predicted by other researchers from laboratory measurements, suggesting that losses of PCBs during daytime tropospheric transport are due at least in part to reactions with the OH radical.

Processes controlling diurnal variations of PCDD/Fs in the New Jersey coastal atmosphere

Consecutive 12 hour day–night air samples (500 m3 each) were taken over 7 days at three land-based sites and an over-water site in coastal New Jersey (NJ) in July 1998, in a campaign designed to shed light on factors controlling ambient PCDD/F concentrations. The sampling sites were chosen to reflect contrasting environments: urban/industrial from the center of the New York (NY)–NJ metropolitan area (Liberty Science Center, LSC); coastal Atlantic (Sandy Hook, SH); suburban NJ (New Brunswick, NB); over-water in Raritan Bay (RB). Despite proximity to the major NY/NJ conurbation, ambient PCDD/F concentrations in the region were low compared to literature data for other urban locations. Mean ∑Cl4–8DD/Fs and ∑TEQ (in fg/m3) were: 1400 and 16 at NB; 1000 and 9.5 over RB; 880 and 8.5 at LSC; and 830 and 6.6 at SH. Di- and tri-chlorinated dibenzo-p-dioxins and -furans (PCDD/Fs) were also measured and dominated the ∑Cl2–8DD/F concentrations. Air–water exchange calculations demonstrated the relative importance of Cl2–3DD volatilizing from the Lower Hudson River Estuary for ambient concentrations (25% of advection), but was of minor importance for the other PCDD/Fs. The study provides evidence that advective transport, local inputs and atmospheric processes combine in a complex manner to control ambient PCDD/F concentrations. These processes generally dominate any local diurnal influence of OH-radical-mediated depletion, which we had hypothesized would be detectable by measuring higher night- and day-time concentrations. Rather, it is implied that changes in the mixed boundary layer height resulted in higher night- than daytime concentrations at the urban and coastal sites. A strong diurnal signal, dominated by the lower chlorinated dioxins and furans, was detected at the rural site (NB) during a period of lower wind speeds.