Monitoring the tidal Delaware River for ambient toxicity.

This study assessed ambient waters in an urbanized area of the Delaware River, to determine whether river water samples exhibited chronic lethal or sublethal toxicity when measured in laboratory experiments. Toxicity was assessed at 16 fixed stations in the main-stem river and 29 stations in tributaries of the tidal Delaware River with salinities from 0 to 15 parts per 1000 (ppt) using Pimephales promelas, Americamysis bahia, Menidia beryllina, and Ceriodaphnia dubia in 7-d tests; Pseudokirchneriella subcapitata in a 96-h test; and Hyalella azteca in a 10-d water-only test. The toxicity tests measured organism survival, growth, and reproduction. Results from testing water samples collected in 4 different y indicated that the samples from sites tested in the main-stem of the Delaware River and from the majority of its tributaries did not produce chronic toxicity. The surveys identified tributaries that warrant further assessment for toxicity.

Air-water exchange of polychlorinated biphenyls in the Delaware River.

The air-water exchange of polychlorinated biphenyls (PCBs) often results in net volatilization, which is thought to be the most important loss process for PCBs in many systems. Previous investigations of the air-water exchange of PCBs have been hampered by difficulties in treatment of the uncertainty in the calculation of air/water fugacity ratios. This work presents a new framework for the treatment of uncertainty, where uncertainty in physical constants is handled differently from random measurement uncertainty associated with random samples, and it further investigates the sorption of PCBs to colloids (dissolved organic carbon). Simultaneous measurements of PCBs in the air and water of five water quality management zones of the Delaware River were taken in 2002 in support of the total maximum daily load (TMDL) process. Gas-phase concentrations of IPCBs ranged from 110 to 1350 pg m(-3), while dissolved water concentrations were between 420 and 1650 pg L(-1). Shallow slopes of log Koc vs. log Kow plots indicated a colloidal contribution to the apparent dissolved-phase concentrations, such that a three-phase partitioning model was applied. Fugacity ratios for individual congeners were calculated under the most conservative assumptions, and their values (log-transformed) were examined via a single-sample T-test to determine whether they were significantly less than 1 at the 95% confidence level. This method demonstrated that air-water exchange resulted in net volatilization in all zones over all cruises for all but seven high molecular weight congeners. Calculated net fluxes ranged from +360 to +3000 ng m(-2) d(-1) for sigma PCBs. The colloidal correction decreased the volatilization flux of sigma PCBs by approximately 30%. The decachlorinated congener (PCB 209), exhibited unusually high concentrations in the suspended solids, especially in the southern portions of the river, indicating that there is a distinct source of PCB 209 in the Delaware River.

Direct and indirect atmospheric deposition of PCBs to the Delaware River watershed.

Atmospheric deposition can be an important source of PCBs to aquatic ecosystems. To develop the total maximum daily load (TMDL) for polychlorinated biphenyls (PCBs) for the tidal Delaware River (water-quality Zones 2-5), estimates of the loading of PCBs to the river from atmospheric deposition were generated from seven air-monitoring sites along the river. This paper presents the atmospheric PCB data from these sites, estimates direct atmospheric deposition fluxes, and assesses the importance of atmospheric deposition relative to other sources of PCBs to the river. Also, the relationship between indirect atmospheric deposition and PCB loads from minor tributaries to the Delaware River is discussed. Data from these sites revealed high atmospheric PCB concentrations in the Philadelphia/Camden urban area and lower regional background concentrations in the more remote areas. Wet, dry particle, and gaseous absorption deposition are estimated to contribute about 0.6, 1.8, and 6.5 kg year-(-1) sigmaPCBs to the River, respectively, exceeding the TMDL of 0.139 kg year(-1) by more than an order of magnitude. Penta-PCB watershed fluxes were obtained by dividing the tributary loads by the watershed area. The lowest of these watershed fluxes are less than approximately 1 ng m(-2) day(-1) for penta-PCB and probably indicates pristine watersheds in which PCB loads are dominated by atmospheric deposition. In these watersheds, the pass-through efficiency of PCBs is estimated to be on the order of 1%.

PCB congener distribution in estuarine water, sediment and fish samples: implications for monitoring programs.

Traditional analyses for PCBs in environmental matrices have focused on commercial Aroclor mixtures with detection limits in the 100 to 1000 part per trillion range. This approach has recently been supplanted by analyses for specific PCB compounds called congeners with detection limits less than 0.5 ppt. At the national level, total PCB determinations based upon selected PCB congeners typically characterize analyses of surface water, sediment and tissue. These federal efforts rely on a suite of 18 to 20 congeners out of a total of 209 congeners to characterize total PCB. The present study compares total PCB estimates based upon this subset of congeners with estimates based upon an expanded list of 81 congeners from water, sediment and fish tissue collected from the Delaware Estuary. Analytical data from monitoring programs conducted in the Delaware Estuary by the Delaware River Basin Commission, NOAA National Ocean Service, U.S. Army Corps of Engineers and the U.S. Environmental Protection Agency from 1996 to 1998 were evaluated. Total PCB estimates derived from the different sets of congeners, including the adjustment factor of 2.0 used by NOAA, were compared. This evaluation indicated that differences exist between total PCB determinations based upon these approaches, and that these differences vary depending on the matrix analyzed. The bias associated with using a smaller set of PCB congeners, and the implications for risk assessment are discussed.