Temporal variability in physical speciation of metals during a winter rain-on-snow event

Particulate matter in urban rivers transports a significant fraction of pollutants, changes rapidly during storm events, and is difficult to characterize. In this study, the physical speciation of trace metals and organic C in an urban river and upstream headwaters site in Torrington, CT, were measured during a winter rain-on-snow event. In addition, a selective fractionation scheme, using membrane and tangential-flow ultrafiltration methods to separate suspended particulate matter into sand, silt, clay, and colloid fractions, was evaluated based on the appropriateness of the chosen size categories. During peak runoff at the urban river site, total-recoverable concentrations of the metals Cu and Pb increased 6- and 13-fold to 16.9 and 9.5 microg L(-1), respectively, compared with baseflow concentrations. Concentrations of Cu and Pb reached only 0.9 and 0.86 microg L(-1) at the headwaters site. For the measured storm event, the majority of metals were transported by the urban river in association with coarse silt (20-80 microm particle diam.) during peak runoff. During peak runoff at the urban site, organic C associated with the large colloid fraction (0.1-1.0 microm) increased from 5% (at baseflow) to 54% of the total C in transport, whereas dissolved organic C and that associated with smaller colloids decreased from 91.5% (at baseflow) to 41% of the total. Other elements that were monitored as part of the study were Na, K, Ca, Mg, Fe, Mn, Al, Cd, Cl-, NO3(-), and SO4(2-). The chosen fractionation scheme was useful to characterize pollutant transport during this event, but further testing should be undertaken to determine the most appropriate size range categories, and to ensure that the sizes measured are comparable to those used in other studies.