ABSTRACT
To evaluate the two hypotheses of locally elevated exposure of persistent organic pollutants (POPs) in ice-associated microenvironments and ice as a key carrier for long-range transport of POPs to the Arctic marginal ice zone (MIZ), dissolved and particulate polychlorinated biphenyls (PCBs) were analyzed in ice, snow, ice-interstitial water (IIW), seawater in the melt layer underlying the ice, and in ice-rafted sediment (IRS) from the Barents Sea MIZ to the high Arctic in the summer of 2001. Ultra-clean sampling equipment and protocols were specially developed for this expedition, including construction of a permanent clean room facility and a stainless steel seawater intake system on the I/B ODEN as well as two mobile 370 l ice-melting systems. Similar concentrations were found in several ice-associated compartments. For instance, the concentration of one of the most abundant congeners, PCB 52, was typically on the order of 0.1-0.3 pg l(-1) in the dissolved (melted) phase of the ice, snow, IIW, and underlying seawater while its particulate organic-carbon (POC) normalized concentrations were around 1-3 ng gPOC(-1) in the ice, snow, IIW, and IRS. The solid-water distribution of PCBs in ice was well correlated with and predictable from K(ow) (ice log K(oc)-log K(ow) regressions: p<0.05, r2=0.78-0.98, n=9), indicating near-equilibrium partitioning of PCBs within each local ice system. These results do generally not evidence the existence of physical microenvironments with locally elevated POP exposures. However, there were some indications that the ice-associated system had harbored local environments with higher exposure levels earlier/before the melting/vegetative season, as a few samples had PCB concentrations elevated by factors of 5-10 relative to the typical values, and the elevated levels were predominantly found at the station where melting had putatively progressed the least. The very low PCB concentrations and absence of any significant concentration gradients, both in-between different matrices and over the Eurasian Arctic basin scale, suggest that ice is not an important long-range transport purveyor of POPs to the Arctic MIZ ecosystem.
ABSTRACT
Lolium multiflorum (ryegrass) was contaminated with technical mixtures of polychlorinated biphenyls (PCBs) via the gas phase and the subsequent elimination of the PCBs from the vegetation was studied under field conditions. There was a pronounced decrease in the concentrations of the di- through to the pentachlorinated congeners over the 240-h elimination period. For many of the congeners the elimination was nearly complete, suggesting that the partitioning of these compounds from the gas phase into ryegrass is largely reversible. The elimination followed first order kinetics. The elimination half-lives were linearly proportional to the plant/air equilibrium partition coefficients (K(PA)) of the PCB congeners and ranged from 22 h for PCBs 8 + 5 to 87 h for PCBs 84 + 101. For the hexa- through to the octachlorinated congeners no significant decrease in the concentration of the vegetation was observed during the elimination experiment. The elimination was described well using a two-resistance model of PCB desorption which indicated that elimination of the di- and trichlorinated PCBs was limited by transport within the plant itself while elimination of the higher chlorinated congeners was limited by transport from the plant surface into the atmosphere. Furthermore, the results demonstrate that if elimination of higher chlorinated PCBs from ryegrass via biological or photochemical degradation occurs, then it is very slow.
