Reductive dechlorination of low concentration polychlorinated biphenyls as affected by a rhamnolipid biosurfactant.

We investigated whether the threshold concentration for polychlorinated biphenyl (PCB) dechlorination may be lower in biosurfactant-amended sediments compared with biosurfactant-free samples. At PCB concentrations of 40, 60, and 120 ppm, the surfactant amendment enhanced the PCB dechlorination rate at all concentrations and the rate was also faster at higher concentrations. On a congener group basis, dechlorination proceeded largely with group A (congeners with low threshold) in both surfactant-free and -amended sediments, accumulating mainly group C (residual products of dechlorination) congeners, and surfactant enhanced the dechlorination rate of group A congeners. Since the PCB threshold concentration for the inoculum in the experiment was lower than 40 ppm, we carried out another experiment using sediments with lower PCB concentrations, 10, 20, and 30 ppm. Sediments with 100 ppm were also performed to measure dechlorination at a PCB saturation concentration. Comparison between the plateaus exhibited that the extent of dechlorination below 40 ppm PCBs was much lower than that at a saturation concentration of 100 ppm. There was no significant difference in the extent of dechlorination between surfactant-free and -amended sediments. Moreover, surfactant did not change the congener specificity or broaden the congener spectrum for dechlorination at PCB concentrations below 40 ppm. Taken together, it seems that at a given PCB concentration, dechlorination characteristics of dechlorinating populations may be determined by not only the congener specificity of the microorganisms but also the affinity of dechlorinating enzyme(s) to individual PCB congeners.

Dechlorination of individual congeners in aroclor 1248 as enhanced by chlorobenzoates, chlorophenols, and chlorobenzenes.

Previous investigations showed that three classes of haloaromatic compounds (HACs; chlorobenzoates, chlorophenols, and chlorobenzenes) enhanced the reductive dechlorination of Aroclor 1248, judging from the overall extent of reduction in Cl atoms on the biphenyl. In the present study, we further investigated the kind of polychlorinated biphenyl (PCB) congeners involved in the enhanced dechlorination by four isomers belonging to each class (2,3-, 2,5-, 2,3,5-, and 2,4,6-chlorobenzoates; 2,3-, 3,4-, 2,5-, and 2,3,6-chlorophenols; and 1,2-, 1,2,3-, 1,2,4-, and penta-chlorobenzenes). Although the PCB congeners involved in the enhanced dechlorination varied with the HACs, the enhancement primarily involved paradechlorination of the same congeners (2,3,4'-, 2,3,4,2'- plus 2,3,6,4'-, 2,5,3',4'- plus 2,4,5,2',6'-, and 2,3,6,2',4'- chlorobiphenyls), regardless of the HACs. These congeners are known to have low threshold concentrations for dechlorination. To a lesser extent, the enhancement also involved meta dechlorination of certain congeners with high threshold concentrations. There was no or less accumulation of 2,4,4'- and 2,5,4'-chlorobiphenyls as final products under HAC amendment. Although the dechlorination products varied, the accumulation of orthosubstituted congeners, 2-, 2,2'-, and 2,6-chlorobiphenyls, was significantly higher with the HACs, indicating a more complete dechlorination of the highly chlorinated congeners. Therefore, the present results suggest that the enhanced dechlorination under HAC enrichment is carried out through multiple pathways, some of which may be universal, regardless of the kind of HACs, whereas others may be HAC-specific.

Effects of a rhamnolipid biosurfactant on the reductive dechlorination of polychlorinated biphenyls by St. Lawrence River (North America) microorganisms.

The effect of a rhamnolipid biosurfactant on the reductive dechlorination of polychlorinated biphenyls was investigated with the use of clean sediments spiked with Aroclor 1248. The surfactant was added to the contaminated sediments at four different concentrations (5, 10, 25, and 50 microg/g sediment [ppm] on a sediment dry wt basis), and dechlorination was followed over a 40-week period. The rate of overall dechlorination was enhanced at the three highest concentrations. Dechlorination at the lowest concentration (5 ppm) was not different from that in surfactant-free sediments. On a congener basis, enhanced dechlorination was mostly found in the congeners that have high threshold concentrations for dechlorination. These congeners are characterized by an initial increase in concentration before dechlorination starts. At the three highest biosurfactant concentrations, this initial concentration increase was absent or dramatically reduced. Therefore, the enhancement in dechlorination appears to be caused by an increase in bioavailability at high surfactant concentrations. The biosurfactant also reduced the lag time before dechlorination began in these congeners. Among those congeners that have low threshold concentrations, dechlorination enhancement was found only in two peaks. For these two, there was no lag period, either with or without the rhamnolipids. The maximum level of dechlorination and the congener pattern of final dechlorination products were identical, regardless of biosurfactant concentration.

Bioconcentration and redeposition of polychlorinated biphenyls by zebra mussels (Dreissena polymorpha) in the Hudson River.

The potential impact of zebra mussel infestation on the dynamics of polychlorinated biphenyls (PCBs) in the Hudson River was determined by investigating the biodeposition and bioconcentration of PCBs, using algal food contaminated with 2,5,2'- and 2,4,2',4'-chlorobiphenyls (CBPs) in the laboratory. Approximately 46-90% of the total food was ingested depending on the supply rate. The highest proportion of ingested congeners was found in biodeposits (64+/-11% for 2,5,2'-CBP, and 52+/-6% for 2,4,2',4'-CBP), followed by tissues (17+/-3% for 2,5,2'-CBP, and 23+/-5% for 2,4,2',4'-CBP), and the lowest in shells. The clearance rate decreased with increasing food concentration, but increased with dilution rate. On the other hand, ingestion rate (IR) increased with food concentration and dilution rate. IR also increased with food supply rate (food concentrationxdilution rate) following the same linear function whether the supply rate was varied through food concentration or dilution rate. Therefore, the dilution rate- or food concentration-dependent variation in IR was due to the change in the food supply rate. IR was independent of the kind of PCB congeners. The trend of bioaccumulation in mussel tissues from food ingestion was similar to that of IR; bioaccumulation increased linearly with food supply rate, whether the supply rate was varied through the dilution rate or the food concentration. The bioaccumulation of 2,4,2',4'-CBP was significantly higher than that of 2,5,2'-CBP (p<0.05). The bioaccumulation was linearly related to the IR or to the total amount of food ingested. Assimilation efficiency, PCB incorporated in the tissue per total ingested PCB, was higher for 2,4,2',4'-CBP than for 2,5,2'-CBP (p<0.05). The congener concentration in biodeposits increased with food supply rate. However, the concentration of 2,5,2'-CBP was significantly greater than that of 2,4,2',4'-CBP in a mirror image of bioaccumulation. These results indicate that zebra mussels may significantly alter PCB dynamics in the Hudson River through redeposition from the water column and through bioconcentration.

Reductive dechlorination of polychlorinated biphenyls: threshold concentration and dechlorination kinetics of individual congeners in Aroclor 1248.

Reductive dechlorination of individual PCB congeners in Aroclor 1248 was investigated using sediment microorganisms from the St. Lawrence River (NY). No dechlorination was observed at Aroclor concentrations below 40 ppm [137 nmol (g of sediment)(-1)]. Above this threshold, congeners could be divided into three categories: group A, congeners that dechlorinated above 40 ppm; group B, congeners that dechlorinated only at high concentrations above 60 ppm [206 nmol (g of sediment)(-1)]; and group C, lower chlorinated congeners that increased in concentration. The dechlorination rate of congeners in groups A and B was a linear function of their initial sediment concentration. For group A congeners, the concentration intercepts of this linear function were the same as their concentrations in the Aroclor at the threshold concentration, and these therefore represented the threshold values. However, the intercepts of group B congeners were significantly higher than their levels at the threshold Aroclor concentration and were equivalent to their concentrations in Aroclor 1248 at about 75 ppm [258 nmol (g of sediment)(-1)]. The final concentrations of group A and group B congeners at the end of dechlorination were the same, regardless of their initial concentrations. These final concentrations were significantly lower than their threshold values. The accumulation rate of group C congeners was a linear function of their initial concentrations, and the total accumulation was greater at higher Aroclor concentrations in sediments.

Kinetics of polychlorinated biphenyl dechlorination by Hudson River, New York, USA, sediment microorganisms.

The kinetics of polychlorinated biphenyl (PCB) dechlorination by Hudson River (New York, USA) sediment microorganisms were investigated using Aroclor 1242 at 10 concentrations ranging from 0 to 900 ppm (0-11.2 micromol Cl/g sediment). The time course of PCB dechlorination and population growth were determined by congener-specific analysis and the most-probable-number technique, respectively, over a 44-week incubation period. Dechlorination rate (nmol Cl removed/g sediment/d) was a linear function of PCB concentrations similar to the dechlorination of Aroclor 1248 by sediment microorganisms from the St. Lawrence River (New York, USA). However, the rate was much slower, with the linear slope being only 24% that of the St. Lawrence River. The threshold concentration below which no dechlorination occurs was (mean +/- standard deviation) 1.06 +/- 0.18 micromol Cl/g sediment (85 +/- 14 ppm), threefold higher than that for the dechlorination of Aroclor 1248. The maximum extent of dechlorination was greater at higher Aroclor concentrations. Dechlorinating microorganisms did not show any significant growth until late in the lag phase of dechlorination, and their maximum was greater at higher initial Aroclor 1242 concentrations. Although dechlorination rates were significantly lower with the Hudson River inoculum, when normalized to the maximum number of dechlorinating organisms, they were not significantly different from those for Aroclor 1248 by St. Lawrence River microorganisms. These results further support the idea that PCB dechlorination is tightly linked to the growth of dechlorinating microorganisms.

Enhancement of microbial PCB dechlorination by chlorobenzoates, chlorophenols and chlorobenzenes.

Abstract We investigated the effects of chlorobenzoates (3-, 2,3-, 2,4-, 2,5-, 2,3,5- and 2,4,6-chlorobenzoate), chlorophenols (2,3-, 3,4-, 2,5-, 2,3,6- and penta-chlorophenol), and chlorobenzenes (1,2-, 1,2,3-, 1,2,4- and penta-chlorobenzene) on polychlorinated biphenyl (PCB) dechlorination and on the enrichment of PCB-dechlorinating microorganisms. When the natural microbial populations eluted from St. Lawrence River sediments were enriched with each of the 15 haloaromatic compounds (HACs) in PCB-free sediments, PCB-dechlorinating microorganisms were found in all but pentachlorophenol-amended sediments. Similarly, dechlorinating microorganisms were also found in PCB-spiked sediments amended with all HACs, except for those with pentachlorophenol. In HAC-amended PCB sediments there was a long lag in PCB dechlorination until the HACs were reduced to a plateau level. Despite this lag, once PCB dechlorination started it was faster in the HAC-amended sediments compared to the unamended controls. The overall extent of PCB dechlorination was significantly enhanced by all HACs except pentachlorophenol and pentachlorobenzene, but the extent as well as the pattern of the enhancement varied. Of the 13 effective HACs, six (2,3-, 2,4- and 2,4,6-chlorobenzoates; 3,4- and 2,3,6-chlorophenols; and 1,2,3-chlorobenzene) enhanced only meta-dechlorination, whereas five (3-chlorobenzoate; 2,3- and 2,5-chlorophenols; and 1,2- and 1,2,4-chlorobenzenes) increased both meta- and para-dechlorination, and two (2,5- and 2,3,5-chlorobenzoates) promoted overall, substitution non-specific dechlorination. When the maximum extent of dechlorination was plotted against the highest number of PCB-dechlorinating microorganisms for each HAC, there was a linear relationship (P<0.01), suggesting that dechlorination enhancement was related to the increase in their population size. However, there was also evidence to suggest that different dechlorinating microorganisms were selected.