Comparative distribution, sourcing, and chemical behavior of PCDD/Fs and PCBs in an estuary environment.

PCDD/F and PCB field data (1041 samples) in five media (dissolved, suspended sediment, bed sediment, catfish, and blue crab) were studied to explore dual contaminant patterns in the Houston Ship Channel, Texas, USA. PCDD/Fs showed greater concentration than PCBs in suspended sediments while PCBs were higher in apparent dissolved (truly dissolved+DOC-associated), fish, and crab. PCDD/Fs at nearly all locations contributed more strongly to dioxin-like toxicity. The fraction of PCB TEQ was, however, enriched in biotic over abiotic media due in large part to the presence of PCB 126, which was mostly undetected in water and sediment and yet exhibited a BAF three times greater than 2,3,7,8-TCDD. Dissolved-suspended sediment and suspended-bed sediment relationships showed that (1) observed apparent dissolved concentration differences (as fraction of total water were mean 10% PCDD/Fs and 63% PCBs) can reasonably be explained by a four-phase partition model (truly dissolved, DOC-associated, suspended OC, and suspended BC) for PCBs but not for PCDD/Fs and (2) the contaminants behaved similarly in bed to suspended sediment concentration ratios (C(bed)/C(susp)) upstream of a major confluence but not downstream. PCA-cluster analysis pointed to the possibility that suspended sediment PCB contamination originates from resuspended bed sediment while PCDD/Fs in suspended sediment originates more probably from other sediment sources such as upstream wash load or air deposition. Finally, examinations of a congener marker ratio (PCB 209/206) seemed to indicate that a source of pure PCB 209 may exist in bed sediment near Patrick Bayou though the source was not completely localized.

PCB dry and wet weather concentration and load comparisons in Houston-area urban channels.

All 209 PCB congeners are quantified in water in both dry and wet weather urban flows in Houston, Texas, USA. Total water PCBs ranged from 0.82 to 9.4ng/L in wet weather and 0.46 to 9.0ng/L in dry. Wet weather loads were 8.2 times higher (by median) than dry weather with some increases of over 100-fold. The majority of the PCB load was in the dissolved fraction in dry weather while it was in the suspended fraction in wet weather. Dissolved PCB loads were correlated with rain intensity and highly developed land area, and a multiple linear regression (MLR) equation was developed to quantify these correlations. PCA generated five PCB components with nearly all positive loadings. They were interpreted as DOC-associated A1248, wet weather primarily suspended fraction A1254/A1260 likely from building sealants, truly dissolved-associated wastewater dechlorination, watershed-sourced PCB 11, and monochlorinated PCBs (likely connected to a different state or source of dechlorination). The PCB 11 component was statistically higher in wet versus dry weather when no other component showed such clear distinctions. Hierarchical cluster analysis (HCA) did not always group dry and wet weather samples from the same location together illustrating the different congener composition that often exists between dry and wet conditions. Four wet weather samples from high percentage developed land (>90%) watersheds had nearly the same fingerprint suggesting a generic "urban" signature in runoff, which in this case was caused by residual A1254/A1260 PCB stocks and currently produced PCB 11 in consumer goods.

Spatial and temporal variation of polychlorinated biphenyls in the Houston Ship Channel.

An on-going study in the Houston Ship Channel (HSC) characterized polychlorinated biphenyl (PCB) levels in sediment, water, and tissue in 2002-2003 and 2008. The observed PCB concentration ranges in all media were higher than those measured in other PCB-impacted water bodies in the world, with the highest concentrations occurring within the industrialized segments. Contrary to polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDD/PCDF) observations, the PCB concentrations in the dissolved phase were greater than the suspended phase. Possible explanations include passage of colloids, competition for adsorption sites from other hydrophobic contaminants, and continuing current sources. The PCB homologue distributions were similar for suspended water, sediment and tissue with the profile normalized around penta-chlorobiphenyls, while the dissolved phase profile normalized around tri-chlorobiphenyls. PCB-209 was detected in the suspended water phase and in sediment (10%) prompting interest into its sources to the HSC since PCB-209 was present only in rare commercial mixtures and is a byproduct in very few manufacturing processes. Inter-media analyses showed a significant correlation and transfer of PCBs. Dioxin-like PCBs contributed significant toxicity to total equivalent in tissue (33%), while they were insignificant in water (<10%) and sediment (<5%). The PCB concentrations over time showed a significant decrease in suspended water, sediment and tissue, while dissolved water concentrations showed insignificant change. The homolog distribution, however, showed a significant change in dissolved water and fish, a minor change in sediment and insignificant change in suspended water. Furthermore, an analysis for six representative congeners showed that they were accurate in predicting the total PCB concentrations and could be thus used as indicator PCBs.

Bioaccumulation of polychlorinated dibenzodioxins and dibenzofurans in catfish and crabs along an estuarine salinity and contamination gradient.

Elevated but variable levels of polychlorinated dibenzodioxins and polychlorinated dibenzofurans (PCDD/Fs) were observed in hardhead sea catfish (HH) and blue crabs (BCs), as well as in water and sediment, of the Houston Ship Channel system, Texas, USA. It is hypothesized that the variation was caused by the spatial variability of PCDD/F contamination, together with the natural mobility of organisms in satisfying prey, temperature, salinity, and reproductive requirements. Structural equation modeling was applied to explore the congener-specific relationships between PCDD/F levels in HH and BC tissues and independent predictors such as PCDD/F contamination levels, environmental factors such as salinity and temperature, temporal-spatial factors such as site depth and season, and biological factors such as length, weight, and lipid content. Contamination levels in both sediment and water were statistically significant predictors of the levels of less chlorinated congeners in both HH and BCs, with the standardized regression weight for sediment concentration roughly twice that for the water concentration. This implies that sediments are the dominant route for PCDDIF exposure and remediation efforts should focus on legacy sediment ontamination. Tissue lipid content was a significant predictor of tissue concentrations in HH but only to a lesser extent in BCs, perhaps due to their low lipid content. Site depth and seasonal factors also were significant predictors of tissue concentrations. For the highly chlorinated congeners, only a small fraction of the variance in tissue concentrations was explained by the independent predictors, possibly indicating that uptake and elimination kinetics, biotransformation processes, or both may be more important factors controlling the bioaccumulation of those congeners.

Concentrations of polychlorinated biphenyls (PCBs) in water, sediment, and aquatic biota in the Houston Ship Channel, Texas.

Polychlorinated biphenyls (PCBs) were quantified in water, sediment, and catfish and crab tissue collected from the Houston Ship Channel (HSC) in Texas. The total concentrations of the 209 PCB congeners ranged from 0.49 to 12.49 ng l(-1), 4.18 to 4601 ng g(-1) dry wt, 4.13 to 1596 ng g(-1) wet wt, and 3.44 to 169 ng g(-1) wet wt, in water, sediment, catfish and crab tissue, respectively. All media showed maximum concentrations greater than studies in other regions with the highest concentrations occurring in the most industrialized segments of the channel. Inter-media correlations suggested that sediment is a source to water. Galveston Bay sediment concentrations compared to a previous study showed a declining trend though the rate of the decline may be slowing. Detailed homolog profiles revealed that the industrialized part of the channel may be receiving PCB-laden sediment from its tributaries. An unusually high fraction of the deca-chlorinated congener (PCB-209) was found in all media. Seen in only a few other studies and in previous air concentrations in the channel, this may point to unusual Aroclor mixtures used in the history of the HSC or to contemporary sources from local industry. A comparison of PCB concentrations obtained using Aroclor, representative congener, and all congener methods, indicated that Aroclors are not an appropriate surrogate for total PCBs and that the NOAA NST method is more representative than the NOAA EPA method.

Depositional flux of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans in an urban setting.

Dry and wet deposition fluxes of the PCDD/F substituted congeners were measured at two different sites (Clinton Drive and Lang Road) in Houston, TX between December 2003 and April 2004. Average total dry deposition fluxes of 351 and 125pgm(-2)d(-1) were found at Clinton Drive and Lang Road, respectively. A wet deposition flux of 2.873pgm(-2)d(-1) was measured at the Clinton Drive site. The results indicated that the dry deposition process exhibited spatial variability. In addition, the results also demonstrated that precipitation, although intermittent, is the most important mechanism for the removal of dioxins from atmosphere in the area of study. Combining the contributions of the dry and wet deposition processes at Clinton Drive resulted in a total bulk deposition flux of 527pg m(-2)d(-1). The total dry and wet deposition fluxes were dominated by OCDD followed by 1,2,3,4,6,7,8-HpCDD at both sites. Overall average dry deposition velocities of 0.35 and 0.15cms(-1) were calculated at Clinton Drive and Lang Road sites, respectively. While these velocities were similar to velocities observed in other geographical areas, the contribution of OCDD to the total deposition flux in Houston was significantly higher, probably reflecting the unique nature and character of Houston dioxin sources. The results also showed that lower chlorinated congeners, primarily present in the gas phase, are more likely to be removed from the atmosphere by precipitation. Relationships between the detected congeners in the dry deposition samples and other routinely measured air pollutants/meteorological parameters were found. The results showed that in general, the dry deposition of these congeners was consistently negatively correlated with SO(2) and NO(x) concentrations in the air and positively correlated with relative humidity. However, more research is needed to ascertain those correlations.

Distribution of polychlorinated dibenzo-p-dioxins and dibenzofurans in suspended sediments, dissolved phase and bottom sediment in the Houston Ship Channel.

Spatial distributions of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) in the water column and bottom sediments of the Houston Ship Channel in Texas were measured three times over a 1-year period. Total TEQ concentrations in water ranged from 0.01 to 0.25 pg/l for the dissolved phase and from 0.09 to 2.91 pg/l for the suspended phase, while TEQ concentrations in bottom sediments varied from 0.9 to 139.8 ng/kg dry wt. The dissolved concentrations were lower than their respective suspended concentrations, with average dissolved/suspended ratios between 0.11 and 0.59 for individual congeners. More than 89% of the total concentration of 2378-substituted PCDD/PCDFs was attributable to OCDD but 2378-TCDD was the major contributor to total TEQ for the three sampled media. Average logs of organic carbon-normalized suspended sediment-dissolved partitioning coefficients (logK(oc)(obs)) varied between 4.92 and 8.59 l/kg-oc; while in the bottom sediment-dissolved interface, logK(oc)(obs) values ranged from 5.48 to 8.48 l/kg-oc. Observed logK(oc)values varied within a factor of 0.64-1.26 from equilibrium logK(oc) values, suggesting fluxes of PCDD/PCDFs across the interfaces. It was found that in the HSC, on average, the tendency of a compound to move from the particulate phase to the dissolved phase decreases with increasing K(ow).

Statistical investigation of polychlorinated dibenzo-p-dioxins and dibenzofurans in the ambient air of Houston, Texas.

Polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (dioxins and furans) are persistent, bioaccumulative and highly toxic chemical constituents that appear in the environment at very low and difficult to measure levels. Although dioxins and furans are widely recognized as toxic contaminants needing regulation, their temporal and spatial concentration profiles and the factors impacting their partitioning and congener distribution are only moderately understood. This paper presents the results from one of the most extensive ambient air dioxin and furan sampling efforts conducted in a geographic area to date. The data consist of monthly ambient concentrations of 17 of the most toxic congeners of dioxins and furans collected at five locations in Houston, Texas over a calendar year. The results showed a total annual mean dioxin and furan congener concentration of 1047 fg/m3 and an annual mean summation operatorI-TEQ concentration of 15 fg I-TEQ/m3 (16 fg WHO-TEQ/m3). These results, when compared with proximate data from the USEPA National Dioxin Ambient Monitoring Network (NDAMN), revealed significant (at the P0.05 level) differences between Houston and the NDAMN sites, suggesting the existence of local dioxin sources. A temporal analysis of the data showed that the congener concentration distribution varies over time, depending on the level of chlorination, type of congener, and temperature. The results also suggested that the fluctuations of congener concentrations and I-TEQ concentrations are closely correlated with minimum relative humidity, mean temperature, and mean NOx concentration.