Application of permeant/polymer diffusional model to the desorption of polychlorinated biphenyls from Hudson River sediments. Reply to comments

Carroll, Kenneth M.; Harkness, Mark

doi:10.1021/es00001a041

Cited by 4 publications

(6 citation statements)

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“…Organic matter of this size should be observable by electron microscopy methods; we have not seen evidence for this. Furthermore, other workers have reported or implied OM thicknesses in natural solids to be on the order of tens of nanometers thick (14,15,58). These nanometer-scale thicknesses require diffusivities like those estimated for "glassy" polymers above.…”

Section: Resultsmentioning

confidence: 99%

“…For the three PAHs we studied, we calculated their diffusion coefficients in natural OM based on the model developed for both elastomer and glassy polymers by Salame (57) and recently applied by Carroll et al (14,15) (Table 4). For naphthalene, acenaphthene, and phenanthrene, the elastomer polymer diffusivities ranged from about 1 × 10 -12 to 3 × 10 -14 cm 2 s -1 , many orders of magnitude lower than the corresponding aqueous diffusivities.…”

Section: Resultsmentioning

confidence: 99%

“…Diffusion rates within natural organic matter [commonly presumed to be the predominant sorbent medium for HOCs interacting with water-wet natural solids containing some minimal OM (10)(11)(12)] should be consistent with diffusion in synthetic organic polymers (e.g., refs [13][14][15][16][17]. We expect that intraorganic matter diffusion should be a function of OM composition, swelling, cross-linking, and dimension.…”

Section: Introductionmentioning

confidence: 89%

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Estimating Sorption Rates of Hydrophobic Organic Compounds in Iron Oxide- and Aluminosilicate Clay-Coated Aquifer Sands

Holmén

Gschwend

1996

Environ. Sci. Technol.

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We hypothesized that retarded diffusion in coatings controls the rate of sorption of hydrophobic organic compounds (HOCs) on quartzitic aquifer sands. Microscopic examination of three sands was used to quantify the coating thicknesses. With measures of the coatings' organic contents and porosities, we predicted the relative sorption rates for (a) multiple HOCs on one sand and (b) one HOC with three sands. The predicted relative rates and equilibrium coef ficients were assessed using observations of HOC transport through short sand columns operated at varying flow rates. We found that the column K d values were always much less than predicted from K oc f oc or observed in batch tests. This suggests that diagenetically produced sorbents may include organic matter that is completely inaccessible for HOC sorption; procedures that disaggregate these sands could expose organic matter that does not sorb HOCs in the environment. Second, by modifying our retarded diffusion expectations with the inferred fraction of available organic carbon, f avail, all observed sorption rates were consistent (within a factor of 4) with k r ≈ 0.001D aq/δ2(1 + K oc f avail), where k r is the desorption rate constant, D aq is the HOC's aqueous diffusivity, δ is the coating thickness, is the ratio of solids-to-water in the coatings, is the organic carbon content of the coating solids, and all other factors affecting sorption rates (e.g., tortuosity) were set equal to 0.001. Since oxide coatings are ubiquitous in aquifer sands, the model described here should have wide applicability.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 89%

See 1 more Smart Citation

Estimating Sorption Rates of Hydrophobic Organic Compounds in Iron Oxide- and Aluminosilicate Clay-Coated Aquifer Sands

Holmén

Gschwend

1996

Environ. Sci. Technol.

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“…In a related study of the leaching of PCBs from PC, Uhler et al (2021) reported that more than 99% of the PCBs in the PCB-paint chips remained trapped in the paint matrix at the cessation of leaching after 1,150 days (i.e., less than 1% of the PCB mass desorbed into the water). This finding is highly indicative of much stronger sorption of PCBs to PC than to sediment, as over 50% of the PCBs desorbed from suspended sediments from contaminated sites in the USA (i.e., Hunters Point Naval Shipyard, Lake Hartwell and Hudson River) over periods ranging from days to weeks (Carroll et al 1994;Zimmerman et al 2004;Werner et al 2005). A proposed mechanism that explains the observed partitioning behavior of PCBs from PCB PC is a process where surface bound PCB molecules partition relatively rapidly into water in contact with the paint chips; the rate of desorption decreases as the PCB molecules on the paint surface become depleted.…”

Section: Discussionmentioning

confidence: 99%

Passive-Sampler-Based Bioavailability Assessment of PCB Congeners Associated with Aroclor-Containing Paint Chips in the Presence of Sediment

Lotufo

Gidley

McQueen

et al. 2021

Arch Environ Contam Toxicol

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This is the first investigation of the bioavailability of PCBs associated with paint chips (PC) dispersed in sediment. Bioavailability of PCB-containing PC in sediment was measured using ex situ polyethylene passive samplers (PS) and compared to that of PCBs from field-collected sediments. PC were mixed in freshwater sediment from a relatively uncontaminated site with no known PCB contamination sources and from a contaminated site with non-paint PCB sources. PC < 0.045 mm generated concentrations in the PS over one order of magnitude higher than coarser chips. The bioavailable fraction was represented by the polymer-sediment accumulation factor (PSAF), defined as the ratio of the PCB concentrations in the PS and organic carbon normalized sediment. The PSAF was similar for both field sediments. The PSAFs for the field sediments were ~ 50–60 and ~ 5 times higher than for the relatively uncontaminated sediment amended with PC for the size fractions 0.25–0.3 mm and < 0.045 mm, respectively. These results indicate much lower bioavailability for PCBs associated with PC compared to PCBs associated with field-collected sediment. Such information is essential for risk assessment and remediation decision-making for sites where contamination from non-paint PCBs sources is co-located with PCB PC.

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“…The bioavailability of weathered organic compounds is generally thought to decline with residence time in the environment (Alexander, 2000). This trend of decreased availability with aging has been observed for PCBs, PAHs, and PBDEs (Carroll and Harkness, 1995;Hatzinger and Alexander, 1995). For instance, previous studies reported that aging of PBDEs may significantly diminish their bioavailability in soil, with a reduction ranging from 22 to 84% compared with freshly spiked soil (Liang et al, 2010).…”

Section: Root Concentration Factor (Rcf) and Log K Owmentioning

confidence: 93%

Plant selective uptake of halogenated flame retardants at an e-waste recycling site in southern China

Wang

Luo

et al. 2016

Environmental Pollution

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Application of permeant/polymer diffusional model to the desorption of polychlorinated biphenyls from Hudson River sediments. Reply to comments

Cited by 4 publications

References 4 publications

Estimating Sorption Rates of Hydrophobic Organic Compounds in Iron Oxide- and Aluminosilicate Clay-Coated Aquifer Sands

Estimating Sorption Rates of Hydrophobic Organic Compounds in Iron Oxide- and Aluminosilicate Clay-Coated Aquifer Sands

Passive-Sampler-Based Bioavailability Assessment of PCB Congeners Associated with Aroclor-Containing Paint Chips in the Presence of Sediment

Plant selective uptake of halogenated flame retardants at an e-waste recycling site in southern China

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