Henry's law constants for polychlorinated biphenyls: experimental determination and structure-property relationships

Brunner, Siegfried; Hornung, Eduard; Santl, Helmut; Wolff, Eric W.; Piringer, O.; Altschuh, Joachim; Brueggemann, Rainer

doi:10.1021/es00081a021

Cited by 102 publications

(102 citation statements)

References 7 publications

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“…Windspeeds corresponding to days of air and water measurements were used to obtain mass transfer coefficients. Henry's law constants (Brunner et al 1990) were corrected for temperature based on results from ten Hulscher et al (1992) according to Hornbuckle et al (1994):…”

Section: Resultsmentioning

confidence: 99%

Biogeochemical cycling of PCBs in lakes of variable trophic status: A paired‐lake experiment

Jeremiason

Eisenreich

Paterson

et al. 1999

Limnology & Oceanography

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A paired whole-lake experiment was conducted on two remote, atmospherically driven lakes in the Experimental Lakes Area (ELA) to examine the stresses of trophic condition on air-water exchange and settling fluxes of polychlorinated biphenyls (PCBs). Lake 227 (L227) and Lake 110 (L110) are similar in volume, surface area, and watershed area but differ significantly in trophic status. The two lakes have similar access to atmospheric PCBs but eutrophic L227 may exhibit enhanced air to water exchange due to greater biotic uptake of dissolved PCBs. ). Greater ⌺PCB settling fluxes in L227 vs. L110 coupled with similar dissolved concentrations after June supports the hypothesis that air-water exchange supports the water column PCB concentrations. Surprisingly, ⌺PCB fugacity gradients in both lakes indicated that net volatilization dominated during the entire ice-free period, requiring another source. A ⌺PCB mass budget in the epilimnion of each lake over the stratified period showed that the major PCB losses were due to settling and volatilization. ⌺PCB settling losses were 2.4 times greater in L227 than in L110 due to higher settling particle fluxes. The mass budgets suggest that the major PCB input to these remote lakes is from the watershed. Our results indicate the intimate environmental linkage between atmospheric, land, and aquatic PCB reservoirs.Two of the greatest problems affecting many freshwater lakes are eutrophication and contamination of fish with organochlorines, such as polychlorinated biphenyls (PCBs). For example, there are active programs to reduce both nutrient levels and PCB concentrations in several of the Great Lakes. Previous studies suggest there may be important interactions between PCB concentrations and trophic condition (Larsson et al. 1992;Taylor et al. 1991). An understanding of the interactions between trophic condition and PCB concentrations is essential for effective management. This study 1 Current address: Minnesota Pollution Control Agency, 520 Lafayette Rd., St. Paul, Minnesota 55155.2 To whom correspondence should be addressed (eisenreich@aesop.rutgers.edu). AcknowledgmentsWe thank J. Embury, M. Lyngh, and other staff at ELA for collecting samples. We are thankful to D. Findlay and H. Kling for microscopic analysis of suspended and settling particles. H. Ilse and J. Trepkau provided outstanding laboratory assistance.

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Section: Resultsmentioning

confidence: 99%

Biogeochemical cycling of PCBs in lakes of variable trophic status: A paired‐lake experiment

Jeremiason

Eisenreich

Paterson

et al. 1999

Limnology & Oceanography

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“…Several QSPR-based models are available for predicting aqueous solubilities, HLCs, and environmental partition coefficients of organic contaminants (1)(2)(3)(4)(5)(6)(7)(8)(9)(10)(11)(12), with some of these approaches allowing the predictive modeling of each chemical parameter (e.g., S, HLC, etc.) directly from structural information.…”

Section: Introductionmentioning

confidence: 99%

Quantitative structure-property relationships for aqueous solubilities and Henry's law constants of polychlorinated biphenyls

Dunnivant¹,

Elzerman²,

Jurs³

et al. 1992

Environ. Sci. Technol.

116

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rn Quantitative structure-property relationship (QSPR) models have been developed which accurately calculate the congener-specific aqueous solubilities (S) and Henry's Law constants (HLCs) of polychlorinated biphenyls (PCBs). QSPRs were generated based on molecular models which were sensitive to slight changes in chemical structure. PCB aqueous solubilities were found to be a function of total surface area, melting point, and third shadow area. Observed HLCs were a function of the second moment of inertia, path-four connectivity index, path-three K index, and the second and third principal polarizabilities. These newly developed models agree well with other model predictions and expand, as well as complement, previous approaches because the new models are capable of accurately calculating S and HLC for structurally similar PCB congeners. Results from this work provide a better understanding of the chemical and structural characteristics governing the solubility of hydrophobic compounds.

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“…This latter paper clearly comes closest to addressing the concerns over possible aggregation, but does not meet the strict criterion of demonstrating concentration independence of the Henry's law constants. However the two values of DG s for compounds in the test set reported by Dunnivant et al [23], at concentrations less than half ''saturated'' were 0.61 kcal/mol less negative than a value based on the generator column technique [20], and within 0.1 kcal/mol of a value [24] based on solutions well below the solubility limit and never exposed to excess compound. If the solubility is spuriously high, then the solvation free energy will be spuriously negative.…”

Section: Transfer Energiesmentioning

confidence: 68%

“…The problem goes on because some direct measurements of Henry's law constants start with ''saturated solutions'' prepared using a generator column and may be subject to the same systematic error problem. For those polychlorinated biphenyls in the test set where direct determination of Henry's law constants has been reported, two papers were based on solutions prepared using generator columns [20,21], one was based on solutions prepared by stirring with excess organic compound and then let stand [22], and one was based on solutions made with enough organic solute to give a solution less than half saturated based on reported solubilities [23]. This latter paper clearly comes closest to addressing the concerns over possible aggregation, but does not meet the strict criterion of demonstrating concentration independence of the Henry's law constants.…”

Section: Transfer Energiesmentioning

confidence: 99%

The SAMPL3 blind prediction challenge: transfer energy overview

Geballe

Guthrie

2012

J Comput Aided Mol Des

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Prediction of the free energy of solvation of a small molecule, or its transfer energy, is a necessary step along the path towards calculating the interactions between molecules that occur in an aqueous environment. A set of these transfer energies were gathered from the literature for series of chlorinated molecules with varying numbers of chlorines based on ethane, biphenyl, and dibenzo-p-dioxin. This focused set of molecules were then provided as a blinded challenge to assess the ability of current computational solvation methods to accurately model the interactions between water and increasingly chlorinated compounds. This was presented as part of the SAMPL3 challenge, which represented the fourth iterative blind prediction challenge involving transfer energies. The results of this exercise demonstrate that the field in general has difficulty predicting the transfer energies of more highly chlorinated compounds, and that methods seem to be erring in the same direction.

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Henry's law constants for polychlorinated biphenyls: experimental determination and structure-property relationships

Cited by 102 publications

References 7 publications

Biogeochemical cycling of PCBs in lakes of variable trophic status: A paired‐lake experiment

Biogeochemical cycling of PCBs in lakes of variable trophic status: A paired‐lake experiment

Quantitative structure-property relationships for aqueous solubilities and Henry's law constants of polychlorinated biphenyls

The SAMPL3 blind prediction challenge: transfer energy overview

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