Abstract
Background, aim, and scope
The behavior of polycyclic aromatic hydrocarbons (PAHs) is affected by dissolved organic matter (DOM) present in pore water of soils and sediments. Since partitioning to DOM reduces the bioavailable or freely dissolved PAH concentration in pore water, it is important to assess the effect of environmental variables on the magnitude of dissolved organic matter to water partition coefficients (K DOC). The objective of this study was to apply passive samplers to measure freely dissolved PAHs allowing depletion from the aqueous phase. The method was applied to determine K DOC at different temperatures for a selection of PAHs with natural DOM of very different origin.
Materials and methods
Freely dissolved concentrations of (spiked) phenanthrene, anthracene, fluoranthene, pyrene, and benzo[e]pyrene were determined by exposing polydimethylsiloxane (PDMS) fibers to aqueous solutions containing DOM extracted from freshwater sediments from Finland and the Netherlands. The K DOC values were subsequently calculated at different temperatures (3.2, 20, and 36°C) by including temperature-dependent PDMS to water partition coefficients (K PDMS) in a mass balance. Furthermore, the effect of temperature on partitioning of PAHs to PDMS fibers or DOM was assessed by comparing the enthalpy of sorption to the excess enthalpy of dissolution of liquid PAHs.
Results and discussion
Partitioning to DOM resulted in a decrease of freely dissolved concentrations with increasing DOM concentrations and a large range in log K DOC values at 20°C for benzo[e]pyrene was observed (log K DOC = 4.93–6.60 L kg−1 organic carbon). An increase of 10°C in temperature resulted in a decrease of K PDMS by 0.09 to 0.13 log units for phenanthrene to pyrene and a decrease of K DOC by 0.13 log units for pyrene. The calculated enthalpies of sorption were less exothermic than the (negative) excess enthalpies of dissolution as expected for non-specific interactions between PAHs and PDMS or DOM.
Conclusions
The bioavailability of PAHs in sedimentary pore waters can be accurately determined by application of PDMS fibers (without requiring negligible depletion) in the presence of natural DOM with different sorption affinity for PAHs. The observed natural variability in log K DOC values for different sediments shows that large differences can occur in freely dissolved PAH concentrations in pore water and properties of DOM should be taken into account in predicting the bioavailability of PAHs. Furthermore, the effect of temperature on the partitioning behavior of PAHs shows that interactions between PAHs and environmental sorbents are comparable to interactions between PAHs in their pure condensed liquid phase and calculated excess enthalpies can be safely used to directly correct partition coefficients for temperature.
Recommendations and perspectives
The application of PDMS fibers in measuring freely dissolved PAH concentrations can be used to study structural and thermodynamic aspects of PAH sorption to natural DOM as well as other environmental processes such as enhanced diffusion phenomena in pore water that are dependent on the amount (or concentration) of DOM, sorption affinity of DOM, and hydrophobicity of PAHs. These environmental factors will therefore give further insight into the site-specific exposure to freely dissolved PAH concentrations in soil and sedimentary pore water.
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Acknowledgments
Paul C.M. van Noort (Deltares, Utrecht, the Netherlands) and Jarkko Akkanen (Joensuu University, Joensuu, Finland) are thanked for supplying the sediment samples from KET and from Finland, respectively. The PDMS fibers were kindly supplied by Thomas L. Ter Laak (KWR Watercycle Research Institute, Nieuwegein, The Netherlands). Chen Yi, Sabina Stoffers, Leo Hoitinga, Joke Westerveld, Frans van der Wielen, and Peter Serné from the Universiteit van Amsterdam (UvA) are acknowledged for their assistance in the analyses. Karsten Kalbitz and Pim de Voogt (UvA) are thanked for remarks and improvements of the manuscript. This research has been funded by the European Commission, project ABACUS (EVK1-2001-00101).
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Haftka, J.J.H., Govers, H.A.J. & Parsons, J.R. Influence of temperature and origin of dissolved organic matter on the partitioning behavior of polycyclic aromatic hydrocarbons. Environ Sci Pollut Res 17, 1070–1079 (2010). https://doi.org/10.1007/s11356-009-0263-9
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DOI: https://doi.org/10.1007/s11356-009-0263-9