NDLI: Influence of temperature and origin of dissolved organic matter on the partitioning behavior of polycyclic aromatic hydrocarbons

Content Provider	Springer Nature Link
Author	Haftka, Joris J. H. Govers, Harrie A. J. Parsons, John R.
Copyright Year	2009
Abstract	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.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.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.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.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.
Starting Page	1070
Ending Page	1079
Page Count	10
File Format	PDF
ISSN	09441344
Journal	Environmental Science and Pollution Research
Volume Number	17
Issue Number	5
e-ISSN	16147499
Language	English
Publisher	Springer-Verlag
Publisher Date	2009-12-02
Publisher Place	Berlin, Heidelberg
Access Restriction	One Nation One Subscription (ONOS)
Subject Keyword	Bioavailability Solid phase microextraction Passive sampling Temperature Enthalpy of sorption Excess enthalpy PAH DOM Industrial Pollution Prevention Waste Water Technology Water Pollution Control Water Management Aquatic Pollution Atmospheric Protection/Air Quality Control/Air Pollution Environment
Content Type	Text
Resource Type	Article
Subject	Environmental Chemistry Health, Toxicology and Mutagenesis Pollution Medicine

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