Effects of sediment manipulation on freely dissolved concentrations of hydrophobic organic chemicals.

The freely dissolved concentration (Cfree) of hydrophobic organic chemicals (HOCs) in pore water is an important parameter in the risk assessment and management of contaminated sediments and soils. It can be determined most conveniently through ex situ passive sampling, i.e., in the laboratory. For this purpose, samples are taken from the field and transported to the laboratory, where they are stored and possibly manipulated by sieving, freezing, drying and/or grinding. Although the objective of ex situ passive sampling often is to determine a Cfree that reflects the metric under in situ conditions, hardly any information is available on possible effects of sample manipulation. Hence, the present study investigated the impact of freezing, freeze-drying, and grinding on Cfree of HOCs in field sediments, as determined with solid phase microextraction (SPME). Freezing increased the Cfree of 3- and 4-ring polycyclic aromatic hydrocarbons (PAHs) with up to a factor of 4, whereas for 5- and 6-ring PAHs hardly any effects were observed. Generally, additional freeze-drying did not further increase Cfree, but subsequently grinding the samples (further) increased Cfree of all PAHs with up to a factor of 4, leading to an overall maximum observed increase in Cfree of a factor of 16. Probably, these effects are caused by a structural change in the sorption matrix, enhancing PAH availability. The results indicate that freezing, freeze-drying, and grinding prior to ex situ Cfree determinations should be avoided, as these treatments may considerably increase the Cfree of HOCs, leading to an overestimation of risks.