Passive sampling to evaluate performance of in situ sediment remediation

In situ passive sampling is the use of a polymer sorbent to directly assess freely dissolved concentration (C [subscript free]) profiles within the environment. The primary focus herein is the use of passive sampling methods to detect and quantify persistent hydrophobic organic compounds (HOCs) in sediment porewater and surface water using solid phase microextraction (SPME) profilers with polydimethylsiloxane (PDMS) as the receiving phase sorbent. Contaminated sediment sites pose a unique challenge in terms of remediation and monitoring for several reasons including: the large number of past and ongoing sources, sediment stability, and the extent of contamination. Capping with a clean layer of material, an accepted remediation approach, can reduce risk by stabilizing the underlying sediments, isolating the water column, and reducing contaminant flux. Evaluating cap performance is challenging due to the long time frames associated with migration of HOCs. Additionally, the non-sorbing nature of most caps limits the usefulness of bulk solid measurements. An alternative is the use of concentrations in the interstitial space or porewater to examine contaminant migration in the sediments and cap. Traditionally, porewater concentrations are obtained through a conversion of bulk sediment concentrations using an assumed sediment-water partitioning coefficient. This assumption often leads to a misrepresentation of risk as not all organic carbon is created equal. An alternative is the use of passive sampling with polymer sorbents to estimate the freely available concentration, C [subscript free]. In this work the focus is on the use of solid phase microextraction with polydimethylsiloxane (SPME PDMS) as the sorbent. C [subscript free] is proportional to chemical activity; therefore an accurate measurement of C [subscript free] is necessary for risk assessment and determination of transport mechanisms and ultimately improved management of contaminated sediment sites. A non-equilibrium correction protocol using performance reference compounds (PRCs) was developed to enhance the accuracy of the SPME PDMS method to assess C [subscript free]. The protocol was validated through laboratory experiments and field trials. Deployment times can be reduced without sacrificing accuracy when using the PRC protocol. Furthermore, it was shown that mathematical models of diffusive and advective flux can be fit using parameters determined from PRC desorption. The SPME PDMS with PRCs method was used at three different remediated contaminated sediment sites, Chattanooga Creek, Eagle Harbor, and the West Branch of the Grand Calumet River, to illustrate its utility at evaluating performance of in situ remediation. Overall, the results from laboratory and field studies suggest that SPME PDMS is a valuable tool for evaluating performance of in situ sediment remediation.