In Situ Passive Sampling of Sediment Porewater Enhanced by Periodic Vibration.

Passive sampling for the measurement of freely dissolved concentrations of organic pollutants in sediment porewater has emerged as a promising approach, but in situ measurements are complicated by slow mass transfer of strongly hydrophobic compounds. The primary resistance to mass transfer arises in the sediment side where a concentration depletion layer develops in the vicinity of the polymeric passive sampling material. The slow mass transfer results in underequilibrated passive sampler measurements that need to be corrected for equilibrium, typically by extrapolation of the loss kinetics of performance reference compounds. Such corrections are prone to large errors, especially when deviation from equilibrium is large. In this research we address the challenge of slow mass transfer by disrupting the external depletion layer around an in situ passive sampler. We report an engineering innovation of adapting low-cost vibration motors for periodically disrupting the depletion layer in a passive sampler deployed in sediments. The uptake of 16 polycyclic aromatic hydrocarbons into polyethylene passive samplers was measured after 7, 14, 28, and 56 days of exposure to sediment under static, vibrating, and fully mixed modes. We demonstrate through laboratory experiments and numerical mass transfer modeling that short periodic shaking of a passive sampler deployed in static sediment enhances the rate of mass transfer and reduces the difference in the extent of equilibrium achieved compared to a well-mixed laboratory equilibrium. The improvement over static sediment deployment is especially evident for the high molecular weight compounds such as benzo(a)pyrene.