Effects of sampling methods on the quantity and quality of dissolved organic matter in sediment pore waters as revealed by absorption and fluorescence spectroscopy

Despite literature evidence suggesting the importance of sampling methods on the properties of sediment pore waters, their effects on the dissolved organic matter (PW-DOM) have been unexplored to date. Here, we compared the effects of two commonly used sampling methods (i.e., centrifuge and Rhizon sampler) on the characteristics of PW-DOM for the first time. The bulk dissolved organic carbon (DOC), ultraviolet-visible (UV-Vis) absorption, and excitation-emission matrixes coupled with parallel factor analysis (EEM-PARAFAC) of the PW-DOM samples were compared for the two sampling methods with the sediments from minimal to severely contaminated sites. The centrifuged samples were found to have higher average values of DOC, UV absorption, and protein-like EEM-PARAFAC components. The samples collected with the Rhizon sampler, however, exhibited generally more humified characteristics than the centrifuged ones, implying a preferential collection of PW-DOM with respect to the sampling methods. Furthermore, the differences between the two sampling methods seem more pronounced in relatively more polluted sites. Our observations were possibly explained by either the filtration effect resulting from the smaller pore size of the Rhizon sampler or the desorption of DOM molecules loosely bound to minerals during centrifugation, or both. Our study suggests that consistent use of one sampling method is crucial for PW-DOM studies and also that caution should be taken in the comparison of data collected with different sampling methods.