Effects of sampling techniques on physical parameters and concentrations of selected persistent organic pollutants in suspended matter.

This study focusses on the effect of sampling techniques for suspended matter in stream water on subsequent particle-size distribution and concentrations of total organic carbon and selected persistent organic pollutants. The key questions are whether differences between the sampling techniques are due to the separation principle of the devices or due to the difference between time-proportional versus integral sampling. Several multivariate homogeneity tests were conducted on an extensive set of field-data that covers the period from 2002 to 2007, when up to three different sampling techniques were deployed in parallel at four monitoring stations of the River Rhine. The results indicate homogeneity for polychlorinated biphenyls, but significant effects due to the sampling techniques on particle-size, organic carbon and hexachlorobenzene. The effects can be amplified depending on the site characteristics of the monitoring stations.

Comparative evaluation of four suspended particulate matter (SPM) sampling devices and their use for monitoring SPM quality.

Representative sampling of suspended particulate matter is fundamental for assessing river sediment quality, including the distribution and physicochemical characterisation of particles at different hydrological events. This study compares time-integrated samplers and discrete sampling methods, focusing on (a) the representativeness of the different methods and (b) the comparability between the various sampling techniques. The study investigates whether different sampling devices used under the same conditions can reproduce the annual mean. Two time-integrated sampling techniques (Binnensammler floating collector (BS); self-constructed Phillips sampler (PS)) and two discrete sampling systems (continuous-flow centrifuge (CFC); hydrocyclone (HC)) were compared. The monitoring program (August 2013 to August 2014) was conducted using a 4-week sampling frequency at two different monitoring stations in the Rhine river basin. The analysis of physicochemical parameters included total organic carbon (TOC), particulate phosphorus (PP), grain size distribution (GSD), metals, and organic pollutants (PCBs, HCB, PAH). A nested analysis of variance (ANOVA) was used to evaluate the dependence of suspended matter quality parameters on the sampling method, the sampling device, and the sampling station. According to ANOVA, physical and chemical parameters as well as persistent organic pollutants are homogenous for the time-integrated samplers PS and BS. Comparing PS and the reference technique CFC, only the mean annual concentration of TOC is significantly higher for CFC (5.91%; PS, 4.53%) due to degradation processes. With the exception of TOC, Ni, and GSD, data of BS was comparable with that of CFC. Comparing CFC and HC, there are significant differences for GSD, Zn, and Ni. An analysis of the time series of GSD < 63 µm and sum of PAHs confirms the findings of the nested ANOVA, showing that HC time series display significant differences compared with the other samplers.

Sediment water (interface) mobility of metal(loid)s and nutrients under undisturbed conditions and during resuspension.

The contribution of the release from sediments to the overall river Trave budget was evaluated with respect to 16 metal(loid)s, three non-metals and the ions PO43- and NH4+. To consider undisturbed conditions and sediment resuspension in-situ dialyses-based and ex-situ suction-based pore water sampling was complemented by sequential extraction and suspension reactor experiments. In the investigated sediments, representative for the study area, metal(loid) partitioning between the different geochemical fractions was very similar despite some higher contaminated spots. Pore water investigations emphasis that profiling and peeper based analyses are comparable and deliver an indication that sediment dwelling organisms are exposed to elevated metal(loid) concentrations. However, higher toxicity of the contaminated sediments compared to the sediment treated as background reference was not revealed. During resuspension only few metal(loid)s exceeded specified guideline values. The maximum amounts released, were only between 10-5 and 10-1% of the average daily load of the river Trave per ton of suspended sediment. Overall the "most pristine sediments" and not the potentially hazardous materials in the study area are found to be from highest concern. The results support requests to better include fractionation and speciation demands in legal assessments of sediments.