Using a polymer probe characterized by MALDI-TOF/MS to assess river ecosystem functioning: From polymer selection to field tests.

Abstract Characterization of river ecosystems must take into consideration both structural and functional aspects. For the latter, a convenient and simple approach for routine monitoring is based on the decomposition of organic matter measured in terms of breakdown of natural organic substrates like leaf litter, wood sticks. Here we extended the method to a synthetic organic material using polymer probes characterized by MALDI-TOF/MS. We first characterized several commercial available polymers, and finally selected polycaprolactonediol 1250 (PCP 1250), a polyester oligomer, as the most convenient for further studies. PCP 1250 was first tested at mesocosms scale under conditions simulating those of the river, with and without nutrient addition for up to 4 weeks. Differences to the starting material measured in terms of changes in the relative ion peak intensities were clearly observed. Ions exhibited a different pattern evolution along time depending on their mass. Greatest changes were observed at longest exposure time and in the nutrient addition treatment. At shorter times, the effect of nutrients (addition or not) was indistinguishable. Finally, we performed an experiment in 11 tributaries of the Ebro River during 97 days of exposure. Principal Component Analysis confirmed the different behavior of ions, which were clustered according to their mass. Exposed samples were clearly different to the standard starting material, but could not be well distinguished among each other. Polymer mass loss rates, as well as some environmental variables such as conductivity, temperature and flow were correlated with some peak intensities. Overall, the interpretation of field results in terms of environmental conditions remains elusive, due to the influence of multiple concurrent factors. Nevertheless, breakdown of synthetic polymers opens an interesting field of research, which can complement more traditional breakdown studies to assess river ecosystem functioning.