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Microplastics in the Rivers Meuse and Rhine

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Microplastics in the Rivers Meuse and Rhine Master’s thesis for Master of Science Environmental Sciences Department of Science, Faculty of Management, Science & Technology, Open University of the Netherlands, Heerlen. Microplastics in the rivers Meuse and Rhine Developing guidance for a possible future monitoring program. Wilco Urgert October 16th, 2015 “Environmental Science is about analyzing, preventing and solving societal problems. For that, you need different disciplines. Which disciplines you will need, depends on the specific problems at hand. Integration of knowledge from different disciplines is a key characteristic of the Environmental Scientist.” Quoted from prof. dr. A.M.J. (Ad) Ragas, professor at the Department of Science, Faculty of Management, Science & Technology, Open University of the Netherlands, Heerlen. In this study, to a greater or lesser extent, I tried to integrate insights from Biology, Hydrology, Analytical chemistry, Organic chemistry, Physics and Mathematics into one coherent whole. The graduation committee consists of the following members: First OU supervisor: dr. A.J. (Ansje) Löhr, assistant professor at the Department of Science, Faculty of Management, Science & Technology, Open University of the Netherlands, Heerlen. Second OU supervisor: dr. F.G.A.J. (Frank) van Belleghem, assistant professor at the Department of Science, Faculty of Management, Science & Technology, Open University of the Netherlands, Heerlen. External supervisor: dr. G. (Gerard) Stroomberg, program manager operational water quality monitoring at Rijkswaterstaat, Lelystad. From October 1st 2014: director at RIWA- Rijn, Nieuwegein. External supervisor: prof. dr. N.M. (Nico) van Straalen, professor at the Department of Ecological Science, Faculty of Earth And Life Sciences, VU University, Amsterdam. External supervisor: dr. ir. C.A.M. (Kees) van Gestel, associate professor at the Department of Ecological Science, Faculty of Earth And Life Sciences, VU University, Amsterdam. Coordinator/secretary: drs. P. (Pieter) Geluk, study coordinator at the Department of Science, Faculty of Management, Science & Technology, Open University of the Netherlands, Heerlen. The image on the front cover represents a transparent spherule collected from the Rhine river. The image was created by a Phenom Scanning Electron Microscope (model 800 07334/PW-100-017) on April 24th, 2014. For optimal image resolution the spherule was first covered with a thin layer of gold. Acknowledgements This master’s thesis is the result of about 15 years of part-time academic study at the Open University of the Netherlands. It all started in the year 2001 with the introductory course ‘Basic course in environmental science: Analysis and solutions to environmental problems’, and resulted in a BSc. degree in natural sciences in 2006. After some exploration of other scientific areas, it ultimately ended up by completing the MSc. program in Environmental Sciences in 2015. In 2001, microplastics were not yet in the picture. Although they were already reported in the early 70’s, they did not receive much attention till a few years ago. Pioneers like Charles Moore, Anthony Andrady and my personal Dutch inspiration Gijsbert Tweehuysen from the independent Dutch foundation Waste Free Waters, pointed out their concerns about increasing environmental problems caused by (micro)plastics, in our fresh and saline ecosystems. This report could not have been completed without the help and guidance of the professionals I met during this rollercoaster-like adventure. I would like to thank prof. dr. N.M. (Nico) van Straalen and dr. ir. C.A.M. (Kees) van Gestel from the Department of Ecological Science, VU University, Amsterdam for suggesting the soil sieve method, for offering me laboratory facilities and for their critical reflections. Also, I would like to express my gratitude to dr. G. (Gerard) Stroomberg, dr. O.J. (Onno) Epema and dr. A (Arnold) Veen for providing me with access to the monitoring stations and the analytical and microbiological laboratory facilities at Rijkswaterstaat, Lelystad. I am thankful to dr. F. (Freek) Ariese for providing me with the opportunity to work with the Raman and Fourier Transform spectroscopic equipment at the Department of Physics & Astronomy, VU University, Amsterdam, and for providing me with critical reflections on the concept texts. Principal Component Analysis would not have come in view without the help of PhD candidate G. (Gerjen) Tinnevelt MSc, at the Radbout University, Institute of Molecules and Materials, Department of Analytical chemistry/Chemometrics, Nijmegen. I would like to thank dr. A (Arjan) Sieben, hydrologist at Rijkswaterstaat, dr. G.J. (Geert) Postma, Radbout University, Institute of Molecules and Materials, Department of Analytical chemistry/Chemometrics, Nijmegen and dr. F.G.A.J. (Frank) van Belleghem, assistant professor at the Department of Science, Open University of the Netherlands, Heerlen for their critical reflections on respectively hydrology aspects, Principal Components Analysis and concept texts. At last, but not least, I am extremely grateful to my supervisor dr. A. (Ansje) Löhr, assistant professor at the Department of Science, Open University of the Netherlands, Heerlen, for her infinite enthusiasm, for critical reflections on numerous occasions, for guiding me through my thesis and for bringing me in touch with many of the above-mentioned people. Abstract Microplastics, plastics fragments smaller than 5 mm, are found in aquatic ecosystems all over the world. Marine life may be harmed when they ingest microplastics, as they can form blockades in the gastro-intestinal tract or carry adhered pollutants. To assess the scale and the urgency of this environmental threat, scientists stress the need build up accurate and comparable datasets on the abundance and composition of microplastics in aquatic systems, among which rivers. Research in rivers, however, is still in its infancy. In this master thesis, an in-depth study on the abundance and composition of microplastics in the Dutch parts of the European rivers Meuse and Rhine was carried out. This study is one of the first, if not the first, that includes an extending series of synchronized samples, collected at exactly the same locations and using the same method, in two running European rivers. From January 10th 2014 up to June 23rd 2014, 17 weekly samples were taken by leading river water through a cascade of soil sieves for 72 hours. Two size fraction are acknowledged: 0.125-0.250 mm and 0.250-5 mm. The samples were cleared from organic debris, inorganic particulate matter and occasionally coal. Hereto a method is developed comprising successively the following steps: digestion with hydrogen peroxide, an interim filtration step using a mini-sieve, sample splitting, density separation with sodium chloride and sonication. Microplastics were visually indentified, counted, and sorted out into four groups: films, white spherules, transparent spherules and miscellaneous microplastics. Occasionally scrubs were sorted out form the latter group as well. Fibres were not taken into account. For each sample, the individual groups were weighed separately. Raman and Fourier Transform spectroscopy were used in combination with Principal Component Analysis (PCA) to indentify the composition of the handpicked particles. Differences between both rivers were observed as in the Meuse no spherules were found. In both rivers films, scrubs and the majority of the miscellaneous microplastics were identified as polyethylene. The white spherules in the Rhine were verified as polystyrene, just as the transparent spherules up to 0.250 mm. For the larger transparent spherules, temporal variations in composition were observed comprising polyethylene, polypropylene and polystyrene. Also a yet unidentifiable polymer was observed. For the size range of 0.125-5 mm, average concentrations of 0.14 mg or 9.7 microplastics per m3 were calculated for the Meuse, and 0.56 mg or 56 microplastics per m3 for the Rhine. These figures form an under limit, as particles can become lost and unevenly distributed during the laboratory processing and demonstrated is that even with secure visual selection, microplastics can become overlooked. Indications were found that the sampled water is not representative for the water column and river width. PCA showed to be a useful tool for studying large numbers of spectral recordings simultaneously. Proper clearing of the microplastics samples improves the distinctiveness and certainty of determination but also increases the processing time. Some of tested clearing methods, among which sonication, is likely to affect microplastics with weak molecular bonds. Spectral quality improvements will increase the certainty of determination and decrease the processing time. Temporal abundance and composition variations could not be related to varying river discharges or turbidity levels. More research is needed on the upstream emission sources, the associated emission intensities and the behaviour of microplastics in relation to the complex river dynamics. Samenvatting Microplastics, kunststof fragmenten kleiner dan 5 mm, worden wereldwijd gevonden in zeeën en zoete wateren. Onderzoek heeft uitgewezen dat microplastics potentiële risico’s kunnen vormen voor de dieren die in die wateren leven. Om de risico’s in kaart te kunnen brengen is er behoefte aan een eenduidige en integrale registratie van de soorten microplastics die wereldwijd worden gevonden. Het meeste onderzoek is tot op heden uitgevoerd in de zeeën, terwijl
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