Elsevier

Environmental Pollution

Volume 212, May 2016, Pages 401-412
Environmental Pollution

Benzotriazole UV stabilizers in sediments, suspended particulate matter and fish of German rivers: New insights into occurrence, time trends and persistency

https://doi.org/10.1016/j.envpol.2016.01.024Get rights and content

Highlights

  • Benzotriazole UV filters (BUVSs) are ubiquitous contaminants in German rivers.

  • BUVSs were detected in sediment, suspended particulate matter and bream liver samples.

  • Time trend analysis was performed for an estimation of future contamination levels.

  • Increasing contamination levels were observed for UV-329, UV-234 and UV-928.

  • None of the BUVSs were degraded in sediment-water batch systems within 100 d.

Abstract

Benzotriazole UV stabilizers (BUVSs) are widely applied in plastics to prevent discoloration and to enhance product stability. This study describes for the first time the occurrence of nine different lipophilic BUVSs (UV-326, UV-320, UV-329, UV-350, UV-328, UV-327, UV-928, UV-234 and UV-360) in sediment, suspended particulate matter (SPM) and bream liver samples of German rivers. All investigated BUVSs were detected in sediments and SPM at concentrations in the low ng/g dry weight (dw) range. The so far rarely analyzed compound UV-360 as well as UV-326 were the predominant BUVSs in sediments and SPM from the river Rhine reaching maximum concentrations of 62 and 44 ng/g dw, respectively. Five BUVSs were also confirmed to bioaccumulate in bream liver, but neither UV-360 nor UV-326 was detected above the limit of quantification (LOQ). In contrast, highest concentrations in bream liver were determined for UV-327 (65 ng/g dw) and UV-328 (40 ng/g dw).

A retrospective time trend analysis of BUVSs in SPM from two sites (river Rhine, 2005 to 2013; river Saar, 2006 to 2013) revealed increasing contamination levels of UV-329 and decreasing levels of UV-320 and UV-350. At one site (river Rhine) time trends of BUVS concentrations were also investigated in bream liver (1995–2013) and supported a considerably reduced exposure to UV-350.

A first assessment of the environmental fate of BUVSs by sediment-water batch systems revealed a rapid partitioning into the sediment and no considerable degradation within 100 d.

Introduction

Benzotriazole UV stabilizers (BUVSs) are widely used in polymeric materials, paints and coatings to improve their UV-stability as they prevent light-induced degradation and yellowing (Himmelsbach et al., 2009). They have been characterized as one of the most effective UV absorbers and thus are additives of very common polymers such as polypropylene (PP) (Jia et al., 2007) and polyvinyl chloride (PVC) (Xiang et al., 2010). In 1996, their consumption volume in Europe was almost 1000 t/a (Crawford, 1999). Certain BUVSs such as UV-328, UV-234, UV-329 (see Table 1 for chemical names and structures) are currently listed as High Production Volume Chemicals (HPVC) by the OECD.

Most BUVSs are highly lipophilic compounds with predicted logKOW values of >6, resulting in a significant bioaccumulation potential. In laboratory studies with carp based on OECD 305C bioconcentration factors (BCFs) of UV-320, UV-327, UV-328 and UV-350 were found to be in the range of 1900 – 12,000, 900–7600, 740–3700, 20,000–34,000, respectively (ECHA, 2013). Using data from a monitoring study in the Ariake Sea (Japan), Nakata et al. (2010) estimated bioaccumulation factors (BAF) of UV-327 and UV-320 in finless porpoises (Neophocaena phocaenoides) of around 6000 and 33,000, respectively.

Studies about the impacts of BUVSs on human health and especially about ecotoxicity are scarce. Long-term exposures of UV-320 to rats according to OECD TG 452 revealed several adverse effects such as histopathological changes in the liver (Hirata-Koizumi et al., 2008). The no observed adverse effect level (NOEC) of UV-320 was as low as 0.1 mg/kg/day for male and 2.5 mg/kg/day for female rats. So far, studies indicate that BUVSs exhibit no estrogenic and androgenic activity (Kawamura et al., 2003, Fent et al., 2014) and no acute toxicity on freshwater crustacean (Daphnia pulex) (Kim et al., 2011a). However, Fent et al. (2014) observed an antiandrogenic activity of the BUVS UV-P at a concentration of 1 μM using in vitro assays and a dose-related activation of the aryl hydrocarbon receptor (AH-receptor) in zebrafish eleuthero-embryos by UV-P and UV-326. The agonistic activity of UV-P (EC50 of 29 μg/L) and UV-326 (EC50 > 3.2 mg/L) was recently confirmed for the human AH-receptor (Nagayoshi et al., 2015).

Recent studies on the occurrence of BUVSs revealed their presence in various environmental matrices which is in accordance with their widespread applications and high consumption volumes. For example, Kameda et al. (2011) determined BUVSs in treated wastewater and in surface water as well as in sediments of rivers and streams in Japan. In water and sediments of heavily polluted rivers UV-328 was detected with maximum concentrations of up to 4800 ng/L and 1700 μg/kg, respectively. Further studies from Spain (Carpinteiro et al., 2010, Montesdeoca-Esponda et al., 2012) and China (Liu et al., 2014) reported the detection of BUVSs in raw and treated wastewater as well as in surface water, with concentrations in the lower ng/L range. In a study of Zhang et al. (2011) BUVSs were frequently detected in river sediments from US and China as well as in activated sludge from China. UV-328 was identified to be the predominant BUVS found at maximum concentrations of 220 ng/g and 5900 ng/g in sediments and sewage sludge, respectively. Lower concentrations in the low to mid ng/g range were detected in sewage sludge from different WWTPs in China (Ruan et al., 2012), Spain (Casado et al., 2013) and Australia (Liu et al., 2012). Concentrations of BUVSs in river and marine sediments from Spain were in the low ng/L range and highest concentration (56 ng/g) were detected for UV-328 (Carpinteiro et al., 2012). Nakata et al. (2009) found BUVSs in river sediments and different marine species such as clams, oysters, gastropods and fish from the Ariake Sea in Japan. Sediment concentrations of BUVSs ranged mainly between 1 and 10 ng/g while concentrations in biota samples reached up to several hundreds of ng/g lipid weight (lw). Similar maximal BUVS concentrations were detected in samples from 20 different fish species from Manila Bay, the Philippines (Kim et al., 2011b) and in mussels collected from several Asian and US coastal waters (Nakata et al., 2012).

However, so far most studies focused on the determination of only a few selected BUVSs, namely UV-P, UV-326, UV-327, UV-328, UV-320 and UV-329 (Montesdeoca-Esponda et al., 2013). Information about the environmental occurrence of several BUVSs, especially for UV-350, UV-234, UV-928 and UV-360 is very scarce. To the best of our knowledge, the occurrence of UV-350 and UV-928 in sediments and biota has not been assessed at all. Moreover, data about the contamination level of particulate suspended solids (SPM) is completely missing. In Europe, data about the environmental occurrence of BUVSs is mainly restricted to sporadic measurements in the course of national screening studies in Sweden (Brorström-Lundén et al., 2011), Norway (Thomas et al., 2014) and the cited studies from Spain. Especially for Europe more data about the environmental occurrence, distribution and persistence of BUVSs are needed to assess their relevance as micropollutants of rivers and streams and to support the current process for review of certain lipophilic BUVSs as Substances of Very High Concern (SHVC) under the European Chemicals Regulation REACH.

Therefore, the aim of the study was to (i) assess the relevance of nine highly lipophilic BUVSs as contaminants of German rivers by tracing their distribution in sediments, SPM and fish tissue collected from different river sites (monitoring study), (ii) provide evidence for a decrease or increase of the contamination levels by a retrospective time trend monitoring of BUVSs in SPM and fish samples from the German Environmental Specimen Bank (ESB, time trend study) and (iii) determine the persistence of all target BUVSs by sediment-water batch systems (fate study).

Section snippets

Chemicals

The nine BUVSs analyzed within this study are listed in Table 1 and were selected based on their high lipophilicity (estimated log KOW > 5). In particular, the BUVSs UV-326, UV-320, UV-329, UV-327 were included, since their environmental relevance has already been described in some previous studies (e.g. Montesdeoca-Esponda et al., 2013). In contrast, UV-350, UV-928, UV-234 and UV-360 were selected, since these BUVSs have only been rarely measured so far. UV-234, UV-329, UV-350 and UV-360 were

Method performance

The analytical method allowed for a selective and sensitive measurement of BUVSs in all three sample matrices, even at relatively small amounts of sample. The chromatographic separation ensured a selective detection of the three structural isomers UV-320, UV-329 and UV-350 (Figure S 2) and all BUVSs could be quantified down to the pg/g level (Table 2). LOQs were lowest for sediment and SPM samples (0.05–0.4 ng/g dw) and only slightly higher for bream liver (0.2–7 ng/g dw), mainly due to the

Conclusions

The results provide first evidence that BUVSs are ubiquitous and rather persistent contaminants of sediments and SPM in German rivers. The previously rarely considered compound UV-360 was one of the most dominant BUVSs. Five of the nine examined BUVSs were also detected in bream liver and confirmed their high bioaccumulation potential. The very first results on the fate of BUVSs in aerated sediment-water systems revealed a complete sorption to the sediment and no significant degradation over a

Acknowledgments

The authors gratefully acknowledge the financial support of the current study by the German Federal Environment Agency (UBA) and the German Federal Ministry of Transport and Digital Infrastructure (BMVI). Furthermore we thank the German Environmental Specimen Bank (German ESB) and especially Heinz Rüdel (Fraunhofer IME) for providing SPM and bream liver samples. We would also like to thank the people from the Department of Earth Science of the University of Berlin and from the Department of

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