Benzotriazole UV stabilizers in sediments, suspended particulate matter and fish of German rivers: New insights into occurrence, time trends and persistency☆
Graphical abstract
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
References (38)
- et al.
Gas chromatography quadrupole time-of-flight mass spectrometry determination of benzotriazole ultraviolet stabilizers in sludge samples
J. Chromatogr. A
(2013) 2(2-hydroxyphenyl)2H-benzotriazole ultraviolet stabilizers
Prog. Polym. Sci.
(1999)- et al.
Benzotriazole UV-stabilizers and benzotriazole: antiandrogenic activity in vitro and activation of aryl hydrocarbon receptor pathway in zebrafish eleuthero-embryos
Sci. Total Environ.
(2014) - et al.
Influence of partition coefficient of lipophilic compounds on bioconcentration kinetics with fish
Water Res.
(1988) - et al.
Determination of polymer additives by liquid chromatography coupled with mass spectrometry. A comparison of atmospheric pressure photoionization (APPI), atmospheric pressure chemical ionization (APCI), and electrospray ionization (ESI)
Polym. Degrad. Stab.
(2009) - et al.
The combination effect of hindered amine light stabilizers with UV absorbers on the radiation resistance of polypropylene
Radiat. Phys. Chem.
(2007) - et al.
Occurrence and profiles of organic sun-blocking agents in surface waters and sediments in Japanese rivers and lakes
Environ. Pollut.
(2011) - et al.
Contamination and bioaccumulation of benzotriazole ultraviolet stabilizers in fish from Manila Bay, the Philippines using an ultra-fast liquid chromatography-tandem mass spectrometry
Chemosphere
(2011) - et al.
Determination of nine benzotriazole UV stabilizers in environmental water samples by automated on-line solid phase extraction coupled with high-performance liquid chromatography-tandem mass spectrometry
Talanta
(2014) - et al.
Occurrence and removal of benzotriazoles and ultraviolet filters in a municipal wastewater treatment plant
Environ. Pollut.
(2012)
Extraction and determination methodologies for benzotriazole UV stabilizers in personal-care products in environmental and biological samples
Trac Trends Anal. Chem.
Asia-Pacific mussel watch for emerging pollutants: distribution of synthetic musks and benzotriazole UV stabilizers in Asian and US coastal waters
Mar. Pollut. Bull.
Determination of benzotriazole and benzophenone UV filters in sediment and sewage sludge
Environ. Sci. Technol.
Bioconcentration
Environ. Sci. Technol.
Screening of benzothiazoles, benzenediamines, dicyclohexylamine and benzotriazoles
IVL Rep. B
Matrix solid-phase dispersion followed by gas chromatography tandem mass spectrometry for the determination of benzotriazole UV absorbers in sediments
Anal. Bioanal. Chem.
Headspace solid-phase microextraction followed by gas chromatography tandem mass spectrometry for the sensitive determination of benzotriazole UV stabilizers in water samples
Anal. Bioanal. Chem.
Member state committee draft support document for 2,4-di-tert-butyl-6-(5-chlorobenzotriazol-2-yl)phenol
Member state committee support document for identification of 2-(2H-benzotriazol-2-yl)-4,6-ditertpentylphenol (UV-328) as a substance of very high concern
Cited by (81)
Uptake, accumulation and metabolism of UV-320 in vegetables and its impact on growth and quality
2024, Science of the Total EnvironmentEnvironmental fate of benzotriazole 2-(2H-benzotriazol-2-yl)-4,6-di-tert-pentylphenol (UV-328) on the surface of plastic films in soil: Migration and phototransformation
2024, Journal of Environmental Chemical Engineering
- ☆
This paper has been recommended for acceptance by Eddy Y. Zeng.