Seasonal Variation of Chloro-S-Triazines in The

VU Research Portal Seasonal variation of chloro-s-triazines in the Hartbeespoort Dam catchment, South Africa Rimayi, Cornelius; Odusanya, David; Weiss, Jana M.; de Boer, Jacob; Chimuka, Luke published in Science of the Total Environment 2018 DOI (link to publisher) 10.1016/j.scitotenv.2017.09.119 document version Publisher's PDF, also known as Version of record document license Article 25fa Dutch Copyright Act Link to publication in VU Research Portal citation for published version (APA) Rimayi, C., Odusanya, D., Weiss, J. M., de Boer, J., & Chimuka, L. (2018). Seasonal variation of chloro-s- triazines in the Hartbeespoort Dam catchment, South Africa. Science of the Total Environment, 613-614, 472- 482. https://doi.org/10.1016/j.scitotenv.2017.09.119 General rights Copyright and moral rights for the publications made accessible in the public portal are retained by the authors and/or other copyright owners and it is a condition of accessing publications that users recognise and abide by the legal requirements associated with these rights. • Users may download and print one copy of any publication from the public portal for the purpose of private study or research. • You may not further distribute the material or use it for any profit-making activity or commercial gain • You may freely distribute the URL identifying the publication in the public portal ? Take down policy If you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim. E-mail address: [email protected] Download date: 28. Sep. 2021 Science of the Total Environment 613–614 (2018) 472–482 Contents lists available at ScienceDirect Science of the Total Environment journal homepage: www.elsevier.com/locate/scitotenv Seasonal variation of chloro-s-triazines in the Hartbeespoort Dam catchment, South Africa Cornelius Rimayi a,b,d,⁎, David Odusanya a,JanaM.Weissc, Jacob de Boer b, Luke Chimuka d a Department of Water and Sanitation, Resource Quality Information Services, Roodeplaat, P. Bag X313, 0001 Pretoria, South Africa b Vrije Universiteit Amsterdam, Environment and Health, De Boelelaan, 1087, 1081HV Amsterdam, The Netherlands c Department of Environmental Science and Analytical Chemistry, Stockholm University, Arrhenius Laboratory, 10691 Stockholm, Sweden d University of the Witwatersrand, School of Chemistry, P. Bag 3, Wits, 2050 Johannesburg, South Africa HIGHLIGHTS GRAPHICAL ABSTRACT • Summer contributed the highest triazine herbicide loads into the Hartbeespoort Dam. • The Crocodile River is the major source of herbicides in the Hartbeespoort Dam. • Atrazine groundwater concentrations in the Hartbeespoort Dam proximity are N130 ng L−1. • DET is the most abundant triazine me- tabolite in the Hartbeespoort Dam catchment. • Atrazine metabolites were detected in fish muscle. article info abstract Article history: Seasonal variation of eight chloro-s-triazine herbicides and seven major atrazine and terbuthylazine degradation Received 29 June 2017 products was monitored in the Hartbeespoort Dam catchment using gas chromatography–mass spectrometry Received in revised form 27 August 2017 (GC–MS) and liquid chromatography-mass spectrometry (LC-MS/MS). Lake, river and groundwater were sam- Accepted 12 September 2017 pled from the Hartbeespoort Dam catchment over four seasons and the downstream Jukskei River was moni- Available online 26 September 2017 tored during the winter season. Triazine herbicide concentrations in the Hartbeespoort Dam were in the order N N N N Editor: D. Barcelo atrazine simazine propazine ametryn prometryn throughout the four seasons sampled. Triazine herbicide concentrations in the Hartbeespoort Dam surface water were highest in summer and gradually decreased in suc- Keywords: cessive seasons of autumn, winter and spring. Terbuthylazine was the only triazine herbicide detected at all sam- Chloro-s-triazine pling sites in the Jukskei River, though atrazine recorded much higher concentrations for the N14 and Kyalami Atrazine sites, with concentrations of 923 and 210 ng L−1 respectively, compared to 134 and 74 ng L−1 for terbuthylazine. Terbuthylazine Analytical results in conjunction with river flow data indicate that the Jukskei and Crocodile Rivers contribute the Metabolites greatest triazine herbicide loads into the Hartbeespoort Dam. No triazine herbicides were detected in the fish Hartbeespoort Dam muscle tested, showing that bioaccumulation of triazine herbicides is negligible. Atrazine and terbuthylazine metabolites were detected in the fish muscle with deethylatrazine (DEA) being detected in both catfish and carp muscle at low concentrations of 0.2 and 0.3 ng g−1, respectively. Desethylterbuthylazine (DET) was detected only in catfish at a concentration of 0.3 ng g−1. With atrazine herbicide groundwater concentrations being N130 ng L−1 for all seasons and groundwater ∑triazine herbicide concentrations ranging between 527 and ⁎ Corresponding author at: Department of Water and Sanitation, Resource Quality Information Services, Roodeplaat, P. Bag X313, 0001 Pretoria, South Africa. E-mail address: [email protected] (C. Rimayi). http://dx.doi.org/10.1016/j.scitotenv.2017.09.119 0048-9697/© 2017 Elsevier B.V. All rights reserved. C. Rimayi et al. / Science of the Total Environment 613–614 (2018) 472–482 473 367 ng L−1, triazine compounds in the Hartbeespoort Dam catchment may pose a risk to humans and wildlife in light findings of endocrine and immune disrupting atrazine effects by various researchers. © 2017 Elsevier B.V. All rights reserved. 1. Introduction atrazine, the vast majority of atrazine was eliminated unmetabolised, indicating a low bioaccumulation (Solomon et al., 2008). The degrada- The presence of chloro-s-triazines in the environment is predomi- tion of triazine herbicides proceeds by microbial, photolytic or non-en- nantly due to herbicide application, particularly from atrazine, simazine, zymatic chemical action such as the benzoxazinone catalysed reaction terbuthylazine, ametryn, gesatamin, propazine and prometon (Wackett (Lin et al., 2008; Wiegand et al., 2001). This results in dechlorination, de- et al., 2002; Zhang et al., 2016). South Africa is historically the 9th big- amination or dealkylation, forming a variety of degradation products gest corn producer in the world and atrazine is often used as the herbi- (Belfroid et al., 1998; Graymore et al., 2001; Loos and Niessner, 1999; cide of choice, with 88% of atrazine in the country being applied on corn, Wang and Xie, 2012). The degradation of atrazine in the environment though in combination with other triazine herbicides (Dabrowski, is mainly due to microbial action (Wackett et al., 2002). Atrazine can 2015; Du Preez et al., 2005). After application, triazine herbicides can be metabolized by plants through N-dealkylation primarily by cyto- seep through soil to contaminate groundwater due to their moderately chrome P-450 followed by a phase II conjugation reaction to glutathione hydrophilic nature, low Kow and weak soil adsorption (Du Preez et al., by glutathione-S-transferase (Ross and Filipov, 2006; Wiegand et al., 2005; Graymore et al., 2001; Solomon et al., 2008). Atrazine is the 2001). Atrazine metabolites have been detected in carp liver of fish ex- most widely used chloro-s-triazine globally and has been detected in posed to different concentrations of atrazine ranging from 4.28 to 428 various water bodies and groundwater throughout South Africa since μgL−1 (Xing et al., 2014)andin vitro atrazine exposure tests have the 1980′s(Ansara-Ross et al., 2012; Takáts et al., 2001). Its use is shown the presence of monodealkylated deethylatrazine and banned in Europe since 2004 due to its relative persistence and risk of desisopropylatrazine. Desisopropylatrazine can also be formed by deg- water contamination, though the use of the other triazine herbicides is radation of both atrazine and simazine whilst deethylatrazine can be still permitted (Ackerman, 2007; Hang et al., 2005; Herranz et al., formed by degradation of atrazine and propazine (Jiang et al., 2005). 2008; Lin et al., 2011; Omotayo et al., 2011; Wang and Xie, 2012). Atra- Terbuthylazine inhibits photosynthesis by altering chloroplast zine is however still used extensively in China, USA, India, South Amer- membrane proteins. Its degradation proceeds primarily either by micro- ica, Africa and Australia (Ansara-Ross et al., 2012; Liu et al., 2016; bial N-dealkylation of one of the s-triazine side chains to form Siddiqua et al., 2010). The maximum allowable limit of atrazine in desethylterbuthylazine (DET) or photolytic hydroxylation and dechlori- drinking water in the USA and India is 3 μgL−1 (Singh and Cameotra, nation of the C2 chlorine to form hydroxyterbuthylazine and 2014) whilst the European maximum permissible level of atrazine in desethylhydroxyterbuthylazine (Bottoni et al., 2013; Sanlaville et al., drinking water is 0.1 μgL−1 (El Sebaï et al., 2011; Herranz et al., 2008; 1996; Velisek et al., 2016). Terbuthylazine is slightly toxic to fish and Omotayo et al., 2011). can also be degraded to desisopropylatrazine and atrazine Triazine herbicide mode of action proceeds by inhibiting photosyn- desethyldesisopropyl which are secondary degradation products arising thetic electron transport and blocking CO2 fixation, causing accumula- from terbuthylazine metabolism (Du Preez et al., 2005). This study aims tion of CO2 in the plant, leading to plant death (Wackett et al., 2002; to assess the degree of triazine

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