A simple and rapid direct injection method for the determination of glyphosate and AMPA in environmental water samples
Glyphosate is currently the most widely used herbicide in the world, yet screening of environmental waters for this chemical is limited by the need for specialized derivatization and measurement methods that can be tedious and time-consuming. In this work, we present a novel method for the detection and quantification at trace levels of glyphosate and aminomethylphosphonic acid (AMPA) in environmental water samples. The detection and quantification of the analytes was performed by liquid chromatography (LC) coupled with tandem mass spectrometry (MS/MS). Chromatographic separation was achieved with an ion-exchange column and a pH-gradient elution of a solution of ammonium hydroxide and ammonium acetate. The limit of detection for glyphosate and AMPA was 0.25 μg L-1 and the limit of quantification was 0.5 μg L-1with a 20-μL injection. The method was used to investigate the levels of glyphosate and AMPA in surface water samples from the Yarra River catchment area and urban constructed stormwater wetlands. The results indicate that at the time of sampling, no glyphosate or AMPA was present in the samples from the Yarra River catchment area (n = 10). However, glyphosate was detected above the limit of quantification in 33% of the wetland samples (n = 12), with concentrations ranging from 1.95 to 2.96 μg L-1. Similarly, AMPA was quantified in 83% of the wetland samples, with concentrations ranging from 0.55 to 2.42 μg L-1. To our knowledge, this is the first report of a pH-gradient LC–MS/MS method for glyphosate and AMPA analysis at ultratrace levels, with minimal sample processing, avoiding costly, time-consuming derivatization and preconcentration steps.
KeywordsDirect injection Ion-exchange column pH gradient Glyphosate
E.O. holds an Endeavour Research Fellowship (5911-2017) from the Department of Education and Training of the Australian Government. The authors thank Agilent Technologies for technical assistance with instrument setup and operation.
Compliance with ethical standards
Conflict of interest
The authors declare that they have no competing interests.
- 2.Australian Pesticides and Veterinary Medicines Authority. Public Chemical Registration Information System. 2018. https://portal.apvma.gov.au/pubcris?p_auth=vQ5V7spW&p_p_id=pubcrisportlet_WAR_pubcrisportlet&p_p_lifecycle=1&p_p_state=normal&p_p_mode=view&p_p_col_id=column-1&p_p_col_pos=2&p_p_col_count=4&_pubcrisportlet_WAR_pubcrisportlet_javax.portlet.action=search. Accessed 30 Jan 2018.
- 9.Yang X, Wang F, Bento CPM, Xue S, Gai L, Dam R Van, et al. Short-term transport of glyphosate with erosion in Chinese loess soil — a flume experiment. Sci Total Environ. 2015;512–513:406–414.Google Scholar
- 15.Hanke I, Singer H, Hollender J. Ultratrace-level determination of glyphosate, aminomethylphosphonic acid and glufosinate in natural waters by solid-phase extraction followed by liquid chromatography-tandem mass spectrometry: performance tuning of derivatization, enrichment and detection. Anal Bioanal Chem. 2008;391(6):2265–76.CrossRefGoogle Scholar
- 16.Hao C, Morse D, Morra F, Zhao X, Yang P, Nunn B. Direct aqueous determination of glyphosate and related compounds by liquid chromatography/tandem mass spectrometry using reversed-phase and weak anion-exchange mixed-mode column. J Chromatogr A. Elsevier B.V. 2011;1218(33):5638–43.CrossRefGoogle Scholar
- 18.Guo H, Riter LS, Wujcik CE, Armstrong DW. Direct and sensitive determination of glyphosate and aminomethylphosphonic acid in environmental water samples by high performance liquid chromatography coupled to electrospray tandem mass spectrometry. J Chromatogr A. 2016;1443:93–100.CrossRefGoogle Scholar
- 19.Department of Environment, Land, Water and Planning. Catchment Management Authority boundaries. 2018. https://www.data.vic.gov.au/data/dataset/catchment-management-authority-boundaries.Accessed 15 Jan 2018.
- 20.National Health and Medical Research Council, National Resource Management Ministerial Council. Australian drinking water guidelines paper 6 national water quality management strategy. Canberra: National Health and Medical Research Council and National Resource Management Ministerial Council; 2011.Google Scholar
- 21.Australian and New Zealand Environment and Conservation Council, Agriculture and Resource Management Council of Australia and New Zealand. Australian and New Zealand guidelines for fresh and marine water quality. 2000. p. 1–103.Google Scholar
- 22.European Union. Council Directive 91/414/EEC. Brussels: European Union; 1991.Google Scholar
- 23.Environmental Protection Agency. 2002 edition of the drinking water standards and health advisories. EPA 822-R-02-038. Washington: US Environmental Protection Agency; 2002. p. 12.Google Scholar
- 24.Federal-Provincial-Territorial Committee on Drinking Water of the Federal-Provincial-Territorial Committee on Health and the Environment. Guidelines for Canadian drinking water quality. 2014. https://www.canada.ca/en/health-canada/services/environmental-workplace-health/reports-publications/water-quality/guidelines-canadian-drinking-water-quality-summary-table.html. Accessed 13 Oct 2018.
- 25.Environmental Protection Agency. Aquatic life benchmarks and ecological risk assessments for registered pesticides. https://www.epa.gov/pesticide-science-and-assessing-pesticide-risks/aquatic-life-benchmarks-and-ecological-risk#ref_2. Accessed 7 Oct 2018.
- 26.Canadian Council of Ministers of the Environment. Appendix V—Canadian water quality guidelines: updates (September 1989), carbofuran, glyphosate, and atrazine. In: Canadian water quality guidelines. Canadian Council of Resource and Environment Ministers. Task Force on Water Quality Guidelines; 1989.Google Scholar
- 27.World Health Organization. Environmental health criteria 159. Geneva: World Health Organization; 1994.Google Scholar
- 28.Borggaard OK, Gimsing AL. Fate of glyphosate in soil and the possibility of leaching to ground and surface waters : a review. Pest Manag Sci. 2008;456:441–56.Google Scholar