Abstract
Glyphosate is considered toxicologically harmful and presents potential association with human carcinogenesis and other chronic diseases, including mental and reproductive behaviors. The challenges to analyse and demonstrate its toxicity are likely due to its metal-chelating properties, the interference of organic compounds in the environment, and similarity with its by-products. Whereas there is a link with serious health and environmental problems, there is an absence of public health policies, which is probably due to the difficulties in detecting glyphosate in the environment, further complicated by the undetectable hazard in occupational safety and health. The historical lenient use of glyphosate in transgenic-resistant crops, corroborated by the fact that it is not easily detected, creates the “Glyphosate paradox”, by which it is the most widely used herbicide and one of the most hardly determined. In this review, we revisited all available technologies for detection and quantification of glyphosate, including their drawbacks and advantages, and we further discuss the needs and challenges. Briefly, most of the technologies require high-end equipments and resources in low throughput, and none of them are adequate for real-time field tests, which may explain the lack of studies on occupational health associated with the chemical hazard. The real-time detection is an urgent and highly demanded need to improve public policies.
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References
Abdel-Hamid MI (1996) Development and application of a simple procedure for toxicity testing using immobilized algae. Water Sci Technol 33:129–138
Alferness PL, Iwata Y (1994) Determination of glyphosate and (aminomethyl)phosphonic acid in soil, plant and animal matrixes, and water by capillary gas chromatography with mass-selective detection. J Agric Food Chem 42:2751–2759
Algar WR, Krull UJ (2008) Quantum dots as donors in fluorescence resonance energy transfer for the bioanalysis of nucleic acids, proteins, and other biological molecules. Anal Bioanal Chem 391:1609–1618
Allinson G, Allinson M, Bui A et al (2016) Pesticide and trace metals in surface waters and sediments of rivers entering the Corner Inlet Marine National Park, Victoria, Australia. Environ Sci Pollut Res Int 23:5881–5891
Anthony S, Stephanie S (2017) Glyphosate pathways to modern diseases VI: prions, amyloidosis and autoimmune neurological diseases. J Biol Phys Chem 17:8–32
Antoniou M, Habib M, Howard CV et al (2012) Teratogenic effects of glyphosate-based herbicides: divergence of regulatory decisions from scientific evidence. J Environ Anal Toxicol S4:006
Arroyave JM, Waiman CC, Zanini GP, Avena MJ (2016) Effect of humic acid on the adsorption/desorption behavior of glyphosate on goethite. Isotherms and kinetics. Chemosphere 145:34–41
Barcelo D (2000) Sample handling and trace analysis of pollutants. Techniques, applications and quality assurance, vol 21, 1st edn. Elsevier, Amsterdam
Barrett KA, McBride MB (2005) Oxidative degradation of glyphosate and aminomethylphosphonate by manganese oxide. Environ Sci Technol 39:9223–9228
Bataller R, Campos I, Laguarda-Miro N et al (2012) Glyphosate detection by means of a voltammetric electronic tongue and discrimination of potential interferents. Sensors 12:17553–17568
Beecham JE, Seneff S (2015) The possible link between autism and glyphosate acting as glycine mimetic—a review of evidence from the literature with analysis. J Mol Genet Med. https://doi.org/10.4172/1747-0862.1000187
Benachour N, Séralini G-E (2009) Glyphosate formulations induce apoptosis and necrosis in human umbilical, embryonic, and placental cells. Chem Res Toxicol 22:97–105
Börjesson E, Torstensson L (2000) New methods for determination of glyphosate and (aminomethyl)phosphonic acid in water and soil. J Chromatogr A 886:207–216
Bradley PM, Journey CA, Romanok KM et al (2017) Expanded target-chemical analysis reveals extensive mixed-organic-contaminant exposure in U.S. streams. Environ Sci Technol 51:4792–4802
Brłnstad JO, Friestad HO (1976) Method for determination of glyphosate residues in natural waters based on polarography of the N-nitroso derivative. Analyst 101:820–824
Byer JD, Struger J, Klawunn P et al (2008) Low cost monitoring of glyphosate in surface waters using the ELISA method: an evaluation. Environ Sci Technol 42:6052–6057
Campanella L, Cubadda F, Sammartino MP, Saoncella A (2001) An algal biosensor for the monitoring of water toxicity in estuarine environments. Water Res 35:69–76
Candela L, Caballero J, Ronen D (2010) Glyphosate transport through weathered granite soils under irrigated and non-irrigated conditions—Barcelona, Spain. Sci Total Environ 408:2509–2516
Cartigny B, Azaroual N, Imbenotte M et al (2004) Determination of glyphosate in biological fluids by 1H and 31P NMR spectroscopy. Forensic Sci Int 143:141–145
Castle LA, Siehl DL, Gorton R et al (2004) Discovery and directed evolution of a glyphosate tolerance gene. Science 304:1151–1154
Cattani D, de Liz Oliveira Cavalli VL, Heinz Rieg CE et al (2014) Mechanisms underlying the neurotoxicity induced by glyphosate-based herbicide in immature rat hippocampus: involvement of glutamate excitotoxicity. Toxicology 320:34–45
Cavalcante DGSM, Martinez CBR, Sofia SH (2008) Genotoxic effects of Roundup® on the fish Prochilodus lineatus. Mutat Res Genet Toxicol Environ Mutagen 655:41–46
Cavaş T, Könen S (2007) Detection of cytogenetic and DNA damage in peripheral erythrocytes of goldfish (Carassius auratus) exposed to a glyphosate formulation using the micronucleus test and the comet assay. Mutagenesis 22:263–268
Çetin E, Şahan S, Ülgen A, Şahin U (2017) DLLME-spectrophotometric determination of glyphosate residue in legumes. Food Chem 230:567–571
Chalubinski M, Kowalski ML (2006) Endocrine disrupters–potential modulators of the immune system and allergic response. Allergy 61:1326–1335
Chang SY, Liao C-H (2002) Analysis of glyphosate, glufosinate and aminomethylphosphonic acid by capillary electrophoresis with indirect fluorescence detection. J Chromatogr A 959:309–315
Chang SY, Wei M-Y (2005) Simultaneous determination of glyphosate, glufosinate, and minomethylphosphonic acid by capillary electrophoresis after 9-fluorenylmethyl chloroformate derivatization. J Chin Chem Soc 52:785–792
Chang Y, Zhang Z, Hao J et al (2016a) A simple label free colorimetric method for glyphosate detection based on the inhibition of peroxidase-like activity of Cu(II). Sens Actuators B Chem 228:410–415
Chang Y-C, Lin Y-S, Xiao G-T et al (2016b) A highly selective and sensitive nanosensor for the detection of glyphosate. Talanta 161:94–98
Chaufan G, Coalova I, Ríos de Molina MDC (2014) Glyphosate commercial formulation causes cytotoxicity, oxidative effects, and apoptosis on human cells: differences with its active ingredient. Int J Toxicol 33:29–38
Che H, Liu S (2014) Contaminant detection using multiple conventional water quality sensors in an early warning system. Proc Eng 89:479–487
Chenier PJ (2002) Sulfuric acid and its derivatives. In: Chenier PJ (ed) Survey of industrial chemistry. Springer, Boston, pp 23–40
Cikalo MG, Goodall DM, Matthews W (1996) Analysis of glyphosate using capillary electrophoresis with indirect detection. J Chromatogr A 745:189–200
Clegg BS, Stephenson GR, Hall JC (1999) Development of an enzyme-linked immunosorbent assay for the detection of glyphosate. J Agric Food Chem 47:5031–5037
Corbera M, Hidalgo M, Salvadó V, Wieczorek PP (2005) Determination of glyphosate and aminomethylphosphonic acid in natural water using the capillary electrophoresis combined with enrichment step. Anal Chim Acta 540:3–7
Coutinho CFB, Mazo LH (2005) Complexos metálicos com o herbicida glifosato: revisão. Quim Nova 28:1038
Coutinho CFB, Coutinho LFM, Mazo LH et al (2007) Direct determination of glyphosate using hydrophilic interaction chromatography with coulometric detection at copper microelectrode. Anal Chim Acta 592:30–35
da Silva AS, Fernandes FCB, Tognolli JO et al (2011) A simple and green analytical method for determination of glyphosate in commercial formulations and water by diffuse reflectance spectroscopy. Spectrochim Acta A Mol Biomol Spectrosc 79:1881–1885
Dai H, Sang M, Wang Y et al (2014) Determination of trace glyphosate in water with a prism coupling optical waveguide configuration. Sens Actuators A Phys 218:88–93
De Almeida LKS, Chigome S, Torto N et al (2015) A novel colorimetric sensor strip for the detection of glyphosate in water. Sens Actuators B Chem 206:357–363
De Góes RE, Muller M, Fabris JL (2017) Spectroscopic detection of glyphosate in water assisted by laser-ablated silver nanoparticles. Sensors 17(954):1–15
de Llasera MPG, Gómez-Almaraz L, Vera-Avila LE, Peña-Alvarez A (2005) Matrix solid-phase dispersion extraction and determination by high-performance liquid chromatography with fluorescence detection of residues of glyphosate and aminomethylphosphonic acid in tomato fruit. J Chromatogr A 1093:139–146
Delmonico EL, Bertozzi J, Evelázio de Souza N, Celestino Oliveira C (2014) Determination of glyphosate and aminomethylphosphonic acid for assessing the quality tap water using SPE and HPLC. Acta Sci Technol 36:513–519
DeLorenzo ME, Lauth J, Pennington PL et al (1999) Atrazine effects on the microbial food web in tidal creek mesocosms. Aquat Toxicol 46:241–251
Dickson SJ, Meinhold RH, Beer ID, Koelmeyer TD (1988) Rapid determination of glyphosate in postmortem specimens using 31P NMR. J Anal Toxicol 12:284–286
Ding X, Yang K-L (2013) Development of an oligopeptide functionalized surface plasmon resonance biosensor for online detection of glyphosate. Anal Chem 85:5727–5733
Ding J, Guo H, Liu W-W et al (2013) Current progress on the detection of glyphosate in environmental samples. J Sci Appl Biomed 2014:2015
Ding J, Guo H, Liu W-W, Zhang W-W, Wang J-W (2015) Current progress on the detection of glyphosate in environmental samples. J Sci Appl Biomed 3(6):88–95
do Carmo Langiano CV, Martinez CBR (2008) Toxicity and effects of a glyphosate-based herbicide on the Neotropical fish Prochilodus lineatus. Comp Biochem Physiol C Toxicol Pharmacol 147:222–231
Ejaz S, Akram W, Lim CW et al (2004) Endocrine disrupting pesticides: a leading cause of cancer among rural people in Pakistan. Exp Oncol 26:98–105
El-Gendy KS, Aly NM, El-Sebae AH (1998) Effects of edifenphos and glyphosate on the immune response and protein biosynthesis of bolti fish (Tilapia nilotica). J Environ Sci Health B 33:135–149
European Commission (2002) Review report for the active substance glyphosate. European Commission 6511/VI/99-final. https://big.assets.huffingtonpost.com/ec.2002.pdf. Accessed 20 April 2018
Fang F, Xu H, Wei RQ et al (2011) Determination of glyphosate by high performance liquid chromatography with o-nitrobenzenesulfonyl chloride as derivatization reagent. Fenxi Ceshi Xuebao 30:683–686
Fang F, Wei RQ et al (2014) Determination of glyphosate by HPLC with a novel pre-column derivatization reagent. Chin J Bioprocess Eng 12(3):69–73
Forlani G, Mangiagalli A, Nielsen E, Suardi CM (1999) Degradation of the phosphonate herbicide glyphosate in soil: evidence for a possible involvement of unculturable microorganisms. Soil Biol Biochem 31:991–997
Franz JE, Mao MK, Sikorski JA (1997) Glyphosate: a unique global herbicide. ACS Monograph 189
Frense D, Müller A, Beckmann D (1998) Detection of environmental pollutants using optical biosensor with immobilized algae cells. Sens Actuators B Chem 51:256–260
Friestad HO, Brønstad JO (1985) Improved polarographic method for determination of glyphosate herbicide in crops, soil, and water. J Assoc Off Anal Chem 68:76–79
Garcia AF, do Carmo Rollemberg M (2007) Determinação voltamétrica do herbicida glifosato em águas naturais utilizando eletrodo de cobre. Quim Nova 30(7):1592–1596
Garcia AF, Rollemberg MC (2007) Voltammetric determination of glyphosate in natural waters with a copper electrode. Quím Nova 30:1592–1596
Garry VF, Harkins ME, Erickson LL et al (2002) Birth defects, season of conception, and sex of children born to pesticide applicators living in the Red River Valley of Minnesota, USA. Environ Health Perspect 110(Suppl 3):441–449
Gasnier C, Dumont C, Benachour N et al (2009) Glyphosate-based herbicides are toxic and endocrine disruptors in human cell lines. Toxicology 262:184–191
Giesy JP, Dobson S, Solomon KR (2000) Ecotoxicological risk assessment for roundup® herbicide. In: Ware GW (ed) Reviews of environmental contamination and toxicology. Springer, New York, pp 35–120
Glass RL (1981) Colorimetric determination of glyphosate in water after oxidation to orthophosphate. Anal Chem 53:921–923
Glass RL (1984) Metal complex formation by glyphosate. J Agric Food Chem 32:1249–1253
Glusczak L, dos Santos Miron D, Crestani M et al (2006) Effect of glyphosate herbicide on acetylcholinesterase activity and metabolic and hematological parameters in piava (Leporinus obtusidens). Ecotoxicol Environ Saf 65:237–241
Glusczak L, dos Santos Miron D, Moraes BS et al (2007) Acute effects of glyphosate herbicide on metabolic and enzymatic parameters of silver catfish (Rhamdia quelen). Comp Biochem Physiol C Toxicol Pharmacol 146:519–524
González-Martínez MA, Brun EM, Puchades R et al (2005) Glyphosate immunosensor. Application for water and soil analysis. Anal Chem 77:4219–4227
Goodwin L, Startin JR, Keely BJ, Goodall DM (2003) Analysis of glyphosate and glufosinate by capillary electrophoresis–mass spectrometry utilising a sheathless microelectrospray interface. J Chromatogr A 1004:107–119
Govindarajulu PP (2008) Literature review of impacts of glyphosate herbicide on amphibians: what risks can the silvicultural use of this herbicide pose for amphibians in B.C.? B.C. Ministry of Environment, Victoria, BC. Wildlife Report No. R-28
Grisolia CK (2002) A comparison between mouse and fish micronucleus test using cyclophosphamide, mitomycin C and various pesticides. Mutat Res 518:145–150
Gui Y-X, Fan X-N, Wang H-M et al (2012) Glyphosate induced cell death through apoptotic and autophagic mechanisms. Neurotoxicol Teratol 34:344–349
Guo Z-X, Cai Q, Yang Z (2005) Determination of glyphosate and phosphate in water by ion chromatography–inductively coupled plasma mass spectrometry detection. J Chromatogr A 1100:160–167
Guo Z-X, Cai Q, Yang Z (2007) Ion chromatography/inductively coupled plasma mass spectrometry for simultaneous determination of glyphosate, glufosinate, fosamine and ethephon at nanogram levels in water. Rapid Commun Mass Spectrom 21:1606–1612
Guo J, Zhang Y, Luo Y et al (2014) Efficient fluorescence resonance energy transfer between oppositely charged CdTe quantum dots and gold nanoparticles for turn-on fluorescence detection of glyphosate. Talanta 125:385–392
Guo H, Riter LS, Wujcik CE, Armstrong DW (2016) 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 1443:93–100
Habekost A (2015) Spectroscopic and electrochemical investigations of N-(phosphonomethyl)glycine (glyphosate) and (aminomethyl)phosphonic acid (AMPA). World J Chem Educ 3(6):134–140
Habekost A (2017) Rapid and sensitive spectroelectrochemical and electrochemical detection of glyphosate and AMPA with screen-printed electrodes. Talanta 162:583–588
Hance RJ (1976) Herbicide usage and soil properties. Plant Soil 45:291–293
Hanke I, Singer H, Hollender J (2008) 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 391:2265–2276
Hao Chunyan, Morse David, Morra Franca, Zhao Xiaoming, Yang Paul, Nunn Brian (2011) 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 1218(33):5638–5643
Heras-Mendaza F, Casado-Fariñas I, Paredes-Gascón M, Conde-Salazar L (2008) Erythema multiforme-like eruption due to an irritant contact dermatitis from a glyphosate pesticide. Contact Dermat 59:54–56
Hidalgo C, Rios C, Hidalgo M et al (2004) Improved coupled-column liquid chromatographic method for the determination of glyphosate and aminomethylphosphonic acid residues in environmental waters. J Chromatogr A 1035:153–157
Ho MW, Cherry B (2010) Glyphosate tolerant crops bring diseases and death. Sci Soc 47:12–15
Hogendoorn EA, Ossendrijver FM, Dijkman E, Baumann RA (1999) Rapid determination of glyphosate in cereal samples by means of pre-column derivatisation with 9-fluorenylmethyl chloroformate and coupled-column liquid chromatography with fluorescence detection. J Chromatogr A 833:67–73
Hokanson R, Fudge R, Chowdhary R, Busbee D (2007) Alteration of estrogen-regulated gene expression in human cells induced by the agricultural and horticultural herbicide glyphosate. Hum Exp Toxicol 26:747–752
Homola J (2003) Present and future of surface plasmon resonance biosensors. Anal Bioanal Chem 377:528–539
Hu J-Y, Zhao D-Y, Ning J et al (2007) Determination of glyphosate residues in soil and apple by capillary gas chromatography with nitrogen-phosphorus detection. Chin J Pestic Sci 3:016
Hu J-Y, Chen C-L, Li J-Z (2008) A simple method for the determination of glyphosate residues in soil by capillary gas chromatography with nitrogen phosphorus. J Anal Chem 63:371–375
Huang Y, Reddy KN, Thomson SJ, Yao H (2015) Assessment of soybean injury from glyphosate using airborne multispectral remote sensing. Pest Manag Sci 71:545–552
Huhn C (2018) More and enhanced glyphosate analysis is needed. Anal Bioanal Chem 410:3041–3045
Humphries D, Anderson A-M, Byrtus G (2005) Glyphosate residues in Alberta’s atmospheric deposition, soils and surface waters. Alberta Environment no. T/806
Ibáñez M, Pozo ÓJ, Sancho JV et al (2005) Residue determination of glyphosate, glufosinate and aminomethylphosphonic acid in water and soil samples by liquid chromatography coupled to electrospray tandem mass spectrometry. J Chromatogr A 1081:145–155
Ibáñez M, Pozo OJ, Sancho JV et al (2006) Re-evaluation of glyphosate determination in water by liquid chromatography coupled to electrospray tandem mass spectrometry. J Chromatogr A 1134:51–55
Jan MR, Shah J, Muhammad M, Ara B (2009) Glyphosate herbicide residue determination in samples of environmental importance using spectrophotometric method. J Hazard Mater 169:742–745
Jayasumana C, Gunatilake S, Senanayake P (2014) Glyphosate, hard water and nephrotoxic metals: are they the culprits behind the epidemic of chronic kidney disease of unknown etiology in Sri Lanka? Int J Environ Res Public Health 11:2125–2147
Jayasumana C, Gunatilake S, Siribaddana S (2015) Simultaneous exposure to multiple heavy metals and glyphosate may contribute to Sri Lankan agricultural nephropathy. BMC Nephrol 16:103
Jiraungkoorskul W, Upatham ES, Kruatrachue M et al (2003) Biochemical and histopathological effects of glyphosate herbicide on Nile tilapia (Oreochromis niloticus). Environ Toxicol 18:260–267
Johal GS, Huber DM (2009) Glyphosate effects on diseases of plants. Eur J Agron 31:144–152
Kaczyński P, Łozowicka B (2015) Liquid chromatographic determination of glyphosate and aminomethylphosphonic acid residues in rapeseed with MS/MS detection or derivatization/fluorescence detection. Open Chem 13:1011–1019
Kataoka H, Ryu S, Sakiyama N, Makita M (1996) Simple and rapid determination of the herbicides glyphosate and glufosinate in river water, soil and carrot samples by gas chromatography with flame photometric detection. J Chromatogr A 726:253–258
Kawai S, Uno B, Tomita M (1991) Determination of glyphosate and its major metabolite aminomethylphosphonic acid by high-performance liquid chromatography after derivatization with p-toluenesulphonyl chloride. J Chromatogr A 540:411–415
Khenifi A, Derriche Z, Forano C et al (2009) Glyphosate and glufosinate detection at electrogenerated NiAl-LDH thin films. Anal Chim Acta 654:97–102
Khrolenko MV, Wieczorek PP (2005) Determination of glyphosate and its metabolite aminomethylphosphonic acid in fruit juices using supported-liquid membrane preconcentration method with high-performance liquid chromatography and UV detection after derivatization with p-toluenesulphonyl chloride. J Chromatogr A 1093:111–117
Kintzios S, Pistola E, Panagiotopoulos P et al (2001) Bioelectric recognition assay (BERA). Biosens Bioelectron 16:325–336
Koblizek M, Masojidek J, Komenda J et al (1998) A sensitive photosystem II-based biosensor for detection of a class of herbicides. Biotechnol Bioeng 60:664–669
Kongtip P, Nankongnab N, Phupancharoensuk R et al (2017) Glyphosate and Paraquat in maternal and fetal serums in Thai women. J Agromed 22:282–289
Koskinen WC, Marek LJ, Hall KE (2016) Analysis of glyphosate and aminomethylphosphonic acid in water, plant materials and soil. Pest Manag Sci 72:423–432
Kudzin ZH, Gralak DK, Drabowicz J, Luczak J (2002) Novel approach for the simultaneous analysis of glyphosate and its metabolites. J Chromatogr A 947:129–141
Kudzin ZH, Gralak DK, Andrijewski G et al (2003) Simultaneous analysis of biologically active aminoalkanephosphonic acids. J Chromatogr A 998:183–199
Laitinen P, Rämö S, Nikunen U et al (2009) Glyphosate and phosphorus leaching and residues in boreal sandy soil. Plant Soil 323:267–283
Lee EA, Zimmerman LR, Bhullar BS, Thurman EM (2002) Linker-assisted immunoassay and liquid chromatography/mass spectrometry for the analysis of glyphosate. Anal Chem 74:4937–4943
Lee HU, Shin HY, Lee JY et al (2010) Quantitative detection of glyphosate by simultaneous analysis of UV spectroscopy and fluorescence using DNA-labeled gold nanoparticles. J Agric Food Chem 58:12096–12100
Lee HU, Jung DU, Lee JH et al (2013) Detection of glyphosate by quantitative analysis of fluorescence and single DNA using DNA-labeled fluorescent magnetic core–shell nanoparticles. Sens Actuators B Chem 177:879–886
Li X, Xu J, Jiang Y et al (2009) Hydrophilic-interaction liquid chromatography (HILIC) with dad and mass spectroscopic detection for direct analysis of glyphosate and glufosinate residues and for product quality control. Acta Chromatogr 21:559–576
Li Y, Zhang S, Zhang Q et al (2016) Binding-induced internal-displacement of signal-on photoelectrochemical response: a glyphosate detection platform based on graphitic carbon nitride. Sens Actuators B Chem 224:798–804
Liao Y, Berthiona J-M, Coleta I et al (2018) Validation and application of analytical method for glyphosate and glufosinate in foods by liquid chromatography–tandem mass spectrometry. J Chromatogr A 1549:31–38
Liu Q, Jiang X, Zhang Y et al (2015) A novel test strip for organophosphorus detection. Sens Actuators B Chem 210:803–810
Lou ZY, Zhu GN, Wu HM (2001) Study on the detection method of glyphosate in pond water. Chin J Ningbo Acad 13(Suppl):142–145
Luo X, Chen L, Zhao Y (2015) Simultaneous determination of three chloroacetic acids, three herbicides, and 12 anions in water by ion chromatography. J Sep Sci 38:3096–3102
Lushchak OV, Kubrak OI, Storey JM et al (2009) Low toxic herbicide Roundup induces mild oxidative stress in goldfish tissues. Chemosphere 76:932–937
Mallat E, Barceló D (1998) Analysis and degradation study of glyphosate and of aminomethylphosphonic acid in natural waters by means of polymeric and ion-exchange solid-phase extraction columns followed by ion chromatography-post-column derivatization with fluorescence detection. J Chromatogr A 823:129–136
Marc J, Mulner-Lorillon O, Bellé R (2004) Glyphosate-based pesticides affect cell cycle regulation. Biol Cell 96:245–249
Martínez Gil P, Laguarda-Miro N, Camino JS, Peris RM (2013) Glyphosate detection with ammonium nitrate and humic acids as potential interfering substances by pulsed voltammetry technique. Talanta 115:702–705
Martins-Júnior HA, Lebre DT, Wang AY et al (2009) An alternative and fast method for determination of glyphosate and aminomethylphosphonic acid (AMPA) residues in soybean using liquid chromatography coupled with tandem mass spectrometry. Rapid Commun Mass Spectrom 23:1029–1034
Martins-Júnior HA, Lebre DT, Wang AY et al (2011) Residue analysis of glyphosate and aminomethylphosphonic acid (AMPA) in Soybean using liquid chromatography coupled with tandem mass spectrometry. In: Ng T-B (ed) Soybean - biochemistry, chemistry and physiology. InTech. https://www.intechopen.com/books/soybean-biochemistry-chemistry-and-physiology/residue-analysis-of-glyphosate-and-aminomethylphosphonic-acid-ampa-in-soybean-using-liquid-chromatog
Mazereeuw M, Hofte AJP, Tjaden UR, van der Greef J (1997) A novel sheathless and electrodeless microelectrospray interface for the on-line coupling of capillary zone electrophoresis to mass spectrometry. Rapid Commun Mass Spectrom 11:981–986
Merás ID, Díaz TG, Franco MA (2005) Simultaneous fluorimetric determination of glyphosate and its metabolite, aminomethylphosphonic acid, in water, previous derivatization with NBD-Cl and by partial least squares calibration (PLS). Talanta 65:7–14
Mesnage R, Bernay B, Séralini G-E (2013) Ethoxylated adjuvants of glyphosate-based herbicides are active principles of human cell toxicity. Toxicology 313:122–128
Metzger JO (1997) Green Chemistry. Designing Chemistry for the Environment. Herausgegeben von PT Anastas und TS Williamson. American Chemical Society, Wahington, DC, 1996. 251 S., geb. 89.95£.-ISBN 0-8412-3399-3. Angew Chem Int Ed Engl 109:812–813
Minami T, Liu Y, Akdeniz A et al (2014) Intramolecular indicator displacement assay for anions: supramolecular sensor for glyphosate. J Am Chem Soc 136:11396–11401
Mol HGJ, van Dam RCJ (2014) Rapid detection of pesticides not amenable to multi-residue methods by flow injection–tandem mass spectrometry. Anal Bioanal Chem 406:6817–6825
Molina M, Silva M (2002) Analytical potential of fluorescein analogues for ultrasensitive determinations of phosphorus-containing amino acid herbicides by micellar electrokinetic chromatography with laser-induced fluorescence detection. Electrophoresis 23:1096–1103
Moraes FC, Mascaro LH, Machado SAS, Brett CMA (2010) Direct electrochemical determination of glyphosate at copper phthalocyanine/multiwalled carbon nanotube film electrodes. Electroanalysis 22:1586–1591
Napoli M, Cecchi S, Zanchi CA, Orlandini S (2015) Leaching of glyphosate and aminomethylphosphonic acid through silty clay soil columns under outdoor conditions. J Environ Qual 44:1667–1673
Nedelkoska TV, Low GK-C (2004) High-performance liquid chromatographic determination of glyphosate in water and plant material after pre-column derivatisation with 9-fluorenylmethyl chloroformate. Anal Chim Acta 511:145–153
Nešković NK, Poleksić V, Elezović I et al (1996) Biochemical and histopathological effects of glyphosate on carp, Cyprinus carpio L. Bull Environ Contam Toxicol 56:295–302
Nielsen JB, Nielsen F, Sørensen JA (2007) Defense against dermal exposures is only skin deep: significantly increased penetration through slightly damaged skin. Arch Dermatol Res 299:423–431
Nortes-Méndez R, Robles-Molina J, López-Blanco R et al (2016) Determination of polar pesticides in olive oil and olives by hydrophilic interaction liquid chromatography coupled to tandem mass spectrometry and high resolution mass spectrometry. Talanta 158:222–228
Okada E, Pérez D, De Gerónimo E et al (2018) Non-point source pollution of glyphosate and AMPA in a rural basin from the southeast Pampas, Argentina. Environ Sci Pollut Res. https://doi.org/10.1007/s11356-018-1734-7
Oliveira GC, Moccelini SK, Castilho M et al (2012) Biosensor based on atemoya peroxidase immobilised on modified nanoclay for glyphosate biomonitoring. Talanta 98:130–136
Paganelli A, Gnazzo V, Acosta H et al (2010) Glyphosate-based herbicides produce teratogenic effects on vertebrates by impairing retinoic acid signaling. Chem Res Toxicol 23:1586–1595
Patsias J, Papadopoulou A, Papadopoulou-Mourkidou E (2001) Automated trace level determination of glyphosate and aminomethyl phosphonic acid in water by on-line anion-exchange solid-phase extraction followed by cation-exchange liquid chromatography and post-column derivatization. J Chromatogr A 932:83–90
Pei MQ, Lai J (2004) Qualitative and quantitative analysis of glyphosate. Chin J Guangdong Police Sci Technol 1:14–15
Pintado S, Amaro RR, Mayén M, Mellado JMR (2012) Electrochemical determination of the glyphosate metabolite aminomethylphosphonic acid (AMPA) in drinking waters with an electrodeposited copper electrode. Int J Electrochem Sci 7:305–312
Pipke R, Amrhein N (1988) Isolation and characterization of a mutant of Arthrobacter sp. Strain GLP-1 which utilizes the herbicide glyphosate as its sole source of phosphorus and nitrogen. Appl Environ Microbiol 54:2868–2870
Poiger T, Buerge IJ, Bächli A et al (2017) Occurrence of the herbicide glyphosate and its metabolite AMPA in surface waters in Switzerland determined with on-line solid phase extraction LC-MS/MS. Environ Sci Pollut Res Int 24:1588–1596
Poletta GL, Larriera A, Kleinsorge E, Mudry M (2009) Genotoxicity of the herbicide formulation Roundup® (glyphosate) in broad-snouted caiman (Caiman latirostris) evidenced by the Comet assay and the Micronucleus test. Mutat Res Genet Toxicol Environ Mutagen 672:95–102
Pollegioni L, Schonbrunn E, Siehl D (2011) Molecular basis of glyphosate resistance–different approaches through protein engineering. FEBS J 278:2753–2766
Poulsen ME, Christensen HB, Herrmann SS (2009) Proficiency test on incurred and spiked pesticide residues in cereals. Accredit Qual Assur 14:477–485
Prasad BB, Jauhari D, Tiwari MP (2014) Doubly imprinted polymer nanofilm-modified electrochemical sensor for ultra-trace simultaneous analysis of glyphosate and glufosinate. Biosens Bioelectron 59:81–88
Ramirez CE, Bellmund S, Gardinali PR (2014) A simple method for routine monitoring of glyphosate and its main metabolite in surface waters using lyophilization and LC–FLD + MS/MS. Case study: canals with influence on Biscayne National Park. Sci Total Environ 496:389–401
Rawat KA, Majithiya RP, Rohit JV et al (2016) Mg2+ ion as a tuner for colorimetric sensing of glyphosate with improved sensitivity via the aggregation of 2-mercapto-5-nitrobenzimidazole capped silver nanoparticles. RSC Adv 6:47741–47752
Relyea RA (2012) New effects of Roundup on amphibians: predators reduce herbicide mortality; herbicides induce antipredator morphology. Ecol Appl 22:634–647
Richard S, Moslemi S, Sipahutar H et al (2005) Differential effects of glyphosate and roundup on human placental cells and aromatase. Environ Health Perspect 113:716–720
Ridlen JS, Klopf GJ, Nieman TA (1997) Determination of glyphosate and related compounds using HPLC with tris(2,2′-bipyridyl)ruthenium(II) electrogenerated chemiluminescence detection. Anal Chim Acta 341:195–204
Roberts SM (1989) Molecular recognition: chemical and biochemical problems: the proceedings of an International Symposium, University of Exeter, April 1989. CRC PressI Llc
Royer A, Beguin S, Tabet JC et al (2000) Determination of glyphosate and aminomethylphosphonic acid residues in water by gas chromatography with tandem mass spectrometry after exchange ion resin purification and derivatization. Application on vegetable matrixes. Anal Chem 72:3826–3832
Rubio F, Veldhuis LJ, Clegg BS et al (2003) Comparison of a direct ELISA and an HPLC method for glyphosate determinations in water. J Agric Food Chem 51:691–696
Rueppel ML, Brightwell BB, Schaefer J, Marvel JT (1977) Metabolism and degradation of glyphosate in soil and water. J Agric Food Chem 25:517–528
Rull RP (2004) Neural tube defects and maternal residential proximity to agricultural pesticide applications and crops. Am J Epidemiol 163:743–753
Sadi B, Vonderheide AP, Caruso JA (2004) Analysis of phosphorus herbicides by ion-pairing reversed-phase liquid chromatography coupled to inductively coupled plasma mass spectrometry with octapole reaction cell. J Chromatogr A 1050:95–101
Samsel A, Seneff S (2013a) Glyphosate’s suppression of cytochrome P450 enzymes and amino acid biosynthesis by the gut microbiome: pathways to modern diseases. Entropy 15:1416–1463
Samsel A, Seneff S (2013b) Glyphosate, pathways to modern diseases II: celiac sprue and gluten intolerance. Interdiscip Toxicol 6:159–184
Sanchís J, Kantiani L, Llorca M et al (2012) Determination of glyphosate in groundwater samples using an ultrasensitive immunoassay and confirmation by on-line solid-phase extraction followed by liquid chromatography coupled to tandem mass spectrometry. Anal Bioanal Chem 402:2335–2345
Sancho JV, Hernández F, López FJ et al (1996) Rapid determination of glufosinate, glyphosate and aminomethylphosphonic acid in environmental water samples using precolumn fluorogenic labeling and coupled-column liquid chromatography. J Chromatogr A 737:75–83
Sato K, Jin JY, Takeuchi T et al (2001) Integrated pulsed amperometric detection of glufosinate, bialaphos and glyphosate at gold electrodes in anion-exchange chromatography. J Chromatogr A 919:313–320
Sato M, Yamashita A, Kikuchi M et al (2009) Simultaneous analysis of phosphorus-containing amino acid type herbicides and their metabolites in human samples using N-acetyl, O-methyl derivatives by LC/MS. Jpn J Forensic Sci Tech 14:35–43
Schafer H, Hettler H, Fritsche U et al (1994) Biotests using unicellular algae and ciliates for predicting long-term effects of toxicants. Ecotoxicol Environ Saf 27:64–81
Schrübbers LC, Masís-Mora M, Rojas EC et al (2016) Analysis of glyphosate and aminomethylphosphonic acid in leaves from Coffea arabica using high performance liquid chromatography with quadrupole mass spectrometry detection. Talanta 146:609–620
Schuette J (1998) Environmental fate of glyphosate. Published by Environmental Monitoring & Pest Management. Department of Pesticide Regulation Sacramento, California ISSN 95824–95624
Scribner EA, Battaglin WA, Gilliom RJ, Meyer MT (2007) Concentrations of glyphosate, its degradation product, aminomethylphosphonic acid, and glufosinate in ground-and surface-water, rainfall, and soil samples collected in the United States, 2001–06. Geological Survey (US). https://pubs.usgs.gov/sir/2007/5122/pdf/SIR2007-5122.pdf
See HH, Hauser PC, Ibrahim WAW, Sanagi MM (2010) Rapid and direct determination of glyphosate, glufosinate, and aminophosphonic acid by online preconcentration CE with contactless conductivity detection. Electrophoresis 31:575–582
Seneff S, Swanson N, Li C (2015) Aluminum and glyphosate can synergistically induce pineal gland pathology: connection to gut dysbiosis and neurological disease. Agric Sci China 6:42
Shao CY, Howe CJ, Porter AJR, Glover LA (2002) Novel cyanobacterial biosensor for detection of herbicides. Appl Environ Microbiol 68(10):5026–5033
Sharma DK, Gupta A, Kashyap R, Kumar N (2012) Spectrophotometric method for the determination of Glyphosate in relation to its environmental and toxicological analysis. Arch Environ Sci 6:42–49
Shehata AA, Schrödl W, Aldin AA et al (2013) The effect of glyphosate on potential pathogens and beneficial members of poultry microbiota in vitro. Curr Microbiol 66:350–358
Shim YK, Mlynarek SP, van Wijngaarden E (2009) Parental exposure to pesticides and childhood brain cancer: U.S. Atlantic coast childhood brain cancer study. Environ Health Perspect 117:1002–1006
Si YB, Sang ZY, Cheng FX et al (2009) Determination of glyphosate in soil by high performance liquid chromatography after derivatization with p-toluenesulphonyl chloride. J Anhui Agric Univ 36:136–139
Sierra EV, Méndez MA, Sarria VM, Cortés MT (2008) Electrooxidación de glifosato sobre electrodos de níquel y cobre. Quim Nova 31:220–226
Simonetti E, Cartaud G, Quinn RM et al (2015) An interlaboratory comparative study on the quantitative determination of glyphosate at low levels in wheat flour. J AOAC Int 98:1760–1768
Singh BK (1998) Plant amino acids: biochemistry and biotechnology. CRC Press, Boca Raton
Skeff W, Recknagel C, Schulz-Bull DE (2016) The influence of salt matrices on the reversed-phase liquid chromatography behavior and electrospray ionization tandem mass spectrometry detection of glyphosate, glufosinate, aminomethylphosphonic acid and 2-aminoethylphosphonic acid in water. J Chromatogr A 1475:64–73
Slager RE, Simpson SL, Levan TD et al (2010) Rhinitis associated with pesticide use among private pesticide applicators in the agricultural health study. J Toxicol Environ Health A 73:1382–1393
Songa EA, Waryo T, Jahed N et al (2009a) Electrochemical nanobiosensor for glyphosate herbicide and its metabolite. Electroanalysis 21:671–674
Songa EA, Arotiba OA, Owino JHO et al (2009b) Electrochemical detection of glyphosate herbicide using horseradish peroxidase immobilized on sulfonated polymer matrix. Bioelectrochemistry 75:117–123
Songa EA, Somerset VS, Waryo T, Baker PG, Iwuoha EI (2009c) Amperometric nanobiosensor for quantitative determination of glyphosate and glufosinate residues in corn samples. J Macromol Sci Part A Pure Appl Chem 81:123–139
Stachowskihaberkorn S, Becker B, Marie D et al (2008) Impact of Roundup on the marine microbial community, as shown by an in situ microcosm experiment. Aquat Toxicol 89:232–241
Sun N, Hu B-X, Mo W-M (2007) Single sweep oscillopolarographic technique for the determination of glyphosate after derivatization with sodium nitrite. PESTICIDES-SHENYANG 46:609
Sun L, Kong D, Gu W et al (2017) Determination of glyphosate in soil/sludge by high performance liquid chromatography. J Chromatogr A 1502:8–13
Szarek J, Siwicki A, Andrzejewska A et al (2000) Effects of the herbicide Roundup™ on the ultrastructural pattern of hepatocytes in carp (Cyprinus carpio). Mar Environ Res 50:263–266
Tadeo JL, Sánchez-Brunete C, Pérez RA, Fernández MD (2000) Analysis of herbicide residues in cereals, fruits and vegetables. J Chromatogr A 882:175–191
Tan MJ, Hong Z-Y, Chang M-H et al (2017) Metal carbonyl-gold nanoparticle conjugates for highly sensitive SERS detection of organophosphorus pesticides. Biosens Bioelectron 96:167–172
Tapsoba I, Paré S, Toé AM et al (2012) SWV determination of glyphosate in Burkina Faso soils using carbon fiber microelectrode. Int J Biol Chem Sci 6:2211–2220
Teófilo RF, Reis EL, Reis C et al (2004) Experimental design employed to square wave voltammetry response optimization for the glyphosate determination. J Braz Chem Soc 15:865–871
Thompson DG, Cowell JE, Daniels RJ et al (1989) Liquid chromatographic method for quantitation of glyphosate and metabolite residues in organic and mineral soils, stream sediments, and hardwood foliage. J Assoc Off Anal Chem 72:355–360
Thongprakaisang S, Thiantanawat A, Rangkadilok N et al (2013) Glyphosate induces human breast cancer cells growth via estrogen receptors. Food Chem Toxicol 59:129–136
Tierney KB, Singh CR, Ross PS, Kennedy CJ (2007) Relating olfactory neurotoxicity to altered olfactory-mediated behaviors in rainbow trout exposed to three currently-used pesticides. Aquat Toxicol 81:55–64
Torul H, Boyaci İH, Tamer U (2010) Attomole detection of glyphosate by surface-enhanced Raman spectroscopy using gold nanorods. FABAD J Pharm Sci 35:179–184
Tsao Y-C, Lai Y-C, Liu H-C et al (2016) Simultaneous determination and quantitation of paraquat, diquat, glufosinate and glyphosate in postmortem blood and urine by LC–MS–MS. J Anal Toxicol 40:427–436
Tseng S-H, Lo Y-W, Chang P-C et al (2004) Simultaneous quantification of glyphosate, glufosinate, and their major metabolites in rice and soybean sprouts by gas chromatography with pulsed flame photometric detector. J Agric Food Chem 52:4057–4063
Tsui MTK, Chu LM (2003) Aquatic toxicity of glyphosate-based formulations: comparison between different organisms and the effects of environmental factors. Chemosphere 52:1189–1197
Tsui MTK, Chu LM (2008) Environmental fate and non-target impact of glyphosate-based herbicide (Roundup®) in a subtropical wetland. Chemosphere 71:439–446
Tsui MTK, Wang W-X, Chu LM (2005) Influence of glyphosate and its formulation (Roundup®) on the toxicity and bioavailability of metals to Ceriodaphnia dubia. Environ Pollut 138:59–68
Tsunoda N (1993) Simultaneous determination of the herbicides glyphosate, glufosinate and bialaphos and their metabolites by capillary gas chromatography—ion-trap mass spectrometry. J Chromatogr A 637:167–173
Tuesca D, Puricelli E (2007) Effect of tillage systems and herbicide treatments on weed abundance and diversity in a glyphosate resistant crop rotation. Crop Prot 26:1765–1770
Vass A, Robles-Molina J, Pérez-Ortega P et al (2016) Study of different HILIC, mixed-mode, and other aqueous normal-phase approaches for the liquid chromatography/mass spectrometry-based determination of challenging polar pesticides. Anal Bioanal Chem 408:4857–4869
Vreeken RJ, Speksnijder P, Bobeldijk-Pastorova I, Noij TH (1998) Selective analysis of the herbicides glyphosate and aminomethylphosphonic acid in water by on-line solid-phase extraction–high-performance liquid chromatography–electrospray ionization mass spectrometry. J Chromatogr A 794:187–199
Waiman CV, Avena MJ, Garrido M et al (2012) A simple and rapid spectrophotometric method to quantify the herbicide glyphosate in aqueous media. Application to adsorption isotherms on soils and goethite. Geoderma 170:154–158
Wang D, Lin B, Cao Y et al (2016a) A highly selective and sensitive fluorescence detection method of glyphosate based on an immune reaction strategy of carbon dot labeled antibody and antigen magnetic beads. J Agric Food Chem 64:6042–6050
Wang S, Liu B, Yuan D, Ma J (2016b) A simple method for the determination of glyphosate and aminomethylphosphonic acid in seawater matrix with high performance liquid chromatography and fluorescence detection. Talanta 161:700–706
Wang L, Bi Y, Hou J et al (2016c) Facile, green and clean one-step synthesis of carbon dots from wool: application as a sensor for glyphosate detection based on the inner filter effect. Talanta 160:268–275
Wang M, Ye H, You L, Chen X (2016d) A supramolecular sensor array using lanthanide-doped nanoparticles for sensitive detection of glyphosate and proteins. ACS Appl Mater Interfaces 8:574–581
Watts M (2009) Glyphosate, monograph, Pesticide Action Network Asia and the Pacific, Penang, Malaysia. Available via PAN ASIA PACIFIC. http://www.panap.net/sites/default/files/attachments/monograph_glyphosate.pdf. Accessed 13 March 16
Wei X, Pu Q (2015) Microchip electrophoresis for fast and interference-free determination of trace amounts of glyphosate and glufosinate residues in agricultural products. Methods Mol Biol 1274:21–29
Wei X, Gao X, Zhao L et al (2013) Fast and interference-free determination of glyphosate and glufosinate residues through electrophoresis in disposable microfluidic chips. J Chromatogr A 1281:148–154
Williams GM, Kroes R, Munro IC (2000) Safety evaluation and risk assessment of the herbicide Roundup and its active ingredient, glyphosate, for humans. Regul Toxicol Pharmacol 31:117–165
Winfield TW (1990) Determination of glyphosate in drinking water by direct-aqueous-injection HPLC, post-column derivatization, and fluorescence detection: test method 547. U.S. Environmental Protection Agency. https://www.o2si.com/docs/epa-method-547.pdf
Woodburn AT (2000) Glyphosate: production, pricing and use worldwide. Pest Manag Sci 56:309–312
World Health Organization et al (1994) Glyphosate environmental health criteria no. 159. WHO, Geneva
Yoshioka N, Asano M, Kuse A et al (2011) Rapid determination of glyphosate, glufosinate, bialaphos, and their major metabolites in serum by liquid chromatography–tandem mass spectrometry using hydrophilic interaction chromatography. J Chromatogr A 1218:3675–3680
Zelenkova NF, Vinokurova NG (2008) Determination of glyphosate and its biodegradation products by chromatographic methods. J Anal Chem 63:871–874
Zhang C, Hu X, Luo J et al (2015a) Degradation dynamics of glyphosate in different types of citrus orchard soils in China. Molecules 20:1161–1175
Zhang L, Chen L, Liu F (2015b) Mutual effect on determination of gibberellins and glyphosate in groundwater by spectrophotometry. Guang Pu Xue Yu Guang Pu Fen Xi 35:966–970
Zhao P, Yan M, Zhang C et al (2011) Determination of glyphosate in foodstuff by one novel chemiluminescence-molecular imprinting sensor. Spectrochim Acta A Mol Biomol Spectrosc 78:1482–1486
Zheng J, Zhang H, Qu J et al (2013) Visual detection of glyphosate in environmental water samples using cysteamine-stabilized gold nanoparticles as colorimetric probe. Anal Methods 5:917–924
Zheng J, Wang Y, Feng Z et al (2015) Preparation of cationic starch microspheres and study on their absorption to anionic-type substance. Water Sci Technol 71:1545–1553
Zhou Y-M, Li N, Niu S et al (2007) Detection glyphosate residues in water by LC. China Meas Technol 3:036
Zhu Y, Zhang F, Tong C, Liu W (1999) Determination of glyphosate by ion chromatography. J Chromatogr A 850:297–301
Acknowledgements
The authors are grateful for the financial support of the state funding agencies Fundação de Amparo à Pesquisa do Estado de Minas Gerais (FAPEMIG-Process: 01/17 CEX APQ 02633/17), Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) and Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES).
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Valle, A.L., Mello, F.C.C., Alves-Balvedi, R.P. et al. Glyphosate detection: methods, needs and challenges. Environ Chem Lett 17, 291–317 (2019). https://doi.org/10.1007/s10311-018-0789-5
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DOI: https://doi.org/10.1007/s10311-018-0789-5
Keywords
- Glyphosate
- Detection
- Methods
- Environment and health