Concentration Distribution and Analysis of Urinary Glyphosate and Its Metabolites in Occupationally Exposed Workers in Eastern China

Feng Zhang1, Yanqiong Xu1, Xin Liu1, Liping Pan2, Enmin Ding1, Jianrui Dou3, Baoli Zhu4,1
1Department of Occupational Disease, Jiangsu Provincial Center for Disease Prevention and Control, Nanjing, 210009, China
2Medical Examination Center, Nanjing Prevention and Treatment Center for Occupational Disease, Nanjing 210038, China
3Department of Occupational Hygiene, Yangzhou City Center for Disease Prevention and Control, Yangzhou 225000, China
4Center for Global Health, School of Public Health, Nanjing Medical University, Nanjing 210008, China

Tóm tắt

Background: There are few published studies concerning occupational exposure to glyphosate (GLY), and these are limited to spraying, horticulture and other agricultural aspects. Therefore, the concentration of glyphosate and its metabolite aminomethylphosphonic acid (AMPA), in the urine of workers exposed to glyphosate during glyphosate production was determined, and the relationship between internal (urinary glyphosate and AMPA concentration) and external exposure dose (time weighted average (TWA) value of glyphosate in the air of workplace) was analyzed. Methods: To avoid the influence of preparations, we selected people who were only involved in GLY production (without exposure to its preparations) as our research subjects. We collected 134 urine samples of workers exposed to GLY (prototype, not preparation). The urinary concentrations of GLY and AMPA (internal exposure dose) were detected by gas chromatography-mass spectrometry. The subjects’ exposure to the amount of GLY in the air (external dose) was determined using ion chromatography. Conventional statistical methods, including quartiles, t-tests and regression analysis, were applied for data processing. Results: An on-site investigation revealed that the workers involved in centrifugation, crystallization, drying, and packaging and feeding were exposed to GLY. The TWA value of GLY in the workshop air was <0.02 mg/m3–34.58 mg/m3. The detection rates of GLY and AMPA in the urine samples were 86.6% and 81.3%, respectively. The concentration of urinary GLY was <0.020–17.202 mg/L (median, 0.292 mg/L). The urinary AMPA concentration was <0.010 mg/L–2.730 mg/L (median, 0.068 mg/L). The geometric means were 0.262 mg/L and 0.072 mg/L for GLY and AMPA, respectively. There was a correlation between the urinary concentration of GLY and AMPA and the TWA value of exposed workers (correlation coefficient [r] = 0.914 and 0.683, respectively; p < 0.01). Furthermore, there was a correlation between the urinary concentration of GLY and AMPA in the exposure group (r = 0.736, p < 0.01). Conclusions: The urinary concentration of GLY and AMPA of workers was correlated with the TWA value of workers’ exposure, which could reflect the actual exposure of the workers.

Từ khóa


Tài liệu tham khảo

Duke, 2008, Glyphosate: A once-in-a-century herbicide, Pest Manag. Sci., 64, 319, 10.1002/ps.1518

Steinmann, 2012, Uses and benefits of glyphosate in German arable farming, Crop Prot., 42, 164, 10.1016/j.cropro.2012.06.015

Gianessi, 2011, Overlooking the obvious: The opportunity for herbicides in Africa, Outlooks Pest Manag., 22, 211, 10.1564/22oct04

Blair, 2005, Cancer incidence among glyphosate-exposed pesticide applicators in the agricultural health study, Environ. Health Perspect., 113, 49, 10.1289/ehp.7340

Williams, 2012, Developmental and reproductive outcomes in humans and animals after glyphosate exposure: A critical analysis, J. Toxicol. Environ. Health Part B Crit. Rev., 15, 39, 10.1080/10937404.2012.632361

Wang, 2011, Parkinsonism after chronic occupational exposure to glyphosate, Parkinsonism Relat. Disorders, 17, 486, 10.1016/j.parkreldis.2011.02.003

Jayasumana, 2015, Drinking well water and occupational exposure to Herbicides is associated with chronic kidney disease, in Padavi-Sripura, Sri Lanka, Environ. Health, 14, 1, 10.1186/1476-069X-14-6

Mesnage, 2015, Potential toxic effects of glyphosate and its commercial formulations below regulatory limits, Food Chem. Toxicol., 84, 133, 10.1016/j.fct.2015.08.012

Trasande, 2020, Glyphosate exposures and kidney injury biomarkers in infants and young children, Environ. Pollut., 256, 113334, 10.1016/j.envpol.2019.113334

Eriguchi, 2019, Parkinsonism relating to intoxication with glyphosate: A case report, Intern. Med., 58, 1935, 10.2169/internalmedicine.2028-18

Wang, 2019, Successful extracorporeal membrane oxygenation support for severe acute diquat and glyphosate poisoning: A case report, Medicine (Baltimore), 98, e14414, 10.1097/MD.0000000000014414

Mink, 2011, Epidemiologic studies of glyphosate and non-cancer health outcomes: A review, Regul. Toxicol. Pharmacol., 61, 172, 10.1016/j.yrtph.2011.07.006

Dedeke, 2018, Comparative assessment on mechanism underlying renal toxicity of commercial formulation of roundup herbicide and glyphosate alone in male albino rat, Int. J. Toxicol., 37, 285, 10.1177/1091581818779553

Zhou, 2013, Research progress on toxicity of glyphosate, Ecol. Environ. Sci., 22, 1737

Gunarathna, 2018, Glyphosate and AMPA of agricultural soil, surface water, groundwater and sediments in areas prevalent with chronic kidney disease of unknown etiology, Sri Lanka, J. Environ. Sci. Health B, 53, 729, 10.1080/03601234.2018.1480157

Tarone, 2018, On the International Agency for Research on Cancer classification of glyphosate as a probable human carcinogen, Eur. J. Cancer Prev., 27, 82, 10.1097/CEJ.0000000000000289

Andreotti, 2018, Glyphosate use and cancer incidence in the Agricultural Health Study, J. Natl. Cancer Inst., 110, 509, 10.1093/jnci/djx233

Mink, 2012, Epidemiologic studies of glyphosate and cancer: A review, Regul. Toxicol. Pharmacol., 63, 440, 10.1016/j.yrtph.2012.05.012

Williams, 2000, Safety evaluation and risk assessment of the herbicide roundup and its active ingredient, glyphosate, for humans, Regul. Toxicol. Pharmacol., 31, 117, 10.1006/rtph.1999.1371

Jauhiainen, 1991, Occupational exposure of forest workers to glyphosate during brush saw spraying work, Am. Ind. Hyg. Assoc. J., 52, 61, 10.1080/15298669191364334

Sierra-Diaz, E., La Rosa, A.C.-D., Lozano-Kasten, F., Trasande, L., Peregrina-Lucano, A.A., Sandoval-Pinto, E., and Gonzalez-Chavez, H. (2019). Urinary pesticide levels in children and adolescents residing in two agricultural communities in Mexico. Int. J. Environ. Res. Public Health, 16.

Connolly, 2017, Exposure assessment using human biomonitoring for glyphosate and fluroxypyr users in amenity horticulture, Int. J. Hyg. Environ. Health, 220, 1064, 10.1016/j.ijheh.2017.06.008

Bolognesi, 2009, Biomonitoring of genotoxic risk in agricultural workers from five Colombian regions: Association to occupational exposure to glyphosate, J. Toxicol. Environ. Health A, 72, 986, 10.1080/15287390902929741

Johnson, 2005, Operator exposure when applying amenity herbicides by all-terrain vehicles and controlled droplet applicators, Ann. Occup. Hyg., 49, 25

Zhang, 2017, Study of the effect of occupational exposure to glyphosate on hepatorenal function, Chin. J. Prev. Med., 51, 615

Chang, 2011, Occurrence and fate of the herbicide glyphosate and its degradate aminomethylphosphonic acid in the atmosphere, Environ. Toxicol. Chem., 30, 548, 10.1002/etc.431

Dimitrakopoulos, 2010, Effect of suppressor current intensity on the determination of glyphosate and aminomethylphosphonic acid by suppressed conductivity ion chromatography, J. Chromatogr. A, 1217, 3619, 10.1016/j.chroma.2010.03.048

Hori, 2003, Determination of the herbicide glyphosate and its metabolite in biological specimens by gas chromatography-mass spectrometry. A case of poisoning by roundup herbicide, J. Anal. Toxicol., 27, 162, 10.1093/jat/27.3.162

Wunnapuk, 2014, Use of a glyphosate-based herbicide-induced nephrotoxicity model to investigate a panel of kidney injury biomarkers, Toxicol. Lett., 225, 192, 10.1016/j.toxlet.2013.12.009

Acquavella, 2004, Glyphosate biomonitoring for farmers and their families: Results from the farm family exposure study, Environ. Health Perspect., 112, 321, 10.1289/ehp.6667

Castellano, 2009, Toxicokinetics of glyphosate and its metabolite aminomethyl phosphonicacid in rats, Toxicol. Lett., 190, 91, 10.1016/j.toxlet.2009.07.008

Panzacchi, 2018, The Ramazzini Institute 13-week study on glyphosate-based herbicides at human equivalent dose in Sprague Dawley rats: Study design and first in-life endpoints evaluation, Environ Health., 17, 52, 10.1186/s12940-018-0393-y

Wester, 1991, Glyphosate skin binding, absorption, residual tissue distribution, and skin decontamination, Fundam Appl. Toxicol., 16, 725, 10.1016/0272-0590(91)90158-Z

Gillezeau, 2019, The evidence of human exposure to glyphosate: A review, Environ. Health, 18, 2, 10.1186/s12940-018-0435-5

Connolly, 2018, Glyphosate in Irish adults—A pilot study in 2017, Environ. Res., 165, 235, 10.1016/j.envres.2018.04.025

Jaime, 2017, Glyphosate residues in groundwater, drinking water and urine of subsistence farmers from intensive agriculture localities: A survey in Hopelchén, Campeche, Mexico, Int. J. Environ. Res. Public Health, 14, 595, 10.3390/ijerph14060595

Knudsen, 2017, Biomonitoring of Danish school children and mothers including biomarkers of PBDE and glyphosate, Rev. Environ. Health, 32, 279, 10.1515/reveh-2016-0067

Parvez, 2018, Glyphosate exposure in pregnancy and shortened gestational length: A prospective Indiana birth cohort study, Rev. Environ. Health, 17, 23, 10.1186/s12940-018-0367-0

Conrad, 2017, Glyphosate in German adults—Time trend (2001 to 2015) of human exposure to a widely used herbicide, Int. J. Hyg. Environ. Health, 220, 8, 10.1016/j.ijheh.2016.09.016

Zouaoui, 2013, Determination of glyphosate and AMPA in blood and urine from humans: About 13 cases of acute intoxication, Forensic. Sci. Int., 226, e20, 10.1016/j.forsciint.2012.12.010

Cartigny, 2008, Quantitative determination of glyphosate in human serum by 1H NMR spectroscopy, Talanta, 74, 1075, 10.1016/j.talanta.2007.07.029

Cho, 2019, Serial measurement of glyphosate blood concentration in a glyphosate potassium herbicide-intoxicated patient: A case report, Am. J. Emerg. Med., 37, 1600.e5, 10.1016/j.ajem.2019.04.042