Quantification of DEET and neonicotinoid pesticide biomarkers in human urine by online solid-phase extraction high-performance liquid chromatography-tandem mass spectrometry

Baker, Samuel E.; Serafim, Amanda Bishop; Morales-Agudelo, Pilar; Vidal, Meghan; Calafat, Antònia M.; Ospina, María

doi:10.1007/s00216-018-1481-0

Cited by 49 publications

(25 citation statements)

References 38 publications

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“…Interestingly, we already detected DME-ACE in the pre-dose urine sample at low levels, suggesting background exposures to ACE in the general population. This finding is in line with previous studies where DME-ACE has been analyzed in urine samples of the general population (Song et al 2021;Baker et al 2019) or after accidental intake of NNI-containing insecticide formulations (Taira et al 2013).…”

Section: Acetamipridsupporting

confidence: 92%

“…So far, with the exception of 5-OH-IMI and DME-ACE (Ospina et al 2019 ; Baker et al 2019 ; Wrobel et al 2020 ; Song et al 2021 ), the majority of published methods proposed the use of unchanged NNIs in urine as biomarkers of exposure (Osaka et al 2016 ; Ichikawa et al 2019 ; Harada et al 2016 ). For the first time, the present study identified promising and, most importantly, specific metabolites of NNIs in humans by a targeted approach, i.e.…”

Section: Discussionmentioning

confidence: 99%

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Human metabolism and urinary excretion of seven neonicotinoids and neonicotinoid-like compounds after controlled oral dosages

et al. 2021

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Few human data on exposure and toxicity are available on neonicotinoids and neonicotinoid-like compounds (NNIs), an important group of insecticides worldwide. Specifically, exposure assessment of humans by biomonitoring remains a challenge due to the lack of appropriate biomarkers. We investigated the human metabolism and metabolite excretion in urine of acetamiprid (ACE), clothianidin (CLO), flupyradifurone (FLUP), imidacloprid (IMI), sulfoxaflor (SULF), thiacloprid (THIAC) and thiamethoxam (THIAM) after single oral dosages at the currently acceptable daily intake levels of the European Food Safety Authority. Consecutive post-dose urine samples were collected up to 48 h. Suspect screening of tentative metabolites was carried out by liquid chromatography–high-resolution mass spectrometry. Screening hits were identified based on their accurate mass, isotope signal masses and ratios, product ion spectra, and excretion kinetics. We found, with the exception of SULF, extensive metabolization of NNIs to specific metabolites which were excreted next to the parent compounds. Overall, 24 metabolites were detected with signal intensities indicative of high metabolic relevance. Phase-I metabolites were predominantly derived by mono-oxidation (such as hydroxy-FLUP, -IMI, and -THIAC) and by oxidative N-desalkylation (such as N-desdifluoroethyl-FLUP and N-desmethyl-ACE, -CLO and -THIAM). IMI-olefin, obtained by dehydration of hydroxylated IMI, was identified as a major metabolite of IMI. SULF was excreted unchanged in urine. Previously reported metabolites of NNIs such as 6-chloronicotinic acid or 2-chlorothiazole-4-carboxylic acid and their glycine derivatives were detected either at low signal intensities or not at all and seem less relevant for human biomonitoring. Our highly controlled approach provides specific insight into the human metabolism of NNIs and suggests suitable biomarkers for future exposure assessment at environmentally relevant exposures.

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Section: Acetamipridsupporting

confidence: 92%

Section: Discussionmentioning

confidence: 99%

Human metabolism and urinary excretion of seven neonicotinoids and neonicotinoid-like compounds after controlled oral dosages

et al. 2021

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“…For instance, CLO is registered in Benin, Côte d'Ivoire, Kenya, South Africa, Namibia, Zambia, and Zimbabwe; TCP formulations are registered in Nigeria, South Africa, Madagascar, Malawi, Zambia, and Zimbabwe; and DIN is legal in Kenya (Network of African Science Academies 2019). However, the massive use of THXM in cash crop and fruit farming systems in Ghana might also account for the high CLO exposure frequency (40%) recorded among the subjects, largely because CLO is a known metabolic product of THXM in mammalian species (Baker et al 2018).…”

Section: Resultsmentioning

confidence: 99%

Human Exposures to Neonicotinoids in Kumasi, Ghana

Nimako

Ikenaka

Akoto

et al. 2021

Enviro Toxic and Chemistry

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Neonicotinoid insecticides (NNIs) are now popular in many agricultural systems across Africa; however, the extent of human exposures to NNIs in African countries is scarcely reported. The present study evaluates neonicotinoid exposures in the consumer population of Kumasi, a cosmopolitan city in Ghana. A total of 75 human urine samples were collected from healthy volunteers (nonfarmers, aged 13-80 yr) and analyzed with a liquid chromatography electrospray ionization tandem mass spectrometry system. Seven NNIs and 3 NNI metabolites were detected in the following pattern (frequency, median concentration, maximum concentration): N-dm-acetamiprid (94.7%, 0.41 µg/L, 8.79 µg/L) > imidacloprid (70.7%, 0.15 µg/L, 211.62 µg/L) > N-(6-chloro-3-pyridylmethyl)-N-ethyl-N′-methylformamidine (62.2%, 0.43 µg/L, 53.85 µg/L) > 2-[N-(6-chloro-3pyridylmethyl)-N-ethylamino]-2-(methylimino)acetic acid (56.8%, 0.10 µg/L, 3.53 µg/L) > clothianidin (40%, >limit of quantification [LOQ], 0.45 µg/L) > nitenpyram (18.7%, >LOQ, 0.14 µg/L) ≈ thiamethoxam (18.7%, >LOQ, 0.21 µg/L) > dinotefuran (12.0%, >LOQ, 1.01 µg/L) > acetamiprid (2.7%, >LOQ, 0.08 µg/L) ≈ thiacloprid (2.7%, >LOQ, 0.14 µg/L). Approximately 92% of the subjects were found to be exposed to multiple neonicotinoids simultaneously. The mean, median, and maximum imidacloprid equivalent of the relative potency factor of NNIs were found to be 1.6, 0.5, and 22.52, respectively. The median estimated daily intakes of acetamiprid, imidacloprid, and nitenpyram were 0.47, 1.27, and 0.02 µg/kg/d for females and 0.91, 0.66, and 0.08 µg/kg/d for males, respectively. The maximum daily intakes of all the NNIs were <1% of their chronic reference doses (cRfDs), except for imidacloprid and thiacloprid which recorded maximum daily intakes corresponding to 17.97 and 8.28% of cRfDs, respectively. To the best of our knowledge, the present study is the first biomonitoring report on neonicotinoid insecticides in Africa.

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“…A method to do so was recently created and applied to the study of the urinary excretion of Roundup MON 52,276 co-formulants in exposed rats [ 146 ]. In the US, the CDC’s National Health and Nutrition Examination Survey [ 122 ] has recently developed new methods to test the most heavily applied herbicide (glyphosate [ 147 ]) and the insecticides people are most frequently exposed to via diet (the neonicotinoids [ 148 ]).…”

Section: Four Solutions To Curtail the Adverse Health Effects Of Pesticidesmentioning

confidence: 99%

Commentary: Novel strategies and new tools to curtail the health effects of pesticides

et al. 2021

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Background Flaws in the science supporting pesticide risk assessment and regulation stand in the way of progress in mitigating the human health impacts of pesticides. Critical problems include the scope of regulatory testing protocols, the near-total focus on pure active ingredients rather than formulated products, lack of publicly accessible information on co-formulants, excessive reliance on industry-supported studies coupled with reticence to incorporate published results in the risk assessment process, and failure to take advantage of new scientific opportunities and advances, e.g. biomonitoring and “omics” technologies. Recommended Actions Problems in pesticide risk assessment are identified and linked to study design, data, and methodological shortcomings. Steps and strategies are presented that have potential to deepen scientific knowledge of pesticide toxicity, exposures, and risks. We propose four solutions: (1) End near-sole reliance in regulatory decision-making on industry-supported studies by supporting and relying more heavily on independent science, especially for core toxicology studies. The cost of conducting core toxicology studies at labs not affiliated with or funded directly by pesticide registrants should be covered via fees paid by manufacturers to public agencies. (2) Regulators should place more weight on mechanistic data and low-dose studies within the range of contemporary exposures. (3) Regulators, public health agencies, and funders should increase the share of exposure-assessment resources that produce direct measures of concentrations in bodily fluids and tissues. Human biomonitoring is vital in order to quickly identify rising exposures among vulnerable populations including applicators, pregnant women, and children. (4) Scientific tools across disciplines can accelerate progress in risk assessments if integrated more effectively. New genetic and metabolomic markers of adverse health impacts and heritable epigenetic impacts are emerging and should be included more routinely in risk assessment to effectively prevent disease. Conclusions Preventing adverse public health outcomes triggered or made worse by exposure to pesticides will require changes in policy and risk assessment procedures, more science free of industry influence, and innovative strategies that blend traditional methods with new tools and mechanistic insights.

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Quantification of DEET and neonicotinoid pesticide biomarkers in human urine by online solid-phase extraction high-performance liquid chromatography-tandem mass spectrometry

Cited by 49 publications

References 38 publications

Human metabolism and urinary excretion of seven neonicotinoids and neonicotinoid-like compounds after controlled oral dosages

Human metabolism and urinary excretion of seven neonicotinoids and neonicotinoid-like compounds after controlled oral dosages

Human Exposures to Neonicotinoids in Kumasi, Ghana

Commentary: Novel strategies and new tools to curtail the health effects of pesticides

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