Organophosphate ester exposure among Chinese waste incinerator workers: Urinary levels, risk assessment and associations with oxidative stress.

Organophosphate esters (OPEs), which are frequently used as flame retardants and plasticizers in versatile products, are readily released to the external environment. Although workers at municipal waste incineration plants may be extensively exposed to OPEs, only scarce health monitoring and risk assessments have been conducted in this population. In this study, we investigated the levels of eight metabolites of organophosphate esters (mOPEs) and the oxidative stress marker 8-hydroxy-2-deoxyguanosine (8-OHdG) in urine samples from 73 waste incinerator workers and 97 general residents from Shenzhen, China between September 2016 and June 2017. The overall detection rate of mOPEs was 82.2 %-100 %, and higher concentrations of di-p-cresyl phosphate and chlorinated mOPEs [bis(2-chloroethyl) phosphate (BCEP), bis(1-chloro-2propyl) phosphate (BCIPP), bis(1,3-dichloro-2-propyl) phosphate) (BDCIPP)] were found among incinerator workers than among general residents. The incinerator workers also showed significantly higher levels of 8-OHdG than general residents, but the measured levels of most mOPEs were not significantly correlated with the level of 8-OHdG; this may be because co-exposure to multiple toxic compounds can lead to oxidative stress. Risk assessment using Monte Carlo simulations revealed that 95 % of the incinerator workers were free from non-carcinogenic effects due to OPEs exposure (hazard index = 0.27, 95 % CI: 0.09, 0.77). However, the carcinogenic risk of tris(2-chloroethyl) phosphate (TCEP) for incinerator workers was between 10-6 and 10-4. These results indicate that incinerator workers are extensively exposed to OPEs, and better protective measures need to be implemented.

Assessment of the effects of early life exposure to triphenyl phosphate on fear, boldness, aggression, and activity in Japanese quail (Coturnix japonica) chicks.

Triphenyl phosphate (TPHP) is an organophosphate ester (OPE) used as a flame retardant (FR) and plasticizer. TPHP has previously been shown to disrupt behaviour in fish and mammals, but to our knowledge, this is the first study on the behavioural effects of TPHP in birds. Early life stage Japanese quail (Coturnix japonica) were exposed to nominal doses of 0 ng/g (vehicle-control), 5 ng/g (low dose), 50 ng/g (mid dose), and 100 ng/g (high dose) TPHP, both as embryos (via air cell injection prior to incubation) and as chicks (via daily gavage until 5 days post-hatch). The low dose reflects TPHP levels recorded in wild avian eggs, but actual environmental exposure levels may be higher given that TPHP is known to be rapidly metabolized in birds. We previously reported that the chicks exposed to TPHP in this study experienced reduced growth and resting metabolic rate, and sex-specific changes in thyroid function. The current study focuses on behavioural endpoints. We found that high-TPHP chicks exhibited less neophobia than vehicle-controls, and low-TPHP chicks exhibited more aggression towards conspecifics. No differences were observed in the responses of Japanese quail chicks to activity or tonic immobility (fear response) tests. These data add weight of evidence to previous findings suggesting that TPHP, among other OPEs, can disrupt ecologically-relevant behaviours in exposed vertebrates.

Simultaneous assessment of phenolic metabolites in human urine for a specific biomonitoring of exposure to organophosphate and carbamate pesticides.

Organophosphate pesticides (OPP) and carbamates are still counted among the most prominent agents used for crops protection. Up to date the determination of dialkylphosphates and their thio derivatives in urine is established for the OPP biomonitoring. However, this approach does not provide information on the exposure to specific OPP agents. A lot of OPP as well as some carbamates also provide specific urinary biomarkers indeed. Analytical methods for the determination of phenolic metabolites of OPP and carbamates have already been established by different working groups. However, these approaches only acquire one or few analytes. Therefore, we developed an analytical procedure which enables the simultaneous assessment of a wide spectrum of phenolic metabolites of OPP, carbamates and other pesticides in human urine using GC-MS/MS. The method includes enzymatic hydrolysis, solid phase extraction, derivatization, and subsequent GC-MS/MS analysis. The method showed detection limits between 0.1 and 0.4 µg/l. Variation coefficients ranged from 1 to 9 % for precision in series and 1 % to 13 % for inter-day precision. Furthermore, recovery rates between 87 and 117 % were determined. Compared with other published analytical procedures, the present method enables the simultaneous monitoring of a much broader spectrum of pesticides and biocides whose structures contain aryl moieties with competitive or improved analytical reliability. Furthermore, the suitability of the developed procedure was verified through the successful application to urine samples of pesticide exposed humans.

Assessment of exposure to pesticides in rural workers in southern of Minas Gerais, Brazil.

The aim of the study was to assess of occupational exposure to pesticides in rural workers using genotoxicity test, bioindicators and clinical evaluation. Blood, urine and buccal samples from persons, rural workers exposed to a complex mixture of pesticides with organophosphates (n=94) and without organophosphates (n=94) were collected to compare the activities of cholinesterases, the levels of urinary dialkyl phosphates, genotoxicity data, from a cytome assay. Biomarkers were analysed by traditional/published methods Control group consisted of 50 other persons, non- occupationally exposed to pesticides from the city of Alfenas, Minas Gerais, Brazil. All subjects underwent a clinical evaluation. In the group exposed to organophosphates, the activity of acetylcholinesterase, butyrylcholinesterase and total cholinesterase was lower by 63.8%, 12.8%, and 14.8%, respectively, and 92.6% of the group had dialkyl phosphates present in their urine. The cytome assay was used to measure biomarkers of DNA damage (micronuclei and/or elimination of nuclear material by budding), cytokinetic defects (binucleated cells), and proliferative potential (basal cell) and/or cell death (condensed chromatin, karyorrhectic, pyknotic, and karyolytic cells). The group exposed to organophosphates showed significant changes in all these parameters compared to the control group and showed significant changes in budding, condensed chromatin and karyolytic cells compared with the group non-exposed to organophosphates. Data from the clinical evaluation showed significant changes in the central nervous, respiratory and auditory systems. The studied biomarkers are able to distinguish occupational and environmental exposure to pesticides and the data showed hazardous exposure to organophosphates and afforded valuable data to estimate the risk to cancer development.

[Epidemiological study of organophosphate and carbamate pesticide exposure in 7 separated zones in Colombia]. / Estudio epidemiológico de exposición a plaguicidas organofosforados y carbamatos en siete departamentos colombianos, 1998-2001.

OBJECTIVE: Acetylcholinesterase activity was measured in workers potentially exposed to pesticides that are frequently used in agriculture in 7 provinces in Colombia between 1998 and 2001. MATERIAL AND METHODS: During this period, local health centers in the Departments (provinces) of Boyacá, Caldas, Huila, Meta, Norte de Santander, Santander and Valle del Cauca monitored a total of 25,242 workers for acetylcholinesterase activity. The Limperos and Ranta method, modified by Edson, was used to detect levels of pesticide exposure. RESULTS: The worker sample consisted of 78.9% men and 21.1% women. Thirty-nine percent of the workers were between 26 and 40 years of age, and 66% had social security. The most common work activities were use of spray applicators (39.1%) and harvesters (24.9%). Of the 25,356 tests for acetylcholinesterase activity, 7.6% showed abnormal activity levels. CONCLUSION: In the zones investigated, organophosphosphates were the most commonly used pesticides (42.4%), followed by carbamates (17.8%), organochlorines (8.4%) and chlorinates (6.6%). The diversity of pesticides in use underlines the need to increase the variety of biomarkers for monitoring exposed workers.