Development and validation of an analytical method for detection and quantification of benzophenone, bisphenol A, diethyl phthalate and 4-nonylphenol by UPLC-MS/MS in surface water

Frederico Goytacazes De Araujo,Eduardo Monteiro Martins,Marcia Marques,Glauco F Bauerfeldt

doi:10.7717/peerj-achem.7

Abstract

Guandu River is the main water source for 9 million inhabitants in Rio de Janeiro city and some others included in the metropolitan region of the Rio de Janeiro State, Brazil. Here, the development of a chromatographic method and its application to assess the occurrence of 4-nonylphenol (4NP), benzophenone (BP), bisphenol A (BPA) and diethyl-phthalate (DEP), known as endocrine disruptors (EDs), is reported. Sample were prepared by solid phase extraction (SPE) with C18 cartridge and methanol as elution solvent. Validation of analytical method followed the United States Environmental Protection Agency protocol (USEPA 8000D guide) and selectivity, matrix effect, linearity, precision, accuracy, robustness, limit of detection (LOD) and limit of quantification (LOQ) were evaluated. The recovery was greater than 90%, accuracy was found between 80% and 115% and relative standard deviation (RSD) below 11.03%. LOQ ranged from 10.0 to 50.0 ng L−1, while the LOD ranged from 0.87 to 5.72 ng L−1. The coefficients of determination (R2) were greater than 0.99 for all compounds within a linear ranges of 10.0 to 500 ng L−1 for 4NP and BP and 50.0 to 500 ng L−1 for BPA and DEP. The method was therefore considered selective and robust for all micropollutants. Matrix effect was observed for BP, 4NP and DEP. The developed method was applied to analyze five samples collected monthly during 2018 at a selected sampling point of a river in Rio de Janeiro State. The maximum concentrations found for BPA, BP, DEP and 4NP were 182.04, 286.20, 2.56×103 and 13.48 ng L−1 respectively. These values are high enough to justify an investigation on the presence of these micropollutants in drinking water as well as to extend the monitoring for the search of similar pollutants and their metabolites.

Highlights

The availability of water resources in the world is gaining increasing attention
Concerns about exposure to the endocrine disruptors (EDs) micropollutants have been increasing over the years due to the possible damage that can be caused to exposed organisms. (Meyer, Sarcinelli & Moreira, 1999; Bila & Dezotti, 2007; Cirja et al, 2008; VelaSoria et al, 2014; Rodríguez-Gómez et al, 2015; Caldas et al, 2016;Vela-Soria et al, 2014; Starling, Amorim & Leão, 2019)
According to the United States Environmental Protection Agency (USEPA), an ED is ‘‘an exogenous agent that interferes with the synthesis, secretion, transport, metabolism, binding or elimination of the body’s natural hormones, which are responsible for homeostasis, reproduction, development and/or behavior’’ (Bila et al, 2007; Camilleri et al, 2015; Kabir, Rahman & Rahman, 2015)

Summary

Introduction

It is frequently associated to climatic factors (drought, climate changes), as well as by the increasing demand for clean water (due to the intense population growth) and decreasing quality. The latter is a direct consequence of the pollution promoted by domestic, rural and industrial activities. (Meyer, Sarcinelli & Moreira, 1999; Bila & Dezotti, 2007; Cirja et al, 2008; VelaSoria et al, 2014; Rodríguez-Gómez et al, 2015; Caldas et al, 2016;Vela-Soria et al, 2014; Starling, Amorim & Leão, 2019). According to the United States Environmental Protection Agency (USEPA), an ED is ‘‘an exogenous agent that interferes with the synthesis, secretion, transport, metabolism, binding or elimination of the body’s natural hormones, which are responsible for homeostasis, reproduction, development and/or behavior’’ (Bila et al, 2007; Camilleri et al, 2015; Kabir, Rahman & Rahman, 2015)

Objectives

Methods

Results

Conclusion