One-Single Extraction Procedure for the Simultaneous Determination of a Wide Range of Polar and Nonpolar Organic Contaminants in Seawater

Vincent Fauvelle,Richard Sempéré,Benoit Carlez,Christos Panagiotopoulos,Natascha Schmidt,Javier Castro-Jiménez

doi:10.3389/fmars.2018.00295

Abstract

A rapid analytical method including one-single solid-phase extraction procedure followed by gas and liquid chromatography coupled with high resolution mass spectrometry detection (GC–MS and LC–HRMS respectively) was developed for the quantification of 40 polar and nonpolar organic compounds (1.6 < log Kow < 9.5) in seawater including both legacy and emerging contaminants, with a focus on the most common plastic organic additives. This new method allowed for the analyses of nine organophosphate esters (OPEs), seven phthalates (PAEs), six bisphenols (BPs), five perfluorinated compounds (PFCs), and thirteen legacy organochorinated compounds (OCs, including polychlorobiphenyles and pesticides) with recoveries in the ranges of 57–124 % for OPEs, 52–163 % for PAEs, 64–118 % for BPs, 63–124 % for PFCs, and 40–95 % for OCs. As a result of i) strict cleanup protocols, ii) material and solvent selection, and iii) the use of an ISO 6 cleanroom for sample treatment, the procedural blank levels were always lower than 5 ng L−1, even for the most abundant and ubiquitous compounds like tris-(2-chloro, 1-methylethyl) phosphate (TCPP) and diethylhexyl phthalate (DEHP). The quantification limits were in the ranges of 0.03–0.75 ng L−1 for OPEs, 0.03–0.25 ng L−1 for PAEs, 0.1–5 ng L−1 for BPs, 0.1–8 ng L−1 for PFCs, and 0.02–1.1 ng L−1 for OCs, matching seawater analysis requirements. Dissolved water phase samples collected in Marseille Bay (NW Mediterranean Sea) were analyzed using the developed method reveling the concentration of PAEs up to 140 ng L−1 (DEHP) and that of OCs up to 70 ng L−1 (α-endosulfan). For the first time, we also provided the concentrations of OPEs (TCPP up to 450 ng L−1), BPs (bisphenol S up to 123 ng L−1), and PFCs (PFOS up to 5 ng L−1) in this area. A sampling station close to the municipal waste water treatment plant outfall exhibited the highest concentration levels for all compounds.

Highlights

Over the past decades, the dramatic increase in chemical diversity, production volume, uses and sources has led to the widespread occurrence of organic contaminants in all waterbodies including marine environments and numerous living organisms (Sousa et al, 2017)
Individual native organophosphate esters (OPEs) and OC standards and labeled 2,4-DDT-d8, 4,4-DDT-d8, and α-endosulfan-d4 were purchased from Dr Ehrenstorfer GmbH (Germany), whereas labeled standards of tri-n-butyl-d27-phosphate, triphenyl-d15-phosphate, tri-n-propyl-d21-phosphate, malathion-d7, α-HCH-d6, and γ-HCH-d6 were obtained from C/D/N Isotopes Inc. (Canada) and tris(2-chloroisopropyl)-d18-phosphate, tris(1,3-dichloro2-propyl)-d15-phosphate, tris(2-chloroethyl)-d12-phosphate, 13C12-polychlorinated biphenyls (PCBs)-28,−118, and−180 were from Cambridge Isotope Laboratories, Inc. (USA)
The method proposed in this study allowed the quantification of 40 organic contaminants presenting a wide range of physicochemical properties and sources in the environment, including both legacy and emerging contaminants

Summary

Introduction

The dramatic increase in chemical diversity, production volume, uses and sources has led to the widespread occurrence of organic contaminants in all waterbodies including marine environments and numerous living organisms (Sousa et al, 2017). The persistence of emerging contaminants, such as perfluorinated flame retardants (PFCs), together with their ubiquitous detection and high toxicity resulting in sub-ppt EU Environmental Quality Standard (EQS) prompted growing concern (Kaserzon et al, 2012). The release of organic compounds initially included in plastic materials, e.g., phthalates (PAEs), organophosphate esters (OPEs), and bisphenols (BPs) is otherwise identified among the most critical hazards associated with plastic discharge in the environment (Hermabessiere et al, 2017; Hahladakis et al, 2018). Most of the above-mentioned chemical families exhibit endocrine-disrupting properties and are potentially associated with both health and environmental deleterious effects whose mechanisms are largely unknown (Messerlian et al, 2017; Barrios-Estrada et al, 2018), especially for mixtures of contaminants (Kim-Tiam et al, 2016). The various classes of contaminants cited above may induce their toxic effect via direct contact or by biomagnifying in the marine food web from phyto- and zooplankton, which are mainly affected by the dissolved water phase fraction of the contaminants (Kim-Tiam et al, 2016)

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