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

Abstract

A rapid analytical method including one-single solid-phase extraction (SPE) 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 organic compounds (1.6 < log K ow < 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 organochlorinated 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.

Organic additive release from plastic to seawater is lower under deep-sea conditions

“…The target list of 25 parent additive chemicals and 7 transformation products comprised a suite of PAEs, PAEs monoesters (MPAEs), OPEs, and BPs: mono and dimethyl phthalate (MMP and DMP), mono and diethyl phthalate (MEP and DEP), mono and diisobutyl phthalate (MiBP and DiBP), mono and di-n-butyl phthalate (MnBP and DnBP), monobenzyl and benzylbutyl phthalate (MBzP and BzBP), mono and diethylhexyl phthalate (MEHP and DEHP), mono and di-n-octyl phthalate (MnOP and DnOP), DiNP, tripropyl phosphate (TPP), tri-iso-buthyl phosphate (TiBP), tri-n-butyl phosphate (TnBP), tris-(2-chloroethyl) phosphate (TCEP), tris-(2-chloro, 1methylethyl) phosphate (TCPP), tris-(2-chloro-, 1-chloromethylethyl) phosphate (TDCP), triphenyl phosphate (TPhP), 2-ethylhexyl-diphenyl phosphate (EDHPP), TEHP, BPA, and its analogs BPAF, BPAP, BPF, BPP, BPS, BPZ. Analysis of all chemicals in seawater was adapted from Fauvelle et al 54 with slight modifications: 70 mL seawater sample volume, PAE monoesters were included in the target list and analyzed from the second elution fraction by liquid chromatography coupled to HRMS. DiNP was also added to the target list and analyzed in the first fraction by gas chromatography coupled to tandem mass spectrometry, after first being identified in the PVC leachates by analyses performed in a full-scan mode.…”

Occurrence of perfluoroalkyl substances in the Bay of Marseille (NW Mediterranean Sea) and the Rhône River

“…Replicate blanks were made during each extraction and no contamination was detected in any of the blanks. Method recoveries obtained during a previous method validation ranged from 73 ± 14 (PFHxS) to 124 ± 5 (PFOA)% (Fauvelle et al, 2018). Method limits of quantification ranged from 0.10 (PFOS) to 8.00 (PFHxA) ng L −1 .…”

“…Dissolved water phase samples were processed by solid phase extraction (SPE), using a method modified after Fauvelle et al (2018) and analyzed for four PFAS (Fig. S1).…”

Analysis of organophosphate pesticides in surface water—Comparison of method optimization approaches

“…[15][16][17][18][19] Usually, methods focusing on a wide range of organic contaminations from seawater utilize solid phase extraction (SPE). 20,21 However, dispersive liquid-liquid micro-extraction (DLLME) as a simple, rapid, and efficient method, introduced to water analysis by Farahani et al, 22 has been deployed frequently.…”

“…Detection methods for OPP in surface water were published mostly for a maximum of six compounds at a time with limits of detection (LOD) in the range of 12 to 250 ng L during the last decades . Usually, methods focusing on a wide range of organic contaminations from seawater utilize solid phase extraction (SPE) . However, dispersive liquid‐liquid micro‐extraction (DLLME) as a simple, rapid, and efficient method, introduced to water analysis by Farahani et al, has been deployed frequently.…”