title: In-cell clean-up pressurized liquid extraction and gas chromatography-tandem mass spectrometry determination of hydrophobic persistent and emerging organic pollutants in coastal sediments.
abstract: The main goal of this work was to develop, optimize and validate a multi-residue method for the simultaneous determination of 97 contaminants, including fragrances, UV filters, repellents, endocrine disruptors, biocides, polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), organophosphorus flame retardants, and several types of pesticides in marine sediment samples. Extraction and cleanup were integrated into the same step using pressurized liquid extraction (PLE) with in-cell clean-up (1g of alumina). The extraction was performed using dichloromethane at 100 °C, 1500 psi and 3 extraction cycles (5 min per cycle). Extracts were derivatized with N-(tert-butyldimethylsilyl)-N-methyltrifluoroacetamide (MTBSTFA) to improve the signal and sensitivity of some target compounds (i.e., triclosan, 2-hydroxybenzophenone). Separation, identification and quantification of analytes were carried out by gas chromatography (GC) coupled to tandem mass spectrometry. Under optimal conditions, the optimized protocol showed good recovery percentages (70-100%), linearity (>0.99) and limits of detection below 1 ng g(-1) for all compounds. Finally, the method was applied to the analysis of sediment samples from different coastal areas from Andalusia (Spain), where occurrence and distribution of emerging contaminants in sediments is very scarce. Twenty five compounds out of 98 were detected in all samples, with the endocrine disruptor nonylphenol and the fragrance galaxolide showing the highest concentrations, up to 377.6 ng g(-1) and 237.4 ng g(-1), respectively.
authors.affiliation: Physical Chemistry Department, Faculty of Marine and Environmental Sciences, University of Cadiz, International Campus of Excellence of the Sea, Cadiz, 11510, Spain.
authors.forename: Marina G
authors.initials: MG
authors.lastname: Pintado-Herrera
authors.affiliation: Physical Chemistry Department, Faculty of Marine and Environmental Sciences, University of Cadiz, International Campus of Excellence of the Sea, Cadiz, 11510, Spain.
authors.forename: Eduardo
authors.initials: E
authors.lastname: González-Mazo
authors.affiliation: Physical Chemistry Department, Faculty of Marine and Environmental Sciences, University of Cadiz, International Campus of Excellence of the Sea, Cadiz, 11510, Spain. Electronic address: pablo.lara@uca.es.
authors.forename: Pablo A
authors.initials: PA
authors.lastname: Lara-Martín
mesh_terms: D001577:Benzophenones / Q000032:analysis; D052244:Endocrine Disruptors / Q000032:analysis; D004784:Environmental Monitoring / Q000379:methods*; D005411:Flame Retardants / Q000032:analysis; D008401:Gas Chromatography-Mass Spectrometry; D019015:Geologic Sediments / Q000737:chemistry*; D009930:Organic Chemicals / Q000032:analysis*; D010575:Pesticides / Q000032:analysis; D011078:Polychlorinated Biphenyls / Q000032:analysis; D011084:Polycyclic Aromatic Hydrocarbons / Q000032:analysis; D013030:Spain; D053719:Tandem Mass Spectrometry; D014874:Water Pollutants, Chemical / Q000032:analysis*
chemical_list: D001577:Benzophenones; D052244:Endocrine Disruptors; D005411:Flame Retardants; D009930:Organic Chemicals; D010575:Pesticides; D011084:Polycyclic Aromatic Hydrocarbons; D014874:Water Pollutants, Chemical; D011078:Polychlorinated Biphenyls; C562127:ortho-hydroxybenzophenone
keywords: Emerging contaminants; Gas chromatography; Mass spectrometry; Persistent organic pollutants; Pressurized liquid extraction; Sediment