title: Tetraphasic polar organic chemical integrative sampler for the determination of a wide polarity range organic pollutants in water. The use of performance reference compounds and in-situ calibration.
abstract: In the present work, a homemade polar organic chemical integrative sampler (POCIS) was studied for the determination of 16 target analytes. The suitability of the combination of triphasic mixture (used in so called pesticides-POCIS) and octadecyl-functionalized silica gel (C18) as sorbent for POCIS was evaluated for the determination of alkylphenols (APs), several hormones, bisphenol-A (BPA), synthetic musk fragrances and herbicides such as trifluralin (Tri) and alachlor (Ala). With this purpose, POCIS laboratory calibration study, using a continuous-flow calibration system, was carried out in order to determine the uptake behavior and sampling rate (Rs) values for each target analyte. While the most hydrophobic compounds, (synthetic musk fragrances, some APs and Tri), showed poor linearity and low accumulation, a linear accumulation was observed for compounds whose logarithmic octanol-water partition coefficient (log Kow) ranged from 5.3 (4-tert-octylphenol, 4t-OP) to 3.1 (cis-androsterone, ADT). The Rsvalues obtained ranged from 0.190Lday-1(4t-OP) to 0.042Lday-1(BPA and equilin, EQ). The addition of C18to the commonly used triphasic mixture increased the applicability of the POCIS sampler to compounds slightly more non-polar, such as 4t-OP. As far as we know, this is the first time that a combination of tetraphasic sorbent composed by the commercially available triphasic sorbent (Isolute ENV+polystyrene divinylbenzene and Ambersorb 1500 carbon dispersed on S-X3 Biobeads) and C18was evaluated for passive sampling of the target analytes. The developed POCIS samplers were applied in field experiments from Halle (Germany) wastewater treatment plant (WWTP) effluent. Concerning the calculation of Rsvalues, the time weighted average (TWA) water concentration CWTWAvalues were determined considering three different approaches: (i) Rsfrom laboratory calibration (ii) Rsfrom laboratory calibration corrected with the use of performance reference compounds (PRCs) and (iii) Rsderived from field experiments or in-situ calibration. Several deuterated compounds such as, [2H3]-17β-estradiol ([2H3]-E2), [2H4]-nonylphenol ([2H4]-NP), [2H4]-equilin ([2H4]-EQ), [2H3]-tonalide ([2H3]-AHTN) and [2H15]-musk xylene ([2H15]-MX) were also studied for their applicability as PRCs. Finally, a reasonable agreement between grab sampling and CWTWAwas found when results from in-situ calibration were considered, but not when PRCs were used for correction.
authors.affiliation: Department of Analytical Chemistry, Faculty of Science and Technology, University of the Basque Country (UPV/EHU), P.K. 644, 48080 Bilbao, Spain. Electronic address: arantza.iparraguirre@ehu.es.
authors.forename: A
authors.initials: A
authors.lastname: Iparraguirre
authors.affiliation: Department of Analytical Chemistry, Faculty of Science and Technology, University of the Basque Country (UPV/EHU), P.K. 644, 48080 Bilbao, Spain.
authors.forename: A
authors.initials: A
authors.lastname: Prieto
authors.affiliation: Department of Analytical Chemistry, Faculty of Science and Technology, University of the Basque Country (UPV/EHU), P.K. 644, 48080 Bilbao, Spain.
authors.forename: A
authors.initials: A
authors.lastname: Vallejo
authors.affiliation: UFZ-Department of Analytical Chemistry, Helmholtz Centre for Environmental Research, Permoserstraße 15, D-04318 Leipzig, Germany.
authors.forename: M
authors.initials: M
authors.lastname: Moeder
authors.affiliation: Department of Analytical Chemistry, Faculty of Science and Technology, University of the Basque Country (UPV/EHU), P.K. 644, 48080 Bilbao, Spain.
authors.forename: O
authors.initials: O
authors.lastname: Zuloaga
authors.affiliation: Department of Analytical Chemistry, Faculty of Science and Technology, University of the Basque Country (UPV/EHU), P.K. 644, 48080 Bilbao, Spain.
authors.forename: N
authors.initials: N
authors.lastname: Etxebarria
authors.affiliation: UFZ-Department of Ecological Chemistry, Helmholtz Centre for Environmental Research, Permoserstraße 15, D-04318 Leipzig, Germany.
authors.forename: A
authors.initials: A
authors.lastname: Paschke
keywords: In-situ sampling rate; Performance reference compound; Polar organic chemical integrative sampler; Time weighted average water concentration