title: Environmental friendly method for urban wastewater monitoring of micropollutants defined in the Directive 2013/39/EU and Decision 2015/495/EU.
abstract: The fate and removal of organic micropollutants in the environment is a demanding issue evidenced by the recent European policy. This work presents an analytical method for the trace quantification of 37 micropollutants including Priority Substances (Directive 2013/39/EU), substances of the recent watch list (Decision 2015/495/EU) and contaminants of emerging concern: pesticides, multi-class pharmaceuticals and a metabolite, estrogens and one industrial compound. The analytical method was based on solid phase extraction (SPE) followed by ultra-high performance liquid chromatography with tandem mass spectrometry (UHPLC-MS/MS), using eco-friendly solvents (ethanol and ultrapure water) both in the SPE and UHPLC, according to green analytical chemistry principles. Briefly, Oasis(®) HLB cartridges were used to preconcentrate 100mL of water samples and the reconstituted extracts were analyzed with a Kinetex™ column under reversed mode, the linear ranges extended to 200ngL(-1) (R(2)>0.99) for all the analytes. The method detection limits were between 0.04 and 2.26ngL(-1) and the method quantification limits were between 0.13 and 6.85ngL(-1). The identity of the compounds was confirmed using two MS/MS transitions and its ion ratios, according to Decision 2002/657/EC. The validated method was applied to wastewater treatment plant samples, assessing the concentration of micropollutants after secondary biological and tertiary UV treatments. Lab-scale photolysis and ozonation experiments were also performed with the secondary effluents, with ozonation showing the best performance for the removal of most of the determined micropollutants.
authors.affiliation: LCM - Laboratory of Catalysis and Materials - Associate Laboratory LSRE-LCM, Faculdade de Engenharia, Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal. Electronic address: ritalado@fe.up.pt.
authors.forename: Ana R
authors.initials: AR
authors.lastname: Ribeiro
authors.affiliation: LCM - Laboratory of Catalysis and Materials - Associate Laboratory LSRE-LCM, Faculdade de Engenharia, Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal.
authors.forename: Marta
authors.initials: M
authors.lastname: Pedrosa
authors.affiliation: LCM - Laboratory of Catalysis and Materials - Associate Laboratory LSRE-LCM, Faculdade de Engenharia, Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal.
authors.forename: Nuno F F
authors.initials: NFF
authors.lastname: Moreira
authors.affiliation: LCM - Laboratory of Catalysis and Materials - Associate Laboratory LSRE-LCM, Faculdade de Engenharia, Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal.
authors.forename: Manuel F R
authors.initials: MFR
authors.lastname: Pereira
authors.affiliation: LCM - Laboratory of Catalysis and Materials - Associate Laboratory LSRE-LCM, Faculdade de Engenharia, Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal.
authors.forename: Adrián M T
authors.initials: AMT
authors.lastname: Silva
mesh_terms: D002851:Chromatography, High Pressure Liquid / Q000379:methods; D004967:Estrogens / Q000032:analysis; D005062:European Union; D010575:Pesticides / Q000032:analysis; D004364:Pharmaceutical Preparations / Q000032:analysis; D011174:Portugal; D052616:Solid Phase Extraction; D012997:Solvents / Q000032:analysis; D053719:Tandem Mass Spectrometry / Q000379:methods; D062065:Wastewater / Q000737:chemistry*; D014874:Water Pollutants, Chemical / Q000032:analysis*
chemical_list: D004967:Estrogens; D010575:Pesticides; D004364:Pharmaceutical Preparations; D012997:Solvents; D062065:Wastewater; D014874:Water Pollutants, Chemical
keywords: Directive 2013/39/EU; Green analytical chemistry; Ozonation; Solid phase extraction; Ultra high performance liquid chromatography–tandem mass spectrometry; Ultraviolet