title: Factors influencing the extraction of pharmaceuticals from sewage sludge and soil: an experimental design approach.
abstract: Pharmaceuticals can enter the environment when organic waste products are recycled on agricultural soils. The extraction of pharmaceuticals is a challenging step in their analysis. The very different extraction conditions proposed in the literature make the choice of the right method for multi-residue analysis difficult. This study aimed at evaluating, with experimental design methodology, the influence of the nature, pH and composition of the extraction medium on the extraction recovery of 14 pharmaceuticals, including 8 antibiotics, from soil and sewage sludge. Preliminary experimental designs showed that acetonitrile and citrate-phosphate buffer were the best extractants. Then, a response surface design demonstrated that many cross-product and squared terms had significant effects, explaining the shapes of the response surfaces. It also allowed optimising the pharmaceutical recoveries in soil and sludge. The optimal conditions were interpreted considering the ionisation states of the compounds, their solubility in the extraction medium and their interactions with the solid matrix. To perform the analysis, a compromise was made for each matrix. After a QuEChERS purification, the samples were analysed by online SPE-UHPLC-MS-MS. Both methods were simple and economical. They were validated with the accuracy profile methodology for soil and sludge and characterised for another type of soil, digested sludge and composted sludge. Trueness globally ranged between 80 and 120 % recovery, and inter- and intra-day precisions were globally below 20 % relative standard deviation. Various pharmaceuticals were present in environmental samples, with concentration levels ranging from a few micrograms per kilogramme up to thousands of micrograms per kilogramme. Graphical abstract Influence of the extraction medium on the extraction recovery of 14 pharmaceuticals. Influence of the ionisation state, the solubility and the interactions of pharmaceuticals with solid matrix. Analysis of different soils and organic waste products.
authors.affiliation: UMR 1402 ECOSYS, INRA, AgroParisTech, Université Paris-Saclay, 78850, Thiverval-Grignon, France.
authors.forename: Sabrina
authors.initials: S
authors.lastname: Ferhi
authors.affiliation: UMR 1402 ECOSYS, INRA, AgroParisTech, Université Paris-Saclay, 78850, Thiverval-Grignon, France. marjolaine.deschamps@grignon.inra.fr.
authors.forename: Marjolaine
authors.initials: M
authors.lastname: Bourdat-Deschamps
authors.affiliation: UMR 518 MIA, AgroParisTech, INRA, Université Paris-Saclay, 75231, Paris, France.
authors.forename: Jean-Jacques
authors.initials: JJ
authors.lastname: Daudin
authors.affiliation: UMR 1402 ECOSYS, INRA, AgroParisTech, Université Paris-Saclay, 78850, Thiverval-Grignon, France.
authors.forename: Sabine
authors.initials: S
authors.lastname: Houot
authors.affiliation: UMR 1402 ECOSYS, INRA, AgroParisTech, Université Paris-Saclay, 78850, Thiverval-Grignon, France.
authors.forename: Sylvie
authors.initials: S
authors.lastname: Nélieu
mesh_terms: D000097:Acetonitriles; D002851:Chromatography, High Pressure Liquid / Q000379:methods; D004784:Environmental Monitoring / Q000379:methods; D006863:Hydrogen-Ion Concentration; D057230:Limit of Detection; D004364:Pharmaceutical Preparations / Q000032:analysis / Q000302:isolation & purification*; D012722:Sewage / Q000032:analysis*; D012987:Soil / Q000737:chemistry*; D012989:Soil Pollutants / Q000032:analysis / Q000302:isolation & purification*; D052616:Solid Phase Extraction / Q000379:methods*; D012997:Solvents; D053719:Tandem Mass Spectrometry / Q000379:methods; D014874:Water Pollutants, Chemical / Q000032:analysis / Q000302:isolation & purification*
chemical_list: D000097:Acetonitriles; D004364:Pharmaceutical Preparations; D012722:Sewage; D012987:Soil; D012989:Soil Pollutants; D012997:Solvents; D014874:Water Pollutants, Chemical; C032159:acetonitrile
keywords: Accuracy profile; Antibiotics; Emerging pollutants; Extraction; Influencing factors; Physical-chemical properties