The new Water Screening PCDL

Transcription

1 The new Water Screening PCDL Content and integration in suspect and non-target screening Dr. Thomas Glauner Senior LC/MS Applications Scientist EMEA Market Development Team 1

2 Accurate mass screening and quantitation Advantages Very high selectivity Virtually unlimited number of analytes Easy acquisition method setup Non-target acquisition with targeted data analysis Requirements High resolution accurate mass Q-TOF LC/MS Databases and libraries Innovative data mining tools Efficient software workflows for Qual and Quant 2

3 Personal Compound Database and Library (PCDL) PCDL Manager software Database - Names, Formulas, Structures - Common identifiers - Monoisotopic masses - Database, easily extendable - Retention times, updated from experimental data - Fully searchable, fully integrated in data mining algorithms Library - Normalized MS/MS spectra - Positive and negative polarity - Different species and collision energies 3

4 The new Water Screening PCDL Database - For more than 1,200 compounds Pesticides, pharmaceuticals, personal care products, transformation products, cyanotoxins All compounds present in major water regulations around the globe (EU WFD; US EPA; CN regulations) Contaminants of emerging concern Library - Accurate mass MS/MS spectra for > 700 compounds - Including all relevant precursor ions ([M+H] +, [M-H] -, further adducts if appropriate) and several collision energies - Fragment ions were corrected for their theoretical formula weight 4

5 Screening strategies How the Water Screening PCDL fits into the workflows Target screening Suspect screening What else is in my sample? Non-target screening De-replication All All Ions Ions MS/MS MS/MS Reference Acquisition standard All Ions MS/MS MS and target (auto) MS/MS MS and target (auto) MS/MS - Find-by-Formula (Subset PCDL) - Assign fragments as Qualifiers (Qual) - Generate Quant Method - Find-by-Formula (Comprehensive PCDL) - Identify compounds - fragment co-elution (PCDL) - library searching (PCDL) - Molecular Feature Extraction - Mass Profiler (2-sample comparison) - Mass Profiler Professional (Multivariate statistics) - Batch overview - Quantitation - Identification (Accurate Mass, Isotopes, Qualifiers (fragments), RTs - Suspect List - Identification by fragment co-elution, library searching - Tentative Identification by in-silico fragmentation (MSC) - Differential results - Identification by MS/MS library searching (PCDL) - Tentative Identification by in-silico fragmentation (MSC) 5

6 Sample overview Effluents of 4 wastewater treatment plants in central Europe 14-day mixed samples, 9 sampling events Different treatment principles and sizes - Simple treatment (category B: mechanical and biological treatment, phosphate elimination) - Conventional treatment (category H: mechanical and biological treatment, phosphate elimination, nitrification and denitrification) Different catchment areas - Peri-urban - Agricultural - Industrial Conventional treatment Simple treatment 6

7 Experimental conditions Agilent 1290 Infinity UHPLC Agilent 6550 ifunnel Q-TOF Water sample Sample storage (3-8 C) Adjust ph, add ISTDs (opt.) Filter with glass fibre syringe filters (opt.) Direct injection of 100 µl Separation column Mobile phase A Mobile phase B MS conditions Calibration range Zorbax SB-Aq 2.1 x 100 mm; 1.8 µm 0.1 mm NH 4 acetate + 0.1% acetic acid 0.1% acetic acid in acetonitrile Positive and negative ESI with Agilent Jet Stream - All Ions MS/MS - Target MS/MS - Auto MS/MS 5 to 1000 ng/l 7

8 Easy method setup using All Ions MS/MS Fragmentation without precursor isolation - Low energy trace (no collision energy, full spectrum acquisition) - At least one high energy trace (e.g. CE = 20 ev, fragment ion spectra) - Extremely fast - Non-target acquisition including product ions 8

9 Easy data mining and identification with high confidence PCDL loads inside MassHunter Workstation Software just run samples and then press search - Find-by-Formula database search - Automatic extraction of major fragment ions from library - Coelution scoring of precursor and fragment ions Diazinon in WWTP effluent (AI-8) 9

10 Efficient Data Review and Quantitation Automatic Creation of Quantitation Method Compound results - Major adducts and fragments - Accurate mass EICs for molecular ions and fragments - Relative responses - Retention times Quantitation method -Automatic selection of quantifier and qualifier(s) -Reporting of qualifier ratios -Isotope pattern comparison and accurate mass metrics as QC 10

11 Quantitation of emerging contaminants Positive and negative All Ions MS/MS Diclofenac Negative ionization MRPL (WFD): 10 ng/l Quinoxyfen Positive ionization EQS (WFD): 15 to 150 ng/l MixedStd_15ppt [Diclofenac] x Area= Area= Area= MixedStd_10ppt [Quinoxyfen] x Area= Area= Area= ng/l 10 ng/l

12 Efficient data review Batch review process using Compounds at a Glance 100 ng/l Effluent AI-8 Effluent AZ-8 12

13 What else is in my sample? Identification of emerging contaminants by All Ions MS/MS Conventional treatment facility with > 50,000 population equivalents Lamotrigine (anticonvulsant) Sitagliptin (antidiabetic drug) Fexofenadine (antihistamine) Cetirizine (antihistamine) Irbesartan (angiotensin receptor blocker) Valsartan (angiotensin receptor blocker) Mass deviation < 5 ppm for precursor and fragment Perfect coelution Consistent ion ratios 13

14 Compound confirmation by library matching MS1 target score 91.4 (out of 100) Library score 84.8 (out of 100) 14

15 Take home message HR Q-TOF LC/MS screening with an Agilent Q-TOF and the new accurate mass MS/MS library for water contaminants allows the identification with high confidence with a single injection, even without standards and in retrospective data analysis. Contaminant screening in WWTP effluents reveals information about the catchment area (pesticides and pesticide metabolites in agricultural areas; pharmaceuticals and personal care products in urban areas) and the efficiency of the treatment process. Coupling the Agilent 1290 Infinity UHPLC to the highly sensitive 6550 ifunnel Q-TOF allows quantitation of a large number of environmental contaminants at relevant concentrations with a large volume direct injection. 15

16 Acknowledgements Jean-Daniel Berset, Amt für Wasser und Abfall, Kantons Bern, for providing the WWTP samples 16