Environmental Mass Spectrometry March 2, 2006 Dr Vince Taguchi Laboratory Services Branch Ministry of the Environment
Acronyms APCI CI DAI DBP DEA DNAPL ECNIMS EDC EI EQ ESI FIA FID FT(ICR)MS GC HRMS IDL LC LRMS MAGIC MDL MS MSD MS/MS MW NICI NIST PB STP TIC TSQ VG VOC ZAB Atmospheric Pressure Chemical Ionization Chemical Ionization Direct Aqueous Injection Disinfection By-product Dissociative Electron Attachment Dense Non-Aqueous Phase Liquid Electron Capture Negative Ion Mass Spectrometry Endocrine Disrupting Compound Electron Ionization Extended geometry Quadrupole ElectroSpray Ionization Flow Injection Analysis Flame Ionization Detector Fourier Transform (Ion Cyclotron Resonance) Mass Spectrometer (Spectrometry) Gas Chromatograph (Chromatography) High Resolution Mass Spectrometer (Spectrometry) Instrument detection limit Liquid Chromatograph (Chromatography) Low Resolution Mass Spectrometer (Spectrometry) Monodisperse Aerosol Generator Interface for Chromatography Method detection limit Mass Spectrometer (Spectrometry) Mass Selective Detector Tandem Mass Spectrometer (Spectrometry) Molecular Weight Negative Ion Chemical Ionization National Institute of Standards and Technology Particle Beam Sewage Treatment Plant Total Ion Chromatogram Triple Stage Quadrupole Vacuum Generators (manufacturer) Volatile Organic Compound Zero Alpha Beta (model) 2
Laboratory Services Branch 3
Dupont 21-491B (1974) 4
Hewlett-Packard 5970A MSD (1985) 5
Hewlett-Packard 5970B MSD (1987) 6
Hewlett-Packard 5973 MSD (1999) 7
Hewlett-Packard 5973 MSD (1999) 8
Finnigan 4000/4500 (1979) 9
Finnigan 4000/4500 (1979) (cont d) 10
Finnigan 4000/4500 (1979) (cont d) 11
Finnigan 4000/4500 (1979/1981) 12
Hewlett-Packard 5970B MSD (1987) 13
Hewlett-Packard 5973 MSD (1999) 14
VG Trio-2 (1990/1991) 15
VG ZAB-2F (1983) 16
VG ZAB-2F (1983) (cont d) 17
VG ZAB-2F (1983) (cont d) 18
VG ZAB-2F (1983/1991) 19
VG ZAB-2F (1983/1991) (cont d) 20
VG AutoSpec (1991) 21
Micromass AutoSpec Ultima (2002) 22
Finnigan MAT TSQ-70 (1987) 23
Finnigan MAT TSQ-70 (1987) (cont d) 24
Varian 1200L (2005) 25
Varian 1200L (2005) (cont d) 26
Micromass Quattro Ultima (2001) 27
Micromass Quattro Ultima (2001) (cont d) 28
Sciex 4000 Q Trap (2005) 29
VG ZAB-EQ (1986) 30
VG ZAB-EQ (1986) (cont d) 31
LC-(ESI)MS (1995) 32
LC-(ESI)MS (1995) (cont d) 33
AutoSpec-Q (1997/2003) 34
Emergency Response (1988) 35
Volatile Organic Compounds 36
Volatile Organic Compounds (cont d) 37
Semi-Volatile Organic Compounds 38
Semi-Volatile Organic Compounds (cont d) 39
The Solution H N H O Cl N Cl 40
Open Characterization 41
Open Characterization Gas chromatography-mass spectrometry (GC-MS) Electron Ionization (EI) NIST database Wiley database 42
Library Search Results (1991) 43
Library Search Result 44
The Hypothesis 45
The Solution 46
Library Search Results (1994) 47
Library Search Result 48
Library Entries 49
Reference Spectrum 50
Accurate Mass Determination 51
The Hypothesis 52
Library Search Results (1995) 53
Library Search Results 54
The Solution 55
Dioxin Analysis by High Resolution Mass Spectrometry (HRMS) (1983) 56
Dioxin Analysis by Tandem Mass Spectrometry (MS/MS) (1987) 57
Instrument Detection Limits 58
LRMS versus HRMS 59
N-nitrosodimethylamine (NDMA) 60
Mutagen-X (MX) 61
2-Methylisoborneol (2-MIB) 62
Direct Aqueous Injection (DAI) 63
Analytes Water soluble/miscible organic compounds, e.g. ethanol, ethylene glycol, 2-butoxyethanol VOCs high temperature purge-and-trap Semi-VOCs extraction with organic solvent and concentration of extract 64
Rationale for DAI Speed of analysis 15 minutes per sample No sample preparation required Ultimate detection limits not required Sub-ppm detection limits achievable High resolution mass spectrometry required 65
Butyl Cellosolve Butyl Cellosolve (2-butoxyethanol) MDL = 5 ppm for DAI/GC-FID MDL = 0.05 ppm for DAI/GC-HRMS 66
Butyl Cellosolve 67
Liquid Chromatography- Mass Spectrometry (LC-MS) 68
Monodisperse Aerosol Generator Interface for Chromatography (MAGIC) 69
Particle Beam (PB) 70
LC-(PB) MS Qualitative analysis of pesticides is possible Detection limits are high Transport efficiency across interface is variable Quantitative LC-(PB) MS must be done by isotope dilution for each analyte Qualitative analysis of thermally-labile organics (e.g. N-nitrosodiphenylamine (NDPhA) with library searching is feasible) 71
Electrospray Ionization (ESI) and Atmospheric Pressure Chemical Ionization (APCI) 72
Electrospray Ionization (ESI) 73
Atmospheric Pressure Chemical Ionization (APCI) 74
Digitoxin Confirmation 75
Digitoxin EI Mass Spectrum 76
Digitoxin ESI Mass Spectrum 77
Rhodamine Dyes 78
Rhodamine Dyes Container of Rhodamine dye discovered Rhodamine B toxic Rhodamine WT non-toxic 79
Rhodamine B 80
Unknown Rhodamine 81
Pesticides 82
Diquat & Paraquat Bipyridylium post-emergence contact herbicides Diquat dibromide and paraquat dichloride The Safe Drinking Water Act (2002) Diquat = 70 ug/l, Paraquat = 10 ug/l Provincial Water Quality Objectives (1994) Diquat = 0.5 ug/l Diquat Paraquat 83
Diquat/Paraquat LC-MS Diquat (183.0922 m/z) Diquat 85 ng Paraquat 100 ng Paraquat- OTFA (299.1007 m/z) 84
Performance Evaluation Program & Inter-laboratory Study MOE-LSB DQ/PQ PEP Program USEPA Water Sample Study WS040 Diquat Recovery (% of expected) 120 100 80 60 40 20 0 PEP0698 PEP0399 PEP0899 PEP1299 Sample # Diquat Paraquat # of Laboratories 116 Design Value (ug/l) 14.8 Acceptable Range (ug/l) 1.98 21.1 MOE-LSB Result (ug/l) 14.4 85
Purple Unknown 86
Purple Unknown Purple unknown found in a high school Analysis by Fourier Transform/Infrared (FT/IR) Spectroscopy in PCLS Section Tentative identification Crystal Violet Confirmation by (ESI)(MS)/MS 87
Crystal Violet 88
Endocrine Disrupting Compounds (EDCs) 89
Nonyl Phenol (NP) & Nonyl Phenol Ethoxylates (NPEs) Non-ionic surfactants (endocrine disruptors) Domestic detergents & cleaners Textile industry Pulp & paper industry Need to monitor STP influent & effluent 90
The Plan Postulate common product ions Parent ion scans Flow injection analysis (FIA) Screening technique Collaborative work with Sciex Jeff Plomley, Yves Mouget 91
Proposed Fragmentation Schemes 92
STP Profiles 93
NPE congeners LC-(APCI) MS/MS Normal phase LC APCI-MS/MS 94
LC-(APCI)MS/MS 95
NPEs STP Samples Typical STP Chromatograms Typical STP Profile 24 20 16 12 8 4 0 0 2 4 6 8 10 12 14 16 # of Ethoxylate Groups Influ ent Effluent 96
Algal Toxins 97
Background 1980s algal blooms responsible for taste and odour problems Geosmin and 2-methylisoborneol Aesthetic problem Are there other problems associated with algal blooms? Is the drinking water safe? 98
Microcystins Microcystins cyclic heptapeptide hepatotoxins produced by cyanobacteria (blue-green algae) > 60 microcystins identified Most abundant congener microcystin-lr Free microcystin surface water Microcystin potential intracellular toxins Total microcystin = free + intracellular 99
Guidelines (Total Microcystin-LR) World Health Organization 1.0 µg/l Health Canada 1.5 µg/l Ministry of the Environment 1.5 µg/l 100
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Surface Water Surveys 2002 2005 >700 samples analysed by LC-(ESI) MS/MS Microcystin-LR, -RR, -YR, -LA and -LW were detected in the raw waters No microcystins were detected in the treated waters 103
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Mass Spectrometric Techniques EI, CI, ESI, APCI molecular weight, M +., [M+H] +, [M-H] - Accurate mass determinations empirical formulae MS/MS fragmentation pathways 105
Disinfection By-products (DBPs) 106
Semi-Volatile Organic Compounds A C B D 107
DBP-A (EI Mass Spectrum) 108
DBP-A (CI Mass Spectrum) 109
DBP-A (EI) 110
DBP-A (CI) 111
AutoSpec-Q 112
AutoSpec-Q 113
Accurate Mass Determinations Double-focusing magnetic sector MS Time-of-flight (TOF) MS Fourier Transform (Ion Cyclotron Resonance) Mass Spectrometer [FT(ICR)MS] Need for high mass accuracy and high resolution 114
Fourier Transform (Ion Cyclotron Resonance) Mass Spectrometer [FT(ICR)MS] 115
FT(ICR)MS GC Interface Superconducting Magnet LC Interface 116
Applications of FT(ICR)MS Enhanced emergency response capabilities Faster analyses and turnaround times through chemical fingerprinting Identification of new and emerging environmental contaminants Enhanced method and technology development 117
Many Tanks for your Attention 118