environmental mass spectrometry...64 analytes • water soluble/miscible organic compounds, e.g....
TRANSCRIPT
Environmental Mass Spectrometry
March 2, 2006
Dr Vince TaguchiLaboratory Services BranchMinistry of the Environment
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AcronymsAPCI Atmospheric Pressure Chemical IonizationCI Chemical IonizationDAI Direct Aqueous InjectionDBP Disinfection By-productDEA Dissociative Electron AttachmentDNAPL Dense Non-Aqueous Phase LiquidECNIMS Electron Capture Negative Ion Mass SpectrometryEDC Endocrine Disrupting CompoundEI Electron IonizationEQ Extended geometry QuadrupoleESI ElectroSpray IonizationFIA Flow Injection AnalysisFID Flame Ionization Detector FT(ICR)MS Fourier Transform (Ion Cyclotron Resonance) Mass Spectrometer (Spectrometry)GC Gas Chromatograph (Chromatography)HRMS High Resolution Mass Spectrometer (Spectrometry)IDL Instrument detection limitLC Liquid Chromatograph (Chromatography)LRMS Low Resolution Mass Spectrometer (Spectrometry)MAGIC Monodisperse Aerosol Generator Interface for ChromatographyMDL Method detection limitMS Mass Spectrometer (Spectrometry)MSD Mass Selective DetectorMS/MS Tandem Mass Spectrometer (Spectrometry)MW Molecular WeightNICI Negative Ion Chemical IonizationNIST National Institute of Standards and TechnologyPB Particle BeamSTP Sewage Treatment PlantTIC Total Ion ChromatogramTSQ Triple Stage QuadrupoleVG Vacuum Generators (manufacturer)VOC Volatile Organic CompoundZAB Zero Alpha Beta (model)
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Open Characterization
• Gas chromatography-mass spectrometry(GC-MS)
• Electron Ionization (EI)• NIST database• Wiley database
64
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
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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
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Butyl Cellosolve
• Butyl Cellosolve (2-butoxyethanol)• MDL = 5 ppm for DAI/GC-FID• MDL = 0.05 ppm for DAI/GC-HRMS
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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)
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Rhodamine Dyes
• Container of Rhodamine dye discovered
• Rhodamine B – toxic
• Rhodamine WT – non-toxic
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Diquat & ParaquatDiquat & 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
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Diquat/Paraquat LCDiquat/Paraquat LC--MSMS
Diquat (183.0922 m/z)
Paraquat- OTFA (299.1007 m/z)
Diquat85 ng
Paraquat100 ng
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Performance Evaluation Program & Inter-laboratory Study
MOE-LSB DQ/PQ PEP Program
0
20
40
60
80
100
120
PEP0698 PEP0399 PEP0899 PEP1299
Sample #
Rec
over
y (%
of e
xpec
ted)
DiquatParaquat
USEPA Water Sample Study WS040Diquat
# of Laboratories 116
Design Value (ug/L) 14.8
Acceptable Range (ug/L) 1.98 – 21.1
MOE-LSB Result(ug/L) 14.4
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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
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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
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The Plan
• Postulate common product ions• Parent ion scans• Flow injection analysis (FIA)
• Screening technique
• Collaborative work with Sciex• Jeff Plomley, Yves Mouget
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NPEs NPEs –– STP SamplesSTP Samples
Typical STP Chromatograms Typical STP Profile
# o f Ethoxyla te Grou ps0 2 4 6 8 10 12 14 1 6
0
4
8
12
16
20
24
Influ ent Efflue nt
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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?
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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
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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
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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
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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
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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
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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