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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Laboratory Services Branch

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Dupont 21-491B (1974)

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Hewlett-Packard 5970A MSD (1985)

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Hewlett-Packard 5970B MSD (1987)

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Hewlett-Packard 5973 MSD (1999)

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Hewlett-Packard 5973 MSD (1999)

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Finnigan 4000/4500 (1979)

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Finnigan 4000/4500 (1979) (cont’d)

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Finnigan 4000/4500 (1979) (cont’d)

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Finnigan 4000/4500 (1979/1981)

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Hewlett-Packard 5970B MSD (1987)

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Hewlett-Packard 5973 MSD (1999)

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VG Trio-2 (1990/1991)

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VG ZAB-2F (1983)

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VG ZAB-2F (1983) (cont’d)

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VG ZAB-2F (1983) (cont’d)

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VG ZAB-2F (1983/1991)

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VG ZAB-2F (1983/1991) (cont’d)

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VG AutoSpec (1991)

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Micromass AutoSpec Ultima (2002)

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Finnigan MAT TSQ-70 (1987)

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Finnigan MAT TSQ-70 (1987) (cont’d)

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Varian 1200L (2005)

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Varian 1200L (2005) (cont’d)

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Micromass Quattro Ultima (2001)

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Micromass Quattro Ultima (2001) (cont’d)

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Sciex 4000 Q Trap (2005)

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VG ZAB-EQ (1986)

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VG ZAB-EQ (1986) (cont’d)

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LC-(ESI)MS (1995)

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LC-(ESI)MS (1995) (cont’d)

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AutoSpec-Q (1997/2003)

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Emergency Response (1988)

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Volatile Organic Compounds

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Volatile Organic Compounds (cont’d)

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Semi-Volatile Organic Compounds

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Semi-Volatile Organic Compounds (cont’d)

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The Solution

Cl

HN

NCl

O

H

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Open Characterization

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Open Characterization

• Gas chromatography-mass spectrometry(GC-MS)

• Electron Ionization (EI)• NIST database• Wiley database

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Library Search Results (1991)

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Library Search Result

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The Hypothesis

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The Solution

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Library Search Results (1994)

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Library Search Result

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Library Entries

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Reference Spectrum

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Accurate Mass Determination

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The Hypothesis

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Library Search Results (1995)

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Library Search Results

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The Solution

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Dioxin Analysis by High Resolution Mass Spectrometry (HRMS)

(1983)

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Dioxin Analysis by Tandem Mass Spectrometry (MS/MS)

(1987)

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Instrument Detection Limits

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LRMS versus HRMS

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N-nitrosodimethylamine (NDMA)

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Mutagen-X (MX)

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2-Methylisoborneol (2-MIB)

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Direct Aqueous Injection (DAI)

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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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Butyl Cellosolve

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Liquid Chromatography-Mass Spectrometry

(LC-MS)

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Monodisperse Aerosol Generator Interface for Chromatography

(MAGIC)

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Particle Beam (PB)

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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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Electrospray Ionization (ESI) and Atmospheric Pressure Chemical

Ionization (APCI)

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Electrospray Ionization (ESI)

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Atmospheric Pressure Chemical Ionization (APCI)

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Digitoxin Confirmation

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Digitoxin – EI Mass Spectrum

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Digitoxin – ESI Mass Spectrum

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Rhodamine Dyes

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Rhodamine Dyes

• Container of Rhodamine dye discovered

• Rhodamine B – toxic

• Rhodamine WT – non-toxic

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Rhodamine B

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Unknown Rhodamine

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Pesticides

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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

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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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Crystal Violet

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Endocrine Disrupting Compounds (EDCs)

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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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Proposed Fragmentation Schemes

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STP Profiles

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LC-(APCI) MS/MS

• NPE congeners

• Normal phase LC

• APCI-MS/MS

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LCLC--(APCI)MS/MS(APCI)MS/MS

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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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Algal Toxins

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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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102

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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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Disinfection By-products (DBPs)

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Semi-Volatile Organic Compounds

A

B

C

D

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DBP-A (EI Mass Spectrum)

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DBP-A (CI Mass Spectrum)

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DBP-A (EI)

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DBP-A (CI)

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AutoSpec-Q

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AutoSpec-Q

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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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Fourier Transform (Ion Cyclotron Resonance) Mass Spectrometer

[FT(ICR)MS]

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FT(ICR)MS

GC Interface LC InterfaceSuperconductingMagnet

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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

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Many Tanks for your Attention

Environmental �Mass SpectrometryAcronymsLaboratory Services BranchDupont 21-491B (1974)Hewlett-Packard 5970A MSD (1985)Hewlett-Packard 5970B MSD (1987)Hewlett-Packard 5973 MSD (1999)Hewlett-Packard 5973 MSD (1999)Finnigan 4000/4500 (1979)Finnigan 4000/4500 (1979) (cont’d)Finnigan 4000/4500 (1979) (cont’d)Finnigan 4000/4500 (1979/1981)Hewlett-Packard 5970B MSD (1987)Hewlett-Packard 5973 MSD (1999)VG Trio-2 (1990/1991)VG ZAB-2F (1983)VG ZAB-2F (1983) (cont’d)VG ZAB-2F (1983) (cont’d)VG ZAB-2F (1983/1991)VG ZAB-2F (1983/1991) (cont’d)VG AutoSpec (1991)Micromass AutoSpec Ultima (2002)Finnigan MAT TSQ-70 (1987)Finnigan MAT TSQ-70 (1987) (cont’d)Varian 1200L (2005)Varian 1200L (2005) (cont’d)Micromass Quattro Ultima (2001)Micromass Quattro Ultima (2001) (cont’d)Sciex 4000 Q Trap (2005)VG ZAB-EQ (1986)VG ZAB-EQ (1986) (cont’d)LC-(ESI)MS (1995)LC-(ESI)MS (1995) (cont’d)AutoSpec-Q (1997/2003)Emergency Response �(1988)Volatile Organic CompoundsVolatile Organic Compounds (cont’d)Semi-Volatile Organic CompoundsSemi-Volatile Organic Compounds (cont’d)The SolutionOpen CharacterizationOpen CharacterizationLibrary Search Results �(1991)Library Search ResultThe HypothesisThe SolutionLibrary Search Results �(1994)Library Search ResultLibrary EntriesReference SpectrumAccurate Mass DeterminationThe HypothesisLibrary Search Results �(1995)Library Search ResultsThe SolutionDioxin Analysis by High Resolution Mass Spectrometry (HRMS)�(1983)Dioxin Analysis by Tandem Mass Spectrometry (MS/MS)�(1987)Instrument Detection LimitsLRMS versus HRMSN-nitrosodimethylamine (NDMA)Mutagen-X (MX)2-Methylisoborneol (2-MIB)Direct Aqueous Injection �(DAI)AnalytesRationale for DAIButyl CellosolveButyl CellosolveLiquid Chromatography-�Mass Spectrometry �(LC-MS)Monodisperse Aerosol Generator Interface for Chromatography �(MAGIC)Particle Beam (PB)Electrospray Ionization (ESI) and Atmospheric Pressure Chemical Ionization (APCI)Electrospray Ionization (ESI)Atmospheric Pressure Chemical Ionization (APCI)Digitoxin ConfirmationDigitoxin – EI Mass SpectrumDigitoxin – ESI Mass SpectrumRhodamine DyesRhodamine DyesRhodamine BUnknown RhodaminePesticidesDiquat & ParaquatDiquat/Paraquat LC-MSPerformance Evaluation Program �& Inter-laboratory StudyPurple UnknownPurple UnknownCrystal VioletEndocrine Disrupting Compounds (EDCs)Nonyl Phenol (NP) &� Nonyl Phenol Ethoxylates (NPEs)The PlanProposed Fragmentation SchemesSTP ProfilesLC-(APCI) MS/MSLC-(APCI)MS/MSNPEs – STP SamplesAlgal ToxinsMass Spectrometric TechniquesDisinfection By-products �(DBPs)Semi-Volatile Organic CompoundsDBP-A (EI Mass Spectrum)DBP-A (CI Mass Spectrum)DBP-A (EI)DBP-A (CI)AutoSpec-Q�AutoSpec-QAccurate Mass DeterminationsFourier Transform (Ion Cyclotron Resonance) Mass Spectrometer [FT(ICR)MS]FT(ICR)MSApplications of FT(ICR)MSMany Tanks for your Attention