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What are the principles behind MS? What do all MS instruments have in common? What are the different types of MS?
8/31/10
Lecture outline: 1) Introduction to mass spectrometry 2) sample introduction systems, mass analyzers popular combinations in geosciences
3)
Separate masses
F Bzv
mv 2 / R Bzv
m / z B 2 R 2 / 2V
Fundamental equation of mass spectrometry Change mass-to-charge (m/z) ratio by changing V or changing B.
r m
m B 2r 2 4.825 x10 5 z V
What magnetic field strength would be required to focus a beam of CO2+ ions on a collector of a mass spectrometer whose analyzer tube as a radius of 31.45cm, assuming a voltage of 1000V? Change your magnetic field strength by -10%, what voltage puts the CO2 ions into the collector?
OR
You can put different masses into multiple cups without changing B or V.
Thermal Ionization
Plasma: Gas stream passes through plasma maintained by RF current and Ar.
Quadrupole: Changes DC and RF voltages to isolate a given m/z ion. PRO: cheap, fast, easy
Magnetic Sector: Changes B and V to focus a given m/z into detector. PRO: turn in geometry means less dark noise, higher precision,
B) Electron multiplier - limited life, linearity issues, high-precision, signals < 2e6 cps
Gas source
Popular combinations
1) Dual inlet isotope ratio mass spec (at GT, Lynch-Steiglitz and Cobb) - O, C, H ratio analyses 2) Elemental analyzer IRMS (at GT, Montoya) - N, C, S ratio analyses 3) Gas chromatograph IRMS (at GT, ????) - compound-specific ratio analyses
Solid source
1) Thermal Ionization mass spec (multi-collector) - heavy metals, REE
ICP 1) ICP quadrupole mass spec (at GT, Taillefert) - trace metal analysis 2) Single collector magnetic sector ICPMS - higher-precision trace metal analysis 2) Multi-collector ICPMS - U/Th dating, TIMS replacement
mass/charge discriminator
sample cone
skimmer cone
instrument housing
atmospheric pressure
1.
or magnetic sector
High-resolution ICPMS
electrostatic analyzer separates ions by charge
2.
High resolution ICPMS aka double-focusing ICPMS aka magnetic sector ICPMS
Multi-collector ICPMS
3.
MC-ICPMS
- same front end as other ICPMS - same magnet and ES as HR-ICPMS - multiple detectors spaced 1amu apart enable simultaneous measurement of many (~7) isotopes
very low concentrations in environmental samples, but high interest (why?) Unfortunately, 56Fe has the same atomic wt as ArO (40Ar+16O)
REMEMBER: all mass spectrometers are black boxes we really have no idea what goes on from sample container to detector signal
Ex: you measure a count-rate of 10,000 cps for a given element, but you need to know how many atoms of that element, or its concentration, were in your sample
measuring isotope ratios is a powerful approach because we can measure samples against standards with known isotopic ratios (its much more difficult to change a materials isotopic ratios than it is to change its elemental concentration!)
ALL measurements need to include blanks and standards (either concentration or ratio standards)
Requirements: 1) The sample has natural (or known) isotopic abundance (usually true). 2) The spike and sample isotopic ratios are different.
Nebulization efficiency the amount of solution that reaches the plasma (~1%) - varies with sample matrix - surface tension, viscosity, and density of solution will affect neb. eff. - usually all standards, spikes, and samples are introduced as 2-5% HNO3 - an acid solution reduces complexation, surface adsorption Matrix effects the changes in ICP characteristics with variable matrices - largely black box (we see these effects, cannot wholly explain/predict them) - you must carefully match the matrices of your standards/samples to obtain quantitative results Ionization efficiency the amount of ions produced per atoms introduced - depends on matrix, focusing of beam through cones, lenses - usually no better than 1/1000
Detection limit defined as 3 x the S.D. of the signal as the concentration of the analyte approaches 0 (measure stability at a variety of concs, extrapolate to 0; or measure 5% HNO3 blank solution)
20m
-prior to AMS samples were 14C-dated by counting the number of decays - required large samples and long analysis times -1977: Nelson et al. and Bennett et al. publish papers in Science demonstrating the utility of attaching an accelerator to a conventional mass spectrometer
Principle: You cannot quantitatively remove interferring ions to look for one 14C atom among several quadrillion C atoms. Instead, you a) destroy molecular ions (foil or gas) b) filter by the energy of the ions (detector) to separate the needle in the haystack.
The AMS at LLNL (10MV)
c) ACCELERATOR generates 2.5 million volts, accelerates C- ions b) INJECTOR MAGNET separates ions by mass, masses 12, 13, and 14 injected d) TERMINAL C- ions interact with stripper gas Ar, become C+ ions, molecular species CH destroyed
f) MAGNETIC SEPARATION 13C steered into cup, 14C passes through to solid detector
g) Si BARRIER DETECTOR pulse produced is proportional to the energy of ion, can differentiate b/t 14C and other ions count rate for modern sample = 100cps
http://www.physics.arizona.edu/ams/education/ams_principle.htm
2) Mass discrimination
- heavier atoms not ionized as efficiently as light atoms - can contribute 1% errors to isotope values - can correct with known (natural) isotope ratios within run, or with known standards between runs
4) Detector gain - what is the relationship between the electronic signal recorded by the detector and the number of ions that it has counted? - usually close to 1 after factory calibration - changes as detector ages - must quantify with standards
Cardinal rule of mass spectrometry: Your measurements are only as good as your STANDARDS!
Standards (both concentration and isotopic) can be purchased from NIST