Quadrupole mass spectrometer technique

Molecular ion mass interferences are not as prevalent for the simpler matrices, as is clear from the mass spectrum obtained for the Pechiney 11630 A1 standard sample by electron-gas SNMSd (Figure 4). For metals like high-purity Al, the use of the quadrupole mass spectrometer can be quite satisfiictory. The dopant elements are present in this standard at the level of several tens of ppm and are quite evident in the mass spectrum. While the detection limit on the order of one ppm is comparable to that obtained from optical techniques, the elemental coverage by SNMS is much more comprehensive. 

Secondary ion mass spectrometry (SIMS) is by far the most sensitive surface technique, but also the most difficult to quantify. When a surface is exposed to a beam of ions (Ar", 0.5-5 keV), energy is deposited in the surface region of the sample by a collisional cascade. Some of the energy will return to the surface and stimulate the ejection (desorption) of atoms, ions, and multi-atomic clusters. In SIMS, positive or negative secondary ions are detected directly with a quadrupole mass spectrometer. 

Currently, HPLC/fiuorescence is still the most common technique for the determination of residues of oxime carbamates. With the introduction of ESI and APCI MS interfaces, HPLC/MS analysis for oxime carbamates in various sample matrices has become widespread. However, for a rapid, sensitive, and specific analysis of biological and environmental samples, HPLC/MS/MS is preferred to HPLC/MS and HPLC/fiuorescence. With time, improved and affordable triple-quadrupole mass spectrometers will be available in more analytical laboratories. With stricter regulatory requirements, e.g., highly specific and conclusive methods with lower LOQ, HPLC/MS/MS will be a method of choice for oxime carbamates and their metabolites. 

Generally FAB produces protonated, MH+, or depro-tonated, (M — H) , quasi-molecular ions with a little excess energy which will sometimes produce fragment ions of low intensity. FAB is therefore a mild to soft ionisation technique which produces primarily molecular weight information and some structural information. Positive and negative ionisation mass spectra are produced with equal facility. FAB was originally used with magnetic sector mass spectrometers, but lately mainly with quadrupole mass spectrometers (Table 6.10). 

Selection of a suitable ionisation method is important in the success of mixture analysis by MS/MS, as clearly shown by Chen and Her [23]. Ideally, only molecular ions should be produced for each of the compounds in the mixture. For this reason, the softest ionisation technique is often the best choice in the analysis of mixtures with MS/MS. In addition to softness , selectivity is an important factor in the selection of the ionisation technique. In polymer/additive analysis it is better to choose an ionisation technique which responds preferentially to the analytes over the matrix, because the polymer extract often consists of additives as well as a low-MW polymer matrix (oligomers). Few other reports deal with direct tandem MS analysis of extracts of polymer samples [229,231,232], DCI-MS/MS (B/E linked scan with CID) was used for direct analysis of polymer extracts and solids [69]. In comparison with FAB-MS, much less fragmentation was observed with DCI using NH3 as a reagent gas. The softness and lack of matrix effect make ammonia DCI a better ionisation technique than FAB for the analysis of additives directly from the extracts. Most likely due to higher collision energy, product ion mass spectra acquired with a double-focusing mass spectrometer provided more structural information than the spectra obtained with a triple quadrupole mass spectrometer. 

FTIR in multiply hyphenated systems may be either off-line (with on-line collection of peaks) [666,667] or directly on-line [668,669]. Off-line techniques may be essential for minor components in a mixture, where long analysis times are required for FT-based techniques (NMR, IR), or where careful optimisation of the response is needed. In an early study a prototype configuration comprised SEC, a triple quadrupole mass spectrometer, off-line evaporative FTIR with splitting after UV detection see Scheme 7.12c [667]. Off-line IR spectroscopy (LC Transform ) provides good-quality spectra with no interferences from the mobile phase and the potential for very high sensitivity. Advanced approaches consist of an HPLC system incorporating a UV diode array, FTIR (using an ATR flow-cell to obtain on-flow IR spectra), NMR and ToF-MS. 

This recently developed technique [13,14] was applied to the analysis of adsorbates on electrodes after tranfer of the electrode from the electrochemical cell to the UHV analysis chamber of a quadrupole mass spectrometer. 

Falkner and Edmond [334] determined gold at femtomolar quantities in seawater by flow injection inductively coupled plasma quadrupole mass spectrometry. The technique involves preconcentration by anion exchange of gold as a cyanide complex, [AulCNjj], using 195Au radiotracer (ti/2 = 183 days) to monitor recoveries. Samples are then introduced by flow injection into an inductively coupled plasma quadrupole mass spectrometer for analysis. The method has a detection limit of 10 fM for 4 litres of seawater preconcentrated to 1 ml, and a relative precision of 15% at the 100 fM level. 

Personnel Choosing an appropriate technique sometimes comes down to having the right person on your staff to perform the technique. If you, or no one in the lab, had had experience with the hydroxyl value titration, it might not have been an option in the Bulging Drum Problem. Certainly, if the operator of your triple quadrupole mass spectrometer is on vacation and there is no back-up operator, another method, or sending the samples to another lab, may be necessary. Should the method need to be transferred to another lab, does that lab have the requisite people for the job ... 

Precursor ion and neutral loss scan functions are unique to a triple quadrupole mass spectrometer. These are powerful techniques for targeted detection of compounds and their related impurities that produces a characteristic neutral loss or a fragment ion corresponding to a unique structural feature. Both neutral loss and... 

Figure A.3A.3 LC/MS analysis of a dietary supplement consisting of extract of Trifolium pratense (red clover). Reversed-phase C18 HPLC and negative ion electrospray ionization mass spectrometry were used with a quadrupole mass spectrometer analyzer (Agilent also see Table A.3A.1). The map illustrates the abundance of information provided by this hyphenated technique with HPLC mass chromatograms in one dimension and mass spectra in another dimension.

Multi-element determination of dissolved metals at ultratrace level may be performed by Inductively Coupled Plasma-Mass Spectrometry (ICP-MS). U.S. EPA s Methods 200.8 and 1638 present a methodology for measuring trace elements in waters and wastes by the above technique. Sample is acid digested and the solution is introduced by pneumatic nebulization into a radio-frequency plasma. The elements in the compounds are atomized and ionized. The ions are extracted from the plasma through a differentially pumped vacuum interface and separated by a quadrupole mass spectrometer by their mass to charge ratios. The mass spectrometer must have a resolution capability of 1 amu peak width at 5% peak height. 

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