Electron-capture negative ionization calibrants for magnetic sector mass spectrometers

Fomblin [poly(perfluoropropylene oxide)], PFK (perfluorokerosene) and FC-43 (perfluorotributylamine) are investigated as mass calibrants in electron-capture negative ionization mass spectrometry on a magnetic sector hybrod mass spectrometer. This work provides exact negative ion mass tables of these three calibrants obtained using high-resolution peak matching of representative ions of the calibrants against ions of known mass. The suitability of these calibrants for full data system control in the negative ionization mode is demonstrated for the techniques of high-resolution scanning, selected ion recording and calibration of the quadrupole sector of a hybrid instrument.     

Determining eosin as a groundwater migration tracer by capillary electrophoresis/laser-induced fluorescence using a multiwavelength laser

Measurements for determining of the path of groundwater migration remain an important tool in the overall assessment of environmental processes and transport of pollutants. This paper examines a multiwavelength laser for the determination of eosin, a groundwater tracer, using capillary electrophoresis/laser-induced fluorescence (CE-LIF) at excitation wavelength 514.5 nm. Eosin was one of four dyes used in a study of adjacent resource conservation and recovery act (RCRA) and Superfund sites (created by the comprehensive environmental response, compensation, and liability act) that routinely relied on spectrofluorimetry for determination as we have previously reported. However, the improved specificity of CE-LIF is further illustrated in this work applied to the analysis of adsorbent pads placed in monitoring wells after dye injection and flushing from injection wells. The multiwavelength laser provided the capability to analyze for several dyes with one laser. The advantages/disadvantages of CE-LIF versus spectrofluorimetry are discussed. Spectrofluorimetry is fast and sensitive and will likely continue to be the primary workhorse technique. CE-LIF could provide confirmation when greater specificity is needed in a regulatory context.     

Multiresidue determination of acidic pesticides in water by HPLC-DAD with confirmation by GC-MS using conversion to the methyl ester with trimethylsilyldiazomethane

A multiresidue pesticide methodology is studied and results for acidics are reported here, with base/neutral to follow. This work studies a literature procedure as a possible general approach to many pesticides and potentially other analytes that are considered to be liquid chromatographic (LC) candidates, rather than gas chromatographic (GC) ones. The analysis of the sewage effluent of a major southwestern U.S. city serves as an example of the application of the methodology to a real sample. Recovery studies were also conducted to validate the proposed extraction step. A gradient elution program was followed for the high-performance LC (HPLC) leading to a general approach for acidics. Confirmation of identity was by electron ionization-GC-mass spectrometry (MS) after conversion of the acids to the methyl ester (or other appropriate methylation) by means of trimethylsilyldiazomethane. The 3,4-dichlorophenoxyacetic acid is used as an internal standard to monitor the reaction, and polychlorobiphenyl #19 is used for the quantitation internal standard. Although others have reported similar analyses of acids, conversion to the methyl ester is by means of diazomethane itself, rather than by the more convenient and safe trimethylsilyldiazomethane. Thus, the present paper supports the use of trimethylsilyldiazomethane with all of these acids (trimethylsilyldiazomethane has been used in environmental work with some phenoxyacetic acid herbicides) and further supports the usefulness of this reagent as a potential replacement for diazomethane. The HPLC approach here could also serve as the separation basis for an LC-MS solution for confirmation of identity, as well as quantitation.     

A mass peak profile generation model to facilitate determination of elemental compositions of ions based on exact masses and isotopic abundances

To identify elemental compositions of ions, a mass peak profile generation model (PGM) was developed to plan data acquisitions and to interpret the data obtained by using a high resolution mass spectrometer (VG70-250SE). The PGM provides a list of all compositions possible for the exact mass of ion M and its error range from which the user selects a hypothetical composition. The PGM then plots [M + 1] and [M + 2] mass peak profiles and calculates masses and abundances of full and partial [M + 1] and [M + 2] profiles relative to the M profile. All possible compositions, calculated values for the exact masses and relative abundances, and measures of profile broadening and the shape of the [M + 2] profile are listed in a table. Pass-fail results for each of six criteria based on a comparison between table entries for the hypothetical composition and each of the other compositions are indicated. Compositions failing one or more criteria will be eliminated if the hypothetical composition is correct. The table provides assurance that all possible compositions based on the elements specified by the user have been considered. The PGM can be used to estimate the minimum resolution and number of determinations necessary to identify the correct composition by eliminating all others. As multiple determinations are made and error limits become smaller, average values are entered into the PGM to determine all compositions consistent with the data, often until only one composition remains.     

Associative Organotin Polymers. 2. Solution Properties of Symmetric Trialkyltin Fluorides

The solubilities and viscosities of four novel symmetric tri-n-alkyltin fluorides in various organic solvents were studied. It is shown that these compounds do behave as transient polymers. Increasing the length of the n-alkyl chain beyond n-butyl imparts considerable solubility to this class of associative polymers and offers no steric hindrance to polymer chain formation. The effects of concentration, solvent type, temperature, and brine on the solution viscosities were also studied. These associative polymers effectively viscosify compressed gases (having liquid-like densities), such as propane and n-butane. They can therefore be used in enhanced oil recovery operations as well as in fracturing of oil wells.     

Capillary liquid chromatography-mass spectrometry and micellar electrokinetic chromatography as complementary techniques in environmental analysis

Applications of capillary electrophoresis (CE) and capillary liquid chromatography (LC) to environmental analysis have been limited. In this work we present applications of micellar electrokinetic chromatography (MEKC) to the analysis of environmental matrices for synthetic dyes. Separations obtained by capillary LC are compared with those obtained under MEKC for seven selected dyes. Both techniques are capable of resolving the subject compounds at high efficiency. Recovery data for spiked water and soil matrices were obtained for four dyes using solid-phase extraction cartridges and disks with determination by MEKC-UV detection. Both pH adjustment via acid and ion-pairing via a cationic surfactant were investigated for isolating dyes. Capillary LC detection was by continuous-flow liquid secondary ion mass spectrometry (CF-LSI-MS) whereas MEKC used UV detection (214 nm). Application of peak-profiling at high mass resolution is illustrated with the capillary LC-MS technique. Interfacing capillary LC under CF-LSI-MS using the coaxial arrangement is easier than interfacing CE with this arrangement. MEKC provides a powerful screening and determinative technique, while capillary LC-MS provides a confirmatory tool.