Solid trace analysis

Laser based mass spectrometric methods, such as laser ionization (LIMS) and laser ablation in combination with inductively coupled plasma mass spectrometry (LA-ICP-MS) are powerful analytical techniques for survey analysis of solid substances. To realize the analytical performances methods for the direct trace analysis of synthetic and natural crystals modification of a traditional analytical technique was necessary and suitable standard reference materials (SRM) were required. Recent developments allowed extending the range of analytical applications of LIMS and LA-ICP-MS will be presented and discussed. For example ... 

Solid-surface room-temperature phosphorescence (RTF) is a relatively new technique which has been used for organic trace analysis in several fields. However, the fundamental interactions needed for RTF are only partly understood. To clarify some of the interactions required for strong RTF, organic compounds adsorbed on several surfaces are being studied. Fluorescence quantum yield values, phosphorescence quantum yield values, and phosphorescence lifetime values were obtained for model compounds adsorbed on sodiiun acetate-sodium chloride mixtures and on a-cyclodextrin-sodium chloride mixtures. With the data obtained, the triplet formation efficiency and some of the rate constants related to the luminescence processes were calculated. This information clarified several of the interactions responsible for RTF from organic compounds adsorbed on sodium acetate-sodium chloride and a-cyclodextrin-sodium chloride mixtures. Work with silica gel chromatoplates has involved studying the effects of moisture, gases, and various solvents on the fluorescence and phosphorescence intensities. The net result of the study has been to improve the experimental conditions for enhanced sensitivity and selectivity in solid-surface luminescence analysis. 

Solid-surface luminescence analysis involves the measurement of fluorescence and phosphorescence of organic compounds adsorbed on solid materials. Several solid matrices such as filter paper, silica with a polyacrylate binder, sodium acetate, and cyclodextrins have been used in trace organic analysis. Recent monographs have considered the details of solid-surface luminescence analysis (1,2). Solid-surface room-temperature fluorescence (RTF) has been used for several years in organic trace analysis. However, solid-surface room-temperature phosphorescence (RTF) is a relatively new technique, and the experimental conditions for RTF are more critical than for RTF. 

Interactions in Solid-Surface Luminescence Temperature Variation. Solid-surface luminescence analysis, especially solid-surface RTF, is being used more extensively in organic trace analysis than in the past because of its simplicity, selectivity, and sensitivity (,1,2). However, the interactions needed for strong luminescence signals are not well understood. In order to understand some of the interactions in solid-surface luminescence we recently developed a method for the determination of room-temperature fluorescence and phosphorescence quantum yields for compounds adsorbed on solid surfaces (27). In addition, we have been investigating the RTF and RTF properties of the anion of p-aminobenzoic acid adsorbed on sodium acetate as a model system. Sodium acetate and the anion of p-aminobenzoic acid have essentially no luminescence impurities. Also, the overall system is somewhat easier to study than compounds adsorbed on other surfaces, such as filter paper, because sodium acetate is more simple chemically. 

Solid-surface luminescence analysis is a useful approach for organic trace analysis because of its simplicity, sensitivity, and selectivity. It will continue to be used in environmental analysis and other areas not only for the reasons mentioned above but also because it is readily adaptable to field work. By developing a fundamental understanding of the interactions responsible for strong RTF and RTF signals, the advantages and disadvantages of the luminescence approach will be more specifically defined in the future. 

Rossbach M, Ostapczuk P, Emons H (1998) Microhomogeneity of candidate reference materials Comparison of solid sampling Zeeman-AAS with INAA. Fresenius J Anal Chem 360 380-383. Rossbach M, Stoeppler M (1987) Use of CRMs as mutual calibration materials and control of synthetic multielement standards as used in INAA. J Radioanal Nud Chem Artides 113 217-223. Sargent M (1995) Development and application of a protocol for quality assurance of trace analysis. Anal Proc 32 71-76. 

Difficult matrix introduction (DMI) is another recently introduced way of automating trace analysis in complex and dirty matrices [101]. The technique may be used for both liquid and dirty solid samples. In DMI a sample extract or sample matrix (solid) is introduced directly into a microvial in the injector. Volatiles are desorbed directly... 

Modem trace analysis is interested in detailed information about the distribution of elements in microareas and their chemical binding forms (specia-tion). The limited sample mass implies methods with absolute detection limits as high as possible. Use of the sputtering process as a sampling technique localises the analytical zone at the outer layers of a solid, and allows analysis to progress into the interior. 

Applications ICP-MS has become the technique of choice for the determination of elements in a wide range of liquid samples at concentrations in the ng L 1 to [igL-1 range. Typical applications of ICP-MS are multi-element analysis of liquids (even with high solid contents) element speciation by hyphenation to chromatographic techniques continuous on-line gas analysis multi-element trace analysis of polymers and trace analysis in high-purity materials. ICP-MS is routinely used for quality control purposes. 

For the analysis of organic additives in polymeric materials, in most cases, prior extraction will be necessary. Depending on the nature of the additive, many different approaches are employed. These include soxhlet extraction with organic solvent or aqueous media, total sample dissolution followed by selective precipitation of the polymer leaving the additive in solution, assisted extraction using pressurised systems, ultrasonic agitation and the use of supercritical fluids. In trace analysis, solid phase extraction (SPME) from solution or solvent partition may be required to increase the analyte concentration. 

The extension of inductively coupled plasma (ICP) atomic emission spectrometry to seawater analysis has been slow for two major reasons. The first is that the concentrations of almost all trace metals of interest are 1 xg/l or less, below detection limits attainable with conventional pneumatic nebulisation. The second is that the seawater matrix, with some 3.5% dissolved solids, is not compatible with most of the sample introduction systems used with ICP. Thus direct multielemental trace analysis of seawater by ICP-AES is impractical, at least with pneumatic nebulisation. In view of this, a number of alternative strategies can be considered ... 

Complex matrixes typically cannot be analysed directly to obtain the selectivity and sensitivity required for most trace analysis applications. To circumvent this problem, solid-phase micro extraction techniques were used to preconcentrate analytes selectively prior to gas chromatography/ion trap mass spectrometry analysis. 

Thermal ionization TI Ionization by heating Atomic ions Isotope ratio, Trace analysis Solid samples... 

Spark source SS Discharge Atomic ions Trace analysis in solid samples... 

Fig. 4.21. Thermogravimetric analysis of a compound capable of being isolated as an anhydrate crystal form (solid trace), and as the monohydrate (dashed trace) and dihydrate (dotted trace) solvatomorphs.

Gorecki, T. and PawUszyn, J. 1997, Eield-portable solid-phase microextraction/fast GC system for trace analysis. Field Anal. Chem. Tech. 1 227—284. 

Solid-phase microextraction (SPME) for preconcentration, followed by GC/ Ion Trap MS, was used for trace analysis of explosives and their metabolites in seawater [9]. NICI was used with methane as reagent gas. Compounds of interest included RDX, TNT and two of its metabofrtes 2-amino-4,6-dinitrotoluene (2ADNT) and 4-amino-2,6-dinitrotoluene (4ADNT). Although the instrument sensitivity was in low-ppb range, the detection limits for SPME with GC/ITMS... 

Environmental Solid and liquid waste Drinking and waste water Priority pollutants Trace analysis Vapor analysis... 

T. Steger-Hartmann, K. Kuemmerer and J. Schecker, Trace analysis of the antineoplastics ifosfamide and cyclophosphamide in wastewater by two-step solid-phase extraction and gas chromatography - mass spectrometry. Journal of Chromatography A, 1996, 726(1 -i-2), 179-184. 

Delaunay, N., Pichon, V, and Hennion, M. C., Immunoaffinity solid-phase extraction for the trace-analysis of low-molecular-mass analytes in complex sample matrices. Journal of Chromatography. B, Biomedical Sciences and Applications 745(1), 15-37, 2000. 

As a result of that reductive process, a deposit of copper metal (denoted in Eq. 2.2 by s for solid ) is formed on the carbon electrode surface. The prominent anodic peak recorded in the reverse scan corresponds to the oxidative dissolution of the deposit of copper metal previously formed. The reason for the very intense anodic peak current is that the copper deposit is dissolved in a very small time range (i.e., potential range) because, in the dissolution of the thin copper layer, practically no diffusion limitations are involved, whereas in the deposition process (i.e., the cathodic peak), the copper ions have to diffuse through the expanding diffusion layer from the solution to the electrode surface. These processes, labeled as stripping processes, are typical of electrochemically deposited metals such as cadmium, copper, lead, mercury, zinc, etc., and are used for trace analysis in solution [84]. Remarkably, the peak profile is rather symmetrical because no solution-like diffusive behavior is observed. 

A high vacuum laser ion source is combined with a dynamic (ToF-MS) or static mass spectrometer (Mattauch-Herzog instrument) for the separation of the ion beams formed and used in LIMS for multi-element major, minor and trace analysis of compact solid samples (bulk analysis).74... 

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