Elemental hair analysis: A review of procedures and applications.

Although exogenous contamination and unreliable reference values have limited the utility of scalp hair as a biomarker of chemical elements exposure, its use in toxicological, clinical, environmental and forensic investigations is growing and becoming more extensive. Therefore, hair elemental analysis is reviewed in the current manuscript which spans articles published in the last 10 years. It starts with a general discussion of history, morphology and possible techniques for elemental analysis, where inductively coupled plasma-mass spectrometry (ICP-MS) is clearly highlighted since this technique is leading quantitative ultra-trace elemental analysis. Emphasis over sampling, quality assurance, washing procedures and sample decomposition is given with detailed protocols compiled in tables as well as the utility of hair to identify human gender, age, diseases, healthy conditions, nutrition status and contamination sites. Isotope ratio information, chemical speciation analysis and analyte preconcentration are also considered for hair. Finally, the potential of laser ablation ICP-MS (LA-ICP-MS) to provide spatial resolution and time-track the monitoring of elements in hair strands instead of conventional bulk analysis is spotlighted as a real future trend in the field.

Determination of volatile elements in biological materials by isotopic dilution ETV-ICP-MS after dissolution with tetramethylammonium hydroxide or acid digestion.

Isotopic dilution for the determination of Ag, Cd, Hg, Pb and Tl in biological materials by ETV-ICP-MS is proposed. The sample was simply dissolved with tetramethylammonium hydroxide (TMAH) or acid digested in a microwave furnace, with an on line matrix separation. When the dissolution was employed, Ir was used as a chemical modifier for Hg and Pb and Pd was used for Cd and Tl. No modifier was used for Ag. The pyrolysis temperatures were taken from pyrolysis temperature curves. The on line preconcentration was performed in a flow injection system with solenoid valves and was based on the analyte complexation with ammonium diethyldithiophosphate and sorption of the complexes on C(18) bonded to silica gel in a minicolumn. For the digested sample submitted to the analyte preconcentration procedure, a modifier, Ir, was only used for Hg. For the other analytes, since a low pyrolysis temperature, 300 degrees C, was employed, no modifier was added. The isotopic dilution calibration was applied to two certified materials, bovine liver and dog fish muscle, dissolved with TMAH or acid digested, and to another two certified materials, corn bran and rice flour, acid digested and submitted to analyte preconcentration. The obtained concentration values agree with the certified ones, showing that this calibration procedure leads to accurate results in the determination of low concentrations of volatile elements. Due to simplicity, the dissolution with TMAH is very attractive.

Determination of arsenic(III) and arsenic(V) by electrothermal atomic absorption spectrometry after complexation and sorption on a C-18 bonded silica column.

A flow injection procedure for the separation and pre-concentration of inorganic arsenic based on the complexation with ammonium diethyl dithiophosphate (DDTP) and sorption on a C-18 bonded silica gel minicolumn is proposed. During the sample injection by a time-based fashion, the As(3+)-DDTP complex is stripped from the solution and retained in the column. Arsenic(V) and other ions that do not form complexes are discarded. After reduction to the trivalent state by using potassium iodide plus ascorbic acid, total arsenic is determined by electrothermal atomic absorption spectrometry (ETAAS). Arsenic(V) concentration can be calculated by difference. After processing 6 ml sample volume, the As(3+)-DDTP complexes were eluted directly into the autosampler cup (120 mul). Ethanol was used for column rinsing. Influence of pH, reagent concentration, pre-concentration and elution time and column size were investigated. When 30 mul of eluate plus 10 mul of 0.1% (w/v) Pd(NO(3))(2) were dispensed into the graphite tube, analytical curve in the 0.3-3 mug As l(-1) range was obtained (r=0.9991). The accuracy was checked for arsenic determination in a certified water, spiked tap water and synthetic mixtures of arsenite and arsenate. Good recoveries (97-108%) of spiked samples were found. Results are precise (RSD 7.5 and 6% for 0.5 and 2.5 mug l(-1), n=10) and in agreement with the certified value of reference material at 95% confidence level.

Determination of Mo, U and B in waters by electrothermal vaporization inductively coupled plasma mass spectrometry.

A method for the determination of Mo, U and B in waters by inductively coupled plasma mass spectrometry, using an electrothermal vaporizer for sample introduction, is described. For Mo and U, NH(4)F was chosen as modifier and for B, synthetic sea water plus mannitol were used. The modifier effect was verified and the optimized pyrolysis and vaporization temperatures were obtained from pyrolysis and vaporization curves, together with the transient signals of the analytes. The masses of the modifiers added to the tube were also optimized. The detection limits were 0.018 or 0.30 ng ml(-1) for Mo, 0.03 ng ml(-1) for U and 0.68 ng ml(-1) for B. The analytes were determined in certified waters and the obtained results agree with the certified or recommended values or, in the case of B in sea waters, with the values obtained by other methods. Uranium could not be measured in the sea water samples due to strong memory effect.