Effects of ammonium fluoride on the decomposition of geochemical samples as fluorinating agent and its analytical application.
In this work, the effects of ammonium fluoride on the decomposition of geochemical samples were investigated by analyzing some certified reference materials (CRM). The major and minor elements were detected by inductively coupled plasma optical emission spectrometry (ICP-OES), while trace and ultra-trace elements were analyzed by inductively coupled plasma mass spectrometry (ICP-MS). Decomposition time, temperature and the amount of ammonium fluoride were studied in detail. In the process of sample decomposition, on one hand, ammonium fluoride was used as the fluorinating agent because ammonium fluoride can be dissociated under acid medium to yield fluoride ions to attack silicon compound effectively. On the other hand, ammonium fluoride was used as a latent solvent since ammonium salt may dissolve insoluble fluorine compounds. The removal of insoluble fluorine compounds decreased the memory effect on digestion vessels caused by fluoride coprecipitation. By testing CRMs and many real samples, it was found that trace and ultra-trace elements could be digested using ammonium fluoride instead of hydrofluoric acid and the dissolution ratios of major and minor elements, for example Al, Ca, Mg, Fe, Na and K, improved noticeably. Moreover, the use of ammonium fluoride instead of hydrofluoric acid contributes to a greener environment and safer for operators.
Hydrofluoride decomposition of natural materials including zirconium-containing minerals
Recently, interest in ammonium hydrogen difluoride (NH4HF2) as a versatile fluorinating agent for the decomposition of natural materials resumed. It is considered to be a new and more efficient than hydrofluoric acid (HF) reagent in analytical chemistry. Thermodynamically possible fluorination reactions with NH4HF2 are exothermic and proceed even at room temperature with the entropy reserve. The fluorination products are of high symmetry phases (tetragonal or cubic) with partial substitution of fluoride ion for oxide (or hydroxide). The fluorination of refractory silicate zircon (ZrSiO4) is kinetically hindered, and its complete decomposition requires the use of a Teflon autoclave at 200oC. The fluorination products are cubic (NH4)3Zr(OH)xF7-x (x ≤ 0.3) and tetragonal double salt (NH4)3SiF7, which can be separated due to incongruent sublimation of (NH4)2SiF6. The mechanism of the latter process is proposed.
Two new organic reference materials for delta13C and delta15N measurements and a new value for the delta13C of NBS 22 oil.
Analytical grade L-glutamic acid is chemically stable and has a C/N mole ratio of 5, which is close to that of many of natural biological materials, such as blood and animal tissue. Two L-glutamic acid reference materials with substantially different 13C and 15N abundances have been prepared for use as organic reference materials for C and N isotopic measurements. USGS40 is analytical grade L-glutamic acid and has a delta13C value of -26.24 per thousand relative to VPDB and a delta15N value of -4.52 per thousand relative to N2 in air. USGS41 was prepared by dissolving analytical grade L-glutamic acid with L-glutamic acid enriched in 13C and 15N. USGS41 has a delta13C value of +37.76 per thousand and a delta15N value of +47.57 per thousand. The delta13C and delta15N values of both materials were measured against the international reference materials NBS 19 calcium carbonate (delta13C=+1.95 per thousand ), L-SVEC lithium carbonate (delta13C=-46.48 per thousand ), IAEA-N-1 ammonium sulfate (delta15N=0.43 per thousand ), and USGS32 potassium nitrate (delta15N=180 per thousand ) by on-line combustion continuous-flow and off-line dual-inlet isotope-ratio mass spectrometry. Both USGS40 and USGS41 are isotopically homogeneous; reproducibility of delta13C is better than 0.13 per thousand, and that of delta15N is better than 0.13 per thousand in 100-microg amounts. These two isotopic reference materials can be used for (i) calibrating local laboratory reference materials, and (ii) quantifying drift with time, mass-dependent fractionations, and isotope-ratio-scale contraction in the isotopic analysis of various biological materials. Isotopic results presented in this paper yield a delta13C value for NBS 22 oil of -29.91 per thousand, in contrast to the commonly accepted value of -29.78 per thousand for which off-line blank corrections probably have not been quantified satisfactorily.