Raman spectroscopy coupled to high-resolution continuum source flame molecular absorption spectrometry for sequential determination of nitrogen species in fertilizers.

Raman spectroscopy (RS) was used to identify and quantify different nitrogen species in fertilizers. This is a fast and inexpensive method that requires no extensive sample preparation. Urea and nitrate were determined at 1000 and 1045 cm-1, respectively. Calibration plots obtained for these analytes showed adequate linearity, with regression coefficients (r) of 0.9989 and 0.9976, respectively. Ammonium was determined by difference after total N determination by high-resolution continuum source flame molecular absorption spectrometry (HR-CS FMAS), which provided a calibration plot with r = 0.9960. The inline coupling of RS and HR-CS FMAS allowed for a fast sequential determination of ammonium, nitrate, and urea, with limits of detection of 0.03 mg/L ammonium, 0.03 mg/L nitrate, and 0.01 mg/L urea. Relative standard deviations were ≤ 11 %, and the external standard calibration method provided accurate results for all analytes determined in certified reference materials, raw materials, and commercial samples of fertilizers. For comparison purposes, all samples were also analyzed by traditional Kjeldahl method. The RS HR-CS FMAS method was further validated by addition and recovery experiments, which provided recoveries in the 93 - 113 % range.

Simultaneous determination of phosphite and phosphate in fertilizers by Raman spectroscopy.

Raman spectroscopy is emerging and powerful technique for identifying oxyanions of phosphorus, but it still is not straightforward applied to identify and quantify simultaneously phosphite and phosphate species in solution. Herein, simultaneous determination of phosphate (PO4) and phosphite (PO3) in fertilizer were evaluated by Raman spectroscopy. The influence of pH on Raman spectra of species was evaluated at various solution pH values, and the results showed accurate and selective analysis for phosphate and phosphite by using pH = 10.0 and bands located at 874 cm-1 and 2321 cm-1, respectively. Linear working range in the 0.15%-6.20% (w/v) P concentration was consistently obtained with regression coefficients (r) of 0.9953 (PO4) and 0.9945 (PO3). The limits of detection were 0.10% (w/v) P (PO4) and 0.05% (w/v) P (PO3). Relative standard deviations were lower than 6% for samples containing 10% P2O5 (PO4) and 31% P2O5 (PO3). Commercial fertilizers were analyzed by the proposed method using external calibration and found concentrations of P were in agreement with those obtained by the comparative spectrophotometric method at the 95% confidence level (paired t-test). Recoveries of spiked samples were in the 92-110% range.

Bismuth as a general internal standard for lead in atomic absorption spectrometry.

Bismuth was evaluated as internal standard for Pb determination by line source flame atomic absorption spectrometry (LS FAAS), high-resolution continuum source flame atomic absorption spectrometry (HR-CS FAAS) and line source graphite furnace atomic absorption spectrometry (LS GFAAS). Analysis of samples containing different matrices indicated close relationship between Pb and Bi absorbances. Correlation coefficients of calibration curves built up by plotting A(Pb)/A(Bi)versus Pb concentration were higher than 0.9953 (FAAS) and higher than 0.9993 (GFAAS). Recoveries of Pb improved from 52-118% (without IS) to 97-109% (IS, LS FAAS); 74-231% (without IS) to 96-109% (IS, HR-CS FAAS); and 36-125% (without IS) to 96-110% (IS, LS GFAAS). The relative standard deviations (n=12) were reduced from 0.6-9.2% (without IS) to 0.3-4.3% (IS, LS FAAS); 0.7-7.7% (without IS) to 0.1-4.0% (IS, HR-CS FAAS); and 2.1-13% (without IS) to 0.4-5.9% (IS, LS GFAAS).

Multiple response optimization of laser-induced breakdown spectroscopy parameters for multi-element analysis of soil samples.

Laser-induced breakdown spectroscopy (LIBS) is an emerging analytical technique to perform elemental analysis in natural samples independent of their physical state (solid, liquid, or gaseous). Due to its instrumental features, LIBS shows promising potential to perform analysis in situ and in environments at risk. Since the analytical performance of LIBS strongly depends on the choice of experimental conditions, each particular application needs a specific instrumental adjustment. The present study evaluated three LIBS instrumental parameters regarding their influences on signal-to-noise ratio (SNR) of seven elements in soil samples: laser pulse energy, delay time, and integration time gate. A multivariate technique was used due to the significant interaction among the evaluated parameters. Subsequently, to optimize LIBS parameters for each individual element response, a method for multiple response optimization was used. With only one simple screening design, it was possible to obtain a good combination among the studied parameters in order to simultaneously increase the SNR for all analytes. Moreover, the analysis of individual response for elements is helpful to understand their physical behavior in the plasma and also how they are embedded in the sample matrix.