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Analysis of stable isotopes has been used as proof of provenance of mineral and biological samples, to estimate a contamination source and to determine geological processes. This kind of analysis needs high accuracy and precision for reliable conclusions. Currently, stable isotope analysis is dominated by mass spectrometric techniques that are time consuming and expensive. Here we present a fast and low cost alternative for isotope analysis of boron and magnesium: high-resolution continuum source graphite furnace molecular absorption spectrometry (HR-CS-GFMAS). Two stable isotope systems were evaluated separately: boron (10B:11B) and magnesium 24Mg:25Mg:26Mg). Their isotope amount ratios were estimated by monitoring their absorption spectra in-situ generated monohydrides. The molecular absorption spectrum of a XH molecule (X= B or Mg) with n isotopes would be a linear combination of n isotopologue spectra and the amount of each component (isotope) could be calculated by a multivariate regression (n= 2 and 3 for B and Mg respectively). For the Analysis of boron certified reference materials (CRM), the band 1→1 for the electronic transition X1Σ+ → A1Π was measured around wavelength 437.1 nm. Since boron has a Memory effect in graphite furnaces, a combination of 2 % (v/v) hydrogen gas in argon, 1 % trifluoromethane in argon, an acid solution of calcium chloride and mannitol as chemical modifiers were used during the BH vaporization at 2600 °C. Partial least square regression (PLS) for analysis of samples was applied. For this, a spectral library with different isotope ratios for PLS regression was created. Magnesium does not have memory effect. Therefore, only 2 % of hydrogen in argon as gas modifier during vaporization at 2500 °C was employed for analysis of magnesium CRM. Absorption spectra of MgH for the X2Σ→A2Π electronic transition (band 0→0) were recorded around wavelength 513.45 nm. A similar PLS procedure to the BH was applied. Results for B and Mg CRM are metrologically compatible with those reported by mass spectrometric methods. An accuracy of 0.08 ‰ for B and 0.1 ‰ Mg was obtained as the average deviation from the isotope CRM. Expanded uncertainties with a coverage factor of k = 2 range between 0.10 - 0.40 ‰.
Analysis of stable isotopes has been used as proof of provenance of mineral and biological samples, to estimate a contamination source and to determine geological processes. This kind of analysis needs high accuracy and precision for reliable conclusions. Currently, stable isotope analysis is dominated by mass spectrometric techniques that are time consuming and expensive. Here we present a fast and low cost alternative for isotope analysis of boron and magnesium: high-resolution continuum source graphite furnace molecular absorption spectrometry (HR-CS-GFMAS). Two stable isotope systems were evaluated separately: boron (10B:11B) and magnesium (24Mg:25Mg:26Mg). Their isotope amount ratios were estimated by monitoring their absorption spectra in-situ generated monohydrides. The molecular absorption spectrum of a XH molecule (X= B or Mg) with n isotopes would be a linear combination of n isotopologue spectra and the amount of each component (isotope) could be calculated by a multivariate regression (n= 2 and 3 for B and Mg respectively). For the analysis of boron certified reference materials (CRM), the band 1→1 for the electronic transition X1Σ+ → A1Π was measured around wavelength 437.1 nm. Since boron has a memory effect in graphite furnaces, a combination of 2 % (v/v) hydrogen gas in argon, 1 % trifluoromethane in argon, an acid solution of calcium chloride and mannitol as chemical modifiers were used during the BH vaporization at 2600 °C. Partial least square regression (PLS) for analysis of samples was applied. For this, a spectral library with different isotope ratios for PLS regression was created. Magnesium does not have memory effect. Therefore, only 2 % of hydrogen in argon as gas modifier during vaporization at 2500 °C was employed for analysis of magnesium CRM. Absorption spectra of MgH for the X2Σ→A2Π electronic transition (band 0→0) were recorded around wavelength 513.45 nm. A similar PLS procedure to the BH was applied. Results for B and Mg CRM are metrologically compatible with those reported by mass spectrometric methods. An accuracy of 0.08 ‰ for B and 0.1 ‰ Mg was obtained as the average deviation from the isotope CRM. Expanded uncertainties with a coverage factor of k = 2 range between 0.10 - 0.40 ‰.
Boron presents two stable isotopes, 10B and 11B and due to their relatively large mass difference (~ 10%) isotope fractionation leads to considerable isotope amount ratio variations n(10B)/n(11B) in natural occurrence. These have been used as a proof of provenance of mineral and biological samples, to estimate a contamination source and to the determination of geological processes by erosion or subduction. Additionally, boron is employed in the nuclear industry due to the capability of its isotope 10B to thermal-neutron capture and therefore 10B enriched boric acid solutions are used in the cooling system of thermonuclear facilities and in the alloying of steel and carbides for protective shielding. Usually, isotope ratio variations are determined by mass spectroscopic methods.
Here an alternative faster and low cost method for isotope ratio determination is proposed: high-resolution continuum source molecular absorption spectrometry (HR-CS-MAS). Boron isotope amount ratios have been determined by monitoring the absorption spectrum of boron monohydride (BH) in graphite furnace HR-CS-MAS. Bands (0→0) and (1→1) for the electronic transition X1Σ+ → A1Π were evaluated around wavelengths 433.1 nm and 437.1 nm respectively. Partial least square regression (PLS) for analysis of samples and reference materials were applied. For this, a spectral library with different isotopes ratios for PLS regression was built. Results obtained around the 433.1 nm and 437.1 nm spectral regions are metrologically compatible with those reported by mass spectrometric methods. Moreover, a precision and accuracy of the method of ± 0.5 ‰ for the evaluated spectral region around 437.1 nm is reported here. This accuracy and precision is comparable with those obtained by thermal ionization mass spectrometry (TIMS) and multiple collector inductively coupled plasma mass spectrometry (MC-ICP-MS) for boron isotope ratio measurements.
Boron presents two stable isotopes, 10B and 11B and due to their relatively large mass difference (~ 10%) isotope fractionation leads to considerable isotope amount ratio variations n(10B)/n(11B) in natural occurrence. These have been used as a proof of provenance of mineral and biological samples, to estimate a contamination source and to the determination of geological processes by erosion or subduction. Additionally, boron is employed in the nuclear industry due to the capability of its isotope 10B to thermal-neutron capture and therefore 10B enriched boric acid solutions are used in the cooling system of thermonuclear facilities and in the alloying of steel and carbides for protective shielding. Usually, isotope ratio variations are determined by mass spectroscopic methods.
Here an alternative faster and low cost method for isotope ratio determination is proposed: high-resolution continuum source molecular absorption spectrometry (HR-CS-MAS). Boron isotope amount ratios have been determined by monitoring the absorption spectrum of boron monohydride (BH) in graphite furnace HR-CS-MAS. Bands (0→0) and (1→1) for the electronic transition X1Σ+ → A1Π were evaluated around wavelengths 433.1 nm and 437.1 nm respectively. Partial least square regression (PLS) for analysis of samples and reference materials were applied. For this, a spectral library with different isotopes ratios for PLS regression was built. Results obtained around the 433.1 nm and 437.1 nm spectral regions are metrologically compatible with those reported by mass spectrometric methods. Moreover, a precision and accuracy of the method of ± 0.5 ‰ for the evaluated spectral region around 437.1 nm is reported here. This accuracy and precision is comparable with those obtained by thermal ionization mass spectrometry (TIMS) and multiple collector inductively coupled plasma mass spectrometry (MC-ICP-MS) for boron isotope ratio measurements.
Boron isotope amount ratios n(10B)/n(11B) have been determined by monitoring the absorption spectrum of boron monohydride (BH) in a graphite furnace using high-resolution continuum source molecular absorption spectrometry (HR-CS-MAS). Bands (0→0) and (1→1) for the electronic transition X1Σ+ → A1Π were evaluated around wavelengths 433.1 nm and 437.1 nm respectively. Clean and free of memory effect molecular spectra of BH were recorded. In order to eliminate the memory effect of boron, a combination of 2% (v/v) hydrogen gas in argon and 1% trifluoromethane in argon, an acid solution of calcium chloride and mannitol as chemical modifiers was used. Partial least square regression (PLS) for analysis of samples and reference materials were applied. For this, a spectral library with different isotopes ratios for PLS regression was built. Results obtained around the 433.1 nm and 437.1 nm spectral regions are metrologically compatible with those reported by mass spectrometric methods. Moreover, for the evaluated region of 437 nm, an accuracy of 0.15‰ is obtained as the average deviation from the isotope reference materials. Expanded uncertainties with a coverage factor of k = 2 range between 0.15 and 0.44‰. This accuracy and precision are compatible with those obtained by mass spectrometry for boron isotope ratio measurements.