Speciation of inorganic arsenic in particulate matter by combining HPLC/ICP-MS and XANES analyses

Inorganic arsenic species in ambient particulate matter (PM10 and PM2.5) have been determined in an urban area, in the vicinity of a metallurgical industrial plant. The developed high performance liquid chromatography inductively coupled plasma mass spectrometry (HPLC/ICP-MS) method allows monitoring of particulate As(iii) and As(v)-species, with a limit of quantification of 0.34 ng m-3 As(iii) and 0.23 ng m-3 As(v), respectively. Good agreement was obtained between the sum of the concentrations of As(iii) and As(v) determined by HPLC/ICP-MS and the total As concentrations determined by XRF, indicating a complete extraction of the As species. During the measuring campaigns for PM10 and PM2.5, a significant conversion (oxidation) up to 54% of exogenous spiked As(iii) was observed. The total amount of the spiked As(iii) was well-recovered (PM10 and PM2.5 on average 108% and 101%, respectively). The extraction of the filter in combination with the sampled air matrix is likely to induce the As(iii) conversion. The average measured As concentration in PM10 during a 40-day monitoring campaign (30 ng m-3) at a hot spot location is above the European target value of 6 ng m-3. The measured As concentration in PM2.5 was half the value of the measured concentration in PM10 and no relative enrichment of total As was observed in either particulate matter fractions. However, in PM10, As(v) was the main component, while in PM2.5, As(iii) was the dominant species. During the monitoring campaign, the fraction of particulate As(iii) varied between 19 and 61% in PM10 and a trend towards a higher fraction of As(iii) with increasing concentration of total As was observed. XANES and XRD analyses were used for the identification of arsenic species in local PM sources and confirmed the presence of Ca3Sr2(AsO4)2.5(PO4)0.5(OH), As2O3 and As2O5 species

Speciation of inorganic arsenic in particulate matter by combining HPLC/ICP-MS and XANES analyses

Inorganic arsenic species in ambient particulate matter (PM10 and PM2.5) have been determined in an urban area, in the vicinity of a metallurgical industrial plant. The developed high performance liquid chromatography inductively coupled plasma mass spectrometry (HPLC/ICP-MS) method allows monitoring of particulate As(iii) and As(v)-species, with a limit of quantification of 0.34 ng m-3 As(iii) and 0.23 ng m-3 As(v), respectively. Good agreement was obtained between the sum of the concentrations of As(iii) and As(v) determined by HPLC/ICP-MS and the total As concentrations determined by XRF, indicating a complete extraction of the As species. During the measuring campaigns for PM10 and PM2.5, a significant conversion (oxidation) up to 54% of exogenous spiked As(iii) was observed. The total amount of the spiked As(iii) was well-recovered (PM10 and PM2.5 on average 108% and 101%, respectively). The extraction of the filter in combination with the sampled air matrix is likely to induce the As(iii) conversion. The average measured As concentration in PM10 during a 40-day monitoring campaign (30 ng m-3) at a hot spot location is above the European target value of 6 ng m-3. The measured As concentration in PM2.5 was half the value of the measured concentration in PM10 and no relative enrichment of total As was observed in either particulate matter fractions. However, in PM10, As(v) was the main component, while in PM2.5, As(iii) was the dominant species. During the monitoring campaign, the fraction of particulate As(iii) varied between 19 and 61% in PM10 and a trend towards a higher fraction of As(iii) with increasing concentration of total As was observed. XANES and XRD analyses were used for the identification of arsenic species in local PM sources and confirmed the presence of Ca3Sr2(AsO4)2.5(PO4)0.5(OH), As2O3 and As2O5 species

Three-dimensional Fe speciation of an inclusion cloud within an ultra-deep diamond by confocal μ\mu-XANES: evidence for late stage overprint

A stream of 1-20 μm sized mineral inclusions having the negative crystal shape of its host within an "ultra-deep" diamond from Rio Soriso (Juina area, Mato Grosso State, Brazil) has been studied with confocal μ-X-ray absorption near edge structure (μXANES) at the Fe K and Mn K edges. This technique allows the three-dimensional nondestructive speciation of the Fe and Mn containing minerals within the inclusion cloud. The observed Fe-rich inclusions were identified to be ferropericlase (Fe,Mg)O, hematite and a mixture of these two minerals. Confocal μ-X-ray fluorescence (μXRF) further showed that Ca-rich inclusions were present as well, which are spatially separated from or in close contact with the Fe-rich inclusions. The inclusions are aligned along a plane, which most likely represents a primary growth zone. In the close vicinity of the inclusions, carbon coated planar features are visible. The three-dimensional distribution indicates a likely fluid overprint along an open crack. Our results imply that an imposed negative diamond shape of an inclusion alone does not exclude epigenetic formation or intense late stage overprint