Trace elements distribution in tropical tree rings through high-resolution imaging using LA-ICP-MS analysis.

BACKGROUND: The distribution of trace elements in tree rings although poorly known may be useful to better understand environmental changes, pollution trends, long-term droughts, forest dieback processes, and biology of trees. METHOD: Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is used for imaging micronutrients and potentially toxic elements distribution, allowing the investigation of trace elements at high spatial resolution within the tree rings. To ensure a more efficient determination of micronutrients and potentially toxic elements, LA-ICP-MS instrumental conditions were optimized and carbon, a major element in wood, is used as an internal standard during analysis to correct for random fluctuations. RESULTS: Spatial distributions maps of Ba, Cu, Fe, Mn, Ni, and Pb in growth layers of six tropical tree species were built-up using the LA-iMageS software, namely: Amburana cearensis (Fabaceae), Cedrela fissilis (Meliaceae), Hymenaea courbaril (Fabaceae), Maclura tinctoria (Moraceae), Parapiptadenia zehntneri (Fabaceae), Peltogyne paniculata (Fabaceae). A correlation between the trace element composition and different cell types (parenchyma, fiber, and vessel) was distinctly observed. It was observed a general pattern of Ba, Cu, Ni, Mn, and Pb accumulation mainly in the axial parenchyma and vessels. But the elemental composition of xylem cells is strongly species dependent. The multivariate analysis also points to a distinct accumulation of minerals between heartwood and sapwood in the same species. CONCLUSIONS: Imaging both essential and deleterious element distributions in the tree rings may improve visualization and can effectively contribute to understanding the lifetime metabolism of trees and evaluating the effects of environmental changes related to climatic seasonality, pollution, and future paleoclimate reconstructions.

Determination of trace sulfur in biodiesel and diesel standard reference materials by isotope dilution sector field inductively coupled plasma mass spectrometry.

A method is described for quantification of sulfur at low concentrations on the order of mgkg(-1) in biodiesel and diesel fuels using isotope dilution and sector field inductively coupled plasma mass spectrometry (ID-SF-ICP-MS). Closed vessel microwave-assisted digestion was employed using a diluted nitric acid and hydrogen peroxide decomposition medium to reduce sample dilution volumes. Medium resolution mode was employed to eliminate isobaric interferences at (32)S and (34)S related to polyatomic phosphorus and oxygen species, and sulfur hydride species. The method outlined yielded respective limits of detection (LOD) and limits of quantification (LOQ) of 0.7 mg kg(-1) S and 2.5 mg kg(-1) S (in the sample). The LOD was constrained by instrument background counts at (32)S but was sufficient to facilitate value assignment of total S mass fraction in NIST SRM 2723b Sulfur in Diesel Fuel Oil at 9.06±0.13 mg kg(-1). No statistically significant difference at a 95% confidence level was observed between the measured and certified values for certified reference materials NIST SRM 2773 B100 Biodiesel (Animal-Based), CENAM DRM 272b and NIST SRM 2723a Sulfur in Diesel Fuel Oil, validating method accuracy.

Application of the interference standard method for the determination of sulfur, manganese and iron in foods by inductively coupled plasma mass spectrometry.

The interference standard method (IFS) is evaluated to improve the accuracy of the determination of S, Mn and Fe in meat and grain samples by inductively coupled plasma quadrupole mass spectrometry (ICP-QMS). Due to ICP-QMS relatively low resolution, polyatomic interferences caused by (16)O(2)(+), ((16)OH)(2)(+), (40)Ar(14)NH(+), and (40)Ar(16)O(+), for example, can compromise determinations at m/z 32, 34, 55, and 56, respectively. In IFS, differently from traditional internal standard methods, plasma naturally occurring species are used to correct for variations in the interference signal rather than the analyte signal. The method is based on the hypothesis that the interfering ion and the IFS probe present similar behaviors in the plasma, and that by using the analytical (analyte plus interference)/IFS signal ratio one could reduce variations due to interference and, consequently, improve accuracy. In this work, this strategy is evaluated in real sample applications and significant improvements on accuracy are observed for (32)S, (34)S, (55)Mn, and (56)Fe determinations. Recoveries ranging from 72% for Mn to 105% for Fe in two different standard reference materials are obtained using the (38)Ar probe. These analytes are successfully determined in meat and grain samples with concentrations ranging from 4.42 µg g(-1) for Mn in corn to 7270 µg g(-1) for S in chicken liver. The method is compared with other strategies such as internal standardization and mathematical correction. No instrumental modification or introduction of foreign gases is required, which is especially attractive for routine applications.

Determination of sulfur in biodiesel microemulsions using the summation of the intensities of multiple emission lines.

A method for the determination of sulfur in biodiesel samples by inductively coupled plasma optical emission spectrometry which uses microemulsion for sample preparation and the summation of the intensities of multiple emission lines has been developed. Microemulsions were prepared using 0.5 mL of 20% v/v HNO(3), 0.5 mL of Triton X-100, 2-3 mL of biodiesel sample, and diluted with n-propanol to a final volume of 10 mL. Summation of the emission intensities of multiple sulfur lines allowed for increased accuracy and sensitivity. The amounts of sulfur determined experimentally were between 2 and 7 mg L(-1), well below legislative standards for many countries. Recoveries obtained ranged from 72 to 119%, and recoveries obtained for the 182.562 nm line were slightly lower. This is most likely due to its lower sensitivity. Using microemulsion for sample preparation and the summation of the intensities of multiple emission lines for the successful determination of sulfur in biodiesel has been demonstrated.