Bioimaging of metals and biomolecules in mouse heart by laser ablation inductively coupled plasma mass spectrometry and secondary ion mass spectrometry.

Bioimaging mass spectrometric techniques allow direct mapping of metal and biomolecule distributions with high spatial resolution in biological tissue. In this study laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) was used for imaging of transition metals (Fe, Cu, Zn, Mn, and Ti), alkali and alkaline-earth metals (Na, K, Mg, and Ca, respectively), and selected nonmetals (such as C, P, and S) in native cryosections of mouse heart. The metal and nonmetal images clearly illustrated the shape and the anatomy of the samples. Zinc and copper were inhomogeneously distributed with average concentrations of 26 and 11 µg g(-1), respectively. Titanium and manganese were detected at concentrations reaching 1 and 2 µg g(-1), respectively. The highest regional metal concentration of 360 µg g(-1)was observed for iron in blood present in the lumen of the aorta. Secondary ion mass spectrometry (SIMS) as an elemental and biomolecular mass spectrometric technique was employed for imaging of Na, K, and selected biomolecules (e.g., phosphocholine, choline, cholesterol) in adjacent sections. Here, two different bioimaging techniques, LA-ICPMS and SIMS, were combined for the first time, yielding novel information on both elemental and biomolecular distributions.

Chromium speciation in mildly heated Cr(VI)-doped latosol soil.

Cr(VI) chemical reduction in natural organic matter (NOM)-bearing latosol soil was investigated under various heating conditions at < or = 378 K. An enhanced Cr(VI) reduction rate has been observed for the reaction at 353-378 K. The effect of Fe(II) naturally occurring in the latosol soil on Cr(VI) chemical reduction is negligible compared with the effect of NOM. Cr(OH)(3) was quantitatively specified by X-ray absorption spectroscopy to be the key chromium species ( approximately 80%) after approximately 90% of Cr(VI) was chemically reduced by NOM at 353-378 K. This study indicates a potential strategy for using the heat extracted from industrial flue gas with a heat exchanger to chemically reduce Cr(VI) in NOM-bearing or organics-amended soils that contain Cr(VI).

Effect of humic substance on thermal treatment of chromium(VI)-containing latosol soil.

Latosol soils contaminated with chromium(VI) [Cr(VI)], which is hazardous, can be recycled as raw materials for porcelain and construction sectors if a proper thermal stabilization process is implemented. This study investigates how thermal treatment affects Cr behavior during the sintering of latosol and deorganic latosol samples; both samples are artificially contaminated with CrO3. Approaches including X-ray absorption spectroscopy, scanning electron microscopy, N2-based Brunauer Emmett Teller surface analyzer, thermogravimetric analyzer/differential scanning calorimeter, and the toxicity characteristic leaching procedure promulgated by Taiwan Environmental Protection Administration are used in this study. After drying the Cr(VI)-contaminated latosol (i.e., containing 37,120 mg of Cr/kg sample) at 105 degrees C, approximately 80% of the doped CrO3 is chemically reduced to Cr(OH)3 by a humic substance naturally existing in the soil. In contrast, in the organics-free CrO3-contaminated latosol dried at 105 degrees C, only 9% of the doped CrO3 is reduced to Cr(OH)3. Heating the samples at 500 and 1100 degrees C transforms hazardous Cr(VI) into Cr(III) that is negligibly toxic; Cr2O3, which is insoluble, is detected as the most abundant Cr species. Moreover, formation of Cr2SiOs, which is suggested to relate to low Cr leaching, is only detected in the sample heated at 1100 degrees C. Surface morphology, surface area, and thermogravimetric analyzer/differential scanning calorimeter results demonstrate that thermal treatment at 1100 degrees C can incur considerable soil sintering/ melting if the humic substance in the soil has been heated off previously. Finally, Cr concentrations in the toxicity characteristic leaching procedure leachates collected from the samples thermally treated at 1100 degrees C for 4 hr are < or =0.21 mg of Cr L(-1) that are much less than the Taiwan Environmental Protection Administration regulatory limit (<5 mg of Cr L(-1)); consequently, these two samples are nonhazardous, and they have the potential for resource recycling. Conversely, Cr concentrations in the leachates from all 500 degrees C and 105 degrees C samples are in the 25.6-1279 mg L(-1) range.

XANES study of Cr sorbed by a kitchen waste compost from water.

A kitchen waste compost was used to sorb Cr for various times from water containing either Cr(NO3)3 or CrO3 in different concentrations. Scanning electron microscopy (SEM) results show that the composts have been partially oxidized by Cr(VI) during the sorption experiments. X-ray absorption near edge structure (XANES) simulation suggests that about 54.1-61.0% Cr sorbed on the compost is in form of organic Cr(III) through ionic exchange process with the rest being existent as Cr(NO3)3 in the Cr(III) sorption case; no Cr(OH)3 is observed or expected because the solution pH after sorption experiments is or= 5.94. Moreover, organic Cr(III) represents about 51.7-69.0% of the total sorbed Cr, and the rest (6.1-28.5%) is Cr(VI).

A magnesium hydroxide preconcentration/matrix reduction method for the analysis of rare earth elements in water samples using laser ablation inductively coupled plasma mass spectrometry.

This paper describes a simple method for simultaneous preconcentration and matrix reduction during the analysis of rare earth elements (REEs) in water samples through laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). From a systematic investigation of the co-precipitation of REEs using magnesium hydroxide, we optimized the effects of several parameters - the pH, the amount of magnesium, the shaking time, the efficiency of Ba removal, and the sample matrix - to ensure quantitative recoveries. We employed repetitive laser ablation to remove the dried-droplet samples from the filter medium and introduce them into the ICP-MS system for determinations of REEs. The enrichment factors ranged from 8 to 88. The detection limit, at an enrichment factor of 32, ranged from 0.03 to 0.20 pg mL(-1). The relative standard deviations for the determination of REEs at a concentration of 1 ng mL(-1) when processing 40 mL sample solution were 2.0-4.8%. We applied this method to the satisfactory determination of REEs in lake water and synthetic seawater samples.

Using dried-droplet laser ablation inductively coupled plasma mass spectrometry to quantify multiple elements in whole blood.

This paper describes a simple procedure for the direct analysis and determination of multiple elements in dried blood samples on a filter membrane using laser ablation coupled with inductively coupled plasma mass spectrometry (LA-ICP-MS). With this technique, we simultaneously quantified 13 elements in whole blood: Be, Mn, Co, Ni, Tl, Bi, Sb, Pb, Cu, Zn, Ba, Mg, and Cd. The measured accuracies was in agreement with the Seronorm CRM certified values, except for Mn, Zn, Ba and Cd, which presented absolute differences higher than the expanded uncertainty for these elements. The within-run precision was less than 5.7% (relative standard deviation, RSD), except for the analyses of Be, and Mn (8.6% and 11.1%, respectively). The reproducibility (between-run precision) was calculated in terms of the RSD obtained for 12 analyses (i.e., four replicates of each sample in three analytical runs). Apart from Be, Mn, and Zn, the reproducibilities of all the elements listed above ranged between 4.0% and 8.5%. In contrast, for Cd, the concentration obtained was significantly different from the certified value; analyses of this element exhibited low reproducibility. Applying the matrix-matched calibration method, the accuracy for Cd measured was in agreement with both SRM966 and BCR 635; thus, matrix-matched calibration is a practical means of overcoming matrix-enhancement effects for the quantification of Cd. Sample throughput (ca. 5 min per sample) made it possible to rapidly screen a larger number of samples relative to other techniques that require time-consuming sample preparation steps (e.g., removal of a portion of the solid sample or digestion).

Lead determination in whole blood by laser ablation coupled with inductively coupled plasma mass spectrometry.

This work describes a simple procedure for blood lead level determination. The proposed method requires little sample pretreatment and subsequent direct analysis of a dried blood spot on a filter membrane using laser ablation coupled with inductively coupled plasma mass spectrometry (LA-ICP-MS). In general, LA-ICP-MS studies are somewhat limited by the lack of matrix-matched standards for calibration purposes. Here we describe aqueous standard calibration and matrix-matched calibration methods. This method was validated by analysis of the reference materials. With the matrix-matched calibration method, the recovery ranged from 97.8% to 112.8%, while the aqueous standard calibration method ranged 90.4% to 122.4%. The lower detection limit was estimated as 0.1 ng mL(-1). The determination precision, expressed as the relative standard deviation (RSD), was not worse than 10% for all results. A sample throughput of approximately 5 min per sample made it possible to rapidly screen a large number of samples.