Lead (Pb) exposure assessment in dried blood spots using Total Reflection X-Ray Fluorescence (TXRF).

Lead (Pb) exposure is often determined through the analysis of whole blood though venipuncture poses ethical, economic, and logistical barriers. Dried Blood Spots (DBS) may help overcome such barriers though past studies measuring Pb in DBS have been challenged with quality control, small sample volumes, and other issues. Total Reflection X-Ray Fluorescence (TXRF) may help address some of these challenges but has yet to be used to measure Pb in DBS. As such, the aim of the current study was to develop, validate, and apply a method to analyze Pb in DBS samples using TXRF for use in human biomonitoring studies. First, we developed a novel method (tested a range of parameters), and then used blood reference materials to validate the method against performance criteria listed in ICH Q2A and Q2B and the European Bioanalysis Forum. Finally, we applied the method to two populations who exemplify divergent conditions (41 university members with relatively low Pb exposures sampled in a clinical environment; 40 electronic waste workers with relatively high Pb exposures sampled in a contaminated field setting). The limits of detection and quantification of the method were 0.28 and 0.69 µg/dL, respectively. The overall precision and accuracy of the method were 15% and 111%, respectively. The mean (±SD) DBS Pb levels by TXRF in the university members and e-waste workers were 0.78 (±0.46) and 3.78 (±3.01) µg/dL, respectively, and these were not different from Pb measures in venous whole blood using ICP-MS. Bland-Altman plot analyses indicated good agreement between DBS Pb measures by TXRF versus whole blood Pb measures by ICP-MS in both groups. By combining data from the two population groups, there was no significant constant bias (intercept of 0.02 µg/dL) or proportional bias (slope was -0.02) between the two measures, and the lower and upper LoA were -0.86 and 0.91 µg/dL, respectively, with a LoA range of 1.77 µg/dL. These results demonstrate that TXRF-based analysis of Pb content in DBS is a good alternative to the gold standard (i.e., ICP-MS analysis of whole blood), and helps overcome some of the challenges associated with current methods.

Bioaccumulation of metal(loid)s in Cardisoma crassum and pollution assessment in a mangrove protected area in Mexico.

The bioaccumulation of several elements in "mouthless crabs" (Cardisoma crassum) and their concentrations in environmental samples were assessed in a mangrove forest within a natural protected area located in the middle of Puerto Vallarta, Mexico. The concentrations of Al, As, Ba, Cd, Cr, Cu, Fe, Ni, Pb, Sr, Si, V, and Zn in sediments, mangrove litterfall, and pore water and their bioaccumulations in the muscle and shell tissue of C. crassum were determined during rainy and dry seasons. Two different sampling sites were compared, selected according to the influence of the tide. The samples were analyzed by ICP-OES. In pore water, half of the elements of interest were below the limits of detection. Pb and Cd concentrations were only detected in the sedimentary phase. Al and Fe presented the highest concentrations at both sampling sites in the sediments and mangrove litterfall. There were no significant differences between sampling seasons in water samples (P > 0.05). Only Cu presented significant differences between sampling seasons in the mangrove litterfall samples and V in the sediment samples (P < 0.05). The sediment quality guidelines indicated that only Cd was above the threshold effect limit. As, Cd, Cr, Ni, and Pb remained below the limits of detection in muscle tissue and shell samples. The biota-sediment accumulation factors (BSAFs) determined for Cu and Zn were above 1.0, indicating the accumulation of these elements in the muscle tissue of C. crassum, while the BSAF values in the shell were above the threshold for Ba, Si, and Sr.