General Applicability of High-Resolution Continuum-Source Graphite Furnace Molecular Absorption Spectrometry to the Quantification of Oligopeptides Using the Example of Glutathione

This communication introduces the first-time application of high-resolution continuum-source molecular absorption spectrometry (HR CS MAS) for the quantification of a peptide. The graphite furnace technique was employed and the tripeptide glutathione (GSH) served as a model compound. Based on measuring sulfur in terms of carbon monosulfide (CS), a method was elaborated to analyze aqueous solutions of GSH. The most prominent wavelength of the CS molecule occurred at 258.0560 nm and was adduced for monitoring. The methodological development covered the optimization of the pyrolysis and vaporization temperatures. These were found optimally to be 250 °C and 2250 °C, respectively. Moreover, the effect of modifiers (zirconium, calcium, magnesium, palladium) on the absorption signals was investigated. The best results were obtained after permanent coating of the graphite tube with zirconium (total amount of 400 μg) and adding a combination of palladium (10 µL, 10 g L−1) and calcium (2 µL, 1 g L−1) as a chemical modifier to the probes (10 µL). Aqueous standard samples of GSH were used for the calibration. It showed a linear range of 2.5–100 µg mL−1 sulfur contained in GSH with a correlation coefficient R2 > 0.997. The developed method exhibited a limit of detection (LOD) and quantification (LOQ) of 2.1 µg mL−1 and 4.3 µg mL−1 sulfur, respectively. The characteristic mass accounted for 5.9 ng sulfur. The method confirmed the general suitability of MAS for the analysis of an oligopeptide. Thus, this study serves as groundwork for further development in order to extend the application of classical atomic absorption spectrometry (AAS).

Occurrence of the heavy metals and PCBs in Accumulation Lake Modrac

The accumulation Lake Modrac is a particularly important source of drinking water for inhabitants of the Tuzla region and few local settlements. The most significant point sources of organic contaminants in the accumulation Lake Modrac are waste water from households and industry. In this area, most of the settlements have neither sewage systems nor facilities for waste water treatment. Other potential point sources of pollutants are industrial plants. The most prominent are coal mines (Banovići and Đurđevik), metal and wood industry, plant for plastic production, and oil and oil derivatives warehouse. Few previously conducted surveys in the region showed the presence of the persistent organic pollutants and heavy metals in large extent. The objective of this study was to conduct a water quality survey targeting selected inorganic (Cd, Cr, Cu, Hg, Ni, Pb and As) and organic pollutants in the accumulation Lake Modrac in Bosnia and Herzegovina. The content of polychlorinated biphenyls (PCBs) determined with ELISA test, ranging from 3.23 to 6.19 µg/L (sum of 7PCBs).The most abundant metals (analyzed by graphite furnace AAS and mercury analyzer) at all five sampling locations were Pb (6.79-36.58 µg/L); Ni (5.81-10.43 µg/L) and Hg (1.08-6.10 µg/L).

Analytical Performance and Validation of a Reliable Method Based on Graphite Furnace Atomic Absorption Spectrometry for the Determination of Gold Nanoparticles in Biological Tissues

Gold nanoparticles (AuNPs) have a wide-ranging application and are widespread in samples with complex matrices; thus, efficient analytical procedures are necessary to identify and characterize this analyte. A sensitive analytical method for determination of AuNPs content in biological tissues, based on microwave-assisted acid wet digestion and graphite furnace atomic absorption spectrometry (GFAAS) validated in accordance with the requirements of Eurachem guideline and ISO 17025 standard, is presented in this study. The digestion procedure was optimized, and the figures of merit such as selectivity, limit of detection (0.43 µg L−1), limit of quantification (1.29 µg L−1, corresponding to 12.9 µg kg−1 in tissue sample, considering the digestion), working range, linearity, repeatability ((RSDr 4.15%), intermediate precision (RSDR 8.07%), recovery in accuracy study (97%), were methodically evaluated. The measurement uncertainty was assessed considering the main sources of uncertainties and the calculated relative expanded uncertainty (k = 2) was 12.5%. The method was applied for the determination of AuNPs in six biological tissues (liver, small intestine, heart, lungs, brain and kidneys) and the found concentrations were generally at low levels, close or lower than LOQ.

Mantle wedge oxidation due to sediment-infiltrated deserpentinisation

The Earth's mantle is oxygen-breathing through the ¬sink of oxidised tectonic plates at convergent margins. Ocean floor serpentinisation increases the bulk oxidation state of iron relative to dry oceanic mantle and results in a variable intake of other redox-sensitive elements such as sulphur. The reversibility of seafloor oxidation in subduction zones during high-pressure dehydration of serpentinite (“deserpentinisation”) at subarc depths and the capacity of the resulting fluids to oxidise the mantle source of arc basalts are highly contested. Thermodynamic modelling, experiments, and metaperidotite study in exhumed high-pressure terrains result in differing estimates of the redox state of deserpentinisation fluids, ranging from low to highly oxidant. Here we show that although intrinsic deserpentinisation fluids are highly oxidant, the infiltration of small fractions of external fluids equilibrated with metasedimentary rocks strongly modulates their redox state and oxidation-reduction capacity explaining the observed discrepancies in their redox state. Infiltration of fluids equilibrated with graphite-bearing sediments reduces the oxidant, intrinsic deserpentinisation fluids to oxygen fugacities similar to those observed in most graphite-furnace experiments and natural metaperidotites. However, infiltration of CO2-bearing fluids equilibrated with modern GLOSS generates sulphate-rich, highly oxidising deserpentinisation fluids. We show that such GLOSS-infiltrated deserpentinisation fluids can effectively oxidise the mantle wedge of cold to hot subduction zones potentially accounting for the presumed oxidised nature of the source of arc basalts.

Effect of occupational co-exposure to lead and cadmium on selected immunomodulatory cytokines

Occupational exposure to heavy metals like lead (Pb) and cadmium (Cd) is associated with the development of several diseases. The objective of this study was to determine the effect of occupational co-exposure to Pb and Cd on the blood levels of selected immune-modulatory cytokines related to T helper (Th), that is, Th1, interleukin-2 (IL-2), Th2, (IL-4 and IL-10), and Th17, (IL-17) cells. The study comprised 207 individuals divided into two groups: exposed ( n = 110) and nonexposed ( n = 97). Blood Pb and Cd were determined using Graphite Furnace Atomic Absorption Spectroscopy, and serum levels of cytokines were measured using enzyme-linked immunosorbent assay (ELISA). The study revealed significantly higher blood Pb and Cd levels in the exposed group. A significant decrease in Th1 cytokine-IL-2 and Th2 cytokine-IL-10 was found, while IL-4 (Th2 cytokine) and IL-17 (Th17) levels were higher in the exposed group. In the mixed exposure analysis, among all the selected cytokines, IL-4 levels were significantly different between individuals having higher levels of both Pb and Cd versus lower levels of Pb and Cd. While IL-2 levels were highest among the low Pb and Cd group, the IL-17 levels were highest among individuals with higher Cd levels. The study demonstrated that co-exposure to low levels of Pb and Cd might have an immune-modulatory effect. The data suggested a metal-induced pro-inflammatory immune response.