Environmental exposure to manganese and health risk assessment from personal sampling near an industrial source of airborne manganese.

Manganese (Mn), despite being a trace element necessary in small quantities for the correct functioning of the organism, at higher concentrations can induce health disorders, mainly in motor and cognitive functions, even at levels found in non-occupational environments. For this reason, US EPA guidelines define safe reference doses/concentrations (RfD/RfC) for health. In this study, the individualised health risk of exposure to Mn through different media (air, diet, soil) and routes of entry into the organism (inhalation, ingestion and dermal absorption) was assessed according to the procedure defined by the US EPA. Calculations related to Mn present in ambient air were made on the basis of data obtained from size-segregated particulate matter (PM) personal samplers carried by volunteers recruited in a cross-sectional study conducted in the Santander Bay (northern Spain), where an industrial source of airborne Mn is located. Individuals residing in the vicinity of the main Mn source (within 1.5 km) were found to have a hazard index (HI) higher than 1, indicating that there is a potential risk for these subjects to develop health alterations. Also, people living in Santander, the capital of the region, located 7-10 km from the Mn source, may have some risk (HI > 1) under some wind conditions (SW). In addition, a preliminary study of media and routes of entry into the body confirmed that inhalation of PM2.5-bound Mn is the most important route contributing to the overall non-carcinogenic health risk related to environmental Mn.

Short- and long-term exposure to trace metal(loid)s from the production of ferromanganese alloys by personal sampling and biomarkers.

The environmental exposure to trace metal(loid)s (As, Cd, Cu, Fe, Mn, Pb, and Zn) was assessed near a ferromanganese alloy plant using filters from personal particulate matter (PM) samplers (bioaccessible and non-bioaccessible fine and coarse fractions) and whole blood as short-term exposure markers, and scalp hair and fingernails as long-term biomarkers, collected from volunteers (n = 130) living in Santander Bay (northern Spain). Bioaccessible and non-bioaccessible metal(loid) concentrations in coarse and fine PM from personal samplers were determined by ICP-MS after extraction/digestion. Metal(loid) concentration in biomarkers was measured after alkaline dilution (whole blood) and acid digestion (fingernails and scalp hair) by ICP-MS as well. Results were discussed in terms of exposure, considering the distance to the main Mn source, and sex. In terms of exposure, significant differences were found for Mn in all the studied fractions of PM, As in whole blood, Mn and Cu in scalp hair and Mn and Pb in fingernails, with all concentrations being higher for those living closer to the Mn source, with the exception of Cu in scalp hair. Furthermore, the analysis of the correlation between Mn levels in the studied biomarkers and the wind-weighted distance to the main source of Mn allows us to conclude that scalp hair and mainly fingernails are appropriate biomarkers of long-term airborne Mn exposure. This was also confirmed by the significant positive correlations between scalp hair Mn and bioaccessible Mn in coarse and fine fractions, and between fingernails Mn and all PM fractions. This implies that people living closer to a ferromanganese alloy plant are exposed to higher levels of airborne metal(loid)s, mainly Mn, leading to higher levels of this metal in scalp hair and fingernails, which according to the literature, might affect some neurological outcomes. According to sex, significant differences were observed for Fe, Cu and Pb in whole blood, with higher concentrations of Fe and Pb in males, and higher levels of Cu in females; and for Mn, Cu, Zn, Cd and Pb in scalp hair, with higher concentrations in males for all metal(loid)s except Cu.

Understanding how methodological aspects affect the release of trace metal(loid)s from urban dust in inhalation bioaccessibility tests.

The bioaccessibility of metal(loid)s in ambient particulate matter (PM) has been recently used to represent the risk of inhalation exposure. Nevertheless, different methodological factors affect the bioaccessibility values; among these, the type and composition of surrogate biological fluids and the liquid to solid ratio have been revealed to be the most important. To better understand how these methodological aspects affect the bioaccessibility, a reference material corresponding to urban dust (SRM1648a) was contacted with synthetic biological fluids commonly used in the literature representing surrogate fluids that may interact with fine (Gamble's solutions, artificial lysosomal fluid (ALF)) and coarse particles (gastric fluid), for liquid to solid (L/S) ratios ranging from 500 to 20,000. Visual MINTEQ 3.1. was used to enhance the discussion on how the solubility of metals in the leaching solution depends on the composition of the simulated fluids and the speciation of metals. The results obtained indicate that a small change in the composition of Gamble's solution (the presence of glycine) may increase significantly the bioaccessibility at a L/S ratio of 5,000. The highest bioaccessibility of most of the studied metal(loid)s at a L/S ratio of 5,000 was found for ALF fluid. The study of the effect of the L/S ratio showed that metal(loid)s bioaccessibility in Gamble's fluid increased logarithmically with increasing L/S ratio, while it remained practically constant in ALF and gastric fluid. This different behavior is explained assuming that the leaching of metal(loid)s in Gamble's solution is solubility-controlled, while in ALF and gastric fluid is availability-controlled.

Head-space gas chromatography coupled to mass spectrometry for the assessment of the contamination of mayonnaise by yeasts.

Head-space (HS) gas chromatography (GC) coupled to mass spectrometry (MS) is proposed for the assessment of the contamination of mayonnaise as an alternative to plate counting, which is the technique commonly used for evaluating microbial contamination. More specifically, this method was applied in the detection of Candida metapsilosis and Zygosaccharomyces bailii, both of great importance in term of food spoilage since they are resistant to many of the common methods of food preservation. Different chemometric models were investigated using the data obtained by GC-MS (m/z profile, area of the chromatographic peaks and entire chromatographic profile), in order to obtain the highest classification success. The best results were obtained using the chromatographic profile (success rate of 92%). Contaminated samples could also be classified according to the concentration of yeast, obtaining a success rate of 87.5%. Finally, a chemometric model was constructed in an attempt to differentiate between strains.

Effect of ion polarization on longitudinal excitations in ionic melts.

A simplified model for a collective dynamics in ionic melts is proposed for the description of optic-like excitations. Within a polarization model of ionic melt, the analytical expressions for optic and relaxation dipole modes are obtained. The considered model allows one to describe a softening of frequency and an increase of damping of optic modes caused by polarization processes in comparison with the rigid-ion model. The contributions related with ion polarization to time correlation functions are calculated.

Statistical description of hydrodynamic processes in ionic melts while taking into account polarization effects.

A statistical description of hydrodynamic processes for molten salts is proposed taking into account polarization effects caused by the deformation of external ionic shells. This description is conducted by means of the Zubarev nonequilibrium statistical operator method, appropriate for researches of both strong and weak nonequilibrium processes. The nonequilibrium statistical operator and the generalized hydrodynamic equations that take into account the polarization processes are acquired for the ion-polarization model of ionic molten salts when the nonequilibrium averaged values of densities of ions number, their momentum, dipole momentum, and total energy are chosen for the reduced description parameters. A spectrum of collective excitations is investigated within the viscoelastic approximation for the ion-polarization model of ionic melts.

Relaxation to the state of molecular hydrodynamics in the generalized hydrodynamics of liquids.

The problem of relaxation of a nonequilibrium state to the state of molecular hydrodynamics is considered for a classical system of interacting particles using the Zubarev nonequilibrium statistical operator method. The wave-vector and frequency dependencies of the dynamical structure factor and momentum-momentum transverse correlation function are investigated on the basis of the appropriate generalized transport equations. Comparison with the results of molecular hydrodynamics and molecular-dynamics simulations is given and the characteristic time intervals of the studied relaxation processes are determined.