Biomonitoring of trace elements is of critical importance in human health assessment. However, trace element concentrations in biological fluids are affected by environmental and physiological parameters, and therefore considerable variations can occur between specific population subgroups. Brazil is a large country with large environmental diversity and with a limited knowledge of the reference values (baseline data) for trace elements in biological fluids. Atomic absorption spectrometry (AAS) and inductively coupled plasma emission spectrometry (ICP-OES) are still the dominant analytical techniques used for biomonitoring trace element analysis in clinical specimens. However, the use of ICP-MS is becoming more usual in clinical laboratory analysis. Then, we evaluated here a simple dilute-and-shoot method for sequential determination of Al, Ba, Be, Cd, Co, Cu, Cs, Mn, Ni, Pb, Pt, Sb, Se, Sn, Tl and U in urine by quadrupole inductively coupled plasma mass spectrometry (q-ICP-MS). Urine samples (500 µL) were accurately pipetted into conical tubes (15 mL) and diluted to 10 mL with a solution containing 0.5 % (v/v) HNO3 + 0.005% (v/v) Triton X-100. Diluted urine samples also contain rhodium, iridium and yttrium added as internal standards. After that, samples were directly analyzed by ICP-MS against matrix-matching calibration. Method detection limit (3s, n = 20) were in the ng L-1 range for all analytes. The method was applied to the analysis of 412 ordinary urine samples from Brazilian healthy and non-exposed subjects to establish reference values. Data validation was provided by the analysis of the standard reference material (SRM) 2670a toxic elements in urine (freeze-dried) (high and low levels) from the National Institute of Standards and Technology (NIST) and reference urine samples from the trace elements intercomparison program operated by the Institut National de Sante' Publique du Quebec, Canada.

A simple and fast method for the determination of Ca, Cu, Fe, Mg, Mn, Se and Zn in bovine semen by quadrupole inductively coupled plasma spectrometry (q-ICP-MS) is described. Prior to analysis, samples (200 µL) were diluted 1:50 in a solution containing 0.01% v/v Triton® X-100 and 0.5% v/v nitric acid and directly analyzed by ICP-MS. The limits of detection of the method are 0.3, 0.03, 0.2, 0.04, 0.04, 0.03 and 0.03 µg L-1 for 44Ca, 63Cu, 57Fe, 24Mg, 64Zn, 82Se and 55Mn, respectively. For purposes of comparison and method validation, four ordinary bovine semen samples were directly analyzed by ICP-MS and by flame atomic absorption spectrometry (FAAS) or graphite furnace atomic absorption spectrometry (GF AAS), with no statistical difference between the techniques at the 95% level when applying the t-test. Then, the proposed method was applied in the determinations of Ca, Cu, Fe, Mg, Mn, Se and Zn in collected samples of bovine semen from different breeds, which are used in reproduction programs and artificial insemination.

Sewage sludge has been used as a fertilizer in agriculture, but human exposure to toxins due to crop exposure has been reported. This study evaluated the uptake of essential and nonessential elements from soil (exposed to sewage sludge) to roots, shoots, and grains of corn, aiming to estimate the daily intake corn consumption to assess the associated health risk. Corn plants were grown in soil amended with 0, 5, 10, and 20 tons of sewage sludge per hectare (t/ha). Soil, root, shoot, and grain samples were analyzed by inductively coupled plasma mass spectrometry. In soil, sludge application at 10 and 20 t/ha enhanced the Zn, Cu, Mo, Cd, Pb, Hg, and Ni concentration compared to control soil. Normally, corn plants exhibited essential and nonessential element concentrations significantly higher in roots than in grains and shoots. Selenium was equally distributed in roots, shoots, and grains but Mo was preferentially stored in grains. Cadmium, As, and Pb were more efficiently trapped in roots than other elements. Considering the estimated daily intake, for Brazilians, the concentrations were below the toxicological or the dietary reference values. In conclusion, chemical elements were efficiently trapped in roots and therefore applying 5 t/ha proportion of sewage sludge might be a sustainable and cost-effective strategy, with a very lower risk of toxicity due to consumption of grains. In contrast, sewage sludge at 20 t/ha enhanced element levels in plant parts and in places with higher corn consumption, estimated daily intakes are expected to rise.

Arsenic is considered a semimetal, and its wide distribution in the Earth's crust in different chemical forms, including organic and inorganic species, has a great deal of influence on the mechanisms of toxicity. Exposure to arsenic can be either through occupational practice (use of pesticides) or by the consumption of water and food containing the element. Rice is considered a fundamental constituent of the basic diet of Brazilians and is usually cultivated in flooded conditions. Such a plantation system results in an increased amount of As in the soil and hence a greater accumulation of As in the plant, which is highlighted by the inorganic species' classification as highly toxic. Besides the use of mitigation techniques to reduce the toxicological risk, monitoring the concentration of As and its chemical species in rice and rice products is required through the establishment of legislation in the area. Thus, some world organizations are conducting improved research to determine and establish acceptable concentrations of As and its chemical species in rice, e. g., in 2012, FDA researchers described a chemical speciation methodology for As in rice and rice products. Hence, the application of existing chemical speciation methods and the establishment of parameters for ensuring food security and exposure risk assessment deserve particular consideration.

Multilayer graphene (G-US) and multilayer graphene muffled (Gm-US) produced by liquid exfoliation ultrasound were used as support for Pd nanoparticles with a load of 20 wt% for application in an alkaline direct ethanol fuel cell (ADEFC) anode. The multilayer graphene–based electrocatalyst (Pd/G-US) exhibited superior current density and less positive onset potential for ethanol oxidation reaction (EOR) than the commercial Pd/C (AA). Also, the Pd/G-US electrocatalyst showed the less positive onset potential for CO oxidation. In ADEFC experiments, the Pd/G-US catalyst exhibited a superior performance with 38 mW cm−2. The findings suggest that the defective graphene structure promotes electron transport, and the presence of oxygenated species increases hydrophilicity facilitating the oxidation of intermediates. Hence, the synthesized material can be considered as promising support for an anode in ADEFC. Graphical abstract: [Figure not available: see fulltext.]