Microwave-induced combustion for petroleum coke digestion: a promising sample preparation strategy for subsequent elemental determination.

The increasing demand for the elemental determination of petrochemical samples by inductively coupled plasma techniques requires the development of suitable sample preparation methods that permit high sample throughput and are in accordance with green chemistry recommendations. For this aim, the development of microwave-induced combustion (MIC) method has been attempted to completely digest petroleum coke samples and address quantitative determination of elements, such as Ag, Al, Ba, Ca, Cd, Co, Cu, Fe, Mg, Mn, Mo, Na, Ni, Pb, Sr, V and Zn, by inductively coupled plasma optical emission spectrometry (ICP OES). A sequential procedure to evaluate the sample mass and the solution to retain the analytes quantitatively was first conducted. Satisfactory results were obtained (residual carbon content in final solutions was lower than 0.5%) by digesting 400 mg of samples using 20 bar of oxygen and analytes were quantitatively retained in a dilute acid solution such as 4.2 mol L-1 HNO3. An agreement better than 87% was achieved using certified reference materials and the performance of the proposed method was also compared to that of the standard procedure recommended by the American Society of Testing and Materials ASTM D 5600. Despite both methods producing similar results, the proposed method by MIC was much simpler, offered a higher sample throughput and the digests were compatible with ICP OES measurements avoiding interferences in the determination step compared the ASTM D 5600 method. These results clearly demonstrated that the proposed MIC method in combination with ICP OES could be a promising alternative to obtain quantitative information about the elemental composition of petroleum coke.

Life-history traits of Farlowella hahni (Siluriformes, Loricariidae) in streams of the Ivinhema River Basin, Upper Paraná Basin.

Brazilian laws allow the catch of some species as ornamental fish; however, in the absence of biological information, such catch can threaten species conservation. Therefore, this study aimed to offer population and reproductive information about Farlowella hahni in streams of the Ivinhema River Basin, Upper Paraná Basin. To accomplish this, a total of 165 F. hahni individuals were analyzed, including 109 females and 48 males, resulting in an important sex ratio difference from 1:1 (χ 2=19.97; p<0.001), indicating a predominance of females throughout the year. Females reach higher standard length than males. Males presented isometric Length-Weight Relationships, while females have positive allometric growth. Gonadosomatic index presented higher values from October through December. The mean fecundity was 100.3±36.4 of vitellogenic oocytes and was positively correlated with standard length (r=0.51; p=0.01). The data presented herein are the first for this species and suggest a need to carefully manage the F. hahni population, considering its low abundance and fecundity.

Changes in levels of essential elements in suckling rats exposed to zinc and mercury.

The effect of mercury and its interaction with zinc on the content of essential metals in tissues from neonate rats was investigated. Three-day-old Wistar rats were treated with saline or 27 mg kg(-1)d(-1) ZnCl2 (s.c.) for five consecutive days. From the 8th to the 12th day of life, the rats received one daily dose of saline or 5.0 mg kg(-1) HgCl2 (s.c). Twenty-four hours after the last injection liver, kidneys and blood were collected for metal quantification. The HgCl(2) exposure induced alterations on metal levels, such as increase of Fe, Hg and Zn in liver, decrease of Fe and Mg and increase of Cu and Hg contents in kidneys. The Hg exposure also increased Hg levels in the blood. The treatment with ZnCl2, administered previously to HgCl2, partially prevented the increase of Fe in the liver, and not only prevented the decrease of renal Mg but also increased it to levels higher than those found in control group. The Zn-Hg rats also presented higher renal Cu levels, and showed partially lower blood and hepatic Hg levels and higher renal Hg levels. The pre-administration of Zn caused no severe alterations in levels of essential metals (Cu, Fe, Mg and Mn). In short, Zn appears to be an alternative treatment of Hg poisoning in young animals in comparison to chelating drugs since these have low metal selectivity.

Life-history traits of Farlowella hahni (Siluriformes, Loricariidae) in streams of the Ivinhema River Basin, Upper Paraná Basin / Traços de história de vida de Farlowella hahni (Siluriformes, Loricariidae) em riachos da Bacia do rio Ivinhema, Bacia do alto Paraná

Abstract Brazilian laws allow the catch of some species as ornamental fish; however, in the absence of biological information, such catch can threaten species conservation. Therefore, this study aimed to offer population and reproductive information about Farlowella hahni in streams of the Ivinhema River Basin, Upper Paraná Basin. To accomplish this, a total of 165 F. hahni individuals were analyzed, including 109 females and 48 males, resulting in an important sex ratio difference from 1:1 (χ 2=19.97; p<0.001), indicating a predominance of females throughout the year. Females reach higher standard length than males. Males presented isometric Length-Weight Relationships, while females have positive allometric growth. Gonadosomatic index presented higher values from October through December. The mean fecundity was 100.3±36.4 of vitellogenic oocytes and was positively correlated with standard length (r=0.51; p=0.01). The data presented herein are the first for this species and suggest a need to carefully manage the F. hahni population, considering its low abundance and fecundity.

Resumo As leis brasileiras permitem a captura de algumas espécies de peixes como ornamentais, no entanto, a ausência de informações biológicas pode tornar esta captura uma ameaça para a conservação destas espécies. Este estudo teve como objetivo oferecer informações populacionais e reprodutivas sobre Farlowella hahni em riachos da Bacia do rio Ivinhema, bacia do Alto Paraná. Um total de 165 indivíduos de F. hahni foi analisado, sendo 109 fêmeas e 48 machos. A proporção de sexo foi diferente de 1:1 (χ2=19,97; p<0,001), com predominância de fêmeas ao longo do ano. As fêmeas atingiram maior comprimento padrão do que os machos. Os machos apresentaram crescimento isométrico e as fêmeas crescimento alométrico positivo. O índice gonadossomático apresentou maiores valores de Outubro a Dezembro. A fecundidade média foi de 100,3±36,4 de ovócitos vitelogênicos e foi correlacionada positivamente com o comprimento padrão (r=0,51; p=0,01). Os dados apresentados são os primeiros para essa espécie e sugerem a necessidade de cuidados no manejo da população de F. hahni considerando baixa abundância e fecundidade.

Focused microwave-induced combustion for digestion of botanical samples and metals determination by ICP OES and ICP-MS.

The advantages and shortcomings of focused microwave-induced combustion (FMIC) for digestion of plant samples were studied. The effects of sample mass, absorbing solution, oxygen gas flow-rate, and time of reflux step on recoveries of major, minor and trace metals were systematically evaluated. Afterwards, Al, Ba, Ca, Co, Cr, Cu, Mg, Mn, Ni, Sr, V, and Zn were determined by inductively coupled plasma optical emission spectrometry (ICP OES) and by inductively coupled plasma mass spectrometry (ICP-MS). The main advantages of FMIC when compared to microwave-assisted wet digestion (MAWD) and focused-microwave-assisted wet digestion (FMAWD) are the possibility to digest larger masses of samples (up to 3g) using shorter heating times and diluted nitric acid solution for absorbing all analytes. Using the selected experimental conditions for FMIC, residual carbon content was lower than 0.7% for all samples and relative standard deviation (RSD) varied from 1.5 to 14.1%. Certified reference materials (NIST 1515 apple leaves and NIST 1547 peach leaves) were used for checking accuracy and determined values for all metals were in agreement with certified values at a 95% confidence level. No statistical difference (ANOVA, 95% of confidence level) was observed for results obtained by FMIC, FMAWD, and MAWD. Limits of detection were lower when using FMIC in the range of 0.02-0.15 µg g(-1) for ICP OES and 0.001-0.01 µg g(-1) for ICP-MS, which were about 3 and 6 times lower than the values obtained by FMAWD and MAWD, respectively. It is important to point out that FMIC was a suitable sample preparation method for major, minor and trace metals by both determination techniques (ICP OES and ICP-MS). Additionally, since it allows lower LODs (because up to 3g of sample can be digested) and diluted acid solutions are used (without any further dilution), the use of ICP-MS is not mandatory.