Trace analysis of parabens preservatives in drinking water treatment sludge,treated, and mineral water samples

Parabens have been widely used as antimicrobial agents, mainly in food products, pharmaceuticals, and cosmetics. Although they are known as safe preservatives, they also cause some harm to human health, which has been discussed lately. Therefore, the aim of this study was to evaluate the occurrence of nine parabens (including isomers) in mineral and drinking waters, besides in drinking water treatment sludge (DWTS) samples with determination by liquid chromatography tandem mass spectrometry (LC-MS/MS). Both methods solid phase extraction (SPE) and QuEChERS were validated. Calibration curves showed a correlation coefficient of 0.99 for all compounds. LOQ values ranged from 0.04 to 4 μg L^?1 in aqueous matrices and from 5 to 500 ng g^?1 in DWTS. Recoveries between 70 and 115% were reached with RSD below 20% for all compounds in SPE whereas recoveries between 62 and 119% were found with RSD below 20% for almost all compounds in QuEChERS. Matrix effect had low values (<?20%); it was only above 20% for methylparaben in the SPE and for pentylparaben in the QuEChERS. Using a quick and simple extraction procedures with SPE, QuEChERS, and LC-MS/MS analyses, these methods proved to be selective and sensitive. They were successfully applied to real samples (treated water, mineral water, and sludge), and methylparaben was detected at concentration levels below 0.242 μg L^?1 in mineral and treated water samples and 10 ng g^?1 in DWTS samples.     

Biochemical biomarkers in Nile tilapia (Oreochromis niloticus) after short-term exposure to diesel oil, pure biodiesel and biodiesel blends

Fossil fuels such as diesel are being gradually replaced by biodiesel, a renewable energy source, cheaper and less polluting. However, little is known about the toxic effects of this new energy source on aquatic organisms. Thus, we evaluated biochemical biomarkers related to oxidative stress in Nile tilapia (Oreochromis niloticus) after two and seven exposure days to diesel and pure biodiesel (B100) and blends B5 and B20 at concentrations of 0.01 and 0.1 mL L⁻¹. The hepatic ethoxyresorufin-O-deethylase activity was highly induced in all groups, except for those animals exposed to B100. There was an increase in lipid peroxidation in liver and gills in the group exposed to the higher concentration of B5. All treatments caused a significant increase in the levels of 1-hydroxypyrene excreted in the bile after 2 and 7 d, except for those fish exposed to B100. The hepatic glutathione-S-transferase increased after 7 d in animals exposed to the higher concentration of diesel and in the gill of fish exposed to the higher concentration of pure diesel and B5, but decreased for the two tested concentrations of B100. Superoxide dismutase, catalase and glutathione peroxidase also presented significant changes according to the treatments for all groups, including B100. Biodiesel B20 in the conditions tested had fewer adverse effects than diesel and B5 for the Nile tilapia, and can be suggested as a less harmful fuel in substitution to diesel. However, even B100 could activate biochemical responses in fish, at the experimental conditions tested, indicating that this fuel can also represent a risk to the aquatic biota.     

Detached leaf culture: viability to evaluate 2,4-D toxicity symptoms in cotton apex leaves

To study the viability of detached leaf culture technique, studies were carried out with detached leaves from cotton apex (true trilobed leaves). The prepared leaves were sprayed with 2,4-D amine and ester, at rates of 10, 30, 70, and 100% of the recommended doses. Detached leaves without herbicide spray were used as controls. Simultaneously, a greenhouse experiment was conducted with the same treatments as used for the detached leaves experiment. Toxicity was measured through a 0-to-5 grading according to the percentage of affected leaf area in the detached leaves experiment or examining the affected rate of whole plant as indicated in the greenhouse. Results showed that the ester form of the herbicide induced earlier and more severe toxicity symptoms in detached leaves and greenhouse grown plants. Positive and significant correlations (p < 0.001) were found between toxicity results obtained at 7 and 14 days after application in detached leaves and greenhouse plants (r = 0.97 and 0.92, respectively). Negative, significant correlations (p < 0.005) were found between the toxicity levels found at 7 and 14 days after application in detached leaves and dry matter of cotton plants grown in the greenhouse (r= - 0.92 and -0.92, respectively).     

Hydrological benefits in the context of Brazilian environmental services program

The Brazilian program of payment for environmental services (PES) is based on ranges of potential erosion decrease (ED) from soil and water conservation proposals estimated from the Universal Soil Loss Equation. Changes in land use and land cover (LULC) result in many alterations of the basin water balance. Therefore, to contribute to the methodological development of Brazilian PES, this paper proposes a quantification of hydrological benefits based on conservation measures. We propose basing the PES program on adding the potential water storage increase (WSI) parameter estimated from the runoff curve number model. Two LULC change scenarios were run considering conservation measures on degraded areas. We found that indicators of ED and WSI were compatible tools for driving the eligibility of soil and water conservation measures. However, the water storage parameter seems to be better at managing the PES mechanism because it is based on water prices and can contribute to appreciation of the efforts performed by the rural producers. The use of the SCS-CN method presents greater feasibility as a tool for the implementation of PES programs in ungauged basins. Thus, an analysis of the success of the innovation proposal of the Brazilian PES program allows inferences to be made about the quantification and financial valuation of hydrological benefits of the potential storage increase and current water price.     

Calibration for the determination of 19 trace elements in serum and urine

A fast, high-throughput and accurate method was developed for determination of Al, As, Ba, Cd, Co, Cr, Cs, Cu, Fe, Mn, Ni, Pb, Se, U, Zn, Sb, Sn, I and Hg in urine and serum by inductively coupled plasma mass spectrometry. The samples were directly analyzed after 1/20 (v/v) dilution in 0.4% (v/v) HNO₃ and 0.005% Triton X-100. Three calibration modes were tested: aqueous and matrix matching with urine and serum. The accuracy was tested using reference materials of serum, urine and spiking. Results showed that the use of matrix matching calibration reduced the interferences and improved the recoveries for Al, Co, Pb and I in urine. The matrix matching did not affect the results considerably for serum. When serum was spiked with As, Co, Cs, Pb, U, Hg, I, Ba, Al, Cr and Ni, only matrix matching presented good recoveries. Helium was used as a collision cell gas reducing effectively polyatomic interferences for Al, Mn, Cu, Ni, Cr, Zn, As and Fe. Selection of the best internal standard was carried out for each element. The use of diluted HNO₃ improved the limit of detection. Finally, the method was applied successfully in samples of urine from workers occupationally exposed.     

40K/137Cs discrimination ratios to the aboveground organs of tropical plants

In the present work, the accumulation of caesium and potassium in aboveground plant parts was studied in order to improve the understanding on the behaviour of monovalent cations in several compartments of tropical plants. We present the results for activity concentrations of (137)Cs and (40)K, measured by gamma spectrometry, from five tropical plant species: guava (Psidium guajava), mango (Mangifera indica), papaya (Carica papaya), banana (Musa paradisíaca), and manioc (Manihot esculenta). Caesium and potassium have shown a high level of mobility within the plants, exhibiting the highest values of concentration in the growing parts (fruits, leaves, twigs, and barks) of the woody fruit and large herbaceous shrub (such as manioc) species. In contrast, the banana and papaya plants exhibited the lowest levels of (137)Cs and (40)K in their growing parts. However, a significant correlation between activity concentrations of (137)Cs and (40)K was observed in these tropical plants. The (40)K/(137)Cs discrimination ratios were approximately equal to unity in different compartments of each individual plant, suggesting the possibility of using caesium to predict the behaviour of potassium in several tropical species.