Use of High-Performance Liquid Chromatography-Mass Spectrometry of Adipose Tissue for Detection of Bioaccumulation of Pyriproxyfen in Adults of Lithobates catesbeianus.

The aims of the study were: (i) evaluate the efficacy of using amphibian adipose tissue as a valid biomarker of water contaminated by pyriproxyfen; and (ii) verify the use of Lithobates catesbeianus in laboratory experiments as a potential bioindicator for bioaccumulation of pesticide in adipose tissue from amphibians. Adult frogs were exposed to different dilutions (0.002 g/L and 0.02 g/L) of Sumilarv® (pyriproxyfen) over 50 days. The average results of the fortified sample were 108%, indicating that the test method was effective. Adult frogs exposed to the standard dose recommended by the World Health Organization (WHO) showed bioaccumulation of pyriproxyfen in adipose tissue significantly higher than control animals. Lithobates catesbeianus proved to be an effective bioindicator and the adipose tissue was an efficient biomarker to bioaccumulation of pyriproxyfen. We conclude that high-performance liquid chromatography-mass spectrometry was effective measuring pyriproxyfen bioaccumulation in adult amphibians.

Low concentration of 2,4,6-tribromophenol (TBP) represents a risk to South American silver catfish Ramdia quelen (Quoy and Gaimard, 1824) population.

The 2,4,6-tribromophenol (TBP) is an environmental persistent pollutant widely used as flame retardant, antimicrobial and insecticide agent in wood preservation and plastic production. Currently, TBP is found in environmental compartments such as soil, freshwater, groundwater, sewage sludge and domestic dust, but the effects to biota and the risk of exposure to aquatic vertebrates are still scarce. In the present study, Rhamdia quelen fish embryos (8 h post-fertilization - hpf) were exposed to 0.3 and 3.0 µg L-1 of TBP until 96 hpf. Biochemical biomarkers, hatching, survival and larvae/embryo malformations were evaluated after exposure. Additionally, a mathematical model was proposed to evaluate the effects along further generations. The results showed that TBP decreased the survival level but did not cause significant difference in the hatching rates. After 72 and 96 hpf, individuals from the highest tested concentration group showed more severe malformations than individuals from control and the lower concentrations groups. The deformities were concentrated on the embryos facial region where the sensorial structures related to fish behavior are present. The biochemical biomarkers revealed both oxidative stress and neurotoxicity signs after exposure to the contaminant, while the application of the mathematical model showed a decrease of population in both tested TBP concentrations. In conclusion, the current results demonstrated that TBP is toxic to R. quelen embryos and represents a risk to population after early life stage exposure.

Distribution and origin of polycyclic aromatic hydrocarbons in surface sediments from an urban river basin at the Metropolitan region of Curitiba, Brazil.

The concentrations of 16 polycyclic aromatic hydrocarbons (PAHs) were determined in surface sediment samples from nine sites located at the Iguaçu River Basin in the Metropolitan Region of Curitiba, Brazil to evaluate their distribution and sources. The total concentration of the PAHs was greater for sediments from highly urbanized areas, while the sediments from the Iraí Environmental Protection Area (Iraí EPA) showed significantly low concentrations. The sediments from the Iguaçu and Barigui rivers were classified as highly contaminated, while those from the Cercado and Curralinho rivers were classified as moderately contaminated. The predominance of PAHs containing two to four aromatic rings in most of the samples suggested the direct input of raw sewage into the water resources evaluated. Benzo[g,h,i]perylene, dibenzo[a,h]anthracene and indeno[1,2,3-cd]pyrene were predominant in sediments from the areas under the greatest urban and industrial development. The correlation between thermodynamic stability and the kinetics of evolution presented by the isomeric pairs indicated that combustion is the predominant source of PAHs in the sediments because the combustion of fossil fuels affected most of the points evaluated, followed by combustion of biomass and eventually combustion of oil product inputs. In general, the results showed that areas under strong urban influence, as well as the Iraí EPA, receive contributions of PAHs from similar sources.

Multifactorial optimization approach for the determination of polycyclic aromatic hydrocarbons in river sediments by gas chromatography-quadrupole ion trap selected ion storage mass spectrometry.

A procedure for the determination of very low polycyclic aromatic hydrocarbons (PAHs) concentrations in sediment samples has been developed by gas chromatography-quadrupole ion trap mass spectrometry (GC-QIT MS) after extraction with dichloromethane and purification by using silica gel cleanup. Identification and quantification of analytes were based on the selected ion storage (SIS) strategy using deuterated PAHs as internal standards. In order to search out the main factors affecting the SIS mass spectrometry efficiency, four MS parameters, including target total ion count (TTIC), waveform amplitude (WA), transfer line (XLT) and ion trap temperatures (ITT) were subjected to a complete multifactorial design. The most relevant parameters obtained (TTIC and WA) were optimized by a rotatable and orthogonal composite design. Optimum values for these parameters were selected for the development of the method involving PAH determination in sediment samples. The optimized method exhibited a range of 111-760% higher signal-to-noise (S/N) ratios for PAHs in comparison with the method operated by the default conditions, demonstrating that the multifactorial optimization contributed to substantially improve the sensitivity of the GC-QIT MS determination. The accuracy of the method was verified by analyzing NWRI EC-3 certified reference material (Lake Ontario sediment). The selectivity, sensitivity (limits of quantification were in the range of 0.02-11.0 ng g(-1)), accuracy (recoveries >or=77%) and precision (RSD

Exotic flora dependence of an unusual Brazilian propolis: the pinocembrin biomarker by capillary techniques.

Significant amounts of pinocembrin (>10%), a dihydroxy-flavanone, was found in the composition of an unusual brand of a subtropical Brazilian propolis. Incidentally, this sealing material was obtained from hives surrounding a large forestry site based on a single exotic flora, namely poplar (Populus sp.). Examination of the different botanical parts of poplar revealed the buds as the main source of the flavanone. Techniques used for the establishment of the chemical correlation between the propolis brand and the poplar buds were TLC/densitometry, capillary GC-MS in the e.i. mode, and CZE with DAD monitoring. Since color enhancement after Al3+ complexation applies just for more hydroxylated flavonoids, the alternative techniques herein applied were of value for pinocembrin detection and estimation. Analytical data indicated the dominance of the main phenolic pinocembrin biomarker as well as the presence of other related flavonoids in the botanical source and in the propolis derived thereof.