Occurrence and bioaccumulation study of PCDD and PCDF from mineral feed additives

Occurrence of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) was evaluated in sepiolite as a widely employed binder and anti-caking agent for animal feed. Also, naturally contaminated kaolinitic clay was used for comparative purposes. Since sepiolite shows remarkable adsorption properties, particular interest was paid to the extraction steps as they become critical for the final determination of these pollutants in such matrixes. Furthermore, classical Soxhlet extraction using different extracting strategies as well as acid treatment were carried out with simultaneous liquid-liquid extraction. Results obtained depended on the extraction procedure applied. Acid treatment or Soxhlet extraction using a mixture of toluene:ethanol as solvent allowed to reach the minimum requirements of recovery rates. However, Soxhlet extraction using a mixture cyclohexane:toluene as extracting solvent did not allow to comply with minimum specifications for recovery. Significant differences were obtained in TEQ units when acid treatment was applied in comparison to Soxhlet extraction. This fact can be explained because the use of drastic acid conditions allows removing strongly adsorbed analytes which can be uniquely extracted after a total destruction of the crystalline structure of sepiolite. On the contrary, Soxhlet extraction was not able to destroy the structure of sepiolite and as a consequence the PCDDs/Fs were strongly adsorbed in the internal structure of the mineral. From biological point of view the availability of these toxicants constitutes a critical aspect playing an important role in the final decision choosing particular analytical procedures. Then, acid conditions in the digestive tract should be taken into account. In this scenario, a bioaccumulation study was conducted to evaluate the transference of PCDDs/PCDFs from the sepiolite into the animal tissues when fed with feed containing sepiolite. To this end, chickens were used as a model to examine the bioavailability of PCDDs/PCDFs. Four groups of chickens were exposed through their diet to a control feed, feed with 3% w/w sepiolite as additive, feed contaminated with PCDDs/PCDFs at concentration around 2.8 pg WHO-TEQ/g and feed with 2% of a contaminated kaolinitic clay (460 pg TEQ/g mineral). Livers of the four studied groups were analyzed throughout the exposure period. Results of this trial showed that the performance of broilers was not affected by the presence of dioxins at levels tested, and chickens did not show any abnormal behaviour. Dioxins intentionally added to the diet were absorbed and accumulated in the liver in a significant manner, whereas the PCDDs/Fs from sepiolite were not available for chickens since livers from broilers fed 3% sepiolite presented similar WHO-TEQ values than those from broilers fed control diet.

The implementation of liquid chromatography tandem mass spectrometry for the official control of lipophilic toxins in seafood: Single-laboratory validation under four chromatographic conditions

We performed a comprehensive study to assess the fit for purpose of four chromatographic conditions for the determination of six groups of marine lipophilic toxins (okadaic acid and dinophysistoxins, pectenotoxins, azaspiracids, yessotoxins, gymnodimine and spirolides) by LC-MS/MS to select the most suitable conditions as stated by the European Union Reference Laboratory for Marine Biotoxins (EURLMB). For every case, the elution gradient has been optimized to achieve a total run-time cycle of 12 min. We performed a single-laboratory validation for the analysis of three relevant matrices for the seafood aquaculture industry (mussels, pacific oysters and clams), and for sea urchins for which no data about lipophilic toxins have been reported before. Moreover, we have compared the method performance under alkaline conditions using two quantification strategies: the external standard calibration (EXS) and the matrix-matched standard calibration (MMS). Alkaline conditions were the only scenario that allowed detection windows with polarity switching in a 3200 QTrap mass spectrometer, thus the analysis of all toxins can be accomplished in a single run, increasing sample throughput. The limits of quantification under alkaline conditions met the validation requirements established by the EURLMB for all toxins and matrices, while the remaining conditions failed in some cases. The accuracy of the method and the matrix effects where generally dependent on the mobile phases and the seafood species. The MMS had a moderate positive impact on method accuracy for crude extracts, but it showed poor trueness for seafood species other than mussels when analyzing hydrolyzed extracts. Alkaline conditions with EXS and recovery correction for OA were selected as the most proper conditions in the context of our laboratory. This comparative study can help other laboratories to choose the best conditions for the implementation of LC-MS/MS according to their own necessities.

Structural and gas-sensing properties of WO3 nanocrystalline powders obtained by a sol-gel method from tungstic acid

WO3 nanocrystalline powders were obtained from tungstic acid following a sol-gel process. Evolution of structural properties with annealing temperature was studied by X-ray diffraction and Raman spectroscopy. These structural properties were compared with those of WO3 nanopowders obtained by the most common process of pyrolysis of ammonium paratungstate, usually used in gas sensors applications. Sol-gel WO3 showed a high sensor response to NO2 and low response to CO and CH4. The response of these sensor devices was compared with that of WO3 obtained from pyrolysis, showing the latter a worse sensor response to NO2. Influence of operating temperature, humidity, and film thickness on NO2 detection was studied in order to improve the sensing conditions to this gas.

Comparison of fatty acid profiles of edible meat, adipose tissues and muscles between cocks and capons

The effect of caponisation on fat composition by parts (wing, breast, thigh, and drumstick) and tissues (skin, subcutaneous adipose tissue, intermuscular adipose tissue and muscle) was examined in the present study and fatty acid profiles of abdominal fat and edible meat by parts and tissue components were determined. The sample was made up of twenty-eight castrated and twenty male Penedesenca Negra chicks reared under free-range conditions and slaughtered at 28 wk of age; the birds were castrated at four or eight weeks. Caponisation significantly increased (P < 0.01) the chemical fat content in all parts (16.31% to 37.98% in breast; 21.98% to 34.13% in wing; 21.09% to 49.57% in thigh; 14.33% to 24.82% in drumstick) and led to minor modifications in fat haracteristics, particularly in the thigh and the drumstick, where the unsaturated vs. saturated fatty acid ratio increased from 1.31 to 1.76 ( P < 0.01) and from 1.48 to 2.07 (P < 0.01), respectively. Delaying the age of castration from 4 to 8 weeks increased this ratio by 0.35 in the edible meat. Even though the profile of the abdominal fat is less saturated in capons, all changes occurring on fat quality after caponisation indicate that increased fatness after castration does not imply worse fat nutritional properties.

Esterification of oleic acid catalayzed by an Aspergillus niger strain. Influence of water activity and alcohol concentration

Effects of water activity and 1-propanol concentration on synthesis of propyl oleate from oleic acid using Aspergillus niger cell-bound lipases in isooctane are described. A. niger produces lipases (EC 3.1.1.3) which partly bind to the mycelium during growth. Ester production was monitored for 72 hours at different 1-propanol concentrations and water activities. Aliquots were sequentially withdrawn and propyl esters were quantified using GC and methyl palmitate as an internal standard. In all assayed conditions A. niger cell-bound lipases catalysed propyl oleate synthesis, but at different degrees.