Evaluation and validation of two different chromatographic methods (HPLC and LC-MS/MS) for the determination and confirmation of ochratoxin A in pig tissues

This study was undertaken to compare two different analytical methods for the determination and confirmation of ochratoxin A (OTA) in blood serum, kidney and liver of pigs. Sample clean-up was based on liquid-liquid phase extraction. The detection of OTA was accomplished with high-performance liquid chromatography (HPLC) combined either with fluorescence detection (FL) or electro spray ionization (ESI+) tandem mass spectrometry (MS–MS). Comparative method evaluation was based on the investigation of 90 samples of blood serum, kidney and liver per animal originating from different regions of Serbia. The analytical results are discussed in view of the respective method validation data and the corresponding experimental protocols. In general, analytical data obtained with (LC–MS–MS) liquid chromatography electro spray tandem mass spectro metry detection offered comparable good results at the sub-ppb concentration level. The results indicate that the liquid chromatography electro spray tandem mass spectrometric (LC-MS/MS) method was more specific and sensitive for the analysis and confirmation of ochratoxin A in pig tissues then high pressure liquid chromatography (HPLC) method after methylation of OTA.     

Identification of magnetic particulates in road dust accumulated on roadside snow using magnetic, geochemical and micro-morphological analyses

The aim of this study is to test the applicability of snow surveying in the collection and detailed characterization of vehicle-derived magnetic particles. Road dust extracted from snow, collected near a busy urban highway and a low traffic road in a rural environment (southern Finland), was studied using magnetic, geochemical and micro-morphological analyses. Significant differences in horizontal distribution of mass specific magnetic susceptibility (χ) were noticed for both roads. Multi-domain (MD) magnetite was identified as the primary magnetic mineral. Scanning electron microscope (SEM) analyses of road dust from both roads revealed: (1) angular-shaped particles (diameter ∼1-300 μm) mostly composed of Fe, Cr and Ni, derived from circulation of motor vehicles and (2) iron-rich spherules (d ∼ 2-70 μm). Tungsten-rich particles (d < 2 μm), derived from tyre stud abrasion were also identified. Additionally, a decreasing trend in χ and selected trace elements was observed with increasing distance from the road edge.     

Seasonal Differences in the Levels of Gaseous Air Pollutants in the Vicinity of a Waste Dump

Hydrogen sulphide, ammonia, nitrogen dioxide, mercaptans and sulphur dioxide (H₂S, NH₃, NO₂, R-SH, SO₂) concentrations were measured at the location in the vicinity of the waste dump to determine the air pollution level of these pollutants prior to the operation of the Mobile Thermal Treatment Plant. Samples were collected over one year period. Seasonal differences, and the influence of meteorological parameters (temperature, relative humidity, pressure and wind direction) on the air pollution levels were studied. Results show relatively low concentrations of H₂S, NO₂, R-SH and SO₂, while NH₃ levels were higher compared to the guideline values. Good weather conditions (high air pressure and low relative humidity) are connected to long range transport of NO₂, while higher temperatures result in elevated NH₃ and R-SH concentrations. Because of the predominant northeast wind direction (the same as the waste dump direction), the contribution of air pollution from the direction of the waste dump at the measuring site is significant, but that does not necessarily mean that the pollutants originated from that source.     

The determination of the extractability of selected elements from agricultural soil

Concentrations of Ag, Al, Ba, Cd, Co, Cr, Cu, Fe, K, Mn, Na, Ni, Pb, Sr, and Zn—isolated by sequential extraction steps from apple orchard soil—were analyzed by inductively coupled plasma-atomic emission spectroscopy and compared to the total amount of metal in soil determined by XRF. The extractable amount of each metal was calculated by the extraction yields of the four steps. The LODs of the different elements in all extracts ware below 3 μg/L except for Ba (steps 1 and 2), Cu (step 1), Fe (all steps), K (steps 1–3), Mn (step 2), Na (steps 1–3), Ni (step 1), Pb (steps 1 and 4), and Zn (steps 1 and 2). The highest LOD (>10 μg/L) was found for Fe, K, and Na (step 1). The recovery of all metals after four sequential extraction steps was 90–112%. The repeatability (<1.1%), the intermediate precision (<5.3%), the day-to-day reproducibility (<6.2%), and the overall uncertainty of measurement (approximately 4–8.5%) for all analyzed metals supports the choice of the method used.     

Determination of the insecticide diflubenzuron in mushrooms by kinetic method and high-performance liquid chromatographic method

In the present study, a new sensitive and simple kinetic-spectrophotometric method for the determination of the insecticide diflubenzuron [1-(4-chlorophenyl)-3-(2,6-diflubenzoil)urea] is proposed. The method is based on the inhibited effect of diflubenzuron on the oxidation of sulphanilic acid (SA) by hydrogen peroxide in phosphate buffer in presence Cu(II) ion. Diflubenzuron was determined with linear calibration graph in the interval from 0.31 to 3.1 μg mL?1 and from 3.1 to 31.0 μg mL?1. The optimized conditions yielded a theoretical detection limit of 0.18 μg mL?1 corresponding to 0.036 mg kg(-1)mushroom sample based on the 3S(b) criterion. The RSD is 5.03-1.83 % and 2.81-0.71 % for the concentration interval of diflubenzuron 0.31-3.1 μg mL?1 and 3.1-31.0 μg mL?1, respectively. The reaction was followed spectrophotometrically at 370 nm. The kinetic parameters of the reaction are reported, and the rate equations are suggested. The developed procedure was successfully applied to the rapid determination of diflubenzuron in spiked mushroom samples of different mushroom species. The HPLC method was used like a comparative method to verify results.     

The Frequency of Micronuclei among Newborns from Kragujevac, Central Serbia, after NATO Bombing in the Spring of 1999

Kragujevac, as an important industrial and economic center of the region, is now placed on the top of the list of environmentally endangered cities in our country. The aim of this biomonitoring study was to evaluate cytogenetic damage in a sample of newborns from Kragujevac after contamination of the environment entailed by the intensive bombing of the industrial zone of this city in the spring of 1999. The frequency of micronuclei (MN) in peripheral blood lymphocytes in a total of 61 phenotypically healthy newborns was analyzed before and after the NATO bombing. Analysis of micronuclei has been performed using the cytokinesis-block technique (CB MN test). Average MN frequency in lymphocytes of newborns before the bombing (N = 25) was 5.77 ± 0.85/1000 analyzed cells. After the bombing (N = 36), the average frequency of MN increased by a factor of 1.4 (8.11 ± 0.85), compared to the control frequency before the bombing. Statistical difference (p < 0.05) was established by Student's t-test. Our data suggest that such changes in genetic material were a direct consequence of contamination of the living environment.     

Heavy metal concentration in fish tissues inhabiting waters of “Buško Blato” reservoar (Bosnia and Herzegovina)

Heavy metals concentration (mercury, lead, cadmium, arsenic, copper, zinc and chromium) in tissues (muscles, liver, kidney and gonads) of Dalmatian barbelgudgeon, the nase, the souffie and brown trout, inhabiting waters of Busko Blato reservoir in Bosnia and Herzegovina, has been determined by atomic absorption spectrophotometry. The meat of the tested fish sorts does not contain elevated concentration of most analyzed heavy metals with exception of lead (higher than MAC in Italy, Germany and Denmark) and mercury (in muscles of brown trout higher than MAC in most countries). The lowest level of all heavy metals is always detected in gonads, with higher values in fry compared to milt for copper, zinc, chromium and arsenic. The highest copper concentration is observed in the liver from the souffie which is suggested as a suitable biomonitor for copper intoxication. In muscles of all fish sorts, lead was always present in much higher concentration than cadmium, while in kidneys of most fish sorts, lead and cadmium concentrations were similar. We showed that bioaccumulation of some heavy metals in the fish sorts analyzed is tissue and sex dependent. Also, we concluded that the small water exchange in reversible shallow reservoir does not induce elevated concentration of heavy metals in fish tissues inhabiting Busko Blato.     

Precipitation composition and wet deposition temporal pattern in Central Serbia for the period from 1998 to 2004

Bulk samples collected on a daily basis at three principal meteorological stations in central Serbia were analyzed on chloride (Cl(-)), nitrate [Formula: see text], sulfate [Formula: see text], sodium (Na(+)), ammonium [Formula: see text], potassium (K(+)), calcium (Ca(2+)), and magnesium (Mg(2+)) in addition to precipitation amount, pH and conductivity measurements over the period 1998-2004. The data were subjected to variety of analyses (linear regression, principal component analysis, time series analysis) to characterize precipitation chemistry in the study area. The most abundant ion was [Formula: see text] with annual volume weighted mean concentration of 242 microeq L(-1). Neutralization of precipitation acidity occurs both as a result of the dissolution of alkaline compounds containing Ca(2+), Mg(2+), and K(+) as well as the absorption of ammonia. The ratio of [Formula: see text] was above 5, which indicated that the combustion process of low-grade domestic lignite for electricity generation from coal-fired thermal power plants was the main source of pollution in the investigated area. A considerable mean annual bulk wet deposition of SO(4)-S determined by precipitation amount and concentrations of sulfate in the precipitation was calculated to be 12-35 kg ha(-1).     

Cybernetic formulation of control in ecosystems

Hierarchical control formulations are given for a simple predator-prey model: self-optimization of one subsystem, natural multi-goal optimization, man's multiparameter control of an ecosystem and man's control of a self-optimizing ecosystem. Natural multigoal optimization suggests how several levels of an ecosystem can be optimized simultaneously. The idea of management of a self-optimizing ecosystem takes into account the reactions of the ecosystem to man's activity.