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.     

Effects of temperature on sorption-desorption processes of imidacloprid in soils of Croatian coastal regions

Sorption-desorption behavior of imidacloprid in six soils collected from five coastal regions in Croatia at 20, 30 and 40°C was investigated using batch equilibrium technique. Isothermal data were applied to Freundlich, Langmuir and Temkin equations, and the thermodynamic parameters ΔH°, ΔG°, ΔS° were calculated. The sorption isotherm curves were non-linear and may be classified as L-type, suggesting a relatively high sorption capacity for imidacloprid. Our results showed that the K( sor ) ( F ) values decreased for all the tested soils as the temperature increased, indicating that the temperature strongly influences the sorption. Values of ΔG° were negative (-4.65 to -2.00 kJ/mol) indicating that at all experimental temperatures the interactions of imidacloprid with soils were spontaneous processes. The negative and small ΔH° values (-19.79 to -8.89 kJ/mol) were in the range of weak forces, such as H-bonds, consistent with interactions and partitioning of the imidacloprid molecules into soil organic matter. The ΔS° values followed the range of -57.12 to -14.51 J/molK, suggesting that imidacloprid molecules lose entropy during transition from the solution phase to soil surface. It was found that imidacloprid desorption from soil was concentration and temperature-dependent, i.e. at lower imidacloprid concentrations and temperature, lower desorption percentage occurred. Desorption studies revealed that hysteretic behavior under different temperature treatments existed, and it was more pronounced at 20°C in the soils with higher OC content. The study results emphasize the importance of thermodynamic parameters in controlling soil pesticide mobility in different geographical locations, seasons and greenhouse conditions.     

Metal contamination recorded in the sediment of the semi-closed Bakar Bay (Croatia)

This study presents metal levels in the sediments of the Bakar Bay, with its main goal to evaluate recent anthropogenic influence, as well as over previous decades. Sediment profiles at 7 sampling points were taken. Chemical contents in bulk sediment were obtained using ICP, ICP-MS, and AAS methodologies, and 20 most significant elements were presented. Concentrations of selected elements were evaluated by factor statistical analyses to identify their source. Also, metal enrichment factor and geoaccumulation index were calculated, and spatial distribution maps for three sediment layers were constructed. Measured metal concentrations in sediment were compared with concentrations in other sediments from the Adriatic Sea. In addition, a set of sediment quality guidelines were also applied in order to predict the probability of adverse biological effects on the benthic community: This was found not to be very serious. Factor analysis clearly demonstrates the segregation between metals of natural origin resulted from soil and bedrock weathering (Li, Al, Cr, Sc), and with two anthropogenic sources originating from the city of Bakar and bulk cargo terminal (Hg, Pb, Zn, Ag, Sn, and Fe). Mercury (max 0.65 μg g^?1) is found to be the heaviest contaminant, followed by lead (max 71.5 μg g^?1), copper (89.3 μg g^?1), and zinc (156 μg g^?1). However, this study shows that Bakar Bay is considerably less polluted with toxic metals than it was believed.     

Metals in the sediment and liver of four fish species from different trophic levels in Tisza River,Serbia

In aquatic environments metals originate from various natural and anthropogenic sources. The degree of contamination in fish tissues depends on the pollutant, fish species, their mode of feeding, sampling site and trophic level. This study presents concentrations of Al, As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Se, Sr and Zn in sediment and liver of four ecologically different fish species: piscivorous northern pike (Esox lucius L.), benthivorous sterlet (Acipenser ruthenus L.) and silver bream (Brama brama L.), and omnivorous common carp (Cyprinus carpio L.). Fish were caught at four sites along the stretch of the River Tisza in Serbia during October 2010. The concentrations of metals have been assessed using the inductively coupled plasma – optical emission spectrometry. Results revealed that metals with the highest values in sediment and fish samples were Al and Fe, respectively and sometimes concentrations of Zn are in the same order of magnitude as Fe concentrations. The highest concentration of metals was recorded in omnivorous common carp.     

Possible health impacts of naturally occurring uptake of aristolochic acids by maize and cucumber roots: links to the etiology of endemic (Balkan) nephropathy

Aristolochic acids (AAs) are nephrotoxic and carcinogenic derivatives found in several Aristolochia species. To date, the toxicity of AAs has been inferred only from the effects observed in patients suffering from a kidney disease called “aristolochic acid nephropathy” (AAN, formerly known as “Chinese herbs nephropathy”). More recently, the chronic poisoning with Aristolochia seeds has been considered to be the main cause of Balkan endemic nephropathy, another form of chronic renal failure resembling AAN. So far, it was assumed that AAs can enter the human food chain only through ethnobotanical use (intentional or accidental) of herbs containing self-produced AAs. We hypothesized that the roots of some crops growing in fields where Aristolochia species grew over several seasons may take up certain amounts of AAs from the soil, and thus become a secondary source of food poisoning. To verify this possibility, maize plant (Zea mays) and cucumber (Cucumis sativus) were used as a model to substantiate the possible significance of naturally occurring AAs’ root uptake in food chain contamination. This study showed that the roots of maize plant and cucumber are capable of absorbing AAs from nutrient solution, consequently producing strong peaks on ultraviolet HPLC chromatograms of plant extracts. This uptake resulted in even higher concentrations of AAs in the roots compared to the nutrient solutions. To further validate the measurement of AA content in the root material, we also measured their concentrations in nutrient solutions before and after the plant treatment. Decreased concentrations of both AAI and AAII were found in nutrient solutions after plant growth. During this short-term experiment, there were much lower concentrations of AAs in the leaves than in the roots. The question is whether these plants are capable of transferring significant amounts of AAs from the roots into edible parts of the plant during prolonged experiments.     

Relationship of safety climate perceptions and job satisfaction among employees in the construction industry: the moderating role of age

This study examines the degree to which construction sector employees perceive that safety is important in their organizations/sites and how job satisfaction affects these perceptions when age is introduced as a moderator variable. Two-way analysis of variance demonstrated that job satisfaction has a strong effect on perceived management commitment to work safety and that this relationship was moderated by respondents’ age. Job satisfaction was associated with perceived accident rate and safety inspection frequency, but the proposed role of age in this linkage was not confirmed. Consequently, the findings indicated that by increasing the level of job satisfaction, perceptions of these safety climate aspects proved to be more positive. The conclusion is that these relationships could further lead to a lower percentage of accidents and injuries in the workplace and better health among employees. A significant relationship between job satisfaction, age and perceived co-workers’ commitment to work safety was not found.     

PAH mass concentrations measured in PM10 particle fraction

This paper presents daily, monthly and yearly variations of PAH mass concentrations measured in PM(10) particle fraction, collected at one measuring site in Zagreb air between 2001 and 2004, and seasonal differences in PAH mass concentrations in PM(10) samples collected from 21 March 2003 to 20 March 2004. Twenty-four hour samples were taken in the northern residential part of Zagreb using a low-volume (50 m(3)) sampler and glass or quartz filters. The analysis was performed using a high-performance liquid chromatograph (HPLC) and fluorescence detector with changeable excitation and emission wavelength. The annual average mass concentrations over the four-year measuring period for BaP ranged from 1.17 ng/m(3) in 2004 to 1.87 ng/m(3) in 2003 and were below the limit value (2 ng/m(3)) set by the Ordinance on Recommended and Limit Air Quality Values in Croatia. The highest concentrations of all PAHs measured in PM(10) samples collected from 21 March 2003 to 20 March 2004 were found in the winter and the lowest in the summer. Winter average of BaP was 2.94 ng/m(3) and summer average 0.12 ng/m(3). Autumn average was 2.76 ng/m(3) and was very similar to winter concentrations. Spring average of 0.58 ng/m(3) was higher than the summer average (0.12 ng/m(3)). Mass concentrations of all measured PAHs were much higher in the autumn than in the spring. Although annual averages for BaP did not exceed the limit value, autumn and winter BaP mass concentrations did, which calls for measures for reducing PAH emissions in the autumn and winter.     

The impact of implementation of the requirements of Standard No. OHSAS 18001:2007 to reduce the number of injuries at work and financial costs in the Republic of Croatia

This article contains the results of research into the impact of implementation of the requirements mentioned in Standard No. OHSAS 18001:2007 to reduce the number of injuries at work and the financial costs incurred in this way. The study was conducted on a determined sample by a written questionnaire survey method in the Republic of Croatia. The objective of the empirical research is to determine the impact of implementation of the requirements of Standard No. OHSAS 18001:2007 to reduce the number of injuries at work and financial costs in Croatia in business organizations that implement these requirements. To provide a broader picture, the research included the collection and analysis of data on the impact of the Standard No. OHSAS 18001:2007 on accidents and fatalities at work. Research findings are based on the analysis of performed statistical data where correlation and regression analysis has been applied.     

Water reclamation during drinking water treatments using polyamide nanofiltration membranes on a pilot scale

The aim of this study was to investigate the performances of polyamide nanofiltration membranes during water reclamation. The study was conducted using nanofiltration concentrates obtained from two different nanofiltration drinking water treatment plants placed in the northern part of Serbia (Kikinda and Zrenjanin). Used nanofiltration concentrates contained high concentrations of arsenic (45 and 451 μg/L) and natural organic matter (43.1 and 224.40 mgKMnO₄/L). Performances of polyamide nanofiltration membranes during water reclamation were investigated under various fluxes and transmembrane pressures in order to obtain drinking water from nanofiltration concentrates and, therefore, reduce the amount of produced concentrates and minimize the waste that has to be discharged in the environment. Applied polyamide nanofiltration membranes showed better removal efficiency during water reclamation when the concentrate with higher content of arsenic and natural organic matter was used while the obtained permeates were in accordance with European regulations. This study showed that total concentrate yield can be reduced to ~5 % of the optimum flux value, in both experiments. The obtained result for concentrate yield under the optimum flux presents considerable amount of reclaimed drinking water and valuable reduced quantity of produced wastewater.