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.

In the present paper, chemical composition, in vitro antimicrobial and antiproliferative activity of the essential oil from the flowers and leaves of Helichrysum italicum (Roth) G. Don (Central Dalmatia, Croatia) as a potential replacement for standard antibiotics and chemotherapeutic agents was analyzed. Essential oil was isolated by steam distillation and analyzed by GC/MS. Antimicrobial activity was carried out by agar-well diffusion and microdilution assays with Gram (+), Gram (-) bacteria and one yeast. Antiproliferative effect, apoptosis induction and cell death on cancer cell lines: HeLa, MCF-7, SW620, CFPAC-1 and MIA PaCa-2 were analyzed by cell viability and Annexin-V assay as well as by flow cytometric analysis. In essential oil, α-pinene, γ-curcumene and neryl acetate was found as major compounds. The antimicrobial assays, showed that essential oil had weak to moderate antimicrobial potential with S. aureus and S. epidermidis as the most sensitive bacterial strains. Essential oil treatment possessed moderate antiproliferative impact on MCF-7 and HeLa cell lines, while analyzing cell cycle treatment had no significant effect on tested cells except on MIA PaCa-2 with the highest cells increase in sub G1 phase cell cycle. However, treatment caused significantly induction of apoptosis in MCF-7 and HeLa cells, but not in MIA PaCa-2 cells. In this cell line, multiple cell death mechanism existed with involving apoptosis, senescence or necrosis. Results of the study provide a promising basis for the evaluation of the potential use of essential oil from H. italicum (Roth) G. Don as a source of alternative nature antibiotics or anticancer agents for the prevention or treatment of different diseases.

The paper examines the antiproliferative, antimicrobial and antioxidative effects of fir (Abies alba Mill.) honeydew honey from mountain region of Croatia (Gorski kotar) as a potential replacement for standard antibiotics and chemotherapeutic agents. Cell viability, annexin V assay and flow cytometry analysis served to analyse the antiproliferative effect on, apoptosis induction in and cell death of cancer cell lines: HeLa, MCF-7, SW620, CFPAC-1, MIA PaCa-2 and normal diploid human fibroblasts (BJ). Antimicrobial activity was tested against Staphylococcus and Acinetobacter strains by agar well diffusion and microdilution assays. The DPPH˙ assay determined the radical scavenging activity, while mathematical models helped to evaluate the kinetic data of DPPH˙ inhibition. Antiproliferative effect on all tested cell lines and the prominent effect on normal diploid human fibroblasts (BJ), colorectal adenocarcinoma (SW620, metastatic) and breast epithelial adenocarcinoma (MCF-7, metastatic) was observable. The mechanisms of antiproliferative effect included accumulation of cells in the sub-G1 phase in all tested cells and induction of apoptosis in SW620 and MCF-7 cells predominantly. The antibacterial assays showed that antibiotic-resistant strains of both bacteria, including multi-resistant strain A. baumannii ATCC® BAA-1605™, were sensitive to all tested honey samples. Radical scavenging assay suggests that antioxidants present in the honey possess different radical suppressing abilities and that they react at different rates with radicals, thereby causing two steps of reaction. The results of the study indicate that Croatian fir honeydew honey has a therapeutic potential due to the strong biological activity and can serve to protect human health.

Imidacloprid (IMI) is an extensively used neonicotinoid insecticide whose occurrence in the environment is a worldwide problem. Its sorption/transport properties are recognized as one of the key knowledge gaps hindering policymaking regarding its international routine monitoring in soils. Therefore, we studied IMI transport behaviour in Croatian Mediterranean soils using column experiments. Breakthrough curves were analysed using the two-site adsorption model and compared against dimethoate (DIM). Transport parameters were correlated to soil physicochemical properties. The results indicate that IMI shows a high degree of preference for soil organic matter over any other soil constituent. For IMI, the clay did not exhibit any sorption activity, while hematite did act as an active sorbent. Contrarily, hematite increased the leachability of DIM by blocking the active sorption sites on clay platelets. Both hematite and clay sorption acted as type-2 (i.e., rate-limiting) sites. In all soils, IMI exhibited lower short-term leachability than DIM. Combined with a body of data concerning other aspects of IMI environmental behaviour, the results indicate that the risk of accumulation of IMI in the soil is greater than the risk of contamination by leaching. Thus, continuous monitoring of IMI in soils should be incorporated into future soil health protection programs.

The antioxidant activity of three types of pumpkin seed oil or oil mixtures (cold- -pressed, produced from roasted seed paste and salad) produced in the northern part of Croatia and the kinetics of their behaviour as free radical scavengers were investigated using DPPH˙. In addition, the involvement of oil tocopherol isomers (α-, γ- and δ-) in different steps of DPPH˙ disappearance and their impact on the rate of reaction were analysed. The kinetics of DPPH˙ disappearance is a two-step process. In the first step, rapid disappearance of DPPH˙ occurs during the first 11 min of the reaction, depending on the oil type, followed by a slower decline in the second step. To describe DPPH˙ disappearance kinetics, six mathematical models (mono- and biphasic) were tested. Our findings showed that γ- and δ-tocopherols affected DPPH˙ disappearance during the first step, and α-tocopherol in the second step of the reaction. Moreover, α-tocopherol demonstrated 30 times higher antioxidant activity than γ- and δ-tocopherols. The results indicated the biphasic double-exponential behaviour of DPPH˙ disappearance in oil samples, due to the complexity of reactions that involve different tocopherol isomers and proceed through different chemical pathways.