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U ovom radu ispitana je mogućnost primjene različitih vrsta zeolita - prirodnog zeolita klinoptilolita (PZ), njegova homoionskog Na - oblika (NaZ3) te sintetskog Zeolite Socony Mobil-5 zeolita (ZSM-5) za uklanjanje fungicida karbendazima iz vodene otopine početne koncentracije γ o ≈ 5 mg/L. Uklanjanje je provedeno procesom adsorpcije šaržnim postupkom pri sobnoj temperaturi miješanjem zeolita i vodene otopine karbendazima u inkubatorskoj tresilici brzinom od 140 okr/min. Proces je praćen mjerenjem pH vrijednosti u određenim vremenskim intervalima te je određivana ravnotežna koncentracija karbendazima na HPLC uređaju. Najbolju učinkovitost uklanjanja od ≈ 95% pokazao je ZSM-5 zeolit, dok je učinkovitost PZ-a i NaZ3 bila u rasponu od 19,5 do 23,3%, odnosno od 22,5 do 29,0%. Ostatna koncentracija karbendazima nakon obrade na ZSM-5 zeolitu iznosila je 0,31 mg/L, dok je za PZ bila u rasponu od 4,46 do 4,83 mg/L te za NaZ3 u rasponu od 3,98 do 4,88 mg/L. Sve ostatne koncentracije bile su iznad propisanih maksimalno dopuštenih koncentracija (MDK) u vodi, koje za svaki pojedini pesticid iznose 0,10 µg/L, odnosno 0,50 µg/L za ukupne pesticide. Da bi se povećala učinkovitost PZ nužno je poboljšati njegova adsorpcijska svojstva za organskim komponentama iz vode modifikacijom s organskim surfaktantima. Nadalje, u svrhu smanjenja ostatne koncentracije karbendazima ispod MDK daljnja istraživanja trebalo bi usmjeriti na višestupanjsku adsorpciju na sintetskom ili modificiranom PZ šaržnim postupkom ili postupkom u koloni. This paper investigated the possibility of using different types of zeolite - natural zeolite (NZ) clinoptilolite, its homoionic Na - form (NaZ3) and synthetic Zeolite Socony Mobil-5 (ZSM-5), for the removal of carbendazim fungicides from aqueous solution of initial concentration γ o ≈ 5 mg/L. The adsorption was performed by batch process at room temperature, by mixing zeolites and carbendazim solution in an incubator shaker at a speed of 140 rpm. The process was monitored by measuring pH at specific time intervals and equilibrium concentration of carbendazim by HPLC. The best removal efficiency of ≈ 95% was achieved by ZSM-5 zeolite, while the efficiency of NZ and NaZ3 was in the range 19.5 - 23.3% and 22.5 - 29.0%, respectively. The residual concentration of carbendazim after treatment on ZSM-5 zeolite was 0.31 mg/L, while for NZ and NaZ3 was in the range of 4.46 - 4.83 mg/L, and of 3.98 - 4.88 mg/L, respectively. All residual concentrations were above the maximum permissible levels (MPL) in water, which for each pesticide equals to 0.10 µg/L, and 0.50 µg/L for total pesticides. In order to increase the efficiency of NZ, it is necessary to improve its adsorption properties for organic components from water by modification with organic surfactants. Furthermore, for the purpose of reducing the residual concentration of carbendazim below the MPL, further studies should be focused on multistage adsorption on a synthetic ZSM-5 zeolite or modified NZ by batch or column method.

Karbendazim je fungicid širokog spektra koji spada u skupinu benzimidazolnih spojeva i djeluje na način da inhibira diobu stanica. Postojan je i slabo topljiv u vodi te nakon tretiranja uzgajanih kultura zaostaje u hrani, predstavlja zdravstveni rizik za ljude i okoliš. Relativno su dobro poznati literaturni navodi o toksičnosti ovog pesticida i njegov utjecaj na ljudsko zdravlje. S obzirom da je utjecaj karbendazima na organizme vodenih ekosustava nedovoljno istražen, posebice na vrstama koje zauzimaju važnu ulogu u trofičkim lancima, cilj ovoga rada je istražiti potencijalno toksično djelovanje karbendazima na vrstu E. viridis. Čista kultura vrste tretirana je različitim rasponom doza karbendazima tijekom 18 dana pri čemu se pratila brojnost populacije. Pri akutnim koncentracijama, tijekom 24 sata karbendazim u koncentracijama od 0.1 nM do 100 nM ne uzrokuje smrtnost populacije, dok sve doze iznad 450 μM uzrokuju smrt kod 90–100 % euglena u populaciji. Utvrđena LC50 doza karbendazima za euglenu je 306,35 μM. Povećanje aktivnosti enzima SOD javlja se pri 200 μM koncentraciji u odnosu na kontrolnu grupu što je u skladu sa porastom intenziteta fluorescencijske boje DHE, koja ukazuje na blago povećanje razine superoksidnog aniona. Carbendazim is a wide spectrum fungicide belonging to the group of benzimidazole compounds and its mechanism of acttion is inhibition of cell division. It is persistent and poorly soluble in water and after the treatment of cultured crops lags behind in food and can represents a health risk for humans and the environment. There are relatively well-known literary allegations about the toxicity of this pesticide and its impact on human health. Since the influence of carbendazim on aquatic organisms on aquatic organisms is insufficiently explored, especially on species that play an important role in trophic chains, the aim of this study is to investigate the potentially toxic effects of carbendazim on E. viridis. The pure culture was treated with a different range of carbendazim doses within 18 days, with the population count being monitored. At acute concentrations, within 24 hours carbendazine at concentrations of 0.1 nM to 100 nM does not cause population mortality, while all doses above 450 μM cause death in 90-100 % euglena in the population. Determined LC50 dose of carbendazole for eugenas is 306,35 μM. Increasing activity of SOD enzymes occurs at 200 μM concentration in relation to the control group, which is consistent with the increase in intensity of the fluorescence dye DHE, which indicates a slight increase in the level of the superoxide anion.

Imazalil, cipermetrin i karbendazim su rezidualno detektibilni u namirnicama u Republici Hrvatskoj. Cilj rada je utvrditi na koji se način mijenja broj leukocita u perifernoj krvi ovisno o toksičnom djelovanju pojedinog pesticida u Swiss miševa izloženih dozama NOAEL pojedinog pesticida i njihovim kombinacijama tijekom 28 dana. Broj leukocita povećan je izlaganjem imazalilu, krabendazimu a smanjen je pri kombinaciji imazalila + karbendazima. U svih skupina izloženih pesticidima i njihovim kombinacijama promijenjeni su postotni udjeli granulocita i agranulocita. Broj limfocita smanjen je u grupi izloženoj imazalilu + krabendazimu a u svih ostalih skupina je povećan, najviše u tretmanu s imazalilom. Broj neutrofila je povećan u svim skupinama od kojih najviše u grupi izloženoj imazalilu i cipermetrinu. Slično je i sa brojem monocita, iako cipermetrin nije jednako jako povećao broj neutrofila. Vjerojatno je u tih skupina povećana potreba za tkivnom makrofagnom aktivnošću. Broj bazofila povećan je u svih skupina ali najviše nakon izloženosti karbendazimu što upućuje na njegov alergeni potencijal. Slično ukazuje i povećan broj eozinofila. Staničnost i težina imunosnih organa mijenjala se specifično s obzirom na pojedini pesticid i njihove kombinacije i ukazuje na dinamiku imunotoksičnosti tijekom pokusa. U skupina u kojima je staničnost i težina slezene, timusa i limfnih čvorova smanjena vjerojatno je već došlo do mobilizacije novo stvorenih stanica u krv gdje doprinose ukupnom povećanju staničnosti do 28 dana. U organima u kojima je broj stanica povećan one su najvjerojatnije još uvijek u fazi diobe potaknute pesticidima i nisu ispuštene u krv. Subkronične niske doze ovih pesticida i njihovih kombinacija imaju imunotoksični, imunostimulativni potencijal osim u skupine tretirane karbendazimom i cipermetrinom koji ima jači citotoksični potencijal pa je i generalno smanjen broj imunokompetentnih stanica u krvi. Imazalil, cypermethrine and carbendazime are rezidually detected in food-stuffs in Republic Croatia. The aim of reasearch is to establish in which way of the number of leukocytes in pheripheral blood depend on the toxicological activity individual pesticide on the immune organs of Swiss mice exposed to them for the 28 days. It is supposed that number of leukocytes in blood will follow pathophysiological conditions in thymus, spleen and lymph node during pesticide treatment. Analysis of leukocytes showed the increase in total number of leukocytes in treatment with imazalil, carbendazime and combination of carbendazime. In all other groups percentage of granulocytes and agranulocytes was changed. The number of lymphocytes was reduced after combination of imazalile and carbendazime, and after imazalile, cypermethrine and carbendazime (used individually) was increased compared to control, especially in group imazalil. A similar thing happened with monocyte number, although the cypermethrine did not strongly increase the number of neutrophils. Probably these pesticides increased macrophage activity. The number of basophils was increased after treatment with all pesticides, especially after carbendazime. Eosinophils showed the similar effect. Cellularity and wight of immune organs was changed specifically to certain pesticide and their combinations and points to the dynamics of immunotoxicity tests. In groups where the cellularity and weigth of spleen, thymus and limph node decreased, it is possible that mobilization of new cells had been ocured in the blood leading to overall cellularity increase up to 28 days. In the organs in which cell number increased, cells are probably still in the phase of separation and not yet released into the blood. Sub-chronic low doses of these pesticides and their combinations are immunotoxic and immunostimulating except the combination of carbendazime and cypermethrine, which showed a strong cytotoxic potential and reduced the number of immunocompetent cells in the blood.

U današnje vrijeme upotreba pesticida za suzbijanje različitih štetnika u proizvodnji hrane je neizbježna. Nažalost, pesticidi koji zaostaju u gotovoj hrani mogu imati štetni utjecaj na zdravlje potrošača. Jedan od takvih široko upotrebljavanih pesticida je metil 2-benzimidazol karbamat, poznat kao i karbendazim, fungicid iz skupine benzimidazolnih spojeva čiji je mehanizam djelovanja inhibicija diobenog vretena za vrijeme stanične diobe. Ovo istraživanje je provedeno s ciljem procjene genotoksičnog utjecaja karbendazima na Swiss miša. Grupe od pet muških miševa i pet ženskih miševa su svakodnevno oralno tretirane NOAEL dozom karbendazima (20 mg/kg tjelesne težine) tijekom 28 dana. Za procjenu genotoksičnog utjecaja korišteni su mikronukleus test in vivo i alkalni komet test. Komet test je proveden na stanicama krvi, limfnih čvorova, slezene i timusa, a mikronukleus test na retikulocitima periferne krvi. Primjenjena NOAEL doza karbendazima tijekom 28 dana kod muških miševa uzrokovala je visoku razinu oštećenja molekule DNA što je rezultiralo istovremenim značajnim povećanjem sva tri parametra kometa u stanicama krvi i timusa. Vidljivo je da postoje razlike utjecaja karbendazima na oštećenje molekule DNA između spolova, odnosno karbendazim uzrokuje intenzivnija oštećenja DNA kod muţjaka nego kod ženki. Karbendazim je inducirao značajno povećanje učestalosti mikronukleusa kod oba spola. In modern times the usage of pesticides to repel pests in food production is a necessity. Unfortunately, the pesticide residues in food can have a negative impact on consumers health. One of those widely used pesticides is metil 2-benzimidazole carbamate, also known as carbendazim, a benzimidazole fungicide whose mode of action is the inhibition of the spindle function during the cell division. This expirement was conducted in order to evaluate the genotoxic effect of carbendazim on the Swiss mouse. Groups of five male and five female mice were oraly given NOAEL dosage of carbendazim (20 mg/kg of body weight) during te period of 28 days. To evaluate the genotoxic effect micronucleus test in vivo and the single cell gel electrophoresis assay (comet assay) were used. The comet assay was conducted on blood, lymph node, spleen and thymus cells while the micronucleus test was conducted on the peripheral blood reticulocytes. The administered NOAEL dose of carbendazim during the 28 days caused high levels of DNA damage in male mice resulting in simultaneous significant increases of all three comet parameters in blood and thymus cells. Results show that there are differences of impact of carbendazim on DNA damage between sexes, that is carbendazim causes more intense DNA damage in male mice than in female mice. Carbendazim induced significant increase in the frequency of micronuclei in both sexes.

The sensitivity of 110 Cercospora beticola (Sacc.) isolates to carbendazime (benzimidazoles) and flutriafol (triazole DMI) was investigated. Isolates on PDA were obtained from diseased sugar leaves collected in 11 localities in Serbia during the August 2007. The medium effective concentration (EC50), the relative sensitivity (b) and the level of resistance (NR) in relation to the most sensitive isolate were calculated the method applied by Karaoglanidis et al. (2000). The obtained results confirmed already resistance of Serbian isolates of C. beticola to carbendazime, but for the first time isolates from Erdevik and Maradik showed a significantly decreased sensitivity to flutriafol. Ispitivana je osetljivost izolata Cercospora beticola (Sacc.), prouzrokovača pegavosti lišća šećerne repe iz 11 lokaliteta u Srbiji prema karbendazimu (grupa benzimidazola) i flutriafolu (grupa triazola DMI) tokom 2007. godine. Uzorkovanje je obavljeno tokom avgusta meseca. Za ispitivane izolate izračunate su srednje efektivne koncentracije (EC50), relativna osetljivost (b) i nivo rezistentnosti (NR) u odnosu na najosetljiviji izolat, po metodi Karaoglanidis i sar. (2000). Dobijeni rezultati su potvrdili već ranije dokazanu rezistetnost izolata C. beticola poreklom iz Srbije na karbendazim, ali po prvi put i značajno smanjenu osetljivost izolata poreklom iz Erdevika i Maradika prema flutriafolu.

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