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Brown rot, caused by Monilinia spp., is one of the most important pre- and postharvest diseases of pome and stone fruit worldwide. The disease is controlled by multiple preharvest fungicide applications, since in most European countries including Serbia, postharvest application of fungicides is not allowed. To reduce the amount of synthetic pesticides in the environment and their residues in food products, eco-friendly alternatives to synthetic pesticides became an object of many studies. Our previous investigations showed that essential oils exhibit a great potential to be used as crop protectants against many fungal plant pathogens. The aim of this study was to determine whether essential oils could be effectively used against Monilinia laxa, Monilinia fructigena and Monilinia fructicola, the most important pathogens of the genus Monilinia in stone and pome fruit in Serbia. Cultures of M. laxa, M. fructigena and M. fructicola were exposed to a volatile phase of numerous essential oils, including tea tree oil that is already on the market as a biofungicide. The results showed that the volatile phase of a thyme and oregano oils exhibited the highest toxicity. Further experiments in vitro, using slightly modified agar overlay technique, showed that developed formulations (emulsifiable concentrates - EC) significantly inhibited mycelial growth of Monilinia spp. Experiments in vivo, performed on inoculated apple fruits, revealed that formulation process successfully decreased evaporation of the oils from the treated areas and provided significant level of Monilinia spp. suppression, 47-61% compared to the control. To our knowledge, EC formulation of the thyme and oregano essential oils for use against Monilinia spp. has never been developed before. Presented results are initial findings and, therefore, evaluation of the activity of the developed products should be continued under field conditions to determine efficacy and to estimate economic aspects of its use.

Novo tehničko rešenje „Preparat na bazi etarskog ulja timijana u zaštiti plodova voćaka od prouzrokovača mrke truleži plodova“ omogućava smanjenje gubitaka tokom procesa skladištenja jabučastog i koštičavog voća koji nastaju usled pojave mrke truleži, pruža ekološki prihvatljivo i zdravstveno bezbedno rešenje, a doprinosi 6 održavanju visokog kvaliteta plodova koje zahteva savremeno tržište. Za primenu posle berbe, u svetu je registrovan ograničen broj sintetičkih preparata, a u našoj zemlji nijedan. Dosadašnja praksa suzbijanja ovih patogena zasnivala se na upotrebi fungicida tokom perioda vegetacije. Međutim, zbog visokih zahteva tržišta proces zaštite plodova od prouzrokovača mrke truleži neophodno je unaprediti uvođenjem novih mera koje se ne zasnivaju na primeni sintetisanih pesticida. Ekološki prihvatljivi biološki preparati, kao što je preparat na bazi etarskog ulja timijana, koji bi bio upotrebljen nakon berbe predstavljaju perspektivno rešenje za unapređenje zaštite uskladištenih plodova jabučastih i koštičavih voćaka.

As primary producers, macrophytes in water bodies represent irreplaceable part of aquatic environment. Negative effects of herbicides in non-target macrophytes, as well as their detection in surface waterbodies have been repeatedly found. One of the most frequently used aquatic macrophytes for pesticide effects assessment is Lemna sp. Pethoxamid is chloroacetamide herbicide, cell division inhibitor. In Serbia it is used as preemergent herbicide for broadleaf and grass weeds control in maize crops. The aim of this study was to evaluate effects of pethoxamid on non-target aquatic macrophytes. For this purpose, the estimation of growth parameters and chlorophyll content in Lemna minor after exposure to series of concentration was performed. Results obtained in this investigation indicated that pethoxamid is toxic for non-target aquatic macrophytes with potential to cause long term adverse effects in the environment.

Acetamiprid je sistemični insekticid širokog spektra delovanja koji pripada hemijskoj grupi neonikotinoida. Zbog dokazanog štetnog delovanja na medonosne pčele i druge oprašivače, neke aktivne supstance iz ove grupe insekticida povučene su iz primene na nivou Evropske unije.. Za razliku od njih, acetamiprid je, na reevaluaciji dobio produženje odobrenja od 15 godina, tako da je u našoj zemlji i Evropskoj Uniji odobren za primenu do 28.02.2033. godine. Usled toksičnosti za akvatične beskičmenjake acetamiprid je deklarisan kao štetan za vodene organizme sa dugotrajnim posledicama. Prema dostupnim rezultatima ispitivanjima nije registrovano njegovo toksično delovanje za ribe . Cilj ovog rada bio je ispitivanje toksičnosti preparata na bazi aktivne supstance acetamiprid (sadržaj a.s. 20%, vodorastvorljivo prašivo – SP) za embrionalni razvojni stadijum slatkovodne ribe zebra vrste Danio rerio. Embrioni starosti do 5 h nakon oplodnje su izlagani u statičnom testu seriji koncentracija preparata na bazi acetamiprida. Tretmani su postavljeni u tri, dok je kontrolna grupa imala šest ponavljanja. Ispitivanje je trajalo 120 h, a izvedeno je prema smernicama metode OECD 210 (2013). Nakon izlaganja embriona u definisanim vremenskim intervalima praćeni su smrtnost, poremećaj motoneuralnog i kardijalnog sistema, kao i pojave razvojnih deformacija: edema, kraniofacijalnih deformacija i izostanak mehura. Izračunavani su sledeći toksikološki parametri: srednja smrtna koncentracija (LC-50, mg as/L); srednje efektivne koncentracie za razvojne deformacije (EC- 50, mg as/L), indeks teratogenosti (TI). Izlaganje embriona D. rerio preparatu na bazi acetamprida dovelo je do statistički značajne smrtnosti u svim, izuzev tretmana sa najnižom ispitivanom koncentracijom. Takođe, registrovan je negativan uticaj na motoneuralni razvoj, srčani ritam i porast embriona, a od razvojnih poremećaja značajan je udeo jedinki kod kojih je izostalo obrazovanje ili nije bio ispunjen mehur. Iz odnosa toksično

Photocatalytic degradation of the carbamate insecticide methomyl and its commercial product Lannate-90 in aqueous suspension of TiO2 and ZnO using an Osram ultra-vitalux lamp (315-400 nm) was investigated. The objective of the investigation was to study and compare the rates of photochemical degradation of the pure active compound and its formulated product in order to find out the impact of inert ingredients on degradation processes. The photo-chemical degradation of pure methomyl was found to be slower than the degradation of its commercial product Lannate-90. Photodegradation was investigated by UV-Vis spectrometry and HPLC, while mineralization was monitored using IC and TOC analyses. Light absorption capabilities of catalysts were characterized by ultraviolet-visible diffuse reflectance spectroscopy method, while the stability of catalysts was studied by infrared analyses. Degradation products of methomyl and its formulated product were identified by high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) results and tentative photodegradation pathways were proposed.

Essential oils have been well-known for their antimicrobial properties for a very long time. Some of them have been effectively used in human medicine for decades. Our earlier investigation revealed a great potential of thyme and oregano essential oils as crop protectants against some postharvest fruit pathogens. The effects of formulated thyme and oregano essential oils on Monilinia laxa and Monilinia fructicola were studied in vitro and in vivo. In vitro antagonistic assays were performed on solidified PDA medium using a slightly modified agar overlay technique, while in vivo experiments were conducted on inoculated apple fruits. In vitro essays showed that the developed formulations (emulsifiable concentrates - EC) significantly inhibited the mycelial growth of Monilinia spp. Experiments in vivo, performed on inoculated apple fruits, revealed that the developed formulations provided a significant level of Monilinia spp. suppression. To our knowledge, another EC formulation of oregano essential oil intended for use in Monilinia spp. control has never been developed before. The presented results are initial findings and evaluation of the activity of the developed products should therefore proceed under field conditions to determine their efficacy and activity spectrum, and to estimate economic aspects of their use., Antimikrobna aktivnost etarskih ulja dobro je poznata i opisana u literaturi, kako u humanoj medicini, tako i u poljoprivredi. Naša prethodna istraživanja pokazala su da etarska ulja timijana i origana ispoljavaju veliki potencijal u suzbijanju nekih biljnih patogena koji mogu prouzrokovati gubitke tokom perioda skladištenja. U radu su proučeni efekti razvijenih formulacija na bazi etarskih ulja timijana i origana na Monilinia laxa i Monilinia fructicola. Bioaktivnost razvijene formulacije testirana je u in vitro i in vivo uslovima. Ogledi in vitro izvedeni su po delimično modifi kovanoj metodi testiranja antimikrobne aktivnosti na površini PDA podloge, dok su in vivo eksperimenti realizovani na inokulisanim plodovima jabuke. In vitro testiranja pokazala su da razvijene formulacije (koncentrat za emulziju - EC) značajno inhibiraju porast micelije Monilinia spp. U ogledima in vivo, na inokulisanim plodovima jabuke, pokazano je da testirane formulacije značajno inhibiraju razvoj mrke truleži ploda. Koliko NAM je poznato, u ovom radu prvi put je razvijena EC formulacija etarskog ulja origana za upotrebu u suzbijanju vrsta roda Monilinia spp. Dobijeni rezultati predstavljaju početak istraživanja koje treba dopuniti rezultatima ispitivanja efekata razvijene formulacije u uslovima praktične primene, proučavanja spektra njenog delovanja, kao i ekonomske isplativosti njene primene.

UV-C irradiation is widely used in the food industry. However, the health effects from dietary exposure to the irradiated pesticide residues retained in foodstuffs are underestimated. In this study, technical chlorpyrifos (TCPF) and its oil in water (EW) and emulsifiable concentrate (EC) formulations were irradiated by UV-C, and their photodegradation products were subjected to toxicity assessment, including determination of acetylcholinesterase (AChE) activity, genotoxicity and oxidative stress using human blood cells as a model system. Toxicity studies were performed using the chlorpyrifos concentrations in the range of those proposed as the maximum residue levels in plant commodities. TCPF, EW and EC photodegradation products induced DNA damage and oxidative stress, and their genotoxicity did not decrease as a function of irradiation time. Irradiated TCPF and EC are more potent AChE inhibitors than irradiated EW. Accordingly, the application of UV-C irradiation must be considered when processing the plants previously treated with chlorpyrifos formulations.

Proučavana je fotokatalitička degradacija model jedinjenja karbamatnog insekticida karbofurana u vodi, u prisustvu polihromatske svetlosti i katalizatora ZnO i TiO2. Ispitivan je uticaj reakcionih parametara, kao što su vreme reakcije i početna koncentracija karbofurana, na fotokatalitičku degradaciju. Ustanovljeno je da je reakcija bila pseudo-prvog reda i primenom optimalnih uslova skoro potpuno uklanjanje 88,4 mg L-1 karbofurana dogodilo se u toku 2 sata. Reakcije su praćene primenom UV spektroskopije i tečne hromatografije visokih performansi (HPLC). Naknadno, upoređena je fotokatalitička efikasnost katalizatora ZnO i TiO2 primenom identičnih reakcionih uslova., Photocatalytic degradation of a model compound of the carbamate insecticide carbofuran in water was studied using polychromatic light and ZnO and TiO2 catalysts. The influence of operational parameters, such as reaction time and initial carbofuran concentration, on photocatalytic degradation was studied. A pseudo-first-order kinetic model was established and an almost complete removal of 88.4 mg L-1 of carbofuran occurred within 2 h under optimized conditions. The reactions were examined by UV spectroscopy and high performance liquid chromatography (HPLC). In addition, the photocatalytic efficiencies of ZnO and TiO2 were compared under the same reaction conditions.

Pesticides play a very important role in reducing losses and maintaining quality in crop production. Although positive effects of pesticide use are undeniable, adverse effects are frequent. This has led to a comprehensive reevaluation of the benefits of pesticide use and potential adverse effects on human health and the environment before placing them on the market. The fact that pesticides are designed to be toxic and are deliberately introduced into the environment, makes them a very important and strictly regulated group of pollutants. The most commonly used group of pesticides are herbicides, and their detection in surface water bodies has been repeatedly reported. In spite of being designed to be toxic to target species, adverse effects on other inhabitants of aquatic environments have also been observed. In order to prevent negative environmental effects, the registration process for active substances and plant protection products involves predictive environmental risk assessments (ERA). Reliable assessment of long-term effects on non-target species, natural populations and ecosystems is a priority and ERA process is constantly being improved., Porast broja stanovnika dovodi do konstantne potrebe za povećanjem produktivnosti biljne proizvodnje, a veoma važnu ulogu u postizanju tog cilja imaju pesticidi, hemijska ili biološka sredstva za zaštitu bilja. Pored nesporno pozitivnih mogu imati i neželjene efekte, a ulažu se veliki napori kako bi se, pre stavljanja u promet, izvršila pravilna procena koristi koju nam upotreba pesticida donosi i potencijalnih neželjenih efekata na čoveka i životnu sredinu. Najmanje dve osobine ih odvajaju od drugih supstanci - dizajnirani su da budu toksični i ciljano se unose u životnu sredinu, pa je stoga njihov promet striktno zakonski regulisan. Najčešće korišćena grupa pesticida su herbicidi, a njihova detekcija u površinskim vodama veoma je česta. Iako su dizajnirani da utiču na ometanje razvoja primarnih producenata, neželjena dejstva registrovana su i na drugim konstituentima vodene životne sredine. U cilju sprečavanja negativnih ekoloških efekata, process registracije aktivnih supstanci i sredstava za zaštitu bilje obuhvata preventivnu ekološku procenu (ERA - Environmental risk assessment). Pouzdana procena dugotajnih efekata u životnoj sredini na neciljne vrste organizama, prirodne populacije i ekosisteme je osnovni zadatak ERA-e.

Brown rot caused by Monilinia spp. is one of the major factors limiting the storage period and market life of stone and pome fruits. Control of postharvest decay is currently based on the use of synthetic fungicides during bloom and preharvest periods, while postharvest use of fungicides is restricted in EU countries, as well as in Serbia. In recent years, the use of environmentally friendly approaches, such as biological control agents, has increased continuously due to public concerns over the risks of pesticide residues remaining in food and their negative impact on the environment. One of the most significant practical constraints in the use of biocontrol products is the required development of their shelf-stable formulations. The aim of this study was to test antifungal properties of numerous bacterial strains from Serbia against Monilinia fructicola, to develop a suspo-emulsion (SE) formulation, and to test its efficacy in apple protection against one of the most damaging brown fruit rot pathogens. We conducted in vitro screening of many bacterial isolates originating from different substrates for their antifungal properties against a M. fructicola isolate as a model organism. In vitro antagonistic activity assays were performed in 90 mm Petri plates using the wells technique. Based on antagonistic effects in vitro, seven of 108 isolates were chosen for further studies. The isolates were identified to the species level based on morphological and molecular characteristics. One the most promising antagonistic strains was then selected to develop a SE biopesticide formulation and test its bioactivity in vivo on apple fruits cv. Golden Delicious. The results showed that the investigated bacteria exhibited antifungal properties against M. fructicola in vitro, and that the B6 strain of Bacillus subtilis qualifies to be selected as the best for further testing in vivo. The experiment on wound-inoculated apple fruits showed that the SE formulation of B6 strain was as

Jabuka je jedna od najznačajnijih vrsta voćaka u Srbiji, koja se prema podacima iz 2014. godine gaji na površini od 23.737 ha (Republički zavod za statistiku Srbije, 2014). S obzirom da je tržište jabuke izuzetno zahtevno a konkurencija veoma velika, veliki je i izazov pred proizvođačima kako bi proizveli zdravstveno bezbedan plod dobrog kvaliteta i odgovarajuće krupnoće. Jedan od najznačajnijih uzročnika smanjenja kvaliteta plodova i mogućih gubitaka jesu bolesti prouzrokovane fitopatogenim gljivama. Osim patogena koji prouzrokuju značajne gubitke tokom vegetacije, mnoge fitopatogene gljive izazivaju ekonomski značajne gubitke posle berbe koji vrlo često premašuju gubitke u samom procesu proizvodnje (Grahovac i sar., 2011). Čak i prosečni potrošač, koji kupuje kvalitetne plodove u hipermarketima, uočava i prepoznaje značaj i trajnost problema, jer je često prinuđen da ubrzo nakon kupovine propale plodove baci. Literaturni podaci pokazuju da oboljenja uskladištenog voća predstavljaju najznačajniji faktor gubitaka u proizvodnji (Tian, 2007), sa gubicima od 5 do 25% u razvijenim, odnosno do 50% u zemljama u razvoju (Ewekeye et al., 2013; Marković et al., 2011).

Photocatalytic degradation of a model compound of the carbamate insecticide carbofuran in water was studied using polychromatic light and ZnO and TiO2 catalysts. The influence of operational parameters, such as reaction time and initial carbofuran concentration, on photocatalytic degradation was studied. A pseudo-first-order kinetic model was established and an almost complete removal of 88.4 mg L–1 of carbofuran occurred within 2 h under optimized conditions. The reactions were examined by UV spectroscopy and high performance liquid chromatography (HPLC). In addition, the photocatalytic efficiencies of ZnO and TiO2 were compared under the same reaction conditions.

Supplementary data 1: Table 1S. The chromatographic gradient profile; Table 2S. CPF concentration decrease (corresponding initial CPF concentration decrease was set as 0%) for all three forms of CPF depending on irradiation time; Table 3S. CPF and CPO concentrations determined chromatographically for TCPF, EW and EC formulations, as the function of irradiation time; % of CPO comparing to initial CPF concentration in all three forms of CPF; Supplementary data 2: Material safety data sheet according to 1907/2006/EC, Article 31/version 1; Supplementary data 3: Material safety data sheet according to 1907/2006/EC, Article 31/version 4

UV-C irradiation is widely used in the food industry. However, the health effects from dietary exposure to the irradiated pesticide residues retained in foodstuffs are underestimated. In this study, technical chlorpyrifos (TCPF) and its oil in water (EW) and emulsifiable concentrate (EC) formulations were irradiated by UV-C, and their photodegradation products were subjected to toxicity assessment, including determination of acetylcholinesterase (AChE) activity, genotoxicity and oxidative stress using human blood cells as a model system. Toxicity studies were performed using the chlorpyrifos concentrations in the range of those proposed as the maximum residue levels in plant commodities. TCPF, EW and EC photodegradation products induced DNA damage and oxidative stress, and their genotoxicity did not decrease as a function of irradiation time. Irradiated TCPF and EC are more potent AChE inhibitors than irradiated EW. Accordingly, the application of UV-C irradiation must be considered when processing the plants previously treated with chlorpyrifos formulations. © 2018 Elsevier Ltd

Herbicidi su najčešće korišćena grupa pesticida, a nakon dospevanja u vodenu sredinu mogu ispoljiti štetno delovanje na neciljne organizme. Na tržištu se nalaze različite formulacije pesticida koje sadrže iste aktivne supstance, pri čemu se postavlja pitanje uticaja oblika formulacije na toksičnost herbicida za neciljne organizme. U okviru ove doktorske disertacije ispitivan je i upoređivan uticaj tehničke supstance i formulisanih preparata klomazona – Rampa® EC i GAT Cenit 36 CS na različite organizme vodene sredine, nakon čega je urađena procena rizika. Delovanje klomazona na primarne producente urađeno je ispitivanjima na dve vrste akvatičnih makrofita – Lemna minor i Myriophyllum aquaticum. Preparat Rampa® EC ispoljio je veću toksičnost za vrstu L. minor, dok je GAT Cenit 36 CS bio toksičniji za M. aquaticum. Ipak, za oba preparata veća inhibicija rasta registrovana je kod ukorenjene vrste M. aquaticum, što potvrđuje uvođenje ove makrofite u procenu rizika od herbicida. Ispitivanja na beskičmenjacima (Daphnia magna), embrionima riba (Danio rerio) i žaba (Xenopus laevis) ukazala su na veću toksičnost preparata Rampa® EC u odnosu na tehničku supstancu i drugi preparat. U studijama sa vrstama D. rerio i X. laevis pored toksičnosti utvrđivan je i teratogeni potencijal tehničke supstance klomazon i oba ispitivana preparata. Ujedno, ovo je prvi rezultat o embriotoksičnosti, kako aktivne supstance, tako i preparata klomazona. Kod izlaganih jedinki registrovani su teratogeni efekti, kao što su: kraniofacijalne i deformacije kičme, pojava edema, smanjen porast (dužina). Kod embriona D. rerio izlagnih tehničkoj supstanci i preparatima registrovan je uticaj na motorne neurone, a kašnjenje u razvoju utvrđeno je kod izlaganja tehničkoj supstanci i preparatu Rampa® EC. Iz odnosa teratogenosti i toksičnosti kod embriona dve vrste utvrđen je indeks teratogenosti (TI) koji je ukazao da tehnička supstanca ima veći teratogeni, a preparat Rampa® EC toksični potencijal..., Herbicides are the most widely used group of pesticides, but they are able to cause adverse effects on non-target organisms after reaching water bodies. Different formulations using the same active ingredient are often available, which raises an issue of potential influence of different types of formulations on herbicide toxicity to nontarget organisms. Experiments were conducted as part of this doctoral dissertation to evaluate the toxicity of technical clomazone and its two formulated products: Rampa® EC and GAT Cenit 36 CS, to several aquatic organisms, and to assess the risks involved in their use. Clomazone effects on primary producers were assessed by examining two species of aquatic macrophytes – Lemna minor and Myriophyllum aquaticum. The Rampa® EC product demonstrated a higher toxicity to L. minor, while GAT Cenit 36 SC was more toxic to M. aquaticum. However, the rooted species M. aquaticum showed a greater inhibition of growth, considering both products, which supports introduction of this macrophyte in risk assessment protocols for herbicides. Experiments with aquatic invertebrate (Daphnia magna), fish (Danio rerio) and frog (Xenopus laevis) embryos revealed a higher toxicity of Rampa® EC than the technical ingredient and the other product. In experiments with D. rerio and X. laevis, teratogenic potential of the clomazone technical substance and both investigated products was determined in addition to toxicity assessment. The present investigation was also the first report on embryotoxicity caused by both clomazone active substance and its different products. Diverse teratogenic effects, such as craniofacial and spine deformities, edema and growth reduction (length), were found in exposed individuals. A significant effect on motoneurons was noted in D. rerio embryos exposed to the technical substance and both products, while underdevelopment was observed only in embryos exposed to the technical substance and Rampa® EC...

Herbicidi su najčešće korišćena grupa pesticida, a nakon dospevanja u vodenu sredinu mogu ispoljiti štetno delovanje na neciljne organizme. Na tržištu se nalaze različite formulacije pesticida koje sadrže iste aktivne supstance, pri čemu se postavlja pitanje uticaja oblika formulacije na toksičnost herbicida za neciljne organizme. U okviru ove doktorske disertacije ispitivan je i upoređivan uticaj tehničke supstance i formulisanih preparata klomazona – Rampa® EC i GAT Cenit 36 CS na različite organizme vodene sredine, nakon čega je urađena procena rizika. Delovanje klomazona na primarne producente urađeno je ispitivanjima na dve vrste akvatičnih makrofita – Lemna minor i Myriophyllum aquaticum. Preparat Rampa® EC ispoljio je veću toksičnost za vrstu L. minor, dok je GAT Cenit 36 CS bio toksičniji za M. aquaticum. Ipak, za oba preparata veća inhibicija rasta registrovana je kod ukorenjene vrste M. aquaticum, što potvrđuje uvođenje ove makrofite u procenu rizika od herbicida. Ispitivanja na beskičmenjacima (Daphnia magna), embrionima riba (Danio rerio) i žaba (Xenopus laevis) ukazala su na veću toksičnost preparata Rampa® EC u odnosu na tehničku supstancu i drugi preparat. U studijama sa vrstama D. rerio i X. laevis pored toksičnosti utvrđivan je i teratogeni potencijal tehničke supstance klomazon i oba ispitivana preparata. Ujedno, ovo je prvi rezultat o embriotoksičnosti, kako aktivne supstance, tako i preparata klomazona. Kod izlaganih jedinki registrovani su teratogeni efekti, kao što su: kraniofacijalne i deformacije kičme, pojava edema, smanjen porast (dužina). Kod embriona D. rerio izlagnih tehničkoj supstanci i preparatima registrovan je uticaj na motorne neurone, a kašnjenje u razvoju utvrđeno je kod izlaganja tehničkoj supstanci i preparatu Rampa® EC. Iz odnosa teratogenosti i toksičnosti kod embriona dve vrste utvrđen je indeks teratogenosti (TI) koji je ukazao da tehnička supstanca ima veći teratogeni, a preparat Rampa® EC toksični potencijal..., Herbicides are the most widely used group of pesticides, but they are able to cause adverse effects on non-target organisms after reaching water bodies. Different formulations using the same active ingredient are often available, which raises an issue of potential influence of different types of formulations on herbicide toxicity to nontarget organisms. Experiments were conducted as part of this doctoral dissertation to evaluate the toxicity of technical clomazone and its two formulated products: Rampa® EC and GAT Cenit 36 CS, to several aquatic organisms, and to assess the risks involved in their use. Clomazone effects on primary producers were assessed by examining two species of aquatic macrophytes – Lemna minor and Myriophyllum aquaticum. The Rampa® EC product demonstrated a higher toxicity to L. minor, while GAT Cenit 36 SC was more toxic to M. aquaticum. However, the rooted species M. aquaticum showed a greater inhibition of growth, considering both products, which supports introduction of this macrophyte in risk assessment protocols for herbicides. Experiments with aquatic invertebrate (Daphnia magna), fish (Danio rerio) and frog (Xenopus laevis) embryos revealed a higher toxicity of Rampa® EC than the technical ingredient and the other product. In experiments with D. rerio and X. laevis, teratogenic potential of the clomazone technical substance and both investigated products was determined in addition to toxicity assessment. The present investigation was also the first report on embryotoxicity caused by both clomazone active substance and its different products. Diverse teratogenic effects, such as craniofacial and spine deformities, edema and growth reduction (length), were found in exposed individuals. A significant effect on motoneurons was noted in D. rerio embryos exposed to the technical substance and both products, while underdevelopment was observed only in embryos exposed to the technical substance and Rampa® EC...

Pesticides are formulated in many different ways. Quizalofop-P-ethyl is selective post emergence herbicide which can be found on the market formulated as emulsifiable concentrate (EC) and suspension concentrate (SC). The objective of this investigation was to develop two types of formulations: emulsifiable concentrate (EC) and went a step forward and developed oil in water (EW) formulation. Oil in water (EW) is a kind of pesticide formulation which contains water instead of almost all organic solvents. EW recently replaces EC as a new excellent environmentally-friendly pesticide formulation. We started investigation with development of EC formulation (50 g a.s./L) and after that developed EW formulation with the same concentration of active ingredient. The results obtained by testing developed formulations according to FAO and WHO recommendations shown that they had necessary stability to be applied in plant protection.

A comparative study on photocatalytic degradation of the pesticide carbofuran and its commercial product Furadan 35-ST in an aqueous suspension of ZnO, irradiated by long-wave light (315-400 nm), is presented in this study. In order to assess the effects of inert ingredients present in the commercial product Furadan 35-ST, non-competitive and competitive adsorption and kinetic studies of carbofuran degradation processes were conducted. A higher photochemical degradation rate was found for pure carbofuran in comparison to a two-component system, carbofuran and single addition of ingredients at appropriate concentrations, and the commercial product Furadan 35-ST. The overall effect of inert ingredients was evaluated from a competitive study using the model system of Furadan 35-ST. The results of a mineralization study, obtained by ion chromatography (IC) and total organic carbon (TOC) analyses, revealed the formation of acetate, oxalate, and formate ions. Photodegradation products of carbofuran, three of them detected for the first time, were identified based on high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) and gas chromatography-mass spectrometry (GC-MS) results, and their photodegradation pathways were proposed.

TiO2 nanopowders were produced by sol-gel technique using TiCl4 as a starting material. For the preparation of crystalline anatase with developed surface area, this aqueous solution has been mixed with 0.05 M or 0.07 M (NH4)(2)SO4 solution in a temperature-controlled bath. The pH values of the suspension were 7, 8 or 9. According to the x-ray diffraction (XRD) analysis the anatase crystallite sizes were about 12 nm, which coincided with the average particle size revealed by scanning electron microscopy (SEM). The Raman scattering measurements have shown the presence of a small amount of highly disordered brookite phase in addition to dominant anatase phase with similar nanostructure in all synthesized powders. BET measurements revealed that all synthesized catalysts were fully mesoporous, except the sample synthesized with 0.07 M (NH4)(2)SO4 at pH=9, which had small amount of micropores. The photocatalytic degradation of herbicide Clomazone was carried out for both the pure active substance and as the commercial product (GAMIT 4-EC) under UV irradiation. The best photocatalytic efficiency was obtained for the catalyst with the largest specific surface area, confirming this parameter as crucial for enhanced photocatalytic degradation of the pure active substance and commercial product of herbicide Clomazone.

TiO2 nanopowders were produced by sol-gel technique using TiCl4 as a starting material. For the preparation of crystalline anatase with developed surface area, this aqueous solution has been mixed with 0.05 M or 0.07 M (NH4)(2)SO4 solution in a temperature-controlled bath. The pH values of the suspension were 7, 8 or 9. According to the x-ray diffraction (XRD) analysis the anatase crystallite sizes were about 12 nm, which coincided with the average particle size revealed by scanning electron microscopy (SEM). The Raman scattering measurements have shown the presence of a small amount of highly disordered brookite phase in addition to dominant anatase phase with similar nanostructure in all synthesized powders. BET measurements revealed that all synthesized catalysts were fully mesoporous, except the sample synthesized with 0.07 M (NH4)(2)SO4 at pH=9, which had small amount of micropores. The photocatalytic degradation of herbicide Clomazone was carried out for both the pure active substance and as the commercial product (GAMIT 4-EC) under UV irradiation. The best photocatalytic efficiency was obtained for the catalyst with the largest specific surface area, confirming this parameter as crucial for enhanced photocatalytic degradation of the pure active substance and commercial product of herbicide Clomazone.

Biopesticidi predstavljaju formulisane proizvode na bazi mikroorganizama kao što su bakterije, virusi, gljive, nematode ili prirodnih proizvoda kao što su biljni ekstrakti i semiohemikalije (npr. feromoni insekata). Udeo biopesticida koji se primenjuju u zaštiti bilja iznosi svega nekoliko procenata od ukupne količine pesticide koja se upotrebljava u te svrhe. Postoji više razloga za ovakvu situaciju kao što su, na primer, skup proizvodni proces, niska stabilnost biopesticida pri skladištenju, osetljivost na klimatske uslove pri kojima se primenjuju, zatim problemi vezani za efikasnost i dr. Neki od navedenih problema mogu da budu prevaziđeni odgovarajućim procesom formulisanja biopesticida. Zahtevi za što kvalitetnijim i efikasnijim proizvodima su sve veći tako da proces formulisanja otvara važan prostor za povećanje i proširenje aktivnosti biopesticida. U ovom radu razmatrane su različite formulacije biopesticida koje se nalaze na tržištu, mogućnosti njihove primene, prikazano je trenutno stanje u ovoj oblasti i date su perspektive daljeg razvoja., Biopesticides are the formulated form of active ingredients based on microorganisms such as bacteria, viruses, fungi, nematodes or naturally-occurring substances, including plant extracts and semiochemicals (e.g. insect pheromones). Application of biopesticides is still limited to only a few percent of all pesticides used for crop protection. There are many factors contributing to that situation, such as expensive production methods, poor storage stability, susceptibility to environmental conditions, efficacy problems, etc. Some of these problems can be overcome by formulation improvements. With many pressures on product performance formulation is becoming the most important area to enhance and extend the activity of biopesticides. In this paper we reviewed different types of biopesticides existing on the market and discussed possibilities for their application and current status. The expected future trends in formulation development of biopesticides are explained.

Poznato je da koncentrati za emulzije (EC) osim dobrih osobina koje nesporno imaju mogu da ispolje negativan uticaj na životnu sredinu i korisnika, pošto u svom sastavu imaju visok procenat rastvarača. Interesovanje za razvoj emulzija ulje u vodi (EW) kao moguće zamene za koncentrate za emulzije (EC), je nastalo upravo zbog problema koji mogu da nastanu usled negativnog uticaja organskih rastvarača prisutnih u velikoj meri. Primenom emulzija ulja u vodi (EW) može da se smanjiti fitotoksičnost, da se suzbije nepovoljno dejstvo na životnu sredinu i korisnika (npr. eliminisanjem dermalne toksičnosti), zatim EW formulacije imaju višu tačku paljenja u poređenju sa EC formulacijama te su bezbednije za transport i skladištenje, a imaju i dodatnu prednost da su pogodnije za zajedničku primenu sa koncentratima za suspenzije (SC), kada je to potrebno. Kada se radi o zaštiti bilja onda može da se zapazi da se vrlo često koriste aktivne materije iz grupe piretroida, na primer cipermetrin koji se primenjuje sam ili u kombinaciji sa drugim aktivnim materijama kao što je recimo hlorpirifos. Kombinacija upravo ove dve aktivne materije je zastupljena u proizvodu koji se već dugo nalazi na tržištu i koji je uglavnom formulisan kao koncentrat za emulziju. U ovom istraživanju je učinjen pokušaj da se razvije formulacija emulzije ulja u vodi (EW) sa istim aktivnim materijama. Razvijena formulacija je ispitana i rezultati su pokazali da je dovoljno stabilna i da bi mogla da se primeni u zaštiti bilja., It is well known that emulsifiable concentrates (EC), besides good properties have problem with a high solvent content thus are not environmental friendly and can cause problems for users. The interest in developing oil-in-water emulsions (EW) instead emulsifiable concentrates is increasing due to toxicological problems with solvents. Oil-in-water emulsions can reduce phytotoxicity, ecotoxicity and dermal toxicity, have a higher flash point than EC and are safer in transport and storage; also EW are more compatible with water based SC formulations for blends of active ingredients. Plant protection often includes the use of some pyretroides as active ingredients, for example Cypermethrin, alone or combined with Chlorpyrifos. It is a very old product which is formulated as EC formulation. In this study oil-in-water emulsion (EW) was developed with the same active ingredients. The EW formulation was tested and the results show that it was stable and therefore could be used in plant protection.

Aktivna materija abamektin ispoljava insekticidno i akaricidno dejstvo, a na našem tržištu se pretežno nalazi formulisana u obliku koncentrata za emulziju (EC). Da bi se povećala efikasnost preparata najćešće se preporučuje njegova primena sa nekim ađuvantom, uglavnom uljem biljnog ili mineralnog porekla. Da bi se prevazišli problemi oko efikasnosti ove aktivne materije, pokušali smo da je formulišemo kao uljnu disperziju (OD) sa sojinim uljem kao disperznom sredinom. Sadržaj aktivne materije u formulaciji iznosio je 1,8%. Razvijena formulacija je ispitivana praćenjem relevantnih parametara i na osnovu dobijenih rezultata zaključeno je da ima potrebnu stabilnost. U narednoj fazi predstoji ispitivanje formulacije pri primeni, odnosno provera efikasnosti., Abamectin was developed as an insecticide, nematocide and acaricide for use on a variety of agricultural and horticultural crops. The products with this active ingredient can be found on the market mostly formulated as emulsifiable concentrate (EC). Usually producers recommend using the EC formulation of abamectin together with some kind of adjuvants (natural oils) to improve efficacy of the active ingredient. To overcome the efficacy problem we tried to formulate the active ingredient abamectin as oil dispersion (OD). Oil dispersion, preferably based on naturally derived oils could improve pesticide efficacy. This type of pesticide formulation contains oil instead of water as in classical suspension concentrate and typically has better retention and coverage. In the case of abamectin, in this investigation soybean oil was used with the mixture of different nonionic emulsifiers. Content of abamecetin in formulation was 1.8 %. The developed formulation was tested for few important parameters. The obtained physicochemical properties for the above mentioned formulation have shown that it is stable and could be used in plant protection.

Adjuvants have been developed to enhance the activity of pesticide and possibly could allow reduction of pesticide rates. This is a very important fact as there are many concerns associated with pesticides use, because of their potential to cause adverse effects to operators, crops and environment. Because of that there is continued government regulatory pressure for safer pesticide products and for reduction of pesticides application rate. Trend towards minimum use of pesticides lead to development of new, more effective adjuvants to enhance biological activity of pesticide formulations, either built-in formulation or added in tank mix just before application. Among others, crop oil concentrates (COC) and soluble concentrates (SL) are bioenhancing adjuvants which enhance the effectiveness of pesticides. In our study we investigated how adjuvants with different compositions influenced bentazone efficacy. The first step was development of ecofriendly crop oil concentrates based on vegetable oils (sunflower oil, soybean oil and esterified rape seed oil) in combination with different surfactants. Then we compared the effects of the crop oil concentrates and the commercial adjuvant (Trend (R) 90, soluble concentrate) during the application with bentazone on two different locations. The results after two year trials confirmed that all investigated adjuvants have beneficial effects on bentazone efficacy, but the effects of the developed crop oil concentrate with esterified rape seed oil was the most pronounced.

Subacute and subchronic toxicity of the herbicide Avalon (R), a mixture of bentazone and dicamba, were tested on rats. Avalon (R) was administered at dose levels of 250, 500 and 1000 mg/kg body weight/day for 28 and 90 days. Alanine aminotransferase (ALT), aspartate aminotransferase (AST) and alkaline phosphatase (ALP) activities were monitored together with biochemistry parameters. The results showed that the mixture caused increases in the activities of ALT, AST and ALP, elevated concentrations of sodium, albumin and albumin/globulin ratio in males. In females, ALT activity, cholesterol and phosphate levels were increased. The changes generally were dose related and, in most cases, females exhibited lower susceptibility than males. The effects of a mixture are, in the most cases, different from the effects of the individual substances. The effects of bentazone were not prevalent which would be expected taking the composition of the mixture into account.

Pesticide metsulfuron-methyl (chemical name: methyl 2-(4-methoxy-6-methyl-1,3,5-triazin-2-ylcarbamoylsulfamoyl) benzoate) is a post-emergence sulfonylurea herbicide which controls most annual grass broadleaf weeds in cereals, and it has been used for a long time. The effect of metsulfuron-methyl on microbiological activity in soil was investigated. Trials were set up in laboratory on chernozem soil (pH 7.0, organic matter 3.5%, sand 26%, silt 45%, clay 29%) at Surcin, Serbia. Metsulfuron-methyl was added at rates 1, 5, 25 i 50 mg/kg soil. Untreated soil served as control. Samples were collected for analysis 5, 20, 40 and 60 days after metsulfuron-methyl application. The effects were assessed on dehydrogenase activity, bacteria abundance and fungi abundance. Metsulfuron-methyl was found to cause different effects on the soil microbial activity in soil and its influence depended on the rate of application and duration of activity. Metsulfuron-methyl applied at 1 and 5 mg/kg soil did not have any effect on microbial parameters. The higher herbicide doses (25 and 50 mg/kg) induced increasing activity from the 5th to 40th day. These experimental data indicated that metsulfuron-methylon affected soil microbial activity, but the effects were only detected at higher doses and they were slight and transitory.

The photocatalytic degradation of the insecticide methomyl in water using TiO2 Merck Eusolex (R) T (anatase) under Osram ultra-vitalux (R) lamp light (315-400 nm, 300W) was studied. The effect of the operational parameters, such as initial concentration of catalyst, initial methomyl concentration, initial salt concentration (NaCl), and pH, was studied. The optimal concentration of catalyst was found to be 2.0 g/L. Using the Langmuir-Hinshelwood mechanism as a base, a pseudo-first-order kinetic model was illustrated and the adsorption equilibrium constant and the rate constant of the surface reaction were calculated (K-MT = 0.079 L/mg and k(C) = 0.134mg/L min, respectively). The photodegradation rate was higher in acidic than in alkaline conditions. The presence of Cl- ions significantly affected the photodegradation of the pollutant. The rate of photodecomposition of methomyl was measured using UV spectroscopy and high performance liquid chromatography, while its mineralization was followed using ion chromatography and total organic carbon analysis. In addition, several photocatalysts were used: ZnO (Merck), TiO2 P-25 (Degussa), TiO2 Merck (anatase), and TiO2 Merck R-706 (rutile), and were compared with TiO2 Merck Eusolex (R) T (anatase).

The effect of mesotrione on microbiological activity in soil was investigated. Trials were set up in laboratory on chernozem soil (pH 7.0, organic matter 3.5%, sand 26%, silt 45%, clay 29%) at Surcin, Serbia. Mesotrione was added at rates 0.5 (field rate), 5, 25 i 50 mg/kg soil. Untreated soil served as control. Samples were collected for analysis 5, 20, 40 and 60 days after mesotrione application. The effects were assessed on bacteria abundance, fungi abundance, and dehydrogenase activity. Mesotrione was found to cause different effects on the soil microbial activity in soil and its influence depended on the rate of application and duration of activity. Mesotrione applied at 0.5 and 5 mg/kg soil did not have any effect on microbial activity. The higher herbicide doses (25 and 50 mg/kg) induced increasing activity from the 5th to 60th day. These experimental data indicated that mesotrione affected soil microbial activity, but the effects were only detected at higher doses far exceeding the recommended field rate.