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Pesticides are chemicals used in agriculture to protect crops from pests. In addition to protection during cultivation, they are also used after harvesting to extend the shelf life of products. Postharvest control stands out, especially when it comes to products imported from distant countries, resulting in increased concentration of pesticides and risk to human health consuming such products. In this study, analyses of pesticide residues were performed on 200 samples of fruits and vegetables. Pesticide residues were identified and quantified in 30 out of 200 samples. Study results revealed imazalil to be the most frequently detected pesticide. Risk assessment was performed on the obtained results, and it was carried out separately for adults and for children under 6 years of age. Imazalil showed the highest ARfD percentage for adults (max% ARfD 251%), and these values were especially high on risk assessment for children, where they amounted up to max% ARfD 1087%. The study of imazalil impact was performed on 16 Swiss albino mice divided into two groups and 4 subgroups. Experimental group animals were treated with the corresponding NOAEL dose of imazalil (10 mg/kg) for 28 days. Body weight was measured before each pesticide application on a digital electronic Sartorius scale. Peripheral blood analysis was performed after 28-day animal exposure to pesticides. Animals were anesthetized, blood samples were obtained by cardiac puncture, and red blood cell (RBC) count, hemoglobin (Hb) concentration, and white blood cell (WBC) count were determined by standard hematological methods. The organs for determination of imazalil concentration were extracted immediately upon animal sacrifice and stored in a freezer at -80°C until analysis. Results show difference in gain weight, and an increase in WBC count was recorded in the experimental group as compared with a control group of animals. The highest imazalil levels were recorded in adipose tissue (45.2‰) which proves tendency to accumulate.

Sredstva za zaštitu bilja pripravci su koji se sastoje ili koji sadržavaju aktivne tvari i dodatne nepesticidne tvari. Jedna od najuobičajenijih metoda za zaštitu bilja i biljnih proizvoda od utjecaja štetnih organizama svakako je uporaba aktivnih tvari u sredstvima za zaštitu bilja. Međutim, moguća posljedica njihove uporabe može biti prisutnost ostatka na tretiranim proizvodima, u životinjama koje se hrane tim proizvodima i u medu koji su proizvele pčele izložene tim tvarima. Analize ostataka pesticida u proizvodima biljnog i životinjskog podrijetla provode se u analitičkim laboratorijima i koriste se multirezidualne metode (MRM) ili pojedinačne metode (SRM). Rezultati analiza ocjenjuju se sukladno Uredbi 396/2005 za konvencionalne proizvode i na temelju Uredbe (EZ) 889/2008 za proizvode iz ekološke proizvodnje.

Mikotoksini su sekundarni produkti plijesni i vrlo česti kontaminanti hrane. Najčešće su njima kontaminirane žitarice, ali istraživanja ukazuju na to da i druge vrste namirnica mogu biti kontaminirane mikotoksinima. Vino je namirnica koja je najčešće kontaminirana ohratoksinom A (OTA), koji nastaje kao produkt plijesni nastale na grožđu ili kasnije tijekom njegove prerade, a kao i većina drugih mikotoksina, štetno utječe na zdravlje ljudi i životinja, te se njihova prisutnost u hrani redovito provjerava. U ovome radu analizirali smo bijela i crna vina iz podregije koprivničko-đurđevačkog vinogorja na prisutnost ohratoksina A kojeg sintetiziraju plijesni iz skupine Aspergillus ochraceus i Penicillium viridicatum. Kao članica Europske Unije, Hrvatska je prihvatila Uredbu 1881/2006 o utvrđivanju najvećih dopuštenih količina određenih kontaminanata u hrani koja jednoznačno utvrđuje najviše dopuštene koncentracije ohratoksina A u određenim vrstama hrane, uključujući i vino. Ukupno je analizirano 34 uzorka vina, 19 bijelih vina i 15 uzoraka crnih vina. Vrijednosti OTA kretale su se u rasponu od 0, 269 do 1, 696 g/L za bijelo vino i od 0, 254 do 0, 565 g/L za crno vino. Nakon izolacije, kvantifikacija ohratoksina A iz vina provedena je imunoenzimskom tehnikom ELISA. Sve dobivene vrijednosti ohratoksina A u analiziranim uzorcima vina niže su od najveće dozvoljene količine koja iznosi 2 g/L, te su ocijenjena sukladnim i prihvatljivim za konzumaciju. Obzirom na dobivene rezultate može se zaključiti da je evidentna prisutnost ohratoksina A u vinima, te je neophodno kontinuirao pratiti njegove vrijednosti u vinima na tržištu, a sve u svrhu zaštite zdravlja potrošača

© 2018 Elsevier Ltd This study was performed in a group of adult vegetarians (N = 40) and matched non-vegetarian subjects (N = 40) in order to analyse differences in health-related biomarkers. Obtained results revealed differences in various biomarkers between subjects on a traditional mixed and vegetarian diet, indicating that vegetarians have a lower nutritional status of some nutrients (Ca, Cu and Zn, and vitamins B12 and D) accompanied with a lower antioxidant defence system (glutathione) and higher homocysteine and genome damage (micronuclei and DNA strand breaks), along with shorter telomeres. This suggests that the supplementation of animal derived nutrients to this particular dietary group would be beneficial for the improvement of some measured health-related biomarkers. However, the level of certain toxic metals (As and Hg) was higher in non-vegetarians. The presented multi-biomarker approach implies the necessity of evaluating a large number of different health-related biomarkers in order to obtain clear insight into dietary preferences and health outcomes.

Ginkgo biloba L. is the eldest plant growing on the Earth; preparations made of its leaves and seeds represent an integral part of the Chinese medicine for over a millennium. The plant species was first discovered by Linnaeus in 1771, its name thereby originating from the Latin words bis (two) and lobus (lobe), which duly illustrate the specific shape of its leaf. Contemporary Ginkgo biloba L. plant based pharmaceuticals mostly comprise extracts recovered from leaves harvested during fall, when the concentration of active components reaches its peak. Recent investigations have managed to establish the chemical composition of the plant leaf, together with the mechanisms underlying its beneficial effects on rheological profile of the blood and acceleration of its flow. High price of these preparations and their vast popularity have soon become an incentive for counterfeiting Ginkgo biloba L. extracts and the release of bogus drugs comprising cheaper extracts coming from other plants. Namely, modern Ginkgo biloba L.-based medicinal products and food supplements comprise extracts recovered from the plant leaf that get to be standardized according to its key pharmacological active components, most often flavone glycosides (represented in the share of 22%-27%) and terpene trilactones (represented in the share of 6%-7%). The flavonoids that predominate such preparations and are most relevant from the pharmacological standpoint are quercetin, kaempferol and isorhamnetin, their total amount and mutual ratios, thereby being an unquestionable indicator of the extract authenticity. Therefore, most of the analyses aiming at verifying the authenticity of a given Ginkgo biloba L.-based product boil down to the analysis of these parameters. Counterfeiting involves partial or full replacement of the Ginkgo biloba L. extract (GBE) with a cheaper plant extract of a similar composition, the latter occasionally being enriched with an additional amount of flavonoids, most often quercetin, not originating from the Ginkgo biloba L. plant. The aim of this study was to verify the authenticity and quality of Ginkgo biloba L.-based products circulating on the Croatian market. To that effect, 10 samples of products produced by various manufacturers were analyzed in a certified laboratory. The parameters based on which the authenticity of the preparations was assessed were the shares of aglycones of typical ginkgo flavone glycosides, that is to say, quercetin, kaempferol and isorhamnetin, and mutual ratios of the established quantities of quercetin to kaempferol as the key clues to unmasking Ginkgo extracts counterfeiting. The amount of ginkgo flavone glycosides was established using high performance liquid chromatography. The analysis proved 80% of the samples analyzed to be conformant to the label statements as regards the total amount of flavone glycosides and their mutual ratios. In 20% of the samples, the ratio of quercetin to kaempferol deviated from normal values; on top of that, the presence of the phytoestrogen genistein, one of the components typically comprised by the Sophora japonica L. plant, was also proven, documenting counterfeiting of the GBE and its replacement by the Sophora japonica L. extracts in the samples under consideration. Due to the untrue label statements descriptive of these products, the information on the presence of pharmacologically active genistein was neglected to be mentioned despite its unfavorable health impact that can be expected in some consumer groups. The results of this study indicated the frequency of counterfeiting the Ginkgo biloba L.-based products found on the Croatian market to be deemed substantial. Therefore, a more rigorous and more thorough control of these products and sanctioning of irresponsible manufacturers and distributers is proposed, so as to contribute to a higher market representation of high-quality products, as well as to avoid health risks and downsize the rate of their counterfeiting., Ginkgo biloba L. najstarija je biljka na zemlji, a pripravci od njegovih listova i sjemenaka dio su kineske medicine već više tisuća godina. Vrstu je 1771. godine otkrio Linnaeus, a ime je dobila od latinskih riječi bis, tj. dva i lobus zbog specifičnog oblika lista. Današnji farmaceutski oblici biljke Ginkgo biloba L. sadrže uglavnom ekstrakte iz listova ubranih ujesen kada je najveća koncentracija aktivnih komponenata. Suvremenim istraživanjima određen je kemijski sastav njegovog lista, a utvrđeni su i mehanizmi njegovog pozitivnog djelovanja na reološka svojstva krvi i ubrzanje njezinog protoka. Visoka cijena i velika popularnost ubrzo su postali poticaj za krivotvorenje ekstrakta biljke Ginkgo biloba L. jeftinijim ekstraktima drugih biljaka. Naime, suvremeni medicinski proizvodi i dodaci prehrani na osnovi biljke Ginkgo biloba L. sadrže ekstrakte njegovog lista koji se standardiziraju prema njegovim ključnim farmakološki aktivnim sastavnicama; najčešće je to 22%-27% flavonoid glikozida i 6%-7% terpenskih trilaktona. Kvercetin, kempferol i izoramnetin su dominantni i farmakološki najvažniji flavonoidi, a njihova ukupna količina i međusobni omjeri nedvojben su pokazatelj autentičnosti ekstrakta. Stoga se i većina analiza za utvrđivanje ispravnosti proizvoda koji sadrže biljku Ginkgo biloba L. temelji na analizi ovih parametara. Krivotvorenja podrazumijevaju djelomičnu ili potpunu zamjenu ektrakta Ginkgo biloba L. nekim jeftinijim biljnim ekstraktom sličnog sastava uz eventualno obogaćivanje dodatnom količinom flavonoida, najčešće kvercetina, koji ne potječu od biljke Ginkgo biloba L. Svrha ovoga rada bila je provjeriti autentičnost i kakvoću pripravaka Ginkgo biloba L. na hrvatskom tržištu. Analizirano je ukupno 10 uzoraka različitih proizvođača. Kao pokazatelji njihove ispravnosti određivani su udjeli aglikona karakterističnih ginkoflavonoglikozida: kvercetin, kempferol i izoramnetin te omjeri nađenih količina kvercetina i kempferola kao ključni pokazatelji krivotvorenja ginkgo-ekstrakta. Količina ginkoflavonoglikozida određena je metodom tekućinske kromatografije visoke djelotvornosti. Analizom je utvrđeno da 80% uzoraka odgovara navodima deklaracije u pogledu ukupne količine flavonoglikozida kao i u pogledu njihovog međusobnog omjera. U 20% uzoraka omjer kvercetina i kempferola odstupao je od uobičajenih vrijednosti, a dokazano je i prisustvo fitoestrogena genisteina, jedne od karakterističnih sastavnica biljke Sophora japonica L., čijim ekstraktom je krivotvoren ginkgo-ekstrakt u analiziranim uzorcima. Zbog neistinite deklaracije na proizvodima koji su sadržavali ove ekstrakte izostalo je i obvezno upozorenje o prisutnosti farmakološki aktivnog genisteina koji može izazvati neželjene zdravstvene posljedice kod pojedinih skupina potrošača. Rezultati ovoga rada ukazuju na značajnu pojavnost krivotvorenja proizvoda biljke Ginkgo biloba L. na hrvatskom tržištu te se zbog toga predlaže njihova temeljitija kontrola kao i sankcioniranje neodgovornih proizvođača i trgovaca, čime bi se doprinijelo većem udjelu kvalitetnijih proizvoda i izbjegli zdravstveni rizici te smanjila pojavnost prijevare.

Cilj: U ovom istraživanju uzorci cvjetnoga meda korišteni su kao bio-pokazatelji onečišćenja okoliša pesticidima. Materijal i metode: Ukupno je prikupljeno 40 (4x10) uzoraka sa 4 različite prostorne lokacije (subregije), u ukupno 16 općina, od proizvođača meda u Varaždinskoj županiji, kao i 20 (2x10) uzoraka s dvije različite lokacije proizvođača u susjednoj županiji, registriranih kao "ekoloških proizvođači", a udaljenih od poljoprivrednih površina pod konvencionalnom proizvodnjom. Analize su provedene korištenjem vezanog sustava plinske kromatografije i spektrometrije masa (GCMS) i tekućinskom kromatografijom visoke djelotvornosti (HPLC). Rezultati: Identificirano je i kvantificirano 78 aktivnih sastojaka pesticide, koji su dio od ukupno cca 400 pesticida koji se analiziraju u voću i povrću, a za koje je laboratorij raspolagao analitičkom opremom koja i dijelom određuje i vrstu i broj pesticida koje se detektiraju. Rezultati analiza ukazali su na mogući uzročno posljedični odnos između konvencionalnih poljoprivrednih aktivnosti u Varaždinskoj županiji s identificiranim i kvantificiranim aktivnim sastojcima pesticida. Iz rezultata dobivenih na udjelima identificiranih i kvantificiranih ostataka pesticida, s obzirom na dopustivost, vidljivo je da je udio dopuštenih pesticida u uzorcima cvjetnoga meda iznosio 55,2%, dok je udio ilegalnih pesticida iznosio 44,8%. Analizirajući broj otkrivenih insekticida i fungicida, ukupno na sve 4 lokacije utvrđeno je da cvjetni med sadrži 13 različitih vrsta insekticida i 3 vrste fungicida. Zaključak: Rezultati i statistička analiza podataka pokazuju da je cvjetni med dobar bio-indikator onečišćenja okoliša pesticidima, te stoga ova studija može poslužiti kao osnova za znanstvenike i stručnjake koji se bave istraživanjem štetnih učinaka pesticida na okoliš i ljudsko zdravlje., Aim: In this research samples of floral honey were used as bio-indicators of environmental pollution by pesticides. Material and methods: A total of 40 (4x10) samples from bee farms were collected at 4 different locations (sub-regions) including 16 municipalities in the Varaždin County, as well as 20 (2x10) samples from two locations – bee-farms registered as "ecological producers" in the neighborhood County, both located far away from conventional agricultural production. Analyses were carried out using the gas chromatography joint system with mass spectrometry (GCMS) and high-performance liquid chromatography (HPLC). Results: Identification and quantification of 78 pesticide active ingredients were performed which are part of a total of approximately 400 pesticides that are usually analyzed in fruits and vegetables whereby the laboratory had available analytical equipment that also determined the number of detected pesticides. Due to identified and quantified active ingredients of pesticides, the results of analyses might indicate a possible cause-effect relationship with conventional agricultural activities in the Varaždin County. It was evident from the obtained results on the shares of identified and quantified pesticide residues, and with respect to admissibility, that the share of permitted pesticides in the samples of floral honey accounted for 55.2%, while the share of illegal pesticides accounted for 44.8%. Analyzing the number of detected insecticides and fungicides, on a total of all 4 locations (sub-regions), it was found that floral honey contained 13 different types of insecticides and 3 types of fungicides. Conclusion: The results and statistical data analysis showed that floral honey is a good bio-indicator of environmental pollution by pesticides, therefore this study can serve as a basis for scientists and experts engaged in the research of harmful effects of pesticides on the environment and human health.

The purpose of this study was to determine and to compare the amount of heavy metals in the meat of white (N = 39) and blue (N = 35) sea fish, considering the spring (N = 38) and fall (N = 36) catch period to study the possible type and seasonal differences especially in Hg concentrations in fish, and to estimate if the amounts registered can have a harmful effect on consumer health. The fish were chosen as an indicator of eco-system contamination with mercury and other heavy metals. The amount of heavy metals, lead (Pb) and cadmium (Cd), in both groups was lower than the Highest Permissible Amounts regulated by law in Croatia and the European Union. Mercury (Hg) exceeded the maximum allowed value in just a number of samples 3/74 (0.04%), while it is relevant for arsenic (As) to be present in almost any sample, although it has simultaneously not been regulated by law. The statistically significant value of arsenic exists in blue fish during the spring period, and the amount of mercury is higher in white fish compared to blue fish. Also a statistically significant difference in mercury levels was recorded during fall compared to spring,. Given the dietary habits and frequent fish consumption in Croatia, there is no risk of harmful health effects., Cilj ovoga rada bio je odrediti i usporediti količinu teških metala u 74 uzorka bijele (N = 39) i plave ribe (N = 35), uzorkovanih u proljetnom (N = 38) i jesenskom razdoblju (N = 36), kako bi se istražila moguća razlika u koncentracijama teških metala, posebice žive, ovisno o sezoni ulova ili tipu ribe i procijenilo mogu li determinirane količine imati štetnih utjecaja na zdravlje potrošača. Riba je izabrana, budući da je ona indikator zagađenja teškim metalima u eko sustavu. Količina teških metala, olova (Pb) i kadmija (Cd), u obje grupe uzoraka, bila je niža od maksimalnih dopuštenih koncentracija prema hrvatskih i europskim zakonima. Količina žive (Hg) bila je više od maksimalnih dopuštenih koncentracija u vrlo malom broju uzoraka 3/74 (0,04%). Međutim, u uzrocima su zabilježene relevantne količine arsena (As), iako količine arsena nisu regulirane hrvatskim propisima. Multivarijatna statistička obrada (neparametrijski Mann-Whitney U test) pokazala je statistički značajne razlike u količini arsena u proljetnom razdoblju u odnosu na jesensko razdoblje, kao što je i izmjerena količina žive statistički značajno bila viša u bijeloj u odnosu na plavu ribu, te ona izmjerena u jesenskom razdoblju u odnosu na proljetno. Uzevši, međutim, u obzir potrošačke navike i učestalost konzumacije ribe u Hrvatskoj, izmjerene koncentracije nisu povezane s rizikom štetnih posljedica na zdravlje potrošača.

The work examines the bioaccumulated persistent organochlorine compounds in Muraena helena to draw attention on this species as a potential bioindicator organism. Fish were caught in East Adriatic, Elaphite islands, near Dubrovnik, Croatia (Lat: 42°45´38.8” ; Long: 17°45´53.6”), on the same location in summer (August, 2009) and winter (January, 2010), at depth from 5-10 m. A total of 9 fish have been caught by long line hooks per each field trip (total in summer and winter, N=18). Not a single animal was recorded to be free of organochlorines but not all pesticides were present in every fish. Array of concentration level was:Endrine>ppDDE>Heptachlorepoxide>Heptachlore>Aldrine>Lindane>βHCH>δHCH> Endrine aldehide). Endrine, was the only pesticide approaching maximal concentrations proposed by low in EU and Croatia (summer maximal concentrations = 14.75 µgkg-1l ; winter maximal concentration = 8.35 µg kg-1). All other pesticides ranged from 0.1-0.7 µgkg-1. Heptachlore was absent in winter and δ-HCH and Endrine aldehide in summer while Lindan and pp-DDE had higher (p≤0.05) concentration in summer. Other residues had similar seasonal concentration level. p-DDT was similar as in other biota from the Adriatic sea or Mediterranean. HCH concentrations corresponded with those found in organisms from Italian side of Adriatic. Endocrine and reproductive disrupting potential of detected OC´s is bases for future studies. Results point that Morays are a good bioindicator model with slight interspecies and seasonal variability in OC bioaccumulation as a consequence of diverse food consumption.

Thirty samples of widely used vitamins and herbal preparations distributed on the Croatian market were analysed by atomic absorption spectrometry in order to estimate contamination with Pb, Cd, As, Hg, Cr, Ni and Zn due to their potential toxicity if present above the maximum allowable levels (MAL). The following concentration ranges were obtained (in g g-1): Pb 0.25-3.86 ; Cd 0.05-0.28 ; As 0.10-0.19 ; Hg 0.02-0.12 ; Cr 0.11-64.38 ; Ni 0.24-338.90 ; and Zn 1.00-95.3. Several analysed formulations had metal levels above the maximum allowable limits (Pb: one honey-based product and one medicinal herb-based product ; Cr: one product containing vitamins ; Ni: two products containing vitamins and one product of animal origin). Moreover, the estimated cumulative daily intakes of several metals from some dietary supplements were higher than the oral permitted daily exposures set by the USP Advisory Panel on metal impurities (Pb: one medicinal herb-based product ; Ni: one product containing minerals and one product of animal origin). Such formulations present a significant additional source of metals in the human diet, and therefore could be harmful for human health.

Croatian market and to compare them with a liver pâté from the EU market. In addition, the effects of temperature and length of storage on N-nitrosamine concentrations were assessed. A total of 630 samples were randomly chosen. Thirty samples of each were analysed immediately upon sampling, whereas another 30 samples were stored for 5 and 10 days at 4 ºC, 22 ºC and 37 ºC, respectively. In the samples stored at 4 ºC, the mean total N-nitrosamine level was 1.3–6.8 μg kg–1 on day 5 and 1.0–5.0 μg kg–1 on day 10. In the samples stored at 22 ºC, the mean total N-nitrosamine level was 3.6–9.3 μg kg–1 (day 0), 11.9–24.5 μg kg–1 on day 5, and 22.7–32.3 μg kg–1 on day 10. In the samples stored at 37 ºC, the mean total N-nitrosamine level was 104.9–231.1 μg kg–1 (day 5) and 801.3–1329.0 μg kg–1 (day 10). Temperature and length of storage were found to be associated with the formation of N-nitrosamines in meat products, but carciongenic diEt in particular, accidentally or not, was not present at all in the products originating from the EU.