FOOD SAFETY IS AN IMPORTANT PUBLIC HEALTH ISSUE: CHLORAMPHENICOL RESIDUES DETERMINATION BY LIQUID CHROMATOGRAPHY TANDEM MASS SPECTROMETRY (LC-MS/MS) IN HONEY

Background: Honey is used for nutritional, medicinal and industrial purposes and antibiotic residues may harm its quality and constitute a danger to human health. The broad spectrum antibiotic chloramphenicol (CAP) was used for curative purposes in veterinary medicine, but is now forbidden in European Union (EU) because of its many serious side effects (e.g. aplastic anaemia, grey syndrome, severe bone marrow depression and hypersensitivity). The aim of this study was to facilitate analyses of the quality and safety of Croatian honey distributed to whole European Union market; an assessment that has not previously been made. Subjects and methods: CAP in honey was qualifying and quantifying by validated liquid chromatography tandem mass spectrometry with negative electrospray ionisation method (LC-MS/MS). The target antibiotic was separated on chromatographic column Zorbax SB C18 (150 mm × 2.1 mm, 3.5 μm) with a gradient elution using acetonitrile - 0.1% formic acid mobile phase at a flow rate of 0.3 mL/min, with column temperature 35 oC for CAP and 5D-CAP as internal standard. Homogenised honey samples were diluted with acetate buffer solution and extracted on Oasis Hydrophilic-Lipophilic-Balanced (HLB) sorbents. The method was used to analyse 280 domestic honey samples collected throughout Croatia between 2005.–2013. Results: Recoveries of the method for real (acacia, chestnut, linden and flower) honey samples were 102% with RSD 8.4%. The value CCα and CCß were 0.09 and 0.12 μg/kg, respectively. Results showed only three subsequent positive detections (1.1%) of CAP in honey. Conlusions: Analysed honey samples from Croatia showed good quality and safety what is the one of the main objective in consumer health policy in EU

Praćenje prisutnosti ftalata u dječjim igračkama- procjena njihove sukladnosti

Phthalates are plasticizers that are often added to children’s toys and other items made of plastic masses, so they are designed in a way to be acceptable to children from early childhood. As a number of studies points out their toxic properties and potential adverse effects on children’s health, this paper presents the results of monitoring their presence in children’s toys for almost six years in order to assess their conformity and their free placement on the Croatian market. In the period from 2010 to mid-2015, a total of 763 samples of children’s toys made of plastic were analyzed. Samples were analyzed for six different phthalates: di-(2-ethylhexyl) phthalate (DEHP), dibutyl phthalate (DBP), benzyl butyl phthalate (BBP), di-isononyl phthalate (DINP), di-isodecyl phthalate (DIDP), and di-n-octyl phthalate (DNOP). After extraction, the methods of gas chromatography and mass spectrometry (GC-MS) were used for identification and quantification of each phthalate. Out of 763 analyzed samples of children’s toys, 105 (13.76 %) samples were assessed as non-conforming. The highest percentage of non-conforming samples was determined in 2013 (23.39 %), followed by the year 2011, when it was found that 15.33 % of children’s toys contained higher phthalate levels than allowed. In 2012, the number of non-conforming samples was 20 (12.9 %), out of 155 samples analyzed. In 2010, 10.77 % of the samples were non-conforming, 7.5 % in 2014, while for the whole first half of 2015, out of 22 samples analyzed, 2 samples (9.1 %) were non-conforming. The results proved that a considerable number of samples of toys analyzed released phthalates in quantities higher than permitted, and were evaluated as non-conforming. Since such toys can harm children’s health, it is necessary to strengthen the systematic control of this type of samples at all levels, such as production, imports and the free sale, especially when the results showed that the number of analyzed samples of toys, after the accession of the Republic of Croatia to the European Union decreased significantly compared to the previous period.Ftalati se kao omekšivala vrlo često dodaju u dječje igračke, ali i u druge predmete od plastič- ne mase, kako bi se one mogle oblikovati tako da budu prihvatljive djeci od najranije dobi. Budući da je niz studija ukazao na njihova toksična svojstva i moguće štetne posljedice na zdravlje djece, u ovom radu prikazani su rezultati praćenja njihove prisutnosti u dječjim igračkama kroz gotovo šest godina, a sve u svrhu ocjene njihove sukladnosti i njihova slobodnoga stavljanja na tržište Republike Hrvatske. U razdoblju od 2010. godine do polovice 2015. godine analizirana su ukupno 763 uzorka dječjih igračaka izrađenih od plastične mase. Uzorci su analizirani na šest različitih ftalata: di-(2- etilheksil) ftalat (DEHP), dibutil ftalat (DBP), benzil butil ftalat (BBP), di-izononil ftalat (DINP), di-izodecil ftalat (DIDP) i di-n-oktil ftalat (DNOP). Za identifikaciju i kvantifikaciju svakoga ftalata, nakon provedene ekstrakcije, primijenjena je metoda plinske kromatografije i spektrometrije masa (GC-MS). Od ukupno 763 analizirana uzorka dječjih igračaka, 105 (13,76 %) uzoraka ocijenjeno je nesukladnima. Najveći postotak nesukladnih uzoraka utvrđen je 2013. godine (23,39 %), slijedi 2011. godina kada je utvrđeno da 15,33% dječjih igračaka sadrži ftalate u količini većoj od dozvoljene. Tijekom 2012. godine broj nesukladnih uzoraka iznosio je 20 (12,9 %) u odnosu na 155 analizirana uzorka. U 2010. godini utvrđeno je 10,77 % nesukladnih uzoraka. Godine 2014. ih je utvrđeno 7,5%. U prvoj polovici 2015. godine analizirana su 22 uzorka, a nesukladnost je utvrđena u dvama uzorcima (9,1%). Iz dobivenih rezultata razvidno je da znatan broj analiziranih uzoraka dječjih igračaka otpušta ftalate u količinama iznad dopuštenih te su ocijenjeni nesukladnima. Budući da takve igračke mogu štetno djelovati na zdravlje djece, potrebno je pojačati sustavnu kontrolu nad tom vrstom uzoraka na svim razinama, od proizvodnje preko uvoza do slobodne prodaje, osobito kada je iz rezultata vidljivo da se broj analiziranih uzoraka dječjih igračaka od ulaska Republike Hrvatske u Europsku uniju znatno smanjio u odnosu na prethodno razdoblje

Selenium, Sulphur, Trace Metal, and BTEX Levels in Soil, Water, and Lettuce from the Croatian Raša Bay Contaminated by Superhigh-Organic- Sulphur Coal

This paper elaborates soil, water, and lettuce contamination status with respect to selenium, sulphur, trace metals, and BTEX (benzene, toluene, ethylbenzene, and xylenes) in a coal- based area (Raša Bay, Adriatic Sea, Croatia). A local coal-fired power plant polluted soil with S, Se, Cd, and PAHs due to the combustion of domestic superhigh-organic-sulphur coal. The locality is dotted with waste from coal mining/separation, coal combustion, former metal factories, untreated municipal and coal mine effluents, along with various harbour activities, which contribute to environmental contamination. The methodology involved ICP-MS and GC-MS for the measurement of trace elements and BTEX, respectively, while soil sulphur was determined with Eschka’s mixture. The max values of the analysed trace elements in soil (mg/kg) are reported: Hg 1.14, Cd 3.29, V 624, Se 10.3, Pb 872, Cr 1860, Zn 6580, Cu 1850, and U 25.2. According to ecological indices, these values fall into the category of an extremely high level of soil pollution. Elevated total Se values in surface water are ascribed to leaching of seleniferous coal, ash, and coal- polluted soil. Levels of BTEX in water samples were very low (0–0.83 g/L). The data provide basic information on the inorganic and organic contamination status of the Raša Bay area

Atrazin u okolišu-zdravstveni rizik (Atrazine in the Environment - A Health Risk)

Herbicidno djelovanje S-triazinskih supstanci (kojima pripada atrazin) otkrila je skupina istraživača 1952.godine u laboratoriju firme CIBA-GEIGY, Basel, Švicarska i izdvojila supstancije koje imaju najmanje fitotoksično djelovanje: simazin, atraton, ametrin, atrazin i dr. Atrazin je selektivni triazinski herbicid koji se koristi pri kontroli širokolisnih i uskolisnih korova. Javlja se u obliku bijelih kristalića ili pudera, bez mirisa. Triazinski herbicidi se već tridesetak godina koriste u Republici Hrvatskoj, a atrazin je često aktivna supstanca u raznim herbicidima. Atrazin ulazi u okoliš raspršivanjem na poljoprivrednim gospodarstvima. Iz tla se podiže rastom biljaka, dok se u njih apsorbira uglavnom kroz korjenje ali i preko listova te se jednom apsorbiran akumulira u vršnim dijelovima biljke, listovima (novim i rastućim) i laticama itd. U nekih vrsta biljaka atrazin sprečava fotosintezu i interferira s drugim enzimskim procesima, dok se u onih koje ga toleriraju metabolizira. Kod tretiranih biljaka atrazin povećava unos arsena u biljke. Većina žitarica može se posaditi na istoj površini godinu dana nakon tretiranja atrazinom. Nažalost, atrazin je relativno postojano zagađivalo okoliša. Jedan je od najznačajnijih zagađivala površinskih i podzemnih voda, te mora

Nitrate in leafy green vegetables and estimated intake

Background: Vegetarian diets are rich in vegetables. Green leafy vegetables are foods that contain considerable amounts of nitrate, which can have both positive and negative effects on the human body. Their potential carcinogenicity and toxicity have been proven, particularly after the reduction of nitrate to nitrite itself or just serving as a reactant with amines and/or amides in the formation of N-nitroso compounds -N-nitrosamines and other nitrogen compounds which may have high levels of nitrate. The aim of this study was to determine whether there is a significant difference, considering the location and seasonal sampling period, in the level of nitrate in certain types of green vegetables, all in order to be able to assess their intake, and possible impact on human health, especially knowing that exposure to nitrate can be potentially higher for vegetarian population group.Materials and Methods: For this purpose, the sampling of 200 different leafy green vegetables was conducted, all of which could be found in free sale in the Republic of Croatia. The sampling was conducted during two seasonal periods - the spring and autumn period. In the springtime, lettuce (sem), spinach (pinacho), kale (kale), chard (mangel) and cabbage (brassica) were sampled, and in autumn lettuce, spinach, kale, chard and arugula. Samples were analyzed using high performance liquid chromatography (HPLC) with UV detection.Results: The results from the spring sampling phase were in the range of 603 mg/kg for cabbage - 972 mg/kg for chard, and for autumn phase of 1.024 mg/kg for chard to 4.354 mg/kg for the arugula. The results showed that there were significant differences (p <0.05) for most of the samples analyzed, considering the sampling locations and time period.Conclusion: The results indicate that the analyzed vegetables contain significant amounts of nitrate in their composition, which represents relatively significant, but still acceptable intake into the human body.Keywords: leafy green vegetables, nitrate, HPLC, season period, daily intak

Geochemistry of Croatian superhigh-organic- sulphur Raša coal, imported low-S coal, and bottom ash: their Se and trace metal fingerprints in seawater, clover, foliage, and mushroom specimens

The Labin city area has represented the major Croatian coal mining, metal industry, and coal- fired electricity centre for more than two centuries. The domestic superhigh-organic- sulphur (SHOS) Raša coal is a unique variety compared to other coal types worldwide, based on its highest organic sulphur values, up to 11%. It was utilized in the Plomin coal-fired power plant during the period 1970-2000, and was replaced by an imported low-S coal afterwards. This paper presents the levels of S, Se, V, U, Hg, Sr, Cd, Cr, Pb, Cu, and Zn in the two coal types, their bottom ash, seawater, and plant (clover, mushroom, and foliage) specimens collected from the Labin city area, while the sulphate was measured in surface stream water. Their levels were compared with relevant legislative as well as the published data from different world localities. Data analysis was interpreted in the context of past and recent coal combustion activities