Dražen Lušić

Volatiles from a Rare Acer spp. Honey Sample from Croatia

A rare sample of maple (Acer spp.) honey from Croatia was analysed. Ultrasonic solvent extraction (USE) using: 1) pentane, 2) diethyl ether, 3) a mixture of pentane and diethyl ether (1:2 v/v) and 4) dichloromethane as solvents was applied. All the extracts were analysed by GC and GC/MS. The most representative extracts were 3) and 4). Syringaldehyde was the most striking compound, being dominant in the extracts 2), 3) and 4) with percentages 34.5%, 33.1% and 35.9%, respectively. In comparison to USE results of other single Croatian tree honey samples (Robinia pseudoacacia L. nectar honey, Salix spp. nectar and honeydew honeys, Quercus frainetto Ten. honeydew as well as Abies alba Mill. and Picea abies L. honeydew) and literature data the presence of syringaldehyde, previously identified in maple sap and syrup, can be pointed out as a distinct characteristic of the Acer spp. honey sample. Headspace solid-phase microextraction (HS-SPME) combined with GC and GC/MS identified benzaldehyde (16.5%), trans-linalool oxide (20.5%) and 2-phenylethanol (14.9%) as the major compounds that are common in different honey headspace compositions.

Evaluation of equivalence between different methods for enumeration of fecal indicator bacteria before and after adoption of the new Bathing Water Directive and risk assessment of pollution

The quality of bathing water is of considerable public importance due to the possibility of fecal contamination. In 2009, Croatia implemented the new European Bathing Water Directive (BWD, 2006/7/EC) establishing stricter microbiological standards for new parameters with new reference methods. This study aims to evaluate the equivalence of different methods according to the old and revised BWD and to provide the possibility of data comparison. Furthermore, the directive requires the establishment of the bathing water profile (BWP) for pollution risk assessment. The estimation of consistency of pollution risk assessment with obtained microbiological results was also performed. Six marine beaches of the Municipality of Rijeka (Croatia) were examined during the 2009 season. Statistical analysis showed equivalence between determination methods for fecal contamination indicators. Based on the current water classification results, the need for correction of estimated pollution risks and recommendations for inclusion of historical microbiological data during BWP enactment was noticed.

Exposure to Phtalates and Their Presence in Alcoholic Beverages

Ftalati su esteri ftalne kiseline i alifatskih alkohola koji se dodaju u plastične mase da bi se poboljšala njihova mekoća, savitljivost i rastezljivost. Zbog svojih fizičko-kemijskih svojstava ftalati su vrlo mobilni i lako migriraju iz plastičnih proizvoda u prostor koji ih okružuje, pa tako dospijevaju u okoliš te su stoga opasni za čovjeka. U radu su ukratko opisana svojstva i raspodjela ftalata u okolišu, toksični učinci na ljudsko zdravlje te zakonska regulativa vezana uz maksimalno dopuštene koncentracije ftalata u vodi za piće i u proizvodima namijenjenima dojenčadi, kao i dopušteni dnevni unos u ljudski organizam. Posebna pažnja posvećena je metodama određivanja ftalata u alkoholnim pićima te razinama ftalata s osvrtom na njihovu pojavnost i koncentracije u šljivovici koja se proizvodi u Hrvatskoj. Obuhvaćena je i tematika vezana za ftalate u denaturiranom alkoholu i neregistriranom alkoholu koji se ilegalno stavlja na tržište. U zaključku su navedene smjernice za učinkoviti nadzor nad putovima izloženosti ljudi ftalatima. Summary Phthalates are phthalic acid and aliphatic alcohol esters used as additives to plastic in order to improve its softness, flexibility, and elongation. Phthalates are highly mobile and migrate easily from plastic products into the environment due to their physical and chemical properties. This study briefly describes the characteristics and distribution of phthalates in the environment, their toxic effects on human health, the legislation regarding the maximum allowed concentration of phthalates in drinking water and products intended for infants, as well as the tolerable daily intake. Special attention is given to the methods of determining phthalates and their levels in alcoholic beverages, with an overview of phthalate occurrences and concentrations in plum brandy made in Croatia. A segment on denatured alcohol and illegally marketed alcohol is also included, as well as guidelines for the effective monitoring of the routes of human exposure to phthalates.

Temporal variations analyses and predictive modeling of microbiological seawater quality

Bathing water quality is a major public health issue, especially for tourism-oriented regions. Currently used methods within EU allow at least a 2.2 day period for obtaining the analytical results, making outdated the information forwarded to the public. Obtained results and beach assessment are influenced by the temporal and spatial characteristics of sample collection, and numerous environmental parameters, as well as by differences of official water standards. This paper examines the temporal variation of microbiological parameters during the day, as well as the influence of the sampling hour, on decision processes in the management of the beach. Apart from the fecal indicators stipulated by the EU Bathing Water Directive (E. coli and enterococci), additional fecal (C. perfringens) and non-fecal (S. aureus and P. aeriginosa) parameters were analyzed. Moreover, the effects of applying different evaluation criteria (national, EU and U.S. EPA) to beach ranking were studied, and the most common reasons for exceeding water-quality standards were investigated. In order to upgrade routine monitoring, a predictive statistical model was developed. The highest concentrations of fecal indicators were recorded early in the morning (6 AM) due to the lack of solar radiation during the night period. When compared to enterococci, E. coli criteria appears to be more stringent for the detection of fecal pollution. In comparison to EU and U.S. EPA criteria, Croatian national evaluation criteria provide stricter public health standards. Solar radiation and precipitation were the predominant environmental parameters affecting beach water quality, and these parameters were included in the predictive model setup. Predictive models revealed great potential for the monitoring of recreational water bodies, and with further development can become a useful tool for the improvement of public health protection.

Escherichia coli in marine water: Comparison of methods for the assessment of recreational bathing water samples

Bathing Water Directive (2006/7/EC) specifies two reference methods for Escherichia coli detection: ISO 9308-1 and 9308-3. The revised ISO 9308-1 is recommended only for waters with a low bacterial background flora. Considering the extended time needed for analysis and, generally, the lack of experience in using ISO 9308-3 in the Mediterranean, the suitability of ISO 9308-1 for the examination of E. coli in bathing water was evaluated. The present study was aimed at a comparison of data obtained by the reference method in seawater samples (110 beaches, N=477) with data received from six alternative methods. Results show that recently used TSA/TBA method may overestimate E. coli numbers in marine waters. The temperature modified ISO 9308-1 (44°C) did not significantly alter the results, but outperformed the antibiotic supplemented agar at reducing non-E. coli bacteria on the plates, allowing the use of the respective method for monitoring coastal water.

Towards better quality criteria of European honeydew honey: Phenolic profile and antioxidant capacity

Concerning the particular nutritive value of honeydew honey compared to blossom honey, and small number of studies defining botanical origin of honeydew honey, comprehensive analysis of phenolic profile of 64 honeydew honey samples of specific botanical origin was performed. Two advanced techniques of liquid chromatography hyphenated with mass spectrometry were used for identification of a total of 52 compounds and quantification of 25 of them. Pattern recognition analysis applied on data on phenolic compounds content confirmed that quercetin, naringenin, caffeoylquinic acid, hydroxyphenylacetic acid, apigenin and genistein, could be considered as potential markers of botanical origin of honeydew honey. Spectroscopic and electrochemical approaches were applied for the evaluation of the antioxidant capacity. Quercus sps. samples, Quercus frainetto and Quercus ilex, showed high biological activity and specific chemical composition. Additionally, cyclic voltammetry profiles were used for characterization and natural clustering of honeydew honey for the first time.

Multi-elemental composition and antioxidant properties of strawberry tree (Arbutus unedo L.) honey from the coastal region of Croatia: Risk-benefit analysis

The concentration of 23 major and trace elements, total phenolic content (TPC) and 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical scavenging activity were determined in nine samples of strawberry tree honey and compared to other types of unifloral honeys. The most abundant elements in strawberry tree honey were potassium, calcium, magnesium and sodium, ranging between 1276 and 2367, 95.2-154, 14.4-74.4 and 13.4-64.3mg/kg, respectively. Strawberry tree honey had generally higher TPC (range: 0.314-0.522g GA/kg) and DPPH (1.94-4.45mM TE/kg) compared to other analysed unifloral honeys. A strong positive relationship was found between TPC and DPPH, TPC and concentration of homogentisic acid (HGA), chemical marker of strawberry tree honey, and between DPPH and HGA. Regarding daily intake of essential elements, strawberry tree honey can be considered nutritionally richer than the majority of unifloral honeys available in Croatia, while contribution to tolerable intake set for potentially toxic elements was very low, corresponding to pristine areas.

Zdravstvena ispravnost vode za piće u Gorskom kotaru u petogodišnjem razdoblju od 2011. do 2015.

Cilj: Osiguranje zdravstveno ispravne vode osnovna je potreba svakog covjeka. S obzirom na dugogodisnje mikrobiolosko oneciscenje u vodoopskrbno

Determination of phthalates in plum spirit and their occurrence during plum spirit production

Phthalates are ubiquitous environmental contaminants that, due to their lipophilicity, migrate more readily into beverages with higher ethanol content. The aim of this work was to study the occurrence of phthalates in samples during the plum spirit production and in the final product, plum spirit manufactured by registered producers from five European countries, using gas chromatography-mass spectrometry (GC-MS). A decreasing trend of mean values was observed for diethyl phthalate (DEP), di-iso-butyl phthalate (DiBP), and di-n-butyl phthalate (DBP) as the distillation process went on. Levels of benzyl-butyl phthalate (BBP) and di-(2-ethylhexyl) phthalate (DEHP) increased in the distillation phase compared to concentrations in the preceding phases. In commercial plum spirits, DEHP and DiBP were detected in the highest concentrations. Results also indicated that a moderate daily consumption of plum spirit does not pose a health risk regarding the Tolerable Daily Intake of BBP, DEHP, and DBP

Modern analytical techniques in the assessment of the authenticity of Serbian honey.

Food authenticity in a broader sense means fulfilling chemical and physical criteria prescribed by the proposed legislation. In the case of honey authenticity, two aspects are of major concern: the manufacturing process and the labelling of final products in terms of their geographical and botanical origin. A reliable assessment of honey authenticity has been a longterm preoccupation of chemists-analysts and it usually involves the use of several criteria and chemical markers, as well as a combination of analytical and statistical (chemometric) methods. This paper provides an overview of different criteria and modern methods for the assessment of honey authenticity in the case of a statistically significant number of authentic honey samples of several botanical types from various regions of Serbia. Izvornost hrane u širem smislu znači udovoljavanje kemijskim i fizikalnim kriterijima koji su propisani zakonodavstvom. U pogledu izvornosti meda, dva su ključna aspekta: proizvodni proces i označavanje proizvoda u smislu zemljopisnog i botaničkog podrijetla. Pouzdana procjena izvornosti meda, koja uobičajeno uključuje korištenje nekoliko kriterija i kemijskih markera te kombinaciju analitičkih i statističkih (kemometrijskih) metoda, već dugo vremena zaokuplja pozornost kemijskih analitičara. Ovaj rad pruža uvid u različite kriterije i moderne metode za procjenu izvornosti meda koristeći se slučajem statistički značajnog broja uzoraka izvornog meda nekoliko botaničkih tipova iz različitih regija u Srbiji.