Dinko Puntarić

Organochlorine Pesticides in Freshwater Fish from the Zagreb Area

Organochlorine Pesticides in Freshwater Fish from the Zagreb Area The aim of this study was to determine the level of organochlorine pesticides in freshwater fish from the Zagreb area, Croatia. The study included 215 freshwater fish samples from three sites: the Sava River, Lake Jarun, and five fishponds from the Zagreb surroundings. Organochlorine pesticides DDT and derivates, HCH, HCB, lindane, aldrin, dieldrin, endrin, heptachlor with epoxide, and methoxychlor were determined using the GC-ECD method. The determined amounts of organochlorine pesticides were within allowed concentration limits in all analysed fish samples. Median values ranged from below the detection limit of 0.01 μg kg-1 for dieldrin and metoxychlor to 2.00 μg kg-1 for DDT in the Cyprinidae fish family from the Sava River, Zagreb sampling site (group 1). This study has confirmed pesticide persistence in the overall ecosystem in our country despite the ban of some thirty years ago, like in many other parts of the world. Organoklorirani Pesticidi u Slatkovodnim Ribama Zagrebačkog Područja Cilj istraživanja bio je utvrditi količinu organokloriranih pesticida u slatkovodnim ribama zagrebačkog područja. Obrađeno je ukupno 215 uzoraka slatkovodne ribe sa sljedećih triju lokacija: rijeka Sava, jezero Jarun i pet tzv. ekoloških jezera u okolici Zagreba. Organoklorirani pesticidi DDT i derivati, HCH izomeri (α-HCH, β-HCH and δ-HCH), HCB, lindan (γ-HCH), aldrin, dieldrin, endrin, heptaklor, heptaklorepoksid i metoksiklor) određivali su se metodom plinske kromatografije uz elektronapsorpcijski način detekcije i uz postignutu granicu detekcije od 0, 01 μg kg-1. Vrijednosti ispitivanih organokloriranih pesticida u svim su uzorcima riba bile mnogo niže od maksimalno dopuštenih koncentracija. Vrijednosti medijana kretale su se od najnižih 0, 01 μg kg-1 za dieldrin i metoksiklor do najviših 2, 00 μg kg-1 za DDT u uzorcima riba porodice Cyprinidae s lokacije Sava - Zagreb. Utvrđeni ostaci preostalih ispitivanih pesticida potvrđuju kako njihovu uporabu na našim područjima tako i njihovu postojanost i prisutnost u cjelokupnom ekosustavu unatoč činjenici da je većina zabranjena u Hrvatskoj prije gotovo 30 godina, kao i u mnogim dijelovima svijeta.

Preliminary investigation of metal and metalloid contamination of homeopathic products marketed in Croatia

BACKGROUNDnDue to their popularity as a complementary therapy in many diseases, homeopathic products of animal, vegetable, mineral and chemical origin should be tested for the presence of contaminants to prevent eventual toxic effects.nnnOBJECTIVEnThirty samples of homeopathic products were analyzed to estimate possible contamination with potentially toxic elements: Pb, Cd, As, Hg, Cr, Ni and Zn, and to assess human exposure to these metals/metalloid as a consequence of their consumption.nnnMETHODSnAtomic absorption spectrometry was used to determine metal and metalloid concentrations.nnnRESULTSnMost tested products had very low metal/metalloid levels (below the limit of quantification of the method), but the metal/metalloid levels in the remaining products were in the following ranges (in microg g(-1)): Pb 0.33-1.29 (6 samples), Cd 2.78 (1 sample), As 0.22 (1 sample), Hg 0.02-0.12 (24 samples), Cr 0.40-10.27 (10 samples), Ni 0.43-55.00 (19 samples), and Zn 2.20-27.80 (11 samples). In the absence of regulatory standards for homeopathic products, the obtained results were compared to maximum allowable levels (MALs) as proposed by USP Ad Hoc Advisory Panel. Some analyzed preparations had metal levels above MALs (Pb: 2 samples; Cd: 1 sample; Ni: 2 samples). However, estimated cumulative daily intakes from tested homeopathic products were in all cases lower than permitted daily exposures for all dosage forms.nnnCONCLUSIONnThe risk of bioaccumulation of metals/metalloid from the homeopathic medicines seems to be rather low, due to small quantities of those products prescribed to be applied per day, as well as insignificant metal contamination of the majority of tested products. However, the fact that particular formulations were contaminated by metals above MALs indicates potential risk and points to the necessity of regular monitoring of homeopathic products for metal contamination, due to their frequent and mostly unsupervised use.

DETECTION OF THALLIUM AND URANIUM IN WELL WATER AND BIOLOGICAL SPECIMENS OF AN EASTERN CROATIAN POPULATION

Abstract Using inductively-coupled plasma mass spectrometry (ICP-MS), we measured the concentrations of thallium and uranium in local water resources from three villages (Ćelije, Draž, and Potnjani) in eastern Croatia, with the aim to determine if they were associated with the levels of these same elements in the serum, urine, and hair collected from the residents of this area. The exposure of the local population to thallium and uranium through drinking water was generally low. ICP-MS was capable of measuring the levels of both of the elements in almost all of the analysed samples. Although there were differences in the concentrations of both elements in water samples and biological specimens taken from the residents, they did not reach the maximum contaminant level in any of the four sample types studied. Although hair was previously reported as an excellent indicator of occupational and environmental exposure to various elements, our study did not confirm it as a reliable biological material for tracing thallium and uranium levels, mainly due to the very low concentrations of these elements, often well below the detection limit. However, our results have shown that the concentration of thallium and uranium in drinking water can be effectively traced in urine samples. Sažetak ODREĐIVANJE RAZINA TALIJA I URANA U BUNARSKOJ VODI I BIOLOŠKIM UZORCIMA STANOVNIŠTVA TRIJU ISTOČNOHRVATSKIH SELA Koristeći masenu spektrometriju induktivno spregnute plazme (ICP-MS), izmjerili smo koncentracije talija i urana u lokalnim izvorima vode triju istočnohrvatskih sela (Ćelije, Draž i Potnjani) radi određivanja jesu li povezane s razinama obaju elemenata u serumu, urinu i kosi stanovnika tih triju sela. Izloženost lokalnog stanovništva taliju i uranu preko pitke vode općenito je bila niska. ICP-MS uspješno je izmjerio razine obaju elemenata u gotovo svim analiziranim uzorcima. Iako je bilo razlika u razinama obaju elemenata u uzorcima vode i biološkim uzorcima stanovnika, nijedan nije prešao maksimalnu dopuštenu granicu. Kosa je prethodno opisana kao izvrstan pokazatelj profesionalne ili okolišne izloženosti različitim elementima, no rezultati našeg ispitivanja nisu potvrdili njenu pouzdanost pri mjerenju talija i urana uslijed vrlo niskih koncentracija obaju elemenata, koje su često bile i ispod razine detekcije. Međutim, pokazali su kako uzorci urina mogu poslužiti kao vrlo dobri indikatori prisutnosti talija i urana u pitkoj vodi.

Sexual behaviour of Croatian blood donors as a threat to the health of blood recipients.

BACKGROUNDnIn this cross-sectional study we assessed the prevalence of the various blood safety sexual risk behaviours among blood donors from East Croatia and the possibilities for improving the present blood donor screening procedure.nnnMATERIALS AND METHODSnThe study included 423 blood donors of both sexes who completed a specially designed anonymous questionnaire immediately after their blood donations. The questionnaire contained questions on demographic data, sexual preferences, and possible sexual risk behaviours in the period before the blood donation.nnnRESULTSnThe study revealed that the most common forms of sexual risk behaviour among Croatian blood donors had been irregular condom use during sexual contacts with new partners (294/423; 69.5%) and five or more sexual partners during the lifetime (213/423; 50.4%). More male than female subjects had had five or more sexual partners during their lifetime (p<0.0001). Compared to married donors, single subjects more frequently reported sexual contacts without using a condom with their new partners in the period from the last blood donation (p<0.0001) and also in the period of 1 month before current blood donation (p=0.0060). A larger number of younger than older subjects had practiced different types of sexual intercourses during the lifetime (p=0.0002) but more older than younger subjects reported irregular use of condom on sexual contacts with a new partner during their lifetime (p=0.0231).nnnCONCLUSIONnBlood donors who were involved in various forms of sexual risk behaviour represent a serious threat to the health of blood recipients. In this respect a new approach to blood donor screening procedure with additional questions on sexual behaviour in anonymous donor questionnaires would improve the safety of transfusion treatment in East Croatia.

The effect of pest control on the incidence of trichinosis in Virovitica-Podravina County, Croatia.

The aim of the study was to assess the role of pest control as a preventive measure in the control of trichinosis. The investigation was designed as a retrospective cohort study in the Virovitica-Podravina County. The incidence of trichinosis was determined according to the presence or absence of exposure to protective pest control measures. Differences in the rate of trichinosis infection were determined by calculating relative risk (RR), i.e., the ratio of absolute risk in the two groups. In this epidemiological study, data collected in the County area regularly covered by pest control (exposure area) were compared with other areas not covered by regular pest control measures (non-exposure area). The study included 132 subjects living in the County and locally infected with trichinosis. Patient data were obtained from their medical history, epidemiological survey and epidemiological questionnaire on the source (autochthony) of the disease. The study also included 133,028 domestic pigs, 875 wild animals (mostly wild boar) and 111 trapped rats. All samples were examined by the method of trichinoscopy at authorized veterinary institutions of the County. Trichinosis infection was recorded in 1012 of 79,534 domestic pigs in the area exposed to pest control measures and in 51 of 53,494 domestic pigs from the rest of the County. RR for the exposure area vs. non-exposure area was 13.35 (95% CI 10.08-17.68; p<0.05); according to particular areas, RR was 3.66 (95% CI 2.62-5.13) for Pitomaca, 22.47 (95% CI 13.27-38.08) for Slatina and 118.89 (95% CI 29.7-476.01) for Orahovica (p<0.05 all). Domestic pigs from the County areas exposed to regular pest control measures had a 13-fold likelihood of infection recorded in pigs from County areas where pest control measures were not or were only occasionally performed. Quite unexpectedly, these results revealed a failure of pest control to reduce the incidence of trichinosis. The spread of trichinosis obviously occurs by some routes obviating the impact of pest control.

Changes in the Lower Drava River Water Quality Parameters Over 24 Years

Changes in the Lower Drava River Water Quality Parameters Over 24 Years The goal of this study was to analyse 13 physico-chemical and microbiological parameters of the Drava River water at three sampling sites in the lower Drava region (eastern Croatia) over two distinct periods: the pre-war period between 1985 and 1992 and the post-war period between 1993 and 2008. Over both periods, most parameters kept within the tolerable water quality limits, while NO3-N, NH4-N and BOD5 were higher. The lower Drava showed slight organic pollution with high concentrations of dissolved oxygen. High levels of total coliforms and heterotrophic bacteria in the post-war period were only found downstream of the town of Osijek. Upstream of Osijek, the river showed a tendency for improvement. Promjene u kvaliteti vode rijeke Drave prije i poslije Domovinskoga rata Cilj ovoga rada bio je procijeniti kvalitetu vode rijeke Drave, klasificirati je i utvrditi postojanje prostornih i vremenskih promjena tijekom perioda od 24 godine. Analizirali smo 13 fizikalno-kemijskih i mikrobioloških parametara vode rijeke Drave na tri mjerne postaje smještene na području donjeg toka Drave (istočna Hrvatska) tijekom dvaju različitih razdoblja: 1985.-1992. (period prije rata) i 1993.-2008. (period poslije rata). Iako su vrijednosti većine podataka prikupljenih tijekom dvaju promatranih razdoblja oscilirale, vrijednosti su im se još uvijek nalazile u granicama za I. i II. vrstu voda. Vrijednosti nekih fizikalno-kemijskih varijabla, kao što su NO3-N, NH4-N i BPK5 još su uvijek iznad granice za II. vrstu. Rezultati ovog istraživanja pokazali su blago organsko onečišćenje vode rijeke Drave s visokim koncentracijama otopljenog kisika. Povećanje broja ukupnih koliformnih i heterotrofnih bakterija u poslijeratnom razdoblju veliki je problem u području nizvodno od Osijeka pri čemu njihov broj katkad dostiže i vrijednosti za V. skupinu površinskih voda. Rezultati analize kvalitete vode rijeke Drave u dva različita razdoblja na dva mjerna mjesta uzvodno od Osijeka upućuju na tendenciju poboljšanja, iako neki od promatranih parametara pokazuju vrijednosti više od onih za II. skupinu riječnih voda. Različitosti, odnosno sličnosti među mjernim postajama istražene su metodom klasterske analize.

Pollen, Physicochemical, and Mineral Analysis of Croatian Acacia Honey Samples: Applicability for Identification of Botanical and Geographical Origin

The aim of the study was to investigate health safety and quality of the Croatian acacia honey, the selected elements in the soil, and whether multivariate methods can provide identification of the origin of honey. The study included 200 acacia honey samples and 100 soil samples from East, Northwest Croatia, and Istria. The proportion of acacia in honey was determined by conducting pollen analysis. Water, free acids, electric conductivity, reducing sugars, saccharose, diastase, and HMF were determined. No significant differences were found using Kruskal-Wallis test regarding the physicochemical parameters ( ), the mineral content of honey ( ), or the mineral composition of the soil ( ). No significant correlation was found between the analyzed elements in honey and soil. Multivariate methods indicated that East Croatia honey samples have higher concentrations of water, HMF, and higher concentrations of measured elements, except for Al. Honey samples from Northwest Croatia are characterized by low concentrations of elements and a higher concentration of saccharose. The Istria samples are richer in reducing sugars, free acids, diastase, higher conductivity, higher content of the acacia pollen grains, and lower concentrations of most metals. Honey from Northwest Croatia and Istria shares the high concentration of Al in honey.

Food Safety System in Croatia

The article focuses on the strengths and weaknesses of the food safety system in the Republic of Croatia. Within the process of accession of the Republic of Croatia to the European Union (EU), Acquis Communautaire in Chapter 12 – Food Safety, Veterinary and Phytosanitary Policy has been transposed into national legislation and food safety system has become more efficient. The Food Act (Official Gazette No. 46/07) is the basic framework law on food safety in Croatia. The Food Act transposes the provisions of Regulation (EC) No 178/2002 and provides the basis for the assurance of a high level of protection of human health and consumers’ interest in relation to food. Food Act covers a general overview and requirements on food safety and hygiene. It lays down the obligations of food business operators and regulates official control system; laboratory operations; crisis and emergency situation management; the rapid alert system for food and feed; and food hygiene. Food Act also stipulates general food quality and labeling requirements, as well as general requirements for food made from, or consisting of, genetically modified organisms (GMO). Moreover, the Food Act is legislative framework for regulating the official control system, setting out the competencies of authorities responsible for carrying out official controls. Enforcement of laws and regulations is done on a central and regional/local level. Ministry of Agriculture, Fisheries and Rural Development (MAFRD) and Ministry of Health and Social Welfare (MHSW) are responsible for the enforcement of legislation both on the central and regional/local level. Integrated EU strategy on food safety: “from farm to fork” should improve efficiency of the whole food safety system and increase confidence of all interested parties in Croatian food safety policy, from farmers to consumers.

P2-423 Cross-sectional biomonitoring of post-war metals in adult population in East Croatia

Aim To determine metal and metalloid exposure in the people of east Croatia exposed to heavy and moderate fighting during the 1991–1995 war in Croatia. Methods The concentrations of 18 elements, that is, aluminium (Al), arsenic (As), barium (Ba), cadmium (Cd), chromium (Cr), copper (Cu), iron (Fe), manganese (Mn), molybdenum (Mo), niobium (Nb), nickel (Ni), lead (Pb), titanium (Ti), uranium (U), vanadium (V), tungsten (W), zinc (Zn) and zirconium (Zr), reported to be associated with military operations, were determined in hair, serum and urine samples using inductively-coupled plasma mass spectroscopy (ICP-MS). A total of 391 participants from east Croatian areas of heavy and moderate fighting were included in this biomonitoring cross-sectional study. Results Higher concentrations of the selected elements associated with fire arms (Al, As, Ba, Cd, Cr, Cu, Mn, Mo, Ni, Pb, U, V, W, Zn i Zr) were determined in one or more samples of study participants from east Croatia as compared with literature data available. Conclusion Study results revealed high concentrations of the selected elements in biological samples of the study population from east Croatia, pointing to the need of comprehensive risk assessment and extensive monitoring of metal and metalloid exposure in the populations living in former conflict zones, emphasising the role of biomonitoring through ecologic and preventive activities.

Influence of Mg, Cr, Fe and Zn from food supplements on selected types of aquatic organisms

Aim was to determine whether uncontrolled disposal of food supplements into the environment, which in its composition contain magnesium (Mg), chromium (Cr), iron (Fe) and zinc (Zn) can cause unwanted effects on selected species of aquatic organisms as indicators of potential toxic effects of such preparations on the environment. Aquatic organisms: the freshwater algae Scenedesmus subspicatus and Raphidocelis subcapitata, great water flea Daphnia maga and duckweed Lemna minor, were exposed to Mg, Cr, Fe and Zn from food supplements by standardized methods. A total of 30 samples were analyzed for each individual micronutrient. The results are expressed as effective concentration 50 (EC50), i.e. the concentration of Mg, Cr, Fe and Zn (mg / L), which inhibits growth or immobilizes 50% of the treated organisms. EC50 metals significantly differ (p <0.001) at all examined test organisms. At Scenedesmus subspicatus the sequnece of EC50 is: Fe(median 46, 9 mg/L)< Zn(59, 8 mg/L)<Mg(73, 0 mg/L)<Cr(88, 1mg/L)(KW-H/3 ; 120/=44, 0963). At Raphidocelis subcapitata the sequnece of EC50 is: Fe(median 44, 9 mg/L) <Zn(52, 6 mg/L) <Mg(62, 2 mg/L) <Cr(76, 8 mg/L)(KW-H/3 ; 120/44, 0936). At Daphnia magna the sequence of EC50 is: Zn(median 59, 4 mg/L) <Cr(79, 2 mg/L) <Fe(80, 8 mg/L) <Mg(82, 0 mg/L)(KW-H/3 ; 120/=39, 2637). At Lemna minor the sequence of EC50 is: Zn(median 131, 0 mg/L) <Fe(186, 8 mg/L) <Mg(192, 5 mg/L) <Cr(240, 4 mg/L)(KW-H/3 ; 120/=58, 6567). Conclusion. Although micronutrients Mg, Cr, Fe and Zn often appear as components of food supplements and belong to the group of essential elements, their uncontrolled disposal into the environment shows harmful effects on aquatic organisms. The use and disposal of supplements should be legally regulated.