Pesticides and Polychlorinated Biphenyls in Milk and Dairy Products in Croatia: A Health Risk Assessment.

The aim of this study was to evaluate contamination levels and the frequency of detection of organochlorine (OCPs) and organophosphate pesticides (OPPs), pyrethroids, carbamates and polychlorinated biphenyls (seven PCB congeners) in a total of 534 samples of cow's, sheep's and goat's milk and dairy products from Croatia. Concentrations above the limit of quantification (LOQ) were measured for fourteen OCPs, nine OPPs, six pyrethroids, one carbamate and PCBs with a total of 172 results, and no concentrations exceeded the maximal residue levels defined by the European Union. The mean concentrations of pesticides and the sum of seven PCBs were determined in the ranges 0.92-17.4 µg/kg and 1.38-2.74 µg/kg. Pesticides were quantified in 27% of samples, and seven PCBs were quantified in 5.23% of samples. Among the three pesticide groups, the highest numbers of quantified results were found for OCPs (12.1-20.8%). The highest frequencies of detection were found for the sum of 4,4'-dichlorodiphenyltrichloroethane and its isomers (DDTs), hexachlorobenzene and seven PCBs. The sum of seven PCBs was quantified within the range of 3.3-6.67% of samples per milk type and dairy products. Among the OPPs, the highest frequency of detection was found for chlorpyrifos in cow's milk. Based on the estimated daily intakes, chronic risk characterisation showed no risk for adults or ten-year-old children for the consumption of cow's milk and dairy products.

Distribution of Pesticides and Polychlorinated Biphenyls in Food of Animal Origin in Croatia.

Pesticides and polychlorinated biphenyls (PCBs) are persistent environmental pollutants. When entering the food chain, they can represent a public health problem due to their negative effects on health. In this study, concentrations of organochlorine pesticides (OCPs), organophosphate pesticides (OPPs), pyrethroids, carbamates, and PCBs-a total 73 compounds-were determined in a total of 2268 samples of fat tissues (beef, pork, sheep, goat, poultry, game, horse, rabbit) and processed fat, meat, and processed meat products collected in Croatia during an 8-year period. In fatty tissues, 787 results exceeded the limits of quantification (LOQ): 16 OCPs, eight OPPs, six pyrethroids, one carbamate, and seven PCBs. The most positive results in fat samples were found for OCPs, with a frequency of quantification in the range of 57.5-87.5%. Hexachlorobenzene (HCB) and dichlorodiphenyldichloroethylene (DDE) were quantified in the highest percentages, in the ranges of 5.5-66.7% and 5.4-55.8%. Concentrations above the MRL values were determined for chlorpyrifos in pork fat and for resmethrin in six fat samples and one pâté. In 984 samples of meat and meat products, only 62 results exceeded the LOQ values. The highest frequency of quantification was determined for OCPs (25 samples), of which 40% were DDT isomers (60% DDE). Frequency quantifications of PCBs in fat samples were between 7.23 and 36.7%. An evaluation of the health risk assessment showed that the consumption of fat, meat, and meat products does not pose a threat to consumer health, since all EDI values were well below the respective toxicological reference values.

The Content of Cobalt, Silver and Vanadium in Raw Cow's Milk in Croatia and Risk Assessment for Consumers.

Concentrations of selected trace elements Ag, Co and V in raw milk sampled from four geographical regions in Croatia were measured. Silver, Co and V were detected above the limit of detection within the range of 9.52%-30.8%, 1.6%-12.1% and 12.4%-30.8%. Silver concentrations were not detected in milk samples from the Croatian Littoral and Mountainous Croatia (CL-MC) region. Similar Ag content was found in Southern, Eastern and Central Croatia. The lowest mean of Co and V of 33.2 and 83.8 µg kg-1 were found in the CL-MC region while the highest of 49.8 and 136.9 µg kg-1 was found in Central Croatia. There were no statistically significant differences in Ag, Co and V contents between the four regions. The estimated daily dietary intakes (EDI) of total mean and total 95th percentile values of Ag, Co and V showed lower values in comparison with available EFSA health-based limits.

Evaluation of Element Concentrations in Beef and Pork Meat Cuts Available to the Population in the Croatian Capital.

The aim of this study was to determine the concentrations of essential, trace, and toxic elements in beef and pork meat cuts available at markets and retail chains in the Croatian capital. Significant differences in the concentrations of Al, Cr, Cu, Fe, Mg, Mn, Mo, Ni, Se, Pb, and Zn were found between bovine cuts (p < 0.01, all) and also between pork cuts (p < 0.01, all). A risk assessment using the estimated intakes based on the lowest and highest mean values of Al, Cr, Ni, and Pb in beef and pork showed low contributions to tolerable toxicological limits. However, consumers whose diets consist of large amounts of beef and pork kidneys may be at risk because the estimated intakes for Cd and Se exceeded the toxicological limits. Consumers of large quantities of beef mixed meat may be at risk due to higher values of estimated As intakes compared to health-based guidance values. Estimation based on the provisional maximum tolerable daily intake values for Cu, Fe, and Zn showed that beef and pork cuts can be considered safe for consumption. A comparison with data from other studies shows that the concentrations of the analyzed elements in beef and pork cuts vary considerably.

Essential and toxic element concentrations in monofloral honeys from southern Croatia.

The concentrations of 24 elements in seven honey types (multifloral, heather, common heather, bearberry, sage, mandarin orange-blossom and honeydew) collected in southern Mediterranean regions of Croatia were determined using ICP-MS. Significant differences were found in the concentrations of Ag, As, Ba, Cu, Co, Fe, K, Mg, Mn, Mo, Na, Ni, Se, Sb, U and Th (p<0.05, all) among honeys. The highest element concentrations were determined in honeydew honeys, with the exception of multifloral (Ca, Cr, Mo, Se), common heather (Mg, Na), bearberry (Ba, Fe, Pb) and sage (Ag) honeys. Among the floral honeys, the highest concentrations were found in multifloral honey (Al, As, Be, Ca, Cr, Mn, Mo, Ni, Se, Th and U), common heather (Co, K, Mg, Na, V), sage (Ag, Cd, Cu), and bearberry (Ba, Fe, Pb, Sb, Zn). The results contribute to the evidence supporting the role of botanical origin on the elemental composition of honey.

Variations in lead, cadmium, arsenic, and mercury concentrations during honeybee wax processing using casting technology.

Beeswax foundations are a necessary material in intensive modern beekeeping. Heavy metals can accumulate in these foundations for decades, as it is a common beekeeping practice to recycle wax. Beeswax samples were analysed using GFAAS for As, Cd, Pb, and Hg concentrations during the production of beeswax foundations using casting technology with a prolonged cooling and sedimentation phase. Significant differences were determined in the concentrations of As, Cd, Pb (p<0.01, all), and Hg (p<0.05) between the three levels of wax in a double-walled steel casting container and comb foundations (CF) during the processing stage. Concentrations (mg kg-1) of the examined metals in comb foundations as the final product ranged as follows: As 0.01-0.88; Cd 1.26-3.55; Pb 82.5-171, and Hg 0.29-1.46. All examined element concentrations demonstrated similar distribution and ratio in different layers, ranging from the lowest concentrations in layers from which wax material is used for comb foundations as the final product, to the highest concentrations in sedimented layer, which represents waste. The obtained results suggest that the described method could effectively eliminate a significant amount of heavy metals from the initial material used for the production of new beeswax foundations.

Lead Concentrations in Raw Cow and Goat Milk Collected in Rural Areas of Croatia from 2010 to 2014.

A total of 249 cow and 33 goat milk samples were collected in rural areas of Croatia during the period 2010-2014. Lead concentrations in milk samples were analyzed by graphite furnace-atomic absorption spectroscopy. Mean Pb concentrations in milk ranged from (µg/kg): cow 10.8-12.2; goat 9.33-60.0. The highest Pb level of 131 µg/kg in cow milk was measured during 2014. There were no significant differences in Pb levels between cow and goat milk and also in goat milk among the analysed years. However, significant differences were found in cow milk among years. The highest Pb was determined in 2011 (157 µg/kg in goat milk). The calculated estimated weekly intakes of Pb concentrations for cow and goat milk contribute only 1.37 % and 1.84 % to the provisional tolerable weekly intake. Therefore, the consumption of milk from both species should not pose a consumer health risk.

Metal Content in Four Shellfish Species from the Istrian Coast of Croatia.

The concentrations of As, Cd, Cu, Hg, Pb and Zn were measured in four shellfish species (oysters, mussels, scallops, warty venus) collected along the Istria Peninsula coast during autumn 2013. Mean metal levels in shellfish ranged as follows (mg/kg): As 1.69-3.91, Cd 0.15-0.99, Hg 0.06-0.2, Pb 0.33-0.74, Cu 1.23-36.2, Zn 16.3-511. Statistical analysis showed a significant difference in As (p<0.05), Cd, Pb, Hg, Cu and Zn (p<0.01, all) levels among shellfish species. The highest metal concentrations were found in oysters (mg/kg): As 3.91, Cd 0.99, Cu 36.2 and Zn 511. The highest means of Pb and Hg were measured in (mg/kg): warty venus 0.74; scallops 0.12. The estimated daily intakes for oysters shown it as a good source of Cu and Zn. The higher contribution of Cd and As levels to the provisional tolerable weekly intake in shellfishes suggest a careful approach for consumption.