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•Essential and toxic elements in raw milk were measured from four regions of Croatia.•As, Cd and Pb were detected above LOD in only 2.3–18.2% of milk samples, Hg in none.•Significant ...differences in Al, Ba, Se and Zn content were found among the regions.•Risk assessment showed low exposure of all elements in milk except for Cd.
Concentrations of selected elements were measured in raw cow milk collected from four geographical regions in Croatia. The highest mean concentrations of Al, Ba, Fe and Zn were measured in milk from Central Croatia. Milk from the Croatian Littoral and Mountain region showed the highest mean content of Cd, Cr, Cu, Ni and Pb. The highest mean concentrations of As and Se were found in milk from Southern Croatia, while Mn had the highest values in Eastern Croatia. Mercury was not determined above the detection limit in any samples. Significant differences in the concentrations of Al, Ba, Se and Zn were found among the regions. A decrease in the Pb content was recorded compared to previous research in milk in Croatia. Estimation of the potential harmful effects of toxic and trace elements through milk consumption by comparing the established highest mean with toxicological limits showed low exposure with regard to Al, As, Ba, Cr, Cu, Hg, Fe, Ni, Se, Pb and Zn in adult populations in Croatia. The only exception was Cd concentrations in milk, which gave a higher contribution to toxicological limits, especially for consumers consuming greater quantities of milk per week.
•24 elements in 7 different honeys collected in southern Croatia were analysed.•Significant differences in element concentrations were found among the honeys.•Honeydew honey had the high ...concentrations of almost all the elements determined.•Mandarin orange-blossom honey had the lowest concentration of elements determined.•Obtained results support the role of botanical origin on the honeys element composition.
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.
The aim of the current study was to validate a screening and confirmatory method for the determination of nitrofuran residues: 3-amino-2-oxazolidinone (AOZ), ...3-amino-5-morpholinomethyl-2-oxazolidinone (AMOZ), 1-aminohydantoin (AHD), semicarbazide (SEM), 3,5-dinitrosalicylic acid hydrazine (DNSAH), nifurpirinol (NPIR), nifuroxazide (metabolite 4-HBH), and nitrovin (metabolite AMG) in muscle, milk, eggs, honey, and casings, in accordance with the legislation 2002/657/EC and 2021/808/EC. Sample preparation included hydrolysis and derivatization, followed by ethyl acetate extraction and measurement by ultra-high performance liquid chromatography coupled with tandem mass spectrometry (UHPLC-MS/MS). Validation parameters specified in this method are specificity/selectivity, trueness, precision, decision limit (CCα), and detection capability (CCβ). In the screening method, the CCβ value ranged from 0.275 to 0.582 µg kg-1, while in the confirmatory method, the CCα value ranged from 0.264 to 0.407 µg kg-1. The recovery values ranged from 93.5% to 127.5%. A total of 497 routine samples from the National Residue Monitoring Control Plan (NRCP) and border inspection were analysed from 2021 to 2022. SEM was detected in a total of 11 samples. Only four samples had a concentration above the Reference Point for Action (RPA = 0.5 µg kg-1). The validated method is suitable for monitoring nitrofuran residues at levels below the recently established RPA.
•A sensitive UHPLC-MS/MS method for the analysis of eight nitrofurans was validated.•New analytes were introduced: nifursol, nifuroxazide, nitrovin, and nifurpirinol.•Method validation was performed on muscle, milk, eggs, honey, and casings.•The validated method was used for the analysis of 497 routine samples.•This method is applicable for monitoring nitrofuran residues in various matrices.
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.
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.
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.
•Concentrations of toxic and essential elements were determined in 11 fishes.•The most abundant elements measured were Fe and Zn followed by As.•Highest As, Cu, Fe, Mn, Ni and Zn levels were measured ...in sardine.•For all elements significant differences between fishes were found.•High As and Hg levels for some fishes suggest a strong public concern for consumers.
Concentrations of toxic (Al, As, Cd, Cr, Hg, Mn, Ni, Pb) and essential elements (Cu, Fe, Zn) were measured in 11 fish species purchased from supermarkets located in different Croatian cities. Mean element concentrations in fishes ranged: mg kg−1: Al 0.13–3.5, As 0.52–3.4, Cu 0.24–0.88, Fe 2.0–19, Mn 0.095–1.6, Zn 3.4–18; μg kg−1: Cd 0.61–123, Cr 5.0–41, Hg 17–130, Pb 2.0–59, Ni 5.5–51. The highest mean concentrations of elements were found in fishes: Al in cod; Cd in bluefin tuna; Cr in rainbow trout; Hg in European sea bass; Pb in canned sardine; As, Cu, Fe, Mn, Ni and Zn in sardine. Significant differences in the concentrations of all elements measured were found between fish species. Mean Cd levels of 123 μg kg−1 for bluefin tuna exceeded the European Commision limit of 100 μg kg−1. An estimation of the dietary intake of elements associated with the consumption of the studied fish species, and its comparison with the toxicological reference values is provided. The obtained results suggest a strong reason for public concern with regard to exposure to As and Hg for consumers who often consume certain types of fishes.
•Pork and bovine liver contain the highest mean of Ag, Co, Cu, Fe, Mn, No, Zn and V.•Pâtés contain the highest mean levels of Al, Ba, Cd, Ni and Se.•Salami contain the highest concentrations of As, ...Ca, Cr, K and Pb.•Risk exposure assessment to As, Ba, Cr, Hg, Ni and Pb are low.•P95 consumers are at risk as Al, Cd, Co, Fe and Se exceed toxicological limits.
This is a comprehensive study of the macronutrient, toxic and non-essential element concentrations in 22 meat, liver and meat products from the Croatian market. The highest mean content of Fe, Mn, Zn and Mo were measured in pork liver, while Ag, Co, Cu and V were highest in bovine liver. Pâtés contain the highest concentrations of Al, Ba, Cd, Ni and Se, while salami products had the highest As, Ca, Cr, K and Pb. Pork meat and pork canned products contained the highest Hg and Mg levels. Using the tolerable daily intake for Cu, Fe, and Zn, and minimal risk levels for Se to check for potential risk, higher exposure was found only in the case of P95 consumers for Fe in liver and Se in meat products. Also, P95 consumers face an exposure to risk since the concentrations of Cd and Co in liver and of Al and Cd in meat products exceeded the toxicological limits. Meat, liver and meat products can be considered safe for adult consumers based on the low contributions to toxicological limits for As, Ba, Cr, Hg, Ni and Pb.
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.
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 (
< 0.01, all) and also between pork cuts (
< 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.