Concentrations of As, Cd, Cu, Hg and Pb were measured by atomic absorption spectrometry (AAS) in muscle tissues of four fish species: anchovy (
Engraulis encrasicholus), mackerel (
Scomber ...japonicus), red mullet (
Mullus surmuletus) and picarel (
Spicara smaris) from the Croatian waters of the Adriatic Sea during 2008 and 2009. Metal levels measured in anchovy were in the following ranges (mg
kg
−1): As 0.01–54.8, Cd 0.001–0.02, Cu 0.001–6.29, Hg 0.001–0.52 and Pb 0.001–0.34
mg
kg
−1. Metal ranges in red mullet were (mg
kg
−1): As 0.01–70.9, Cd 0.002–0.85, Cu 0.001–57.3, Hg 0.001–2.07 and Pb 0.001–0.27
mg
kg
−1. Metal level ranges measured in mackerel were (mg
kg
−1): As 0.01–36.4, Cd 0.001–0.1, Cu 0.001–15.9, Hg 0.001–0.78 and Pb 0.002–0.24
mg
kg
−1. In picarel, metal level ranges were (mg
kg
−1): As 0.01–54.6, Cd 0.001–0.1, Cu 0.08–32.9, Hg 0.001–0.207 and Pb 0.001–0.46
mg
kg
−1. Significant differences in metal concentrations were found among fish species. The results presented on metal contents in the examined species give an indication of the environmental conditions. Concentrations of Cd, Cu, Hg and Pb obtained were far below the established values by the European Community regulations. However, arsenic levels found in red mullet were higher than the recommended legal limits for human consumption and as such may present a human health issue.
► Element contents decreased in the following order: Cu>Pb>As>Hg>Cd. ► Copper and lead were the most abundant elements in the Centre region of Croatia. ► Lead contents in Croatian honey were higher ...than most findings in other European countries.
The concentrations of As, Cd, Cu, Hg and Pb were determined in 54 multi-floral honey samples collected from five regions of Croatia during 2009 and 2010. Element contents decreased in the following order: Cu>Pb>As>Hg>Cd. Significant differences in lead and copper levels were observed between regions. Mean levels of elements (μgkg−1) in all honey samples measured were: 19.7 for As, 1.51 for Cd, 1074 for Cu, 2.72 for Hg and 65.2 for Pb. Copper and lead were the most abundant elements in the Centre region, with range and mean contents of 108–41,271 and 3232μgkg−1 and 22.0–440 and 131μgkg−1, respectively. The highest element contents were: As 23.8μgkg−1 in the South region, Cd 2.11μgkg−1 in the Southwest region and Hg 2.63μgkg−1 in the Northeast region. The finding that lead contents in Croatian honey were higher than most reported lead levels in honey from other European countries is of particular concern. These indicate that attention must be focused on setting positions for honey production hives in areas distant from highways and railways.
Aflatoxin M1 (AFM1) concentrations were measured in bulk cow milk samples from eastern Croatia, and in cow, goat, sheep and donkey bulk milk samples from other parts of Croatia during the period ...July–September 2013. AFM1 levels in milk were measured in the ranges (ng/L): cow 3.65–162.3 (eastern Croatia) and 2.69–44.9 (other regions of Croatia); goat 2.78–40.8; sheep 2.11–5.87; donkey 3.43–10.4. The concentration of AM1 exceeded the EU MRL in 6.7% of cow milk samples from eastern Croatia. The highest level measured was 162.3 ng/L. AFM1 levels exceeded the LOQ value (23.2 ng/L) in only 59 samples of cow milk and two samples of goat milk of the total 402 samples analysed. A significant difference was found between the mean AFM1 concentrations of cow milk from eastern and other regions of Croatia (P < 0.05). The elevated AFM1 levels in cow milk from eastern Croatia indicate the use of contaminated supplementary feedstuff in some farms during the study period.
•The AFM1 levels in cow, goat, sheep and donkey milk from Croatia were determined.•In 15.2% of samples AFM1 concentrations exceeded quantification limit of the method.•In 6.7% of cow milk from eastern Croatia AFM1 levels exceeded the EU limit.•A significant difference between the cow milk from eastern and other part of Croatia were found.
Monitoring beehive health and timely prevention of possible infections by bacteria, mould, viruses or parasites is exceptionally important in beekeeping. Antibiotics originating from the environment ...can be found in honey and due to improper beekeeping practices. Enabling the detection of antibiotic residues in honey and suppressing the development of antibiotic resistance require the development of a sensitive multi-class method for the determination of antibiotics. For the purpose of analysing honey, a screening and confirmatory method for the determination of 36 antibiotics was developed. The QuEChERS procedure and ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) was selected to achieve high sensitivity and selectivity. Validation according to the new Commission Implementing Regulation (EU) 2021/808 included the following performance characteristics: selectivity, trueness, precision, decision limit (CCα), detection capability (CCβ) and relative matrix effect. The method was validated in the measurement range from 1 to 10 μg/kg, where maximum trueness and acceptable coefficients of variation were achieved. The detection capability (CCβ) equals the lowest concentration level for all analytes, ranging from 0.1 μg/kg to 2.5 μg/kg, as the false compliant rate less than 5% was confirmed at this level of interest. For unauthorised pharmacologically active substances, the CCα was determined and ranged from 0.16 μg/kg for sulfaquinoxaline to 3.67 μg/kg for difloxacin. The high matrix influence of floral and chestnut honey indicated the need for quantitative analysis using the matrix calibration curve.
Display omitted
•Screening and confirmatory UHPLC-MS/MS method for 36 antibiotics was validated.•QuEChERS extraction procedure allows for fast and specific extraction.•Highly sensitive method for the determination of residues in the range from 0.1 to 10 μg/kg.•Compliance of samples according to the decision limit (CCα).
Top marine predators present high mercury concentrations in their tissues due to biomagnification in the marine food chain. This study reports mercury (Hg) and selenium (Se) status, and the Hg:Se ...molar ratio assessment in bottlenose (Tursiops truncatus), striped (Stenella coeruleoalba) and Risso's dolphins (Grampus griseus). Total Hg and Se concentrations were determined in muscle, liver, kidney, lung, spleen, adipose tissue and skin collected from 186 specimens stranded in the Croatian part of Adriatic Sea from 1995 to 2014. Total Hg concentrations in tissue samples ranged from 0.001 in the spleen to 2238 mg/kg wet weight in liver. Se concentrations in dolphin samples ranged from 0.010 to 2916 mg/kg ww. Minimum Se concentration was found in muscle and maximum Se concentration were found in liver of bottlenose dolphin. Hg and Se levels in Risso's dolphins showed higher concentrations in all tissues in comparison to bottlenose and striped dolphins. Significant and positive correlations were observed between age and Hg concentrations (P < 0.05). In 66.6 % of Risso's, 15.3 % of bottlenose dolphins and one stranded striped dolphin in this study, the hepatic concentration of Hg exceeded the higher toxic thresholds (400 mg/kg w.w.) previously defined as evidence of liver damage in marine mammals. The Hg:Se molar ratio in the liver of Risso's dolphin was 0.670. The liver of adult bottlenose dolphins showed expected values (0.870), while the liver of young dolphins had a high ratio (0.750), non-specific for the age group. The Hg:Se molar ratio in the liver of striped dolphins was 0.390, which is lower than the literature values.
Display omitted
•Hg and Se were determined in 186 specimens stranded in the Adriatic Sea.•64 individuals exceeded the lower critical level (Hg = 100 mg/kg) in liver.•The upper critical level in the liver (Hg = 400 mg/kg) exceeded 29 dolphins.•Bioaccumulation of Hg and Se was found in the liver of dolphins.
► Higher cadmium and mercury levels found in the southern than in the northern region. ► In both regions lead levels found were above the maximum residue levels. ► Similar mean copper levels found in ...both regions. ► Arsenic levels exceed the maximum residue levels in only 2–9% of samples.
A total of 157 raw milk samples were collected from tankers arriving at processing facilities from rural areas in northern and southern regions of Croatia during 2009 and 2010. Concentrations of As, Cd, Cu, Hg and Pb in the samples were analysed by graphite furnace-atomic absorption spectroscopy. Mean Pb concentrations in northern and southern regions were 58.7 and 36.2μgl−1, respectively, and both exceeded the maximum recommended level. Arsenic concentrations ranged from 1 to 283μgl−1 in the southern and to 1019μgl−1 in the northern regions. Mean Cd and Hg levels were: 1.76 and 1.59 in the northern and 3.4 and 7.1μgl−1 in the southern region. Significantly higher Cd and Hg levels were observed in the southern than in the northern region (p<0.001, both). Similar mean Cu levels were found in both regions: 931.9 in the north and 848.4μgl−1 in the south. The results indicate that particular attention should be paid to Pb residues. In future studies, a greater number of milk samples and grass samples from pastures from different regions of Croatia should be controlled to confirm the absence of possible toxicological risks.
Quality and safety of food, including honey, is one of the leading priorities regarding residues of anthropogenic chemicals with proven adverse health effects. In total, 61 honey samples of known ...botanical origin were collected in period 2018–2019 from Croatian registered organic and conventional beekeepers (N = 16 organic and N = 45 conventional honey samples). Eleven trace metal(loid)s (Al, As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn; quantitated by ICP-MS), 24 antibiotics (LC-MS/MS, ELISA, microbiological inhibition test), six indicator PCBs (GC-MS/MS) and 121 pesticides (LC-MS/MS, GC-MS/MS) originating from environment and/or beekeeping practice were measured to assess possible differences in contaminant residues between organic and conventional honeys. All honey samples had contaminant residues below the legal maximum levels and are considered safe for consumers. However, 2/16 organic and 34/45 conventional honeys contained one or two synthetic acaricides (most frequently coumaphos), while other pesticides, antibiotics and PCBs were not quantified. Also, organic honey contained lower levels of coumaphos, amitraz and amitraz metabolite N-(2,4-dimethylphenyl) formamide than conventional honeys, on average. Higher levels of Cr (p = 0.006) were detected in organic compared to conventional chestnut honeys. This study pinpointed beehive disease control treatment as prominent pesticide residue source, which was to some extent reduced in organic honeys. Quantified pesticide and metal(loid) levels were within range or lower than reported in recent literature regarding honey of the same botanical origin.
Display omitted
•Contaminants level differed in organic vs. conventional Croatian honey.•Lower content and frequency detection of synthetic acaricides in organic honey.•Chromium higher in organic vs. conventional honey.•Pesticides and PCB residues from environment, and antibiotics in honey not detected.
Display omitted
•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.
A total of 3543 raw cow milk samples were collected in three regions of Croatia: western, eastern and other regions during four seasons. Samples were measured for aflatoxin M1 (AFM1) concentrations ...using the enzyme immunoassay method. Elevated levels (>50 ng/kg) of AFM1 were analysed by validated liquid chromatography with triple quadruple mass spectrometry (LC-MS/MS). The limits of detection (LOD) and quantification (LOQ) of the LC-MS/MS method were 7.3 and 28 ng/kg, respectively. The mean AFM1 levels measured in the three regions over four seasons were in the ranges (ng/kg): eastern Croatia 7.25–26.6; western Croatia 5.91–9.26; other regions of Croatia 7.17–13.6. The highest incidence of samples exceeding the EU MRL (50 ng/kg) of 9.32% was measured in autumn (October–December) in the eastern region. Only eight samples were found to exceed the EU MRL in winter. The highest AFM1 levels were measured in December (764.4 ng/kg) and January (383.3 ng/kg). Elevated AFM1 levels were found in summer in only four samples from the western and other regions, and two samples in the eastern region. This can be attributed to localized and random usage of contaminated feed for dairy cows in those regions. The much lower incidence of elevated AFM1 in comparison to a previous study showed that the outbreak of the crisis due to elevated AFM1 levels in 2013 resulted in a more careful approach to the control of supplementary feedstuff for lactating cows.
•AFM1 concentrations in milk were monitored during one year period in Croatia.•During autumn 9.32% samples exceeding the EU MRL in the eastern region.•In other seasons there were no differences in AFM1 levels between three regions.•Only a few samples with elevated concentrations were found during the summer.
•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.
