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.
This study’s objective was to estimate the seasonal occurrence of aflatoxin M1 (AFM1) in cow’s milk between winter 2016 and winter 2022 and to assess dietary exposure and risk assessment for the ...adult Croatian population. In total, 5817 cow milk samples were screened for AFM1 concentrations using the enzyme immunoassay assay (ELISA). For confirmation purposes of AFM1 concentration above the European Union maximum permitted level (MRL), ultra high-performance liquid chromatography with tandem mass spectrometry was performed. In 94.7% of milk samples, AFM1 levels were below the detection limit (LOD) of the ELISA test. For 3.47% of samples, the AFM1 was between the LOD and MRL values. Only 1.87% of all samples exceeded the MRL. The mean value of elevated AFM1 in different seasons ranged between 59.2 ng/kg (autumn 2017) and 387.8 ng/kg (autumn 2021). The highest incidences of positive AFM1 were determined in autumn and winter and the maximum (6.4%) was in winter 2019/2020. The largest percentage of positive samples (69.7%) was found in central Croatia. The estimated daily intakes for positive samples ranged between 0.17 and 2.82 ng/kg body weight/day. Risk assessment indicated a high level of concern during autumn and winter, especially for consumers of large amounts of milk.
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 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.
The aim of this study was to monitor the biochemical and chemical parameters of the blood of commercial chickens following treatment with one of three coccidiostats: maduramycin, monensin or ...diclazuril. Chickens received feed treated with maduramycin at concentrations of 5, 10 and 15 mg kg-1, monensin at 125, 225 and 325 mg kg-1 or diclazuril at 1, 5 and 10 mg kg-1. A control group of chickens consumed feed without the addition of coccidiostats. Following treatment, blood was sampled for 11 days and analysed for the following biochemical and chemical parameters: aspartate aminotransferase (AST), bile acid (BA), creatine kinase (CK), uric acid (UA), glucose (GLU), cholic acid (CA), total protein (TP), albumin (ALB), globulin (GLOB) and phosphorus (PHOS). Administration of different concentrations of maduramycin, monensin and diclazuril did not affect the concentration of the parameters AST, UA, GLU, BA, TP, ALB, GLOB and PHOS in experimental groups of broilers in relation to the control group. However, significant differences were observed in the concentrations of CK and CA between the experimental and control groups. Significant differences were also found in the concentrations of AST, CA and UA between experimental groups. Key words: maduramycin; monensin; diclazuril; chickens; biochemical and chemical parameters SPREMEMBE BIOKEMIJSKIH IN KEMIJSKIH PARAMETROV V KRVI KOKOŠI PO ZDRAVLJENJU Z MADURAMICINOM, MONENZINOM IN DIKLAZURILOM Namen raziskave je bil spremljanje biokemijskih in kemijskih parametrov krvi industrijsko gojenih piščancev po zdravljenju z enim od treh kokcidiostatikov: maduramicinom, monenzinom ali diklazurilom. Piščanci so dobivali krmo z maduramicinom v koncentracijah 5, 10 in 15 mg/kg, monenzin v koncentracijah 125, 225 in 325 mg/kg ali diklazuril v koncentracijah 1, 5 in 10 mg/kg. Kontrolna skupina piščancev je dobila krmo brez dodatka kokcidiostatikov. Enajsti dan po zdravljenju je bila piščancem odvzeta kri in analizirani so bili naslednji biokemijski in kemijski parametri: koncentracija aspartatne aminotransferaze (AST), žolčnih kislin (BA), kreatininske kinaze (CK), sečne kisline (UA), glukoze (Glu), skupnih beljakovin (TP), albuminov (ALB), globulinov (GLOB) in fosforja (Phos). Dodajanje različnih koncentracij maduramicina, monenzina in diklazurila ni vplivalo na koncentracijo parametrov AST, UA, Glu, BA, TP, ALB, GLOB in Phos v poskusnih skupinah pitovnih piščancev v primerjavi s kontrolno skupino. Statistično značilne razlike so bile ugotovljene v koncentracijah CK in CA med poskusnimi in kontrolno skupino. Značilne razlike so bile ugotovljene tudi v koncentracijah AST, CA in UA med posameznimi poskusnimi skupinami. Ključne besede: maduramicin; monenzin; diklazuril; piščanci; biokemijski in kemijski parametri
Concentrations of the anthelmintic agent levamisole were measured in a total of 85 raw cow milk samples collected during 2014 from dairy farms across Croatia. The liquid chromatographytandem mass ...spectrometry (LC-MS/MS) method used for levamisole quantification was validated according to the criteria set by Commission Decision 2002/657/EC. The following validation parameters were determined: limit of decision (CCα) 0.55 μg kg-1, detection of capability (CCβ) 0.59 μg kg-1, limit of detection (LOD) 0.06 μg kg-1, limit of quantification (LOQ) 0.22 μg kg-1, precision and accuracy (expressed as recovery) 97.3-100 %, intra-laboratory reproducibility (RSD) 4.2-5.6 %. Levamisole levels for 45 of the total of 85 samples were below the LOD value (0.06 µg kg-1). In the remaining 40 milk samples, levamisole was measured in the range from 0.061 to 0.142 µg kg-1 and the mean value was 0.092 µg kg-1. Accordingly, all concentrations analysed were below the LOQ value (0.22 µg kg-1) and limit of decision (CCα) of the method used.
A screening and confirmatory method for the determination of 13 antibiotic groups including 91 substances was developed for muscle samples and validated using ultra-performance liquid chromatography ...(UPLC) coupled to time-of-flight mass spectrometry. Optimisation of the parameters was performed for every analyte and personal compound database library was created, comprising the mass spectra for following collision energies; 0, 10, 20 and 40 eV. Validation plan scheming and calculation of the parameters was performed using validation software, which included following performance characteristics; selectivity, trueness, precision, decision limit (CCα), detection capability (CCβ) and relative matrix effect.
High resolution mass spectrometry operated in a narrow mass window and resolving power of 50,000 FWHM (2 GHz). Accurate mass measurements with mass accuracy below 10 ppm for all analytes were obtained in spiked muscle samples. The validation experiments showed good selectivity and specificity. The method was validated in the measurement range from 0.5 to 1000 μg/kg, where a specific analyte mixed standard solution was prepared depending on the defined maximum residue limit (MRL) or lowest calibration level (LCL). For screening analysis, detection capabilities (CCβ) below the set MRL values or at LCL concentration levels were defined. CCβ, as the concentration above which the sample can be considered suspect, ranged from 0.63 to 207.8 μg/kg. For confirmation of the analyte, CCα was calculated at LCL or at the MRL, where it ranged from 0.38 to 14.3 μg/kg for unauthorised substances and from 13.8 to 1492.6 μg/kg for authorised substances. Relative within-laboratory reproducibility standard deviation ranged from 5.1 to 34.2%. Satisfactory z-score values in the range from −0.87 to 1.88 were obtained as a result of participating in four proficiency tests organized by European Union Reference Laboratories.
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•Screening and confirmatory HRMS method for 91 antibiotics.•Wide validation range around the established residue limits.•CCβ and CCα as parameters for screening and confirmatory analysis.•Satisfactory proficiency results as confirmation of good method performance.
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.
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•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).
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.
•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.
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