Element differences and evaluation of the dietary intake from farmed oysters and mussels collected at different sites along the Croatian coast of the Adriatic Sea

Concentrations of the macroelements Ca, Mg, K and Na, microelements Cr, Cu, Fe, Mn and Zn and toxic metals As, Cd, Hg and Pb were determined in oysters and mussels collected at farming sites in the northern, central and south Adriatic Sea. Mean concentrations in oysters were (mg kg⁻¹): As 4.51, Ca 1551, Cd 1.44, Cu 53.6, Cr 0.23, Fe 45.9, Hg 0.047, K 2476, Mg 895, Mn 2.80, Na 7148, Pb 0.52, Zn 675. Mean values in mussels were (mg kg⁻¹): As 4.71, Ca 601, Cd 0.37, Cu 1.91, Cr 0.29, Fe 49.6, Hg 0.026, K 2246, Mg 1043, Mn 2.49, Na 7992, Pb 0.58, Zn 28.8. Significant differences in the concentrations of toxic metals and elements were found in oysters and mussels among farming sites. Obtained Cd, Hg and Pb concentration in oysters and mussels were lower than the limit levels set by the European Community. However, Cd concentration exceeded the limit level of 1 mg kg⁻¹ in oysters from all locations except Lim Bay. The estimated daily intakes (EDIs) indicate that oysters are a good source of Ca, Cu and Zn. The higher Cu and Zn concentrations than the toxicity reference values suggest a risk for consumers if larger quantities of oysters are consumed frequently.     

Geographical discrimination of Italian honey by multi-element analysis with a chemometric approach

In this study the concentrations of K, Ca, Mg, Na, Al, Zn, Fe, Mn, Cu, Cr, Ni, Se, Pb, Cd, and As in 39 honey samples of different botanical (orange-blossom, lemon-blossom, chestnut, eucalyptus, acacia, sulla and wildflower honeys) and geographical (Sicily and Calabria, Italy) origin were determined by ICP-OES and ICP-MS. The most abundant minerals decreased in the following order: K (mean value: 1.57 mg g⁻¹) > Ca (0.2 mg g⁻¹) > Mg (0.121 mg g⁻¹) > Na (0.092 mg g⁻¹). Recommended Dietary Allowance (RDA) values and benchmark levels were employed to assess the honey quality and safety. The data excluded toxicological risks: for an adult of 60 kg, a daily intake of 2 g of honey covered maximum 0.40% of Tolerable Weekly Intake (TWI) for Al, 0.33% of Benchmark Dose of 1% Extra Risk (BMDL01) for Pb, and 0.07% of Tolerable Daily Intake (TDI) for Ni. Mineral content marks the differences in honey samples from different geographical origin despite the botanical factor weight and can be used as a tool to assess the traceability of honeys. The discrimination between Sicilian and Calabrian honeys was achieved by Principal Component Analysis (PCA), and also the results of Canonical Discriminant Analysis (CDA) indicate that the 100% of total samples are correctly classified. This research contributes to the studies to determine the geographical origin of honeys.     

Calcium,magnesium, sodium and potassium levels in foodstuffs from the second French Total Diet Study

Calcium (Ca), magnesium (Mg), sodium (Na) and potassium (K) contents in 1319 foodstuffs habitually consumed by the French population were determined for the second French Total Diet Study (TDS), using micro-sampling flame atomic absorption spectrometry after microwave-assisted digestion. Concentration and distribution of these minerals in food samples were reported and compared with results from the previous French TDS. For Ca, the results indicate that the food presenting the highest levels are dairy products (1597 mg kg^?1), tofu (802 mg kg^?1) and some fish and cereal products; for Mg, tofu (1340 mg kg^?1), “Sweeteners, honey and confectionery” (672 mg kg^?1) especially dark chocolate (2225 mg kg^?1) and certain grains such as nuts and oilseeds (1069 mg kg^?1) and some cereal products; for Na, processed meats such as delicatessen (12,422 mg kg^?1), “Salts, spices, soup and sauces” (21,028 mg kg^?1), some cheeses and cereal products; and for K, “Cereal and cereal products” (4378 mg kg^?1), “Meats and offal” (3993 mg kg^?1), “Nuts and oilseeds” (7355 mg kg^?1) and “Sweeteners, honey and confectionery” (3445 mg kg^?1) (especially chocolate).     

Content of macro- and microelements and evaluation of the intake of different dairy products consumed in Croatia

Macromineral and microelement contents were measured by inductively coupled plasma-optical emission spectrometry in 51 dairy products (milk, four types of cheese and butter). Significant differences in the concentrations of Ca, K, Na, Mg, Zn and Cu were observed (p < 0.05, all) between dairy products. Higher levels of Ca, Na, Mg and Se were measured in hard cheese than in semi-hard, fresh and cream cheese samples. The highest mean levels of elements were measured in products (mg kg⁻¹): milk: K 2070; hard fat cheese: Ca 10,700, Na 10,300, Mg 440, Zn 91.3, Se 0.78; cream cheese: Cu 3.12, Fe 3.9; butter: Se 0.79. The estimated daily intakes (EDIs) calculated for milk show contribution to the recommended dietary allowance (RDA) for the elements (%): Ca 42, K 13.2, Mg 10.3–13.3, Zn 11.4–15.7, Se 13.1. The highest contribution of elements to the RDA values was determined for hard fat cheese (%): Na 7.93, Zn 16.6–22.8, Se 28.4. However, a contribution to the RDA of less than 1% was determined for K, Mg and Fe in cheeses. The contribution of Cu to the RDA value ranged in cheese samples between 2.78 and 6.93%, though this was less than 1% in milk.     

Arsenic,cadmium, cobalt,copper, lead,mercury, molybdenum,selenium and zinc concentrations in liver,kidney and muscle in Australian sheep

Matched muscle, liver and kidney samples from 152 sheep in different states of Australia were analysed for trace elements. Mean levels found in muscle, livers and kidneys were 0.010, 0.010 and 0.011 mg kg⁻¹ (fresh weight) for arsenic; 0.0035, 0.280 and 0.853 mg kg⁻¹ for cadmium; 0.006, 0.060 and 0.044 mg kg⁻¹ for cobalt; 0.74, 66.0 and 2.72 mg kg⁻¹ for copper; 0.007, 0.040 and 0.057 mg kg⁻¹ for lead; 0.0025, 0.0034 and 0.0061 mg kg⁻¹ for mercury; 0.014, 1.05 and 0.44 mg kg⁻¹ for molybdenum; 0.09, 0.31 and 0.95 mg kg⁻¹ for selenium; and 40.4, 37.2 and 20.8 mg kg⁻¹ for zinc. The lead, mercury and arsenic concentrations in meat and organs may be regarded as low, but the concentrations of cadmium in kidney and livers are sometimes relatively high. Apart from cadmium, lead and selenium, tissue trace element concentrations were not related to the age of the investigated animals. Differences in essential and non-essential trace element accumulation in sheep reared in different regions (states and territories) of Australia were also evaluated. Cadmium, lead and selenium were the only elements that appeared to show significant regional differences. Overall the results show that concentrations of the elements considered are within current acceptable ranges.     

Comparison of the chemical composition of British and Continental European bottled waters by multivariate analysis

The elemental composition of 37 bottled waters from the UK and continental Europe has been determined. Ca, K, Mg, Na, Al, As, Ba, Cd, Cr, Co, Cu, Fe, Mn, Mo, Ni, Pb, Sb, Sr, U, V and Zn were determined by ICP-OES and ICP-MS, in addition to inorganic and total organic carbon. The composition of all the waters analysed fell within the guideline values recommended by the World Health Organization. Na, Ca, Sr and Ba showed the widest variation in concentrations, ranging over two orders of magnitude. Levels of Fe were below the limit of detection (30 μg L⁻¹) in all samples analysed. Waters produced in the UK generally showed lower levels of most major elements and trace metals, with the exception of Ba (up to 455 μg L⁻¹). Italian waters showed the highest concentrations of Sr (3000–8000 μg L⁻¹) and U (8–13 μg L⁻¹), whereas waters produced in Slovakia and the Czech Republic showed the highest levels of Pb (0.7–4 μg L⁻¹). The use of multivariate analysis reveals an association between high alkaline metal content and high concentrations of As and Cr. There also appears to be a correlation between high Ca and Sr content and high levels of U. Analysis of variance (ANOVA) indicates that the composition of bottled water can be distinguished primarily by the country of origin, over other factors including the geological environment of the source. This would suggest that composition reflects, and is biased towards, consumer preferences.     

Essential and non-essential elements in Brazilian infant food and other rice-based products frequently consumed by children and celiac population

Rice and its derivatives are important source of essential and non-essential elements. Essential elements as cobalt (Co) and selenium (Se) are vital for human homeostasis. However, non-essential elements such as arsenic (As), cadmium (Cd) and lead (Pb) may be present in rice-based food and consequently, people can be exposed—especially children and the celiac population. This study aimed to determine essentials and non-essentials elements in rice-based products and baby food and also to evaluate nutritional risk by estimating the daily intake of non-essential elements. Regarding essential elements, Co and Se presented the highest concentrations in rice flour (56 μg kg⁻¹) and porridge (254 μg kg⁻¹), respectively. For non-essential elements, the highest concentrations of As, Cd and Pb were 104 μg kg⁻¹ (porridge), 16 μg kg⁻¹ (flour), and 188 μg kg⁻¹ (bread), respectively. Total As concentration in Brazilian rice-based baby food was <29 μg kg⁻¹. However, As-speciation revealed inorganic-As (i-As) as the main specie. The highest estimated daily intake of Cd, Pb and i-As were 1.37 (rice-based baby food); 10.39 (pasta); and 3.34 (pasta) μg d⁻¹, respectively. Therefore, continuous food monitoring for nutritional and toxicological purpose is necessary, especially concerning these particular populations and discussions for maximum levels of non-essential elements.     

Strontium,silver, tin,iron, tellurium,gallium, germanium,barium and vanadium levels in foodstuffs from the Second French Total Diet Study

A total of 28 minerals and trace elements from 1319 food samples typically consumed by the French population were determined during the second French Total Diet Study (TDS). Among the main trace elements analysed by inductively coupled plasma-mass spectrometry (ICP-MS) after microwave-assisted digestion, strontium (Sr), silver (Ag), tin (Sn), barium (Ba), iron (Fe), tellurium (Te), gallium (Ga), germanium (Ge) and vanadium (V) were retained for this work and their occurrence data reported here. The contents were compared using data from worldwide total diet studies. Data for tin in canned food and beverages were compared with European guidelines. The food groups with the highest levels were “Sweeteners, honey and confectionery” with dark chocolate (for Sr, Ag, Sn, Te, Ba, Fe Ga, Ge and V), “Fish and fish products” and particularly “Shellfish” (for Sr (14.3 mg kg^?1), Ag (5.18 mg kg^?1), Ga (0.002 mg kg^?1), Ge (0.004 mg kg^?1), Te (0.003 mg kg^?1) and V (0.234 mg kg^?1)), “Tofu” (for Sr (2.71 mg kg^?1), Fe (29.0 mg kg^?1) and Ba (0.824 mg kg^?1)), “Ice cream” (Ba (0.621 mg kg^?1), Fe (45.5 mg kg^?1), Ag (0.193 mg kg^?1)) and “Fat and oil” (for Te, Ga and Ge). Moreover, the highest concentrations of Sn were found in “Fruits and vegetables” (0.522 mg kg^?1).     

Comparisons and selection of rice mutants with high iron and zinc contents in their polished grains that were mutated from the indica type cultivar IR64

Developing rice varieties biofortified with iron (Fe) and zinc (Zn) is an important strategy to alleviate nutritional deficiencies in developing countries, where polished rice is consumed as the staple food. In this study, the contents of several macro- and micro-minerals in polished rice grains of cultivar IR64 and its 254 sodium azide-induced mutants (M8 generation) were assessed. The results indicated that the contents of potassium, phosphorus, calcium, magnesium, iron, manganese, copper, and zinc varied among the tested mutants. The polished rice grains of mutants M-IR-75 and M-IR-58 accumulated more Fe (28.10 and 27.26 mg kg⁻¹, respectively) than cultivar IR64 (3.90 mg kg⁻¹). Mutant M-IR-75 also produced higher yield (average of 8.65 ton ha⁻¹ over two crop seasons) than cultivar IR64 (average of 7.27 ton ha⁻¹). Mutants M-IR-180, M-IR-49 and M-IR-175 contained more Zn (26.58, 28.95 and 26.16 mg kg⁻¹, respectively) than cultivar IR64 (16.00 mg kg⁻¹), but only mutant M-IR-180 showed a grain yield comparable to cultivar IR64. Thus, the mutant M-IR-75 can be recommended to rice growers to produce Fe-rich rice grains. Additionally, the high-Fe (M-IR-75 and M-IR-58) and high-Zn (M-IR-180, M-IR-49 and M-IR-175) mutants can be used as genetic resources for rice improvement programs.     

The risk of high mercury accumulation in edible mushrooms cultivated on contaminated substrates

Mercury (Hg) exposures represent a significant worldwide health issue. At the same time its content in cultivated mushrooms is not effectively regulated. The present study investigated how substrate contamination with Hg (0.1–0.5 mM) affects its accumulation in stipes and caps of Agaricus bisporus E58, Pleurotus ostreatus H195 and Hericium erinaceus HE01, mushroom growth and composition of macronutrients. The greatest Hg accumulation was demonstrated for caps. Generally, Hg uptake increased in a concentration-dependent manner and exceeded 44 mg kg⁻¹ (P. ostreatus), 116 mg kg⁻¹ (A. bisporus) and 53 mg kg⁻¹ (H. ercinaceus) in caps after 0.5 mM was added to the substrate. Importantly, an increase in Hg accumulation was also significant and potentially hazardous for human health at the lowest assayed concentration. A. bisporus and P. ostreatus revealed high resistance to Hg and declined its biomass only at 0.4 and 0.5 mM concentration. The presence of Hg did not alter the macronutrient composition (total carbohydrates, proteins and fats). These results highlight the significant role of proper substrate selection in mushroom cultivation to avoid exposing consumers to harmful Hg levels and further health consequences.     

Assessment of hydroxymethylfurfural and furfural in commercial bakery products

A survey was conducted on the presence of hydroxymethylfurfural (HMF) and furfural in bread and bakery products; for this purpose a reliable extraction procedure followed by high performance liquid chromatography (HPLC) was applied. The performance of the method was evaluated in terms of linearity (r always > 0.99); detection limits (0.001 mg L⁻¹ for furfural and 0.006 mg L⁻¹ for HMF); recovery percentages (98.5–100.5% for HMF and 94.9–98.9% for furfural); intraday precision (<4.65%) and interday precision (<7.51%). Two batches of a wide variety of products commercially available were analysed (a total of 88 samples). HMF and furfural levels presented high variability between products and batches of the same product. Cake/pastry samples showed the lowest HMF content (3.0 mg kg⁻¹ fw) while biscuits showed the highest content (7.8 mg kg⁻¹ fw) (p < 0.05). Regarding furfural, bread samples presented the highest furfural content (5.3 mg kg⁻¹ fw) (p < 0.05), cake/pastry and biscuits showed the lowest content (1.9 and 3.0 mg kg⁻¹ fw, respectively). Chocolate containing samples presented higher amounts of furfural (>20 mg kg⁻¹). These results indicate that special attention should be given to furfural content of bread (due to its daily high consumption) and re-evaluation of dietary exposure.     

Exposure assessment of arsenic speciation in different rice types depending on the cooking mode

Total (As_t), inorganic arsenic (As_i = As(III) + As(V)) and dimethylarsonic acid (DMA) were determined in 37 commercial rice samples collected in France. As_t was measured by inductively coupled plasma-mass spectrometry (ICP-MS) whereas anion-exchange chromatography – ICP-MS was used for As_i and DMA determination. As_t in raw rice varied from 0.041 to 0.535 mg kg⁻¹ whereas As_i varied from 0.025 mg kg⁻¹ (polished Basmati rice) up to 0.471 mg kg⁻¹ (organic rice duo). The daily intake and associated health risk for different population groups as a function of age and gender was also assessed. The intake varied between 0.002 and 0.184 μg kg⁻¹ body weight for As_t and 0.002 and 0.153 μg kg⁻¹ body weight for As_i, which do not pose a chronic toxicity risk. Organic wholegrain rice may entail a risk for children in the case of sole consumption at the expense of polished rice. The impact of rice cooking/boiling in terms of the overall toxicological risk related to As species was also investigated. Pre-rinsing and boiling the raw rice by using an excess of water is the most efficient mode to obtain a significant As_i removal and further reduction of the toxicological risk for children, particularly for white rice varieties.     

Optimization of cheese sample preparation methodology for free amino acid analysis by capillary isotachophoresis

The objective of this work was the evaluation of different conditions for the selected free amino acids extraction from cheese samples, followed by capillary isotachophoresis analysis. Parameters of the extraction: concentration and type of extraction reagents (solvents: methanol, ethanol and mineral acids: perchloric acid, trichloroacetic acid, sulphuric acid and hydrochloric acid), time and temperature, and isotachophoretic separation conditions (voltage, time) were studied. Repeatability, reproducibility and stability of this method at different conditions are discussed. The best yield of free amino acids was obtained after triple extraction (30 min each process) with 0.1 M hydrochloric acid at 50 °C. Histidine, lysine, arginine, ornithine, tyrosine, and phenylalanine were determined using calibration curves and the standard additions method in different types of cheeses. The highest level of amino acids was determined in semi-hard cheese (2626.3 mg 100 g⁻¹ – calibration curve, and 2679.2 mg 100 g⁻¹ – standard additions method), whereas the lowest were found in sheep cheese (426.3 mg 100 g⁻¹ and 455.7 mg 100 g⁻¹, respectively), and Gouda type cheese samples (441.5 mg 100 g⁻¹ and 472.8 mg 100 g⁻¹, respectively).     

Variability of biogenic amine and free amino acid concentrations in regionally produced goat milk cheeses

The free amino acid composition and biogenic amine content were analysed in pasteurised goat milk cheeses produced in different regions in Spain. These goat cheeses are made with pasteurised milk to which a mesophilic starter culture is added; they are enzymatically coagulated, uncooked, pressed cheeses. They have a firm texture with a slight but typical goat milk aroma and flavour. The total free amino acids varied markedly among the samples, ranging from 1400 to 28,000 mg kg⁻¹ DM (dry matter). Of the 20 amino acids analysed, the most abundant were leucine, proline, valine, glutamic acid, lysine, glutamine, ornithine and γ-aminobutyric acid, which accounted for over 60% of the total free amino acids. The goat milk cheeses presented low concentrations of biogenic amines, the most abundant being tyramine and/or histamine, with values ranging from 4.2 to 50.7 and from 10.2 to 60.5 mg kg⁻¹ DM, respectively. Total biogenic amine content ranged between 26.4 mg kg⁻¹ DM and 175.1 mg kg⁻¹ DM, and was always below the level that is considered dangerous for humans. Therefore, taking into consideration the concentrations of BAs, these goat milk cheeses, produced under good hygienic conditions, can be considered safe for consumers.     

A magnetic ion-imprinted polymer for lead(II) determination: A study on the adsorption of lead(II) by beverages

In this work a variety of beverage samples had been kept in a contaminated area to investigate their lead adsorption. To determine the adsorbed Pb(II), a novel magnetic lead ion-imprinted polymer, grafted onto Fe₃O₄ nanoparticles, was synthesized and used as a selective sorbent for the preconcentration of Pb(II) ions. The sorbent was characterized by different techniques. The synthesized sorbent was applied for highly accurate and selective determination of Pb(II) ions absorbed from polluted air in several beverages and results were compared. To validate the method, three certified reference materials were analyzed by the proposed method and the results showed that pre-concentrating by this sorbent and subsequent determination by flame atomic absorption spectroscopy is an accurate method for lead determination in beverage samples (recoveries higher than 95%). The limits of detection and the relative standard deviations were less than 1.7 μg kg⁻¹ and 4.1%, respectively. The sorption capacity of this new sorbent was 51.8 mg g⁻¹. Finally, this method was used for the determination of Pb(II) ions in polluted beverage samples, and the results revealed that under equal conditions, coffee exhibits more tendency to adsorb Pb(II) ions.     

Nutritional value of tomatoes (Solanum lycopersicum L.) grown in greenhouse by different agronomic techniques

The relevance of agronomic practices on the nutritional quality greenhouse-grown tomatoes has been recognized. We investigated the influence of (1) cultivar: two local (Pera-Girona and Montserrat) and one commercial (Caramba) varieties; (2) nitrogen dose in nutrient solution (low vs. standard N dose); (3) treatment for plant disease control (sulfur vs. Milsana^®) and (4) ripeness (orange vs. full-red color) on levels of carotenoids, phenolic compounds, ascorbic acid and minerals of fruits. Carotenoids and ascorbate were mainly influenced by variety and ripening stage, while N dose slightly affected minerals in fruits; treatments against plant diseases exerted only negligible effects on measured compounds. Local tomato varieties appear more promising as food source of carotenoids, mainly lycopene, and of hydroxycinnamates, such as 5-caffeoylquinic acid and caffeoylquinic derivatives, than commercial variety (total carotenoids: 67.43 mg kg⁻¹ fw vs. 56.34 mg kg⁻¹ fw of Pera-Girona vs. Caramba and total hydroxycinnamates: 90.87 mg kg⁻¹ fw vs. 37.90 mg kg⁻¹ fw of Montserrat vs. Caramba, at full-red color). Tomato variety and harvest maturity of fruit were the main factors affecting nutritional value of tomatoes, while Milsana^® treatment did not result in evident nutritional benefits. However, the use of this elicitor might be appropriate considering the increasing environmentally friendly attitudes of consumers.     

Direct atomic absorption spectrometry determination of arsenic,cadmium, copper,manganese, lead and zinc in vegetable oil and fat samples with graphite filter furnace atomizer

The article presents the results of optimization of operation parameters, investigation of analytical characteristics and the abilities of a graphite filter-furnace (FF) atomizer for the direct electrothermal atomic absorption spectroscopy (ET AAS) determination of trace amounts of Mn, As, Pb, Cu, Cd and Zn in some vegetable oils and fats. The effect of pyrolysis and atomization temperatures of the graphite FF atomizer on atomic absorbance values of the listed elements at their evaporation from some organic solutions in the presence of a Pd-Mg chemical modifier (CM) was investigated. For the ET AAS determination of As, Pb, Cd and Zn with Pd-Mg CM, the temperature of the graphite FF atomizer for the pyrolysis step can be raised by 250–350 °C. This mode allows to eliminate the background absorption, to increase the sensitivity of the elements to be analyzed and to enhance the total content of vegetable oils or fats in organic solutions up to 0.5 g mL⁻¹. The obtained limits of quantification for Mn, As, Pb, Cu, Cd and Zn were 0.002, 0.004, 0.004, 0.002, 0.0008, 0.0004 mg kg⁻¹, respectively. The relative standard deviation (RSD) varied between ∼3 and 8% and the time of one element determination did not exceed ∼3–5 min. The reliability of the proposed method was checked using the reference method. A paired Student's t-test showed no significant difference between the results obtained by both methods on a 95% confidence level.     

Major and trace elements in sclerotium of Pleurotus tuber-regium (Ósū) mushroom—Dietary intake and risk in southeastern Nigeria

This paper presents the results of the determination of Ag, Al, Ba, Ca, Cd, Co, Cr, Cu, Fe, Hg, K, Mg, Mn, Na, Ni, P, Pb, Rb, Sr and Zn in 30 specimens of the sclerotia of Pleurotus tuber-regium mushroom from two markets in southeastern Nigeria. The elements were determined by inductively coupled plasma atomic emission spectroscopy (ICP-AES). The K and Mg contents ranged from 500 to 10,000 μg/g (dry weight), followed by Ca and Na ranging from 19 to 1700 μg/g. The median concentrations of Fe, Zn, Al, and Mn were generally >10 μg/g, followed by Rb, Cu, Sr, Ba, and P with median between 1.1 and 11 μg/g, while Cr, Ni, Ag, Co, and Cd were <1 μg/g. The Hg concentrations were between 0.0033 and 0.15 μg/g. The Pb (0.05–2.2 μg/g) and Cd (0.0027–0.16 μg/g) contents were below EU limits for these metals in fungi, and thus safe for human consumption. Principal component analysis (PCA) showed that the concentrations of Ba, Ca, Mg, P, Rb and Sr in sclerotia did not vary considerably, depending on the sampling location, as did Cd, Cu, and Mn. PCA also revealed that the Hg and Pb in sclerotia could be related to anthropogenic sources.     

Determination of biogenic amines in different cheese samples by LC with evaporative light scattering detector

The paper presents the application of liquid chromatography coupled with evaporative light scattering detector (LC-ELSD) for the determination of biogenic amines in different cheese samples, as their presence and relative amounts give useful information about freshness, level of ripening and quality of storage. Forty samples from different types of milk – hard-ripened, ripened and unripened – were considered. Results showed that the amine contents varied in relation to the manufacturing process, the highest concentration being in hard-ripened cheeses followed by ripened and then unripened. In hard-ripened cheeses amines were β-phenylethylamine (PHE) (69.8–136.6 mg kg^?1), tyramine (TYR) (19.7–147.1 mg kg^?1), spermidine (SPD) (nd–73.1 mg kg^?1), cadaverine (CAD) (nd–64.7 mg kg^?1), histamine (HIS) (17.6–48.2 mg kg^?1), spermine (SPM) (nd–47.4 mg kg^?1), putrescine (PUT) (nd–44.1 mg kg^?1) and agmatine (AGM) (nd–4.2 mg kg^?1); while in ripened cheese TYR (nd–116.7 mg kg^?1), PUT (nd–82.9 mg kg^?1), HIS (nd–57.7 mg kg^?1), PHE (nd–51.1 mg kg^?1), SPD (nd–31.5 mg kg^?1), CAD (nd–30.7 mg kg^?1), SPM (nd–26.9 mg kg^?1) and AGM (nd–4.8 mg kg^?1). On the basis of literature limits, in this study only hard ripened cheeses could represent a possible risk for consumers as they exceeded a proposed limit for PHE and total biogenic amines amount.     

Development of HPLC-DAD method for determination of neonicotinoids in honey

After the EU banned the use of the neonicotinoids in flowering crops that honeybees might visit, there has been an increased interest in determining the neonicotinoid residues in honeybee products such as honey. The aim of this study was to develop and optimize an HPLC-DAD analytical method with dispersive liquid–liquid microextraction (DLLME) and QuEChERS sample preparation procedures for the simultaneous analysis of seven neonicotinoids (dinotefuran, nitenpyram, thiametoxam, clothianidin, imidacloprid, acetamiprid and thiacloprid) in honey samples. The liquid chromatographic conditions were optimized by Response surface methodology with Box–Behnken design and Derringer's desirability. The optimized method was validated to fulfill the requirements of SANCO/12571/2013 standard for both sample pretreatment procedures providing results for accuracy (73.1–118.3%), repeatability (3.28–10.40%) and within-laboratory reproducibility (6.45–17.70%), limits of detection (1.5–2.5 μg kg⁻¹) and quantification (5.0–10.0 μg kg⁻¹) with the use of matrix-matched calibration to compensate the matrix effects. For the first time 104 honey samples from Vojvodina were analyzed. The presence of thiacloprid, imidacloprid and thiametoxam was found in a small number of samples implicating the usefulness of ongoing control of honey. Residues were confirmed by LC–MS/MS.