Method development for the analysis of phthalate esters in tea beverages by ionic liquid hollow fibre liquid-phase microextraction and liquid chromatographic detection

A novel method, termed ionic liquid-based hollow fibre liquid phase microextraction (IL-HF-PLME), coupled with high-performance liquid chromatography (HPLC) was developed for separation and preconcentration of three phthalate esters (PAEs) in tea beverage. In the present study, ionic liquid 1-butyl-3-methy-limidazolium hexafluorophosphate ([BMIm]PF₆) was placed in the porous-walled polypropylene hollow fibre as the acceptor phase, and nonanol was used as the supported liquid membrane phase that accomplished extraction. Several important parameters influencing the extraction efficiency were investigated in detail. Under the optimized conditions, good linearity occurred in the range of 5–1000 ng mL⁻¹ with the correlation coefficients values above 0.998. The limits of detection ranged from 0.67 to 1.73 ng mL⁻¹. Recoveries of three PAEs in two kinds of spiked tea beverage samples (PAEs, 10.0–100.0 ng mL) were between 94.2 and 103.4%, with relative standard deviations (RSDs) ranged from 1.77 to 3.02%. The enrichment factors were 200. The developed IL-HF-PLME method allowed the simple, rapid, and sensitive determination of phthalate esters in tea beverage samples with an extraction time of just 4 min.     

Three years of monitoring of PCDD/F,DL-PCB and NDL-PCB residues in bovine milk from Lombardy and Emilia Romagna regions (Italy): Contamination levels and human exposure assessment

In the three-years period 2012–2014, 160 cow milk samples from farms located in Lombardy and Emilia Romagna regions (Italy) were analyzed during the implementation of the Italian National Residues Monitoring Plan to assess the presence of PCDD/F, DL-PCB and NDL-PCB residues. The obtained contamination data were combined with cow milk consumption data from the Italian national dietary survey to estimate PCDD/F, DL-PCB and NDL-PCB human dietary exposure through the consumption of whole, semi skimmed and skimmed bovine milk. The exposure assessment was carried out separately for children, teenagers, adults and elderly. Average contamination levels of the analyzed samples were found to be 1.26 pg WHO-TEQ/g fat for the sum of PCDD/Fs and DL-PCBs and 9.30 ng/g fat for the sum of the 6 NDL-PCB indicators. PCB 126 was found to be the main contributor to the total WHO-TEQ. Using the upper bound approach, the estimated mean dietary intakes ranged from 0.07 pg WHO-TEQ/kg bw per day to 0.39 pg WHO-TEQ/kg bw per day for the sum of PCDD/Fs and DL-PCBs and considering exposure from whole milk. NDL-PCB mean dietary intakes resulted between 0.52 ng/kg bw per day and 2.86 ng/kg bw per day for consumption of whole milk. Children and teenagers were found to be the most exposed groups. This is the first time that Italian consumers exposure to NDL-PCBs is assessed using contamination data of cow milk produced in Italy.     

Low temperature cleanup combined with magnetic nanoparticle extraction to determine pyrethroids residue in vegetables oils

To quantify trace pesticide residue in vegetable oil rapidly, low temperature cleanup combined with magnetic nanoparticle based solid phase extraction was developed to determine eight pyrethroids in vegetable oils, including tetramethrin, fenpropathrin, cypermethrin, decamethrin, fenvalerate, acrinathrin, permethrin and bifenthrin. Polystyrene coated magnetic nanoparticles were synthesised by a modified chemical coprecipitation combined with emulsion polymerisation method. The nanoparticles were afterwards characterised by Fourier transform-infrared spectroscopy, X-ray diffraction, transmission electron microscopy as well as vibrating sample magnetometer, and successfully employed as adsorbents for the magnetic solid phase extraction of pyrethroids which were cleaned up using low temperature approach in advance. Critical impact factors on the efficiency of the extraction method such as the mass of adsorbents used, volume and type of eluent solvent, extraction time as well as elution time were optimised subsequently. Regression analysis of the calibration curves of the eight pyrethroids yielded satisfactory correlation coefficients within the range of 0.980–0.998. Limit of detection and limit of quantification were calculated to be between 0.0290-0.0658 and 0.0890–0.1994 ng g⁻¹, respectively. Intra-day and inter-day reproducibility at different concentration levels also produced satisfactory recovery rates of 83.18–112.79% with relative standard deviations not exceeding 10.84% and 12.01%, respectively, suggesting desirable stability of the proposed method.     

Simultaneous determination of mycotoxin in commercial coffee

Mycotoxins are secondary metabolites produced by filamentous fungi that usually contaminate food products. Coffee is a natural product susceptible to mycotoxin contamination. The present study evaluates the presence of nivalenol, deoxynivalenol, T-2 and HT-2 Toxin, diacetoxyscirpenol, aflatoxin B₁, aflatoxin B₂, aflatoxin G₁, aflatoxin G₂, fumonisin B₁, fumonisin B₂, ochratoxin A, zearalenone, enniatin A, enniatin A₁, enniatin B, enniatin B₁, and beauvericin in coffee samples, using liquid chromatography tandem mass spectrometry (LC-MS/MS). The results show that zearalenone was not present in any sample. In the positive samples the contents of fumonisins ranged from 58.62 to 537.45 μg/kg, emerging mycotoxins ranged from 0.10 to 3569.92 μg/kg, aflatoxins ranged from 0.25 to 13.12 μg/kg, and trichothecenes, excepting nivalenol, ranged from 5.70 to 325.68 μg/kg. Nivalenol presented the highest concentrations, from 0.40 to 25.86 mg/kg. Ochratoxin A ranged from 1.56 to 32.40 μg/kg, and five samples exceeded the maximum limit established by the European Commission.     

Occurrence and co-occurrence of Fusarium mycotoxins in wheat grains and wheat flour from Romania

In this study, the presence of fourteen Fusarium mycotoxins, legislated by the European Union – deoxynivalenol, zearalenone, HT-2 and T-2 toxins (EC/1881/2006; 2013/165/EU), or non-legislated (five trichothecens and five “emerging” mycotoxins), was evaluated in 31 whole unprocessed wheat samples and 35 white wheat flour samples from different areas of Romania. For this purpose, a validated multi-mycotoxins liquid chromatography tandem mass spectrometry method was applied. Seventy three percent of the analyzed samples contained at least one mycotoxin. The highest occurrence was for enniatin B, 71% of the analyzed samples being positive (21–407 μg kg⁻¹). Regarding the legislated mycotoxins, deoxynivalenol was detected in 14% (111–1787 μg kg⁻¹) of the samples, while zearalenone was detected in 9% (51–1135 μg kg⁻¹). Only one sample was positive for neosolaniol. Concerning the co-occurrence, 42% of the samples were contaminated with two to five mycotoxins, the most frequent being the binary or tertiary combinations of enniatins. This is the first study applied to Romanian wheat grains and flour samples using a high sensitive multi-mycotoxins method, and which included also “emerging” mycotoxins.     

A novel approach for simultaneous determination of E/Z-fluoxastrobins in vegetables and fruits by UHPLC-DAD

In this work, a novel analytical method was established for simultaneous determination of E-fluoxastrobin and Z-fluoxastrobin in vegetables and fruits. After extracted by acetonitrile, the samples were cleansing with dispersive solid liquid extraction (d-SLE) process, and analyzed by ultra high performance liquid chromatography coupled to diode array detection (UHPLC-DAD). The effectiveness of the optimized method was validated by determining the linearity (R² > 0.99), sensitivity (limits of quantification of 30 μg/kg), recovery (71.3–113.2%), and precision (relative standard deviations, RSDs ≤ 13.9%) in eight vegetable and fruit samples. The results suggested that this method was simple, reliable, and feasible to determine the residues of E-fluoxastrobin and Z-fluoxastrobin in vegetable and fruit samples, which could be further applied to 160 various vegetable and fruit samples.     

Comparison of perfluoroalkyl substances contamination in farmed and wild-caught European sea bass (Dicentrarchus labrax)

Perfluoroalkyl substances (PFASs) are a family of persistent pollutants of anthropic origin which can reach humans mainly through diet, causing potentially dangerous effects on health. Fish and fishery products are a major source of exposure, but intra- and inter-specific contamination can be extremely variable. In the present study a single species monitoring of the presence of perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA), the two main compounds of the family, was performed on 140 farmed and wild caught European sea basses (Dicentrarchus labrax) from different places in the Mediterranean area. The results highlight a strong correlation between the level of contamination and the origin of fishes, if wild or farmed: on average, wild caught sea basses (PFOS: 112-12,405 ng/kg, median 1345 ng/kg; PFOA: 9–487 ng/kg, median 28 ng/kg) showed higher levels than intensively farmed sea basses (PFOS: 11–105 ng/kg, median 32 ng/kg; PFOA: 9–51 ng/kg, median 21 ng/kg). Significant differences among the various rearing systems were also observed, with extensively-farmed subjects presenting relatively higher levels of both compounds compared to intensively farmed. Moreover, a certain variability among wild fish caught from different sampling sites was observed, confirming that PFASs contamination, which reached in some cases noticeable concentrations, might be influenced by the geographical origin.     

Effect of nutmeg (Myristica fragrans) essential oil on the oxidative and microbial stability of cooked sausage during refrigerated storage

This paper examines the oxidative and microbial stability of cooked sausages, produced with the addition of 10 ppm (NO1) and 20 ppm (NO2) nutmeg (Myristica fragrans) essential oil. Instrumental parameters of color (CIE L*, CIE a* and CIE b*), Thiobarbituric acid-reactive substance (TBARS) values, microbial profile and sensory properties of aroma have been determined on the 1st, 30th, 45th, and 60th day of storage. Addition of the nutmeg essential oil had no effect on the color of cooked sausages. At the end of the storage, NO2 sausages had the best oxidative and microbial stability. TBARS values of NO1 and NO2 sausages were 1.21 mg MDA/kg and 0.95 mg MDA/kg, respectively, and were significantly lower (P < 0.05) compared to control (1.53 mg MDA/kg). Total number of aerobic mesophilic bacteria was lowest in NO2 sausages (78.3 cfu/g) and highest in control (185 cfu/g). After 45 and 60 days of storage, sensory properties of aroma of NO1 (4.21; 3.92) and NO2 sausages (4.39, 4.28) were better compared to those in control (4.07, 3.25). Hence, the addition of nutmeg essential oil in amount of 20 ppm can be successfully applied in order to extend the shelf life of cooked sausages.     

Contamination of vegetable oils marketed in Italy by phthalic acid esters

More than 90% of the phthalic acid esters (PAEs) produced in Europe is used to plasticize polyvinyl chloride (PVC). Animal studies have shown that some PAEs can damage the liver and interfere with the endocrine system, whereas data on the toxic effects on humans are inconsistent. For the general population, the diet is believed to be the main source of PAEs. Food can be contaminated from environmental pollution, industrial food processing (PVC tubing) and certain storage containers. The present study evaluates the contamination levels of the four main PAEs named Di(2-ethylhexyl) phthalate (DEHP), dibutyl phthalate (DBP), diisobutyl phthalate (DIBP), diisononyl phthalate (DINP), in 172 samples of vegetable oils marketed in Italy. Diluted oils were directly analysed by GC–MS. PAEs concentrations in vegetable oils were lower than those reported in other studies. Olive-derived oils showed the highest levels. Considering their high consumption in Italy, this finding is significant and some hypotheses on environmental or technological causes have been made. In the case of extravirgin olive oil, the higher levels of PAEs can be ascribed to the absence of the refining process since it has been verified that this technological treatment partially decontaminates the final product while for olive and olive pomace oils, both refined oils, the reasons for a higher contamination are less clear. Probably, a different plant uptake of PAEs from the air, water and soil could give account of this finding. Finally, the percentage Italian intake of PAEs due to the various types of vegetable oils analysed has been calculated.     

Multiple mycotoxin co-occurrence in maize grown in three agro-ecological zones of Tanzania

In this study, the co-occurrence of multiple mycotoxins in maize kernels collected from 300 households' stores in three agro-ecological zones in Tanzania was evaluated by using ultra high performance liquid chromatography/time-of-flight mass spectrometry (TOFMS) with a QuEChERS-based procedure as sample treatment. This method was validated for the analysis of the main eleven mycotoxins of health concern that can occur in maize: aflatoxin B₁ (AFB₁), aflatoxin B₂ (AFB₂), aflatoxin G₁ (AFG₁), aflatoxin G₂ (AFG₂), ochratoxin A (OTA), deoxynivalenol (DON), fumonisin B₁ (FB₁), fumonisin B₂ (FB₂), HT-2 toxin, T-2 toxin and zearalenone (ZEN). From each zone one major maize producing district for home consumption was chosen and 20 villages for each district were randomly selected for sampling. All mycotoxins of health concern, except for T-2 toxin, were detected in the maize samples. Particularly high levels of AFB₁ (50%; 3–1,081 μg kg⁻¹), FB₁ (73%; 16–18,184 μg kg⁻¹), FB₂ (48%; 178–38,217 μg kg⁻¹) and DON (63%; 68–2,196 μg kg⁻¹) were observed. Some samples exceeded the maximum limits set in Tanzania for aflatoxins or in European regulations for other mycotoxins in unprocessed maize. Eighty seven percent of samples were contaminated with more than one mycotoxin, with 45% of samples co-contaminated by carcinogenic mycotoxins, aflatoxins and fumonisins. Significant differences in contamination pattern were observed among the three agro-ecological zones. The high incidence and at high levels (for some) of these mycotoxins in maize may have serious implications on the health of the consumers since maize constitute the staple food of most Tanzanian population. Effective strategies targeting more than one mycotoxin are encouraged to reduce contamination of maize with mycotoxins.     

Aflatoxin contamination in unrecorded beers from Kenya – A health risk beyond ethanol

Samples of unrecorded opaque beers (n = 58; 40 based on maize, 5 on sorghum and 13 on other plants) and recorded wines (n = 8) in Kenya were screened for aflatoxins using a rapid ELISA technique followed by confirmation using liquid chromatography-tandem mass spectrometry. Six of the maize beers were obtained from Kibera slums in Nairobi County. Aflatoxin contamination was detected in six unrecorded beers (10%), but in none of the recorded wines. Remarkably, three of the aflatoxin positive samples were from the Kibera slums.The mean concentration of aflatoxins in the positive samples was 3.5 μg/L (range 1.8–6.8 μg/L), corresponding for an average consumption of 500 mL (1 standard drink) to a margin of exposure (MOE) of 36 (range: 15–58), which is considered as ‘risk’. On the other hand, the alcoholic strength of the aflatoxin positive samples had a mean of 4.3% vol (range 3.5–4.8%) corresponding to a MOE of 2.5 (range of 2.2–3.0) for the equivalent consumption volume. While aflatoxins pose a risk to the consumer, this risk is about 10 times lower than the risk of ethanol.The Joint FAO/WHO Expert Committee on Food Additives sets no acceptable daily intake for aflatoxins since they are genotoxic carcinogens and instead recommends for the reduction of aflatoxin dietary exposure as an important public health goal, particularly in populations who consume high levels of any potentially aflatoxins-contaminated food. Nevertheless, ethanol still posed a considerably higher risk in the unrecorded beers examined. However, consumers should be informed about aflatoxins, as these are an involuntary and unknown risk to them. In addition, producers should be educated about measures to reduce aflatoxins in alcoholic beverages.     

The effects of tangerine peel (Citri reticulatae pericarpium) essential oils as glazing layer on freshness preservation of bream (Megalobrama amblycephala) during superchilling storage

This work was aim to the application of tangerine peel essential oils (TPEOs) as glazing layer on fish preservation. In this paper, essential oils were respectively extracted from the peel of ponkan, bitter orange and sweet orange. Their compositions were analyzed using GC–MS method. Fresh sample of bream was immersed into different TPEO for the formation of glazing layers on the surface and stored at −1 ±0.2 °C for 25-days storage. A thorough study of freshness evaluation was carried out and statistics analysis was performed to analyze the effect of TPEO. The result showed that the glazing layers of TPEO can effectively slow down the degradation process of fish samples and the resulting variations in electrical, moisture, chemical, microbial, sensory and textural characteristics. Additionally, statistical analysis showed that there are significant (most of p is less than 0.05) difference between control and treated sample, but insignificant (most of p is more than 0.05) differences among the samples with glazing layer of different TPEOs.The work indicated TPEOs had remarkable effect in the storage of aquatic products.     

Effect of sulfur dioxide and ethanol concentration on fungal profile and ochratoxin a production by Aspergillus carbonarius during wine making

Fungal profiles and ochratoxin A (OTA) accumulation during wine making were investigated using five different wine grape cultivars, Cabernet Sauvignon, Pinot Noir, Merlot, Syrah and Petit Verdot and the intrinsic influences caused by sulfur dioxide, ethanol and combine effect of ethanol and reducing sugar were analyzed using Cabernet Sauvignon and inoculation of Aspergillus carbonarius. Aspergillus spp. and Penicillium spp. were found as the major fungi in all winemaking processes and were highly correlated with OTA accumulation in wine. Most fungi died and OTA production decreased after 48 h of alcoholic fermentation, being consistent with the period when ethanol accumulation increased. The addition of SO₂ significantly inhibited the growth and OTA production of A. carbonarius with complete inhibition at 500 mg/L. When the ethanol concentration in the must increased to the range of 2–4%, growth and OTA production of A. carbonarius were significantly inhibited. Reducing sugar concentration had no significant effect on the growth and OTA production of A. carbonarius within the levels changing during the winemaking. Therefore, the increase of ethanol concentration played an important role in causing the decrease of fungal contamination and OTA accumulation during winemaking.     

Detection of selected corticosteroids and anabolic steroids in calf milk replacers by liquid chromatography–electrospray ionisation – Tandem mass spectrometry

The use of corticosteroids and anabolic steroids in food producing animals is regulated or banned in the European Union (EU). However, their use as growth promoters cannot be excluded. Milk replacers, considered by EU legislation as feeds, may be a good way of administration of these compounds. In order to improve the control of growth promoter utilization in animal husbandry and preventing possible consequences to animal welfare, we developed a method for multiresidue analysis of prednisolone, prednisone, dexamethasone, cortisone, cortisol, 17α- and 17β-boldenone and their precursor androstadienedione (ADD), testosterone, epitestosterone, 17α- and 17β-nandrolone, and trenbolone in powdered milk for calves. All analytes were extracted, after a common deproteinization and defatting sample pre-treatment, by a unique immunoaffinity column and analysed by liquid chromatography tandem mass spectrometry (LC–MS/MS) in both positive and negative electrospray ionization (ESI) modes. The method was validated according to the criteria of the Commission Decision 2002/657/CE. The analytical limits were from 0.39 to 0.73 ng mL⁻¹ for the decision limit (CCα) and 0.46–0.99 ng mL⁻¹ for detection capability (CCβ). The analysis of 50 samples of milk replacers for calves, always revealed the presence of cortisol and cortisone (average concentrations 2.56 and 1.06 ng mL⁻¹, respectively), frequently testosterone and epitestosterone (1.24 and 0.63 ng mL⁻¹, respectively), occasionally β-nandrolone (0.82 ng mL⁻¹) and prednisolone (0.41 ng mL⁻¹). The other anabolic steroids were never found.     

Occurrence and molecular identification of anisakid nematodes isolated from Pacific cod (Gadus macrocephalus) caught off Korea

Anisakids nematodes from Pacific cod (Gadus macrocephalus) in Korea were investigated and their molecular identification was conducted, to assess the epidemiological role of Pacific cod in human anisakidosis in Korea. Totally 238 Pacific cod were caught from 5 different areas around Korean peninsula. Fish were dissected and carefully examined for collecting nematodes. PCR-RFLP and the subsequent sequencing were conducted for molecular identification of those nematodes. A high prevalence of infection (193/238, 81.1%) in Pacific cod was observed, and 1694 nematodes were collected. 79.1% (1340/1694) of the nematodes were found freely in the body cavity of Pacific cod, and the rest of them (20.9%, 354/1694) were in the digestive tract or attached to other organs. PCR-RFLP analysis using HinfI and RsaI restriction enzymes revealed 3 different banding patterns corresponding to Anisakis pegreffii, Hysterothylacium aduncum and hybrid genotype (Anisakis simplex × A. pegreffii), respectively. Of 1694 nematodes, 1280 (75.6%) were identified as A. pegreffii and 406 (24.0%) were H. aduncum. A. pegreffii occupied 84.0% (1125/1340) of the nematodes in the body cavity and 40.0% (132/330) of them in the digestive tract, but no nematodes were found in Pacific cod muscles.     

Antimicrobial effects of cinnamon bark oil on microbial composition and quality of grass carp (Ctenopharyngodon idellus) fillets during chilled storage

In this study, 11 essential oils were initially screened for antimicrobial activity against Aeromonas veronii, Acinetobacter johnsonii, Shewanella putrefaciens, and Pseudomonas jessenii. Cinnamon bark oil exhibited the highest antimicrobial activity and was used as a natural preservative in grass carp fillets stored at 4 ± 1 °C. Sensory assessment, total volatile basic nitrogen (TVB-N), color, biogenic amines, adenosine triphosphate (ATP)-related compounds, K-value, and presence of microbiota were analyzed during storage. Cinnamon bark oil treatment was found to be effective in enhancing organoleptic quality, inhibiting microbial growth, and delaying the increase of TVB-N, putrescine, cadaverine and K-value. Based on sensory analysis, shelf-life of grass carp fillets was 8 days for the control and 12 days for the treatment group. According to high-throughput sequencing, Aeromonas and Pseudomonas were the predominant microbiota in fresh grass carp. As storage time progressed, the microbial composition of both control and treatment samples became less diverse. Pseudomonas followed by Aeromonas were dominant in spoiled control samples. However, there were significant differences in microbial composition between control and treatment samples at the end of storage. Cinnamon bark oil treatment inhibited the growth of Aeromonas and Shewanella, and Pseudomonas was the only predominant microbiota found in spoiled treatment samples.     

Vegetable oil as fat replacer inhibits formation of heterocyclic amines and polycyclic aromatic hydrocarbons in reduced fat pork patties

Formation of heterocyclic amines (HCAs) and polycyclic aromatic hydrocarbons (PAHs) was examined to evaluate the impact of using vegetable oil as fat replacement on carcinogen formation in meat product. Pork patties were formulated with 40% fat replacement by olive oil, sunflower oil or grape seed oil, respectively and cooked at 180 °C or 220 °C. Control patties contained the highest amount of HCAs compared with all other patties at both temperatures. Olive oil and sunflower oil replacement completely inhibited formation of MeIQ (2-amino-3, 4-dimethylimidazo[4,5-f]quinoline), while grape seed oil completely inhibited MeIQx (2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline), 4,8-DiMeIQx (2-amino-3,4,8-trimethylimidazo[4,5-f]quinoxaline) and PhIP (2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine) in patties. Grape seed oil achieved the highest inhibition capacity compared with sunflower oil and olive oil. HCAs increased significantly with cooking temperature (p < 0.05), but no difference was observed in total PAHs for patties cooked at different temperature (p > 0.05). In conclusion, fat replacement with sunflower oil, olive oil or grape seed oil in pork patties could reduce the formation of HCAs without compromising eating quality.     

Determination,content analysis and removal efficiency of fining agents on ochratoxin A in Chinese wines

A simple and convenient HPLC-FD detection method for ochratoxin A (OTA) with a high detection limit and a short run time has been developed. OTA has been found in most samples of Chinese market wine, including domestic and imported wines, but the content was not very high. Only a few wines showed an OTA content that exceeded the EC and OIV limits, indicating that most Chinese market wines were safe. The OTA intake for Chinese from wine was 0.017 ng/kg (bw) per day, which was lower than the SCF and JECFA limits and also lower than in many other countries. This was mainly due to the low per capita wine consumption in China, but it is still necessary for the Chinese government and wine makers to monitor OTA levels in wine and to establish relevant regulations. An egg white treatment (0.20 mg/mL, 48 h) was the best removal method for OTA.     

Determination of heavy metals in selected black sea fish species

Heavy metals can be accumulated by marine organisms thought a variety of pathways, including respiration, adsorption and ingestion. The levels of heavy metals are known to increase drastically in marine environment through mainly anthropogenic activities. Fish are good indicators for the long term monitoring of metal accumulation in the marine environment. The aim of this study was to determine the levels of Cd, As, Hg, Pb, Zn and Cu in edible part and gill of seven most consumed Bulgarian fish species collected from north-east coast of Black Sea. These fish species are sprat (Sprattus sprattus sulinus), Mediterranean horse mackerel (Trachurus mediterraneus ponticus), Black sea gobies (Neogobius melanostromus), shad (Alosa pontica), Atlantic bonito (Sarda sarda), bluefish (Pomatomus saltatrix) and grey mullet (Mugil cephalus). The fish samples were collected during 2010. The analytical determination of As, Cd, Pb, Zn and Cu were performed by using flame and graphite furnace atomic absorption spectrometry after microwave digestion procedure. The total mercury determination was determined using a direct mercury analyzer (DMA-80). The metal concentration of analyzed elements was highest in the gill for all fish species. The maximum metal concentration was measured for Cu (1.40 mg kg⁻¹ w.w), Zn (11 mg kg⁻¹ w.w) and Pb (0.08 mg kg⁻¹ w.w) in muscle tissues of shad and sprat. The edible part of horse mackerel has the maximum value for Hg (0.12 mg kg⁻¹ w.w) while Atlantic bonito predominantly accumulates As (1.10 mg kg⁻¹ w.w). The analytical results obtained from this study were compared within acceptable limits for human consumption set by various health institutions.     

Determination of nitrofuran metabolites in shrimp muscle by liquid chromatography-photo diode array detection

The use of nitrofurans on any animal in the European Union (EU) and any animal or animal food products intended for export to the EU was banned in 1993 (except furazolidone which was banned in 1995) due to the carcinogenicity of the parent drugs and their metabolites. Thereafter, the screening of food of animal origin for nitrofurans and their metabolites became mandatory for all exports to the EU. This paper describes a High Performance Liquid Chromatography – Diode Array Detection (HPLC-DAD) method to detect tissue bound nitrofuran metabolites, namely 3-amino-2-oxazolidinone (AOZ), 3-amino-5-morpholino-methyl-1,3-oxazolidinone (AMOZ), semicarbazide (SEM) and 1-aminohydantoin (AHD). The bound residues were hydrolysed and derivatized into the corresponding nitrophenyl derivatives (NPAOZ, NPAMOZ, NPSEM and NPAHD) with 2-nitrobenzaldehyde and analysed by HPLC-UV at 275 nm. The linearity of the photometric detector response to the four derivatized nitrofuran metabolites was verified using matrix-matched calibration standards in the range of 1–20 μg/kg and the average correlation coefficients for NPAOZ, NPAMOZ, NPSEM and NPAHD were 0.9960, 0.9951, 0.9984 and 0.9993, respectively. The decision limit of the method was below the Minimum Required Performance Limit (MRPL) of 1 μg/kg, for all four nitrofuran metabolites, which makes it compatible with the EU requirements. The average recoveries for (fortified samples between 1 and 5 μg/kg) AOZ, AMOZ, SEM and AHD were 107%, 107%, 115% and 114%, respectively. This is the first report of a HPLC-DAD method detecting nitrofuran metabolites below the MRPL according to our understanding. This method has been successfully used with aquaculture and poultry products; however, currently it is validated according to EU guidelines only for shrimp muscle tissue.