Determination of metals in fish species from Aegean and Mediterranean seas

Determination of metal levels in muscles and livers of twelve fish species from Aegean Sea and Mediterranean Sea by ICP-AES was made. The levels of Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn in muscles of fish were <0.01–0.39, <0.01–0.45, 0.07–1.48, 0.51–7.05, 9.18–136, 0.18–2.78, 0.03–1.72, 0.21–1.28 and 3.51–53.5 mg kg⁻¹, respectively. Metal levels in muscles were generally lower than those in livers. Metal concentrations in the edible parts of fish were assessed for human uses according to provisional tolerable weekly intake (PTWI) and provisional tolerable daily intake (PTDI). The estimated values of all metals in muscles of fish in this study were below the established values. Therefore, it can be concluded that these metals in edible parts of the examined species should pose no health problems for consumers.     

Metal content determination in four fish species from the Adriatic Sea

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.     

Determination of metals in fish and mussel species by inductively coupled plasma-atomic emission spectrometry

The concentrations of cadmium, iron, lead, zinc, copper, manganese, nickel, chromium and cobalt were determined by ICP-AES in muscles, livers, gills and skins of two fish (Clarias gariepinus and Carasobarbus luteus), and in muscles and gills of two mussel species (Unio terminalis and Potamida littoralis) sampled from the Lake Gölba??. Iron showed the highest levels in all examined tissues of both fish species. Following Fe; Zn showed the second highest levels in all examined tissues of both fish species except Mn levels in muscle and gill of C. luteus. In both mussel species, to the contrary fish, manganese showed the highest levels in examined tissues, and followed by Fe. In both fish species, the all metal concentrations in livers were higher than those in muscles. Concentrations in tissues of the analyzed metals were significantly affected by species. There were differences between the metal levels in the similar tissues of the different species (p < 0.05). At the same time, there was also the differences between the metal concentrations in different tissues of the same species (p < 0.05). Metal levels in tissues were compared with national and international permissible limits. Metal concentrations in both edible and other tissues of the sampled species were within the permissible safety levels for human uses.     

Trace element levels in honeys from different regions of Turkey

A survey of 25 honey samples from different botanical origin, collected all over the Turkey was conducted to assess their trace element contents. The aim of this study was to determine the levels of cadmium (Cd), lead (Pb), iron (Fe), manganese (Mn), copper (Cu), nickel (Ni), chromium (Cr), zinc (Zn), aluminium (Al) and selenium (Se) in honey samples from different regions of Turkey. Trace element contents were determined by a flame and graphite furnace atomic absorption spectrometry technique after dry-ashing, microwave digestion and wet-digestion. The accuracy of the method was corrected by the standard reference material, NIST-SRM 1515 Apple leaves. The contents of trace elements in honey samples were in the range of 0.23–2.41 μg g⁻¹, 0.32–4.56 μg g⁻¹, 1.1–12.7 μg g⁻¹, 1.8–10.2 μg g⁻¹, 8.4–105.8 μg kg⁻¹, 2.6–29.9 μg kg⁻¹, 2.4–37.9 μg kg⁻¹, 0.9–17.9 μg kg⁻¹, 83–325 μg kg⁻¹ and 38–113 μg kg⁻¹ for Cu, Mn, Zn, Fe, Pb, Ni, Cr, Cd, Al and Se, respectively. Iron was the most abundant element while cadmium was the lowest element in the Turkish honeys surveyed. The results showed that trace element concentrations in the honeys from different regions were generally correlated with the degree of trace element contamination of the environment.     

Fish and food safety: Determination of formaldehyde in 12 fish species by SPME extraction and GC–MS analysis

The formaldehyde (FA) content in different fish products was evaluated using a solid phase microextraction (SPME)-GC–MS method based on fiber derivatisation with pentafluorobenzyl-hydroxyl-amine hydrochloride. LOD and LOQ values of 17 and 28 μg kg⁻¹, respectively were calculated. Fish quality was assessed by the analysis of 12 species (sea-fish, freshwater-fish and crustaceans), revealing variable FA levels. Fresh, deep frozen, canned, boiled and roasted fish were analysed; cooking always produced a decrease in the analyte content. Fish belonging to the Gadidae family were the samples with the highest FA concentration (from 6.4 ± 1.2 mg kg⁻¹ to 293 ± 26 mg kg⁻¹), in four cases out of 14 exceeding the value of 60 mg kg⁻¹ proposed by the Italian Ministry of Health. Storage on ice was also investigated, showing moderate FA production also at temperature around 0 °C. FA contents lower than 22 mg kg⁻¹ were finally found in all the other samples.     

HPLC–MS identification and quantification of flavonol glycosides in 28 wild and cultivated berry species

Berries and red fruits are rich dietary sources of polyphenols with reported health benefits. More than 50 different flavonols (glycosides of quercetin, myricetin, kaempferol, isorhamnetin, syringetin and laricitrin) have been detected and quantified with HPLC–MSⁿ in fruits of blueberry, bilberry, cranberry, lingonberry, eastern shadbush, Japanese wineberry, black mulberry, chokeberry, red, black and white currants, jostaberry, red and white gooseberry, hardy kiwifruit, goji berry, rowan, dog rose, Chinese and midland hawthorn, wild and cultivated species of blackberry, raspberry, strawberry and elderberry. The phenolic constituents and contents varied considerably among the analyzed berry species. Elderberry contained the highest amount of total flavonols (450–568 mg kg⁻¹ FW), followed by berry species, containing more than 200 mg kg⁻¹ FW of total: chokeberry (267 mg kg⁻¹), eastern shadbush (261 mg kg⁻¹), wild grown blackberry (260 mg kg⁻¹), rowanberry (232 mg kg⁻¹), american cranberry (213 mg kg⁻¹) and blackcurrants (204 mg kg⁻¹). Strawberry (10.5 mg kg⁻¹) and white currants (4.5 mg kg⁻¹) contained the lowest amount of total flavonols. Quercetins represent the highest percentage (46–100%) among flavonols in most analyzed berries. In wild strawberry and gooseberry the prevailing flavonols belong to the group of isorhamnetins (50–62%) and kaempferols, which represent the major part of flavonols in currants (49–66%). Myricetin glycosides could only be detected in chokeberry, rowanberry and species from the Grossulariaceae, and Adoxaceae family and Vaccinium genus. Wild strawberry and blackberry contained from 3- to 5-fold higher total flavonols than the cultivated one.     

Trace element content of Boletus tomentipes mushroom collected from Yunnan,China

The contents of As, Cd, Cr, Cu, Fe, Hg, Mg, Mn, Ni, Pb, and Zn in eleven fruiting bodies of Boletus tomentipes were determined. The results showed the values of the studied elements decreased in the order: Mg (208–279 mg kg⁻¹) > Fe (106–137 mg kg⁻¹) > Mn (29.5–46.8. mg kg⁻¹) > Zn (18.7–23.1 mg kg⁻¹), > Cu (11.4–15.8 mg kg⁻¹) > Cr (3.36–4.78 mg kg⁻¹) > Pb (1.38–3.88 mg kg⁻¹) > Ni (1.68–3.01 mg kg⁻¹) > Cd (0.16–0.32 mg kg⁻¹) > As (0.10–0.24 mg kg⁻¹) > Hg (<0.06 mg kg⁻¹).     

Concentration of biologically active polyamines in meat and liver of sheep and lambs after slaughter and their changes in mutton during storage and cooking

Putrescine (PUT), spermidine (SPD) and spermine (SPM) concentrations using a UPLC method, in chilled mutton, lamb and livers 24 h after slaughter were determined. PUT concentrations were quantifiable only in some samples. Mean SPD concentrations were 4–6, 13.5 and 16.8 mg kg⁻¹ in the meats, sheep and lamb livers, respectively. The respective SPM concentrations were 17–25, 128 and 79 mg kg⁻¹. SPD and SPM losses of about one fifth and half of the initial level, respectively, were apparent in mutton loins stored at −18 °C for 6 months. Significant losses of SPD and SPM were found in mutton loins stored aerobically, vacuum-packaged or in a modified atmosphere at + 2 °C. Boiling and stewing of mutton legs caused SPD and SPM losses of about 40% and roasting of about 60% of the initial content.     

Elemental composition of cephalopods from Portuguese continental waters

Essential and contaminant elements concentrations were determined in the muscle tissue of octopus (Octopus vulgaris), squid (Loligo vulgaris) and cuttlefish (Sepia officinalis), caught off the Portuguese coast in 2004–2005. As expected, the largest concentrations found correspond to Cl, S, K, Na, P and Mg (average values between 629 mg (100 g)⁻¹, for Cl, and 435 mg kg⁻¹, for Mg, in octopus and squid, respectively). Above average concentrations of Zn, Cu, Fe and Sr were also found. The highest total Hg concentration was found in cuttlefish (0.36 mg kg⁻¹); however, this value did not exceed the recommended limit proposed by EU (0.5 mg kg⁻¹). Lead levels observed in all samples were always significantly lower than the EU limit (1.0 mg kg⁻¹). Regarding Cd, the 1.0 mg kg⁻¹ limit was only exceeded in two octopus samples. It may be concluded that the cephalopods studied do not constitute cause for concern, in terms of toxic elements, and could be safely used for daily intake of essential elements. Nevertheless, the squid contribution for elemental DI is minor in comparison to the other two species.     

Simultaneously determination of methyl and inorganic mercury in fish species by cold vapour generation atomic absorption spectrometry

A simple and rapid non-chromatographic method was developed to determine methylmercury (MeHg) and inorganic mercury (iHg) levels in muscles tissues of 10 freshwater fish species. The MeHg and iHg were determined by cold vapour atomic absorption spectrometry after alkaline wet digestion of samples. The digested samples were reduced sequentially with stannous chloride and sodium tetrahydroborate for iHg and MeHg, respectively. Parameters such as carrier gas flow rate (argon), volume of oxidizing and potassium persulphate solutions were investigated in detail. The accuracy of the technique was evaluated by using certified reference material (DORM-2) and spiking the both Hg species in muscles tissue of a fish. The limits of detection were 0.117 and 0.133 μg kg⁻¹ for MeHg and iHg, respectively. The concentrations of MeHg and iHg in muscles tissues of ten fish species were found in the range of (28.4–56.3) and (3.01–8.11) μg kg⁻¹, respectively.     

Simplified pesticide multiresidues analysis in fish by low-temperature cleanup and solid-phase extraction coupled with gas chromatography/mass spectrometry

A simple and fast method for the simultaneous analysis of thiobencarb, deltamethrin and 19 organochlorine pesticide residues in fish by gas chromatography–mass spectrometry was investigated in this study. Samples are extracted with acetonitrile. Most of lipids in the extract are eliminated by low-temperature cleanup, prior to solid-phase extraction cleanup. The lipids extracted from the fish samples were easily removed without any significant losses of the pesticides. Aminopropyl (NH₂) cartridge was effective to eliminate the remaining interference. Spiked experiments were carried out to determine the recovery, precision and limits of detection (LODs) of the method. The method detection limits ranged from 0.5 μg kg⁻¹ to 20 μg kg⁻¹, whilst recoveries of the pesticides were in the range of 81.3–113.7% with relative standard deviations ?13.5% at a spiked concentration of 0.05 mg kg⁻¹, 0.02 mg kg⁻¹ and 0.1 mg kg⁻¹. The newly developed method is demonstrated to give efficient recoveries and LODs for detecting pesticide multiresidues in fish.     

Selected arsenic species: As(III), As(V) and dimethylarsenic acid (DMAA) in Xerocomus badius fruiting bodies

The aim of the study was to determine the content of As(III), As(V) and DMAA (dimethylarsinic acid) in Xerocomus badius fruiting bodies collected from selected Polish forests from areas subjected to very low or high anthropopressure and some commercially available samples obtained from the Polish Sanitary Inspectorate. The arsenic species determination was provided by two independent HPLC–HG-AAS hyphenated systems. The results show high levels (up to 27.1, 40.5 and 88.3 mg kg⁻¹ for As(III), As(V) and DMAA, respectively) of arsenic and occurrence of different species in mushrooms collected from areas subjected to high anthropopressure and two commercially available samples. For mushroom samples collected from areas not subjected to high anthropopressure and two commercially available samples the arsenic species level was below 0.5 mg kg⁻¹ for each arsenic form. Therefore, the accumulation of arsenic by mushrooms may lead to high (toxic for humans) arsenic concentrations, and arsenic species levels should be monitored in mushroom foodstuffs.     

Flavonols (kaempeferol,quercetin, myricetin) contents of selected fruits,vegetables and medicinal plants

The concentrations of flavonols (kaempeferol, quercetin, myricetin) were determined in 22 plant materials (9 vegetables, 5 fruits, and 8 medicinal plant organs). The materials were extracted with acidified methanol (methanol/HCl, 100:1, v/v) and analyzed by reverse phase high-performance liquid chromatographic (RP-HPLC) with UV detection. The total flavonols contents varied significantly (P < 0.05) among vegetables, fruits and medicinal plant organs ranged from 0 to 1720.5, 459.9 to 3575.4, and 2.42 to 6125.6 mg kg⁻¹ of dry matter, respectively. Among vegetables, spinach and cauliflower exhibited the highest amounts of flavonols (1720.5 and 1603.9 mg kg⁻¹, respectively), however, no flavonols were detected in garlic. Within fruits, highest level of flavonols was observed in strawberry (3575.4 mg kg⁻¹), whereas, the lowest in apple fruit (459.9 mg kg⁻¹). Of the medicinal plant organs, moringa and aloe vera leaves contained the highest contents of flavonols (6125.6 and 1636.04 mg kg⁻¹), respectively, whereas, lowest was present in barks (2.42–274.07 mg kg⁻¹). Overall, leafy green vegetables, soft fruits and medicinal plant leaves exhibited higher levels of flavonols.     

Chemical composition of cultivated seaweed Ulva clathrata (Roth) C. Agardh

Samples of cultivated Ulva clathrata were collected from a medium scale system (MSS, 1.5 × 1.5 m tank), or from a large scale system (LSS, 0.8 ha earthen pond). MSS samples were dried directly while the LSS sample was washed in freshwater and pressed before drying. Crude protein content ranged 20–26%, essential amino acids accounting for 32–36% of crude protein. The main analysed monosaccharides were rhamnose (36–40%), uronic acids (27–29%), xylose (10–13%) and glucose (10–16%). Some notable variations between MSS and LSS samples were observed for total dietary fibre (26% vs 41%), saturated fatty acids (31% vs 51%), PUFAS (33% vs 13%), carotenoids (358 vs 169 mg kg⁻¹ dw) and for Ca (9 vs 19 g kg⁻¹), Fe (0.6 vs 4.2 g kg⁻¹), Cu (44 vs 14 mg kg⁻¹), Zn (93 vs 17 mg kg⁻¹) and As (2 vs 9 mg kg⁻¹). The chemical composition of U. clathrata indicates that it has a good potential for its use in human and animal food.     

Heavy metals in three commercially valuable fish species from İskenderun Bay,Northern East Mediterranean Sea,Turkey

Concentrations of cadmium, iron, lead, zinc, copper, manganese, nickel, chromium, cobalt and aluminum were determined in three commercially valuable fish species, Saurida undosquamis, Sparus aurata, Mullus barbatus, from İskenderun Bay in August 2003. The concentration of metals was measured by atomic absorption spectrophotometry (AAS). Concentrations of the heavy metals in examined fish species ranged as follows: Cd 0.01–4.16; Fe 0.82–27.35; Pb 0.09–6.95; Zn 0.60–11.57; Cu 0.04–5.43; Mn 0.05–4.64; Ni 0.11–12.88; Cr 0.07–6.46; Co 0.03–5.61; Al 0.02–5.41 mg kg⁻¹ dry weight, respectively. The concentration of metals was significantly affected by the sampling site and fish species. Heavy metals in the edible parts of the investigated fish were in the permissible safety levels for human uses.     

Multiresidue method for determination of 88 pesticides in berry fruits using solid-phase extraction and gas chromatography–mass spectrometry: Determination of 88 pesticides in berries using SPE and GC–MS

A method using solid phase extraction (SPE) cleanup followed by gas chromatography–mass spectrometry (GC–MS) has been established for quantitative determination of 88 pesticide residues in berry fruits including raspberry, strawberry, blueberry and grape. Based on an appraisal of the characteristics of GC–MS, validation experiments were conducted for 88 pesticides. In the method, solid-phase extraction was carried out using Envi-Carb cartridge coupled with NH₂-LC cartridge with acetonitrile–toluene (3:1, v/v) as the eluted solvent. In the linear range of each pesticide, the correlation coefficient was R² ? 0.99. At the low, medium and high three fortification levels of 0.05–0.5 mg kg⁻¹, recoveries fell within 63–137%. The relative standard deviation was between 1% and 19% for all 88 pesticides. Low limits of detection (0.006–0.05 mg kg⁻¹) and quantification (0.02–0.15 mg kg⁻¹) were readily achieved with this method for all tested pesticides.     

Comparison of the cell wall composition for flesh and skin from five different plums

Cell walls were isolated from flesh and skin of five plum varieties corresponding to three species (Prunus domestica L., Prunus salicina Lindl. and Prunus insititia Lindl.) using the alcohol-insoluble solids (AIS) procedure. Yields varied from 83 to 114 g kg⁻¹ dry weight in the flesh and from 192 to 361 g kg⁻¹ dry weight in the skins. Their main sugars were uronic acid (224–322 mg g⁻¹ AIS), cellulosic glucose (139–170 mg g⁻¹ AIS), galactose and arabinose. Galactose and arabinose ratio were variable between the varieties. The degrees of methylation were high (62–84).     

Determination of heavy metals (Cd,Pb) and trace elements (Cu,Zn) in sediments and fish of the Southeastern Aegean Sea (Turkey) by atomic absorption spectrometry

The Bay of Güllük in Southeastern Aegean Sea (Turkey) is very important by the potential of marine product in the Aegean Sea. There are various polluting elements in Güllük Bay. The current situation of the bay and impact of pollutants have became necessity. Dicentrarchus labrax are frequently used for human consumption. In this study, heavy metals (Pb, Cd) and trace elements (Cu, Zn) were analyzed in fish (D. labrax) and sediments in the Bay of Güllük by atomic absorption spectrometry. The average metal concentrations in the fish varied in the following ranges: Pb; <0.02–0.4, Cd; <0.01–0.04, Cu; <0.1, Zn; <0.5–7.2 mg kg⁻¹. In addition, seven sediment samples were analyzed and avarage concentrations of them were found as Zn; 80.8 ± 0.45, Cu; 25.2 ± 0.14, Pb; 20.0 ± 2, Cd; 0.560.08 mg kg⁻¹. The accuracy and precision of our results were checked by using International Certified Reference samples (fish: DORM-2, sediment: HISS-1).     

Contaminant metals in black scabbard fish (Aphanopus carbo) caught off Madeira and the Azores

Total mercury, cadmium and lead concentrations were measured in black scabbard fish (Aphanopus carbo), caught off Madeira and the Azores archipelagos (Portugal). The metal contents were expressed in mg kg⁻¹ wet weight. The mean mercury levels in liver were 4.50 and 2.37 whereas, in skin, such values were 0.59 and 0.36 (Madeira and Azores, respectively). On average, the muscle content was around 0.9 in fish from both areas. Cadmium maximum levels in muscle and skin were found in Azores samples (0.09 and 0.11, respectively). Mean lead contents in all samples were always below than 0.10. In general, the results obtained did not allow the establishment of any relationship between metal accumulation and fish weight or length. According to the permissible WHO and FAO levels, these results, suggest that this species does not represent a risk for human consumption if the liver is excluded and the edible part consumed with moderation.     

Multi-residue method for determination of seven neonicotinoid insecticides in grains using dispersive solid-phase extraction and dispersive liquid–liquid micro-extraction by high performance liquid chromatography

A method using dispersive solid-phase extraction and dispersive liquid–liquid micro-extraction cleanup followed by high performance liquid chromatography (HPLC) has been established for determination of seven neonicotinoid insecticides residues in grains including brown rice, maize, millet and oat. Based on an appraisal of the characteristics of HPLC, validation experiments were conducted for seven neonicotinoid insecticides. In the method, dispersive solid-phase extraction was carried out using PSA and bonded C₁₈ coupled with graphitised carbon black with acetonitrile as the eluted solvent. In the linear range of each pesticide, the correlation coefficient was R² ? 0.99. At the low, medium and high three fortification levels of 0.05–0.8 mg kg⁻¹, recoveries fell within 76–123%. The relative standard deviation was between 0.9% and 12.6% for seven neonicotinoid pesticides. Low limits of detection (0.002–0.005 mg kg⁻¹) and quantification (0.007–0.018 mg kg⁻¹) were readily achieved with this method for all tested pesticides.