Methylmercury levels in predatory fish species marketed in Canada

Mercury was detected in all analysed samples of swordfish, marlin, shark and tuna purchased from major supermarket outlets and fish retailers in three cities across Canada. Total mercury and methylmercury levels ranged up to 3845 and 2346 ng g^-1, respectively. Swordfish contained the highest levels, followed by shark, fresh/frozen tuna and marlin. Levels in canned tuna were considerably less than the other examined samples. Methylmercury was extracted with toluene from enzymatically hydrolysed samples after the addition of sulphuric acid and potassium bromide. An L-cysteine back-extraction was used to separate the methylmercury from most organic co-extractives. Analysis of methylmercury (as methylmercury bromide) was by gas chromatography with pulsed discharge detection.     

Content of mercury and cadmium in fish (Thunnus alalunga) and cephalopods (Eledone moschata) from the south-eastern Mediterranean Sea

Mercury and cadmium concentrations were measured in the flesh and liver (or hepatopancreas) of albacore (Thunnus alalunga) and horned octopus (Eledone moschata) to establish whether the concentrations exceeded the maximum levels fixed by the European Commission. In both species, mercury and cadmium mean concentrations were higher in liver (albacore: mercury = 2.41 μg g^-1 wet wt, cadmium = 9.22 μg g^-1 wet wt; horned octopus: mercury = 0.76 μg g^-1 wet wt, cadmium = 6.72 μg g^-1 wet wt) than in flesh (albacore: mercury = 1.56 μg g^-1 wet wt, cadmium = 0.05 μg g^-1 wet wt; horned octopus: mercury = 0.36 μg g^-1 wet wt, cadmium = 0.33 μg g^-1). Mercury concentrations exceeding the prescribed legal limit of 1 μg g^-1 wet wt were found in almost all albacore samples (flesh: 71.4%; liver: 85.7%). For horned octopus, concentrations above 0.5 μg g^-1 wet wt were observed solely in hepatopancreas, while in flesh, the concentrations were below this limit in all the samples examined. Of the flesh samples of albacore, 42.8% exceeded the proposed tolerance for cadmium for human consumption, whilst for horned octopus, the established limit was not exceeded in any sample.     

Mercury in UK imported fish and shellfish and UK-farmed fish and their products

Total mercury concentrations were measured in fish and shellfish and their products imported into the UK and also in UK-produced farmed salmon and trout. Three hundred and thirty-six samples were collected using a two-stage sampling plan. The sample plan was weighted to reflect consumption, but with some bias towards fish that might accumulate higher levels of mercury, such as large predatory fish at the top of the food chain. The highest levels of total mercury were found in billfish (swordfish and marlin) and shark. Mercury concentrations in the five samples of fresh/frozen shark ranged from 1.006 to 2.200 mg kg -1 , all above the European Commission limit for the species, and concentrations in 20 samples of fresh/frozen billfish ranged from 0.153 to 2.706 mg kg -1 with 13 samples above the 1.0 mg kg -1 limit for the species. One sample of Antarctic ice fish was collected and had a mercury concentration of 0.664 mg kg -1 . The limit for this species was 0.5 mg kg -1 . One sample of fresh/frozen tuna out of the 20 collected had a mercury concentration above the limit of 1.0 mg kg -1 (1.5 mg kg -1 ), but all other fresh tuna samples were well within the regulatory limit (average 0.4 mg kg -1 ). Mercury concentrations in canned tuna were lower with concentrations on average half that measured in fresh/frozen tuna. Mercury concentrations in UK-farmed salmon and trout were relatively low. The maximum concentration found in 46 samples of fresh/frozen or smoked trout and salmon was 0.103 mg kg -1 .     

Cadmium and mercury in cephalopod molluscs: Estimated weekly intake

Cadmium and mercury concentrations were measured in the flesh and hepatopancreas of different species of cephalopod molluscs (European squid, common octopus, curled octopus, horned octopus, pink cuttlefish, common cuttlefish) in order to establish whether the concentrations exceeded the maximum levels fixed by the European Commission. In hepatopancreas, the levels of cadmium were substantially higher than those in flesh (flesh 0.11-0.87 µg g^-1 wet weight, hepatopancreas 2.16-9.39 µg g^-1 wet weight), whilst the levels of mercury (flesh 0.13-0.55 µg g^-1 wet weight, hepatopancreas 0.23-0.79 µg g^-1) were approximately double those in flesh. Concentrations exceeding the maximum permitted limit of cadmium were found in 39.8 and 41.0% of common octopus and pink cuttlefish flesh, respectively. For mercury, concentrations above the limit were found only in octopuses, and precisely in 36.8, 50.0 and 20.0% of flesh samples of common, curled and horned octopus, respectively. In the hepatopancreas, concentrations of cadmium and mercury were above the proposed limits in all the samples examined. The estimated weekly intake of between 0.09 and 0.49 µg kg^-1 body weight for cadmium and between 0.05 and 0.24 µg kg^-1 body weight for mercury made only a small contribution to the provisional tolerable weekly intake (cadmium 1.3-7.0%, mercury 1.0-4.8%) set by the WHO.     

Survey of total mercury and methylmercury levels in edible fish from the Adriatic Sea

Total mercury and methylmercury concentrations were measured in the muscle tissue of different fish species from the Adriatic Sea to ascertain whether the concentrations exceeded the maximum level fixed by the European Commission. Large species-dependent variability was observed. The highest total mercury mean concentrations were in benthic (0.20-0.76 μg g^-1 wet wt) and demersal fish (0.22-0.73 μg g^-1 wet wt), while pelagic species showed the lowest levels (0.09-0.23 μg g^-1 wet wt). In 15% of frost fish, in 42% of skate and in 30% of angler fish samples total mercury concentrations exceeded the maximum level fixed by the European Commission (Hg = 1 μg g^-1 wet wt); for the species for which the maximum level was set to 0.5 μg g^-1 wet wt, concentrations exceeding the prescribed legal limit were observed in 6.4% of bokkem, in 6.6% of pandora, in 20% of megrin, in 12.5% of four-spotted megrim, in 16% of striped mullet, in 5.0% of forkbeard and in 5.3% of picarel samples. In all the different species, mercury was present almost completely in the methylated form, with mean percentages between 70 and 100%. Weekly intake was estimated and compared with the provisional tolerable weekly intake recommended by the FAO/WHO Expert Committee on Food Additives. A high exposure was associated with the consumption of only skates, frost fish and angler fish, thought the consumption of the other species, such as, megrim, four spotted megrim, red fish striped mullet and forkbeard, resulted in a weekly intake slightly below the established provisional tolerable weekly intake.     

Hair mercury levels in relation to fish consumption in a community of the Moroccan Mediterranean coast

Coastal populations with high seafood consumption in the Mediterranean have a significant exposure to dietary methylmercury, and areas where environmental mercury pollution is an issue due to industrial activities are of special concern. The study was undertaken with the aim of assessing methylmercury exposure through fish consumption in a community of north Morocco and characterizing the relevant health risk. Concentrations of total mercury were determined in human hair, a biomarker of methylmercury exposure, and in locally consumed fish by cold vapour atomic absorption spectrophotometry. Based on consumption frequencies reported by the 108 subjects included in the study the weekly intake of methylmercury was estimated and biomarker data were evaluated in relation to the estimated intake and the sociodemographic characteristics of the population. Multiple regression analysis was employed for the interpretation of hair mercury data in relation to fish consumption frequency, gender and the age of individuals. Mercury concentrations in hair ranged from 0.22 to 9.56 µg g^-1 (geometric mean = 1.79 µg g^-1) and were closely related to fish intake. Fisherman and their families consumed fish three to five times per week and were the most exposed population subgroup. A high proportion of women of child-bearing age (50%) had relatively high levels of mercury in their hair (3.08-7.88 µg g^-1).     

Survey of total mercury in total diet food composites and an estimation of the dietary intake of mercury by adults and children from two Canadian cities, 1998-2000

Total mercury was measured in 259 total diet food composites from two Canadian cities. Levels were generally low, with 46% of the composites having concentrations below the limit of detection, which ranged from 0.026 to 0.506 ng g^-1. The fish category contained the highest mercury concentrations, which averaged 67 ng g^-1 and ranged from 24 to 148 ng g^-1. All composites were below the Canadian guideline for total mercury in fish of 0.5 ppm. Dietary intakes of mercury averaged 0.022 μg kg^-1 body weight/day (μg kg^-1 day^-1), and ranged from 0.012 μg kg^-1 day^-1 for females over 65 years old to 0.062 μg kg^-1 day^-1 for 0-1-month-old infants. For fish consumers, fish contributed to more than half of the ingested mercury. All intakes were well below Joint FAO/WHO Expert Committee on Food Additives Provisional Tolerable Weekly Intakes, expressed on a daily basis, of 0.71 μg kg^-1 day^-1 total mercury and 0.47 μg kg^-1 day^-1 methyl mercury, and also below a recent Health Canada recommended maximum methyl mercury intake of 0.2 μg kg^-1 day^-1 for children and women of child-bearing age.     

Survey of formaldehyde, acetaldehyde and oligomers in polyethylene terephthalate food-packaging materials

Polyethylene terephthalate (PET) is frequently used as a packaging material for beverage bottles, fruit and vegetable trays, and egg crates in Japan. Levels of formaldehyde (FA), acetaldehyde (AA) and PET oligomers in various PET food packaging were determined. PET samples were initially dissolved in trifluoroacetic acid with 2,4-dinitrophenylhydrazine to derivatize formaldehyde and acetaldehyde to their dinitrophenylhydrazones. The stable derivatives along with the oligomers were analysed using HPLC with ultraviolet light detection at 360 and 254 nm, respectively. The PET pellets contained 3.5-12.4 µg g^-1 AA and 4.0-7.2 mg g^-1 oligomers, while FA was below the determination limit. FA, AA and oligomer levels in Japanese bottles were 0.6-3.0 µg g^-1, 8.4-25.7 µg g^-1 and 5.0-8.7 mg g^-1, ND-1.6 µg g^-1, 5.0-13.1 µg g^-1 and 4.9-8.2 mg g^-1 in French and Italian bottles, and ND-1.2 µg g^-1, 9.1-18.7 µg g^-1 and 5.6-8.0 mg g^-1 in US and Canadian bottles, respectively. Compared with European bottles, Japanese bottles contain higher FA and AA levels. In sheet-moulding products, their contents were determined as ND-1.1 µg g^-1, 11.5-43.1 µg g^-1 and 4.6-9.2 mg g^-1, respectively. The results show that sheet-moulding products contain lower FA and higher AA in comparison with bottles. FA and AA are considered to be generated from PET during the heating process for moulding the pellets to bottles or sheet-moulding articles and de-aeration during the sheet-moulding process is effective in removing FA. In contrast, the level of the oligomers remains unchanged during the moulding process from pellets to bottles or sheet products.     

Methylmercury determination in fish and seafood products and estimated daily intake for the Spanish population

The mercury content of 25 samples of fish and seafood products most frequently consumed in Spain was determined. A simple method comprising cold vapour and atomic absorption spectrometry was used to determine separately inorganic and organic mercury. In all samples inorganic mercury content was below 50 µg kg^-1. There was wide variability, among not only the mercury levels of different fish species, but also for different samples of the same species — with the methylmercury content ranging from below 54 to 662 µg kg^-1. The highest mean methylmercury content was found in fresh tuna. Based on an average total fish consumption of 363 g/person week^-1, the methylmercury intake was estimated to be 46.2 µg/person week^-1. Therefore, the mercury intake of Spanish people with a body weight ≤ 60 kg is lower than the Joint FAO/WHO Expert Committee on Food Additives (JECFA) provisional tolerable weekly intake (PTWI) of 1.6 µg kg^-1 body weight, but exceeds the US National Research Council (NRC) limit of 0.7 µg kg^-1 body weight week^-1 based on a benchmark dose.     

Acrylamide in Asian foods in Hong Kong

About 400 food samples, mainly Asian foods available in Hong Kong, were tested for acrylamide by an LC-MS/MS method using [1, 2, 3-¹³C₃]-acrylamide as surrogate. The acrylamide levels in the more commonly consumed food items in the food groups such as rice and rice products, noodles, bakery and batter-based products, were generally less than 60 μg kg^-1. Higher levels were found in the food groups such as biscuit-related products and crisps. The highest levels were detected in potato crisps (1500-1700 μg kg^-1). Lower levels were found in rye flour-based crisps (440 μg kg^-1), followed by corn-based (65 to 230 μg kg^-1) and wheat flour-based crisps (61-200 μg kg^-1), and then rice flour-based crisps (15-42 μg kg^-1). The acrylamide formation during deep frying of a wheat flour-based product, Chinese fried fritter, was studied. Deep-frying at 170°C resulted in gentle but steady rise in acrylamide content. A steep rise for frying at 210°C was recorded. The moisture content of the product decreased with frying time, but the fat content increased. It is proposed that the reaction for the formation of acrylamide was initiated on the surface and then penetrated into the interior of the food matrix by heat transfer via radiation/conduction and diffusion of hot oil.     

Migration of trimellitic acid from epoxy anhydride can coatings into foods

The migration of trimellitic acid and its esters from epoxy anhydride coatings was determined in simulants as well as in canned foods. The most appropriate simulant was a combination of EC simulants B and C: 2% acetic acid/10% ethanol in water. The average migration into food was 900 μg kg^-1. This far exceeds the 50 μg kg^-1 for which the safety of trimellitic acid and its anhydride is ensured and the Swiss legal limit (QM(T) of 5 mg kg^-1 coating). Furthermore, much trimellitic acid migrated as (unidentified) esters, i.e. toxicological testing of free trimellitic acid is inadequate for the material that in reality migrates.     

Total and organic mercury concentrations in the white muscles of swordfish (Xiphias gladius) from the Indian and Atlantic oceans

A total of 226 swordfish samples collected from Taiwanese fishing vessels in the Indian and Atlantic oceans were examined for total mercury (THg) and organic Hg (OHg). Analysis of 56 pooled white muscle samples showed that THg and OHg concentrations ranged from 0.056 to 3.97 (1.3 ± 0.97) and from 0.043 to 3.92 (1.01 ± 0.82) µg g^-1 flesh mass, respectively. These values were similar to those from various previous studies during the past three decades. THg and OHg were significantly linearly correlated with fork length (FL, cm) of the fish from Indian and Atlantic oceans; however, there was no significant OHg%-FL relationship. OHg and THg also were significantly correlated. Fishes with FL ≤ 140 cm met the methyl Hg (meHg) regulatory standard set by the European Commission Decision (meHg ≤ 1.0); and fish with FL ≤ 211 cm met the Taiwanese Food and Hygiene Standard (meHg ≤ 2.0). Weekly swordfish consumption rates and amounts are recommended accordingly.     

Occurrence of polybrominated diphenyl ethers and polychlorinated biphenyls in shark liver oil supplements

Results are reported of a pilot survey of concentrations of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) in shark liver oil supplements. Eleven brands of dietary supplements were analysed using an isotope dilution GC/MS method. Total concentrations of 10 PBDE congeners (BDE-28, -47, -49, -66, -99, -100, -153, -154, -155 and -183) ranged from 0.1 to 53 ng g^-1 oil weight and total concentrations of six PCB congeners (CB-28/31, -52, -118, -153 and -180) in the samples ranged from 16 to 340 ng g^-1 oil weight (undetected values are not included). Two brands of Japanese deep-sea shark liver oil contained the highest levels of PBDEs (49-53 ng g^-1 oil weight) and PCBs (290-340 ng g^-1 oil weight). These results indicate that PBDEs may have entered Japanese deep-sea waters.     

Survey of ochratoxin A and deoxynivalenol in stored grains from the 1999 harvest in the UK

Three hundred and twenty samples from the 1999 UK harvest comprising wheat (201 samples), barley (106) and oats (13) were analysed for ochratoxin A and deoxynivalenol. A small number of organic samples was also obtained. Samples were collected from farms, central stores, mills, maltings and ports from across the UK from February to April 2000. Ochratoxin A and deoxynivalenol analysis was by affinity column clean up and high-performance liquid chromatography with fluorescence and ultraviolet light detection, respectively, with limits of detection of 0.2 and 20 μg kg^-1. The survey found ochratoxin A at below 5 μg kg^-1 in 97% of the samples indicating satisfactory storage conditions. The remaining 3% of the samples contained ochratoxin A at levels between 5.2 and 231 μg kg^-1, but none of these samples was intended for human consumption. Deoxynivalenol was detected in 88% of all samples, with 83% below 100 μg kg^-1; the maximum level was 600 μg kg^-1. Twenty samples containing deoxynivalenol at or above 150 μg kg^-1 by high-performance liquid chromatography were all confirmed by gas chromatography/mass spectrometry. Nivalenol was also detected by gas chromatography/mass spectrometry at levels of 50 μg kg^-1 or higher in 18 of 20 samples where deoxynivalenol was confirmed.     

Migration of formaldehyde and acetaldehyde into mineral water in polyethylene terephthalate (PET) bottles

The levels of formaldehyde (FA) and acetaldehyde (AA) in polyethylene terephthalate (PET) bottles and in commercial mineral water are reported. All the water samples bottled in Japan contained detectable levels of FA (10.1-27.9 μg l^-1) and AA (44.3-107.8 μg l^-1). Of 11 European bottled water samples, eight did not contain either FA or AA, while the remaining three had detectable levels of FA (7.4-13.7 μg l^-1) and AA (35.9-46.9 μg l^-1). In three North American bottled water samples, two contained FA (13.6 and 19.5 μg l^-1) and AA (41.4 and 44.8 μg l^-1), and one did not. Regardless of the region of origin, all the sterilized water samples contained FA and AA, whilst in contrast, none of the unsterilized water without carbonate contained FA or AA. Of the carbonated water samples, three contained FA and AA, and one did not. When fortified with FA and AA, the commercial water sample without otherwise detectable FA and AA was able to reduce levels, although the commercial water sample containing FA and AA could not. The presence of bacteria in the commercial water samples was investigated using an ATP-based bioluminescent assay and heterotrophic plate count method. The commercial water without FA and AA contained heterotrophic bacteria, whilst the commercial water with FA and AA did not contain detectable bacteria. It is suggested that in this case both FA and AA migrated from PET materials, but were subsequently decomposed by the heterotrophic bacteria in the unsterilized water.     

Levels of total mercury in predatory fish sold in Canada in 2005

Total mercury was analysed in 188 samples of predatory fish purchased at the retail level in Canada in 2005. The average concentrations (ng g(-1), range) were: sea bass 329 (38-1367), red snapper 148 (36-431), orange roughy 543 (279-974), fresh water trout 55 (20-430), grouper 360 (8-1060), black cod 284 (71-651), Arctic char 37 (28-54), king fish 440 (42-923), tilefish 601 (79-1164) and marlin 854 (125-2346). The Canadian standard for maximum total mercury allowed in the edible portions of fish sold at the retail level is 1000 ng g(-1) for shark, swordfish, marlin, orange roughy, escolar and both fresh and frozen tuna. The standard is 500 ng g(-1) for all other types of fish. In this study, despite the small number of samples of each species, the 1000 ng g(-1) maximum was exceeded in five samples of marlin (28%). The 500 ng g(-1) maximum was exceeded by six samples of sea bass (20%), four of tilefish (50%), five of grouper (24%), six of king fish (40%) and one of black cod (13%).     

Justifying the need to prescribe limits for toxic metal contaminants in food-grade silver foils

The use of silver foils in various food preparations is a common practice in Middle Eastern and South East Asian countries. The FAO/WHO Joint Expert Committee on Food Additives (JECFA) has included silver in the list of food additives, but specifications were not prepared. Indian food legislation has included food-grade silver foil and laid down a purity requirement of 99.9%. This leaves an unspecified margin of 0.1% or 1000 µg g^-1 for contaminants. Therefore, a study to investigate the levels of metallic contaminants in food-grade silver foil was undertaken. Of 178 foils analysed, 161 (90%) contained silver, whilst 10% were fraudulently made up of aluminium. In the case of silver foils, 46% of the samples adhered to the desired purity requirement of 99.9%, while 54% had a lower silver content. Copper was present in 86.3% of the silver foils, while chromium, nickel and lead contamination was found in over 54% of samples. Cadmium levels were detected in 28% of the silver foils and manganese was present in 6.8% of samples. In silver foils showing metal contaminants, average levels were found for nickel (487 µg g^-1), lead (301 µg g^-1), copper (324 µg g^-1), chromium (83 µg g^-1), cadmium (97 µg g^-1) and manganese (43 µg g^-1), which being appreciable justify the need to prescribe limits for some metals in food-grade silver foil as well as for silver powder used in confectioneries and medicinal preparations. The work reported here should encourage manufacturers to use high-purity raw materials and take suitable precautions to reduce unwarranted exposure of consumers to toxic metal contaminants.     

Quantitative analysis of Fusarium mycotoxins in maize using accelerated solvent extraction before liquid chromatography/atmospheric pressure chemical ionization tandem mass spectrometry

A method for the simultaneous quantitative determination of deoxynivalenol (DON), fumonisin B1 (FB1) and zearalenone (ZEN) in maize by liquid chromatography-atmospheric pressure chemical ionization tandem mass spectrometry (LC-APCIMS/MS), using stable isotopically labelled and structural analogues internal standards, is described. The procedure involves accelerated solvent extraction followed by two solid-phase clean-up steps on strong anion exchange resin and a Mycosep® column. Typical recoveries were calculated by spiking blank maize at three different concentrations for deoxynivalenol (200, 400 and 1000 μg kg^-1) at 70%, for fumonisin B1 (100, 200 and 1000 μg kg^-1) at 90%, and for zearalenone (50, 100 and 200 μg kg^-1) at 40%. LC-APCIMS/MS analyses were realized in collision-induced dissociation on an ion-trap instrument to provide a high degree of selectivity and sensitivity. Extraction of ions from two transition reactions, monitored by LC-APCIMS/MS for each analyte, enabled a limit of detection for DON, FB1 and ZEN at, respectively, 10, 20 and 3 μg kg^-1, and a limit of quantification at, respectively, 50, 50 and 10 μg kg^-1. The robustness of the method was also evaluated with the analysis of wheat samples.     

Analysis of veterinary drug residues in fish and shrimp composites collected during the Canadian Total Diet Study, 1993-2004

Thirty shrimp, marine fish, freshwater fish, and canned fish composite samples collected and prepared as part of the Canadian Total Diet Study were analysed for 39 different veterinary drug residues. The analyses were undertaken to obtain baseline data that could be used to estimate the dietary exposure of Canadians to these residues. The most frequently observed residue was AOZ (four out of 30 samples), the metabolite of furazolidone, at a range of 0.50 to 2.0 ng g^-1 wet weight. Other residues detected included enrofloxacin (three samples; 0.3-0.73 ng g^-1), leucomalachite green (three samples; 0.73-1.2 ng g^-1), oxolinic acid (two samples; 0.3-4.3 ng g^-1), AMOZ (the metabolite of furaltadone; one sample; 0.40 ng g^-1), chloramphenicol (one sample; 0.40 ng g^-1), and SEM (the metabolite of nitrofurazone; one sample; 0.8 ng g^-1). The results of this survey indicate that Canadians are exposed to low ng g^-1 concentrations of some banned and unapproved veterinary drug residues via the consumption of certain fish and shrimp.     

Occurrence of aflatoxin M1 in domestic milk in Japan during the winter season

A total of 208 samples of commercial pasteurized milk gathered from retail outlets across Japan during the winter season were analysed for aflatoxin M₁ (AFM₁). Japan was divided into 11 regions from north to south, and nine to 45 milk samples from each region were randomly purchased between December 2001 and February 2002. Each milk sample was cleaned up by an immunoaffinity column, and AFM₁ was quantified by liquid chromatography with fluorescence detection in four independent laboratories. The limit of detection of the method was 0.001 μg kg^-1. The identity of the putative AFM₁ in milk sample was confirmed by the formation of AFM₁ hemi-acetal with trifluoroacetic acid. Based on the results obtained with spiked samples (0.05 μg AFM₁ kg^-1), the mean recovery was 91.4%, the relative standard deviation for repeatability was 4.6%, and the relative standard deviation for reproducibility was 8.0% among four independent laboratories. AFM₁ was detected in 207 (99.5%) of 208 milk samples at 0.001-0.029 μg kg^-1, with a mean of 0.009 μg kg^-1 and a 90th percentile of 0.014 μg kg^-1. No significant difference of the level of AFM₁ contamination was observed among the regions.