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.     

Analysis of heat-processed corn foods for fumonisins and bound fumonisins

Thirty retail samples of heat-processed corn foods, i.e. corn flakes, corn-based breakfast cereals, tortilla chips and corn chips, were analysed for fumonisins — fumonisin B₁ (FB₁), fumonisin B₂ (FB₂) and hydrolysed FB₁ (HFB₁) — as well as for protein- and total-bound FB₁. Bound (hidden) fumonisins cannot be detected by conventional analysis. Improved methods for the determination of bound FB₁ were developed. The protein-bound FB₁ was extracted with 1% sodium dodecylsulfate (SDS) solution. The SDS, which interfered with high-performance liquid chromatography (HPLC) analysis, was then separated from protein-bound FB₁ by complexing with methylene blue followed by solvent extraction and hydrolysis with 2 N KOH. To measure total-bound FB₁, the sample itself was hydrolysed with KOH. In both cases, clean-up was accomplished on an OASIS polymeric solid-phase extraction column and the bound fumonisins were determined by HPLC measurement of HFB₁. Fourteen of 15 samples of corn flakes and other corn-based breakfast cereals analysed contained detectable levels of FB₁ with a mean in positive samples of 67 ng g^-1 (13-237 ng g^-1). Two samples also had detectable levels of FB₂ (21-23 ng g^-1). Bound FB₁ was found in all samples; the mean protein-bound FB₁ measured was 58 ng g^-1 (22-176 ng g^-1) and the mean total-bound FB₁ measured was 106 ng g^-1 (28-418 ng g^-1), reported as FB₁ equivalents after correction for recoveries of HFB₁. There was an average of about 1.3 times more FB₁ in the bound form compared with extractable FB₁, and this was about twice as much as protein-bound FB_1. Seven of the 15 samples of alkali-processed corn-based foods, such as tortilla chips and corn chips, contained FB₁ and three contained HFB₁ with means in measurable positive samples of 78 (48-134) and 29 (13-47) ng g^-1, respectively. Five of these alkali-processed corn foods contained bound FB₁; the mean measurable protein-bound FB₁ was 42 ng g^-1 (39-46 ng g^-1) and the mean measurable total-bound FB₁ was 100 ng g^-1(54-209 ng g^-1). HFB₁ derived from bound FB₁ in selected samples was confirmed by HPLC with mass spectrometry (MS).     

Effect of cooking on enrofloxacin residues in chicken tissue

The aim of this study was to determine the effect of different cooking processes (microwaving, roasting, boiling, grilling and frying) on naturally incurred enrofloxacin residues in chicken muscle. Enrofloxacin and its metabolite, ciprofloxacin, were analysed using a validated LC-MS method with limits of detection (LOD) and quantification (LOQ), respectively, of 2 and 5 ng g^-1 quinolones in muscle samples. The method was shown to be linear over the range 5-500 ng g^-1. Mean intra-day relative standard deviation (RSD) at a concentration of 50 ng g^-1 (n = 6) was 6%; inter-day RSD was 12%. A recovery study demonstrated that 65-101%, of the drug and metabolite could be recovered from the tissue. The RSD with naturally incurred roasted chicken breast was 9.18% at a concentration of 11 ± 1.01 ng g^-1 (n = 6). In water, enrofloxacin remained stable for 3 h when heated at 100°C. It was concluded that residue data from raw tissue are valid for estimation of consumer exposure to this drug, as well as the ADI calculations because cooking procedures did not affect enrofloxacin residues, which remained stable during heating. However, there was an apparent decrease in quinolone concentration in tissue because some was lost by exudation into the liquid used for cooking. Conversely, for a cooking procedure with water loss, there was an apparent increase in residue concentration.     

Distribution and elimination of fumonisin analogues in weaned piglets after oral administration of Fusarium verticillioides fungal culture

The distribution and elimination of fumonisins after oral administration of 50 mg FB₁, 20 mg FB₂ and 5 mg FB₃ per animal day^-1 for 22 days was studied in weaned barrows. At the end of the trial, the lung, heart, liver, kidney, spleen, brain, serum, bile, muscle, fat, urine and faeces samples were collected and their content of fumonisins (FB₁, FB₂) determined by LC-MS. The highest FB₁ concentrations were found in the liver (99.4 ± 37.5 ng g^-1) and kidneys (30.6 ± 10.1 ng g^-1), whilst the highest average amount of FB₂ was in the liver (1.4 ± 2.3 ng g^-1) and fat (2.6 ng g^-1 ± 4.8) samples. Comparing the FB₁/FB₂ ratio in different organs (19/1), it was found that the ratio in the abdominal and subcutaneous fat samples (4/1) was markedly different from those in all other tissues, namely the relative proportion of FB₂ was higher in latter cases. Of the total quantity of FB₁, the 13% taken up during 5 days was excreted unchanged with the faeces and urine. On average, in the urine and faeces, FB₁ was detected in nine- and 14-fold quantities, as compared with FB₂.     

Migration of bisphenol A from can coatings—effects of damage, storage conditions and heating

Bisphenol A (BPA) is an important monomer used in the manufacture of epoxy resins for internal food can linings. Experiments were conducted to investigate the effects of different storage conditions and can damage on the migration of BPA to foods. These experiments were conducted in a systematic fashion by filling empty epoxyphenolic coated cans with four foods: soup, minced beef, evaporated milk and carrots and a food simulant (10% ethanol). Filled cans of each food type or simulant were then sealed and processed using appropriate conditions, before storage at three different temperatures: 5°C, 20°C and 40°C. For each of the storage regimes, 50% of the cans were dented to establish if this would lead to increased BPA migration. Cans were removed from these stocks at intervals of 1, 3 and 9 months storage at 5°C and 20°C or 10 days, 1 and 3 months at 40°C. Some initial problems of heterogeneity between samples was overcome by determining the amount of BPA in food as well as in the can lining. It was found that 80-100% of the total BPA present in the coating had migrated to foods directly after can processing by pilot plant filling with food or simulant, sealing and sterilization. This level was not changed by extended storage (up to 9 months) or can damage, indicating most migration was occurring during the can processing step. There was no noticeable difference, in this respect, between the different foods or the food simulant. Analysis of control samples (foods fortified with ∼0.1 mg kg^-1 BPA and contained in Schott bottles) showed that BPA was stable under both processing and storage. Experiments were also conducted to investigate the potential effects, on the migration of BPA from can coatings, of cooking or heating foods in the can prior to consumption. Food cans were purchased and the food either cooked or heated in the can. BPA was analysed prior to and after the heating/cooking process. It was concluded from the results that there were no appreciable differences in the BPA level before and after cooking or heating.     

N-methyl carbamate pesticide residues in conventional and organic infant foods available on the Canadian retail market, 2001-03

Seven parent N-methyl carbamate insecticides, in addition to two transformation products of aldicarb (aldicarb sulfoxide and aldicarb sulfone), and a single transformation product of carbofuran (3-hydroxycarbofuran) were measured in infant and junior foods available on the Canadian retail market between 2001 and 2003. Carbaryl and methomyl were the only analytes present at levels above the limits of detection in juice, cereals, fruit, vegetables or meat samples analysed. Carbaryl was the most frequently (7.6%) detected compound and concentrations ranged from 0.6 to 18 ng g^-1. Detectable levels of carbaryl were most frequently found in foods prepared with fruit. Methomyl was detected (0.8 ng g^-1) in one chicken with broth sample analysed in the present study. In all cases, the concentrations observed were orders of magnitude below the maximum residue limits established for these compounds in the corresponding raw food commodities in Canada (100-10 000 ng g^-1). Dietary intakes of carbaryl and methomyl based on the consumption of infant foods tested ranged between 0.2-343 and 0.4-2.0 ng kg^-1 body weight day^-1, respectively.     

Determination of ochratoxin A in grapes of Greek origin by immunoaffinity and high-performance liquid chromatography

A simple analytical method for ochratoxin A (OTA) determination in grapes is described, using aqueous methanolic extraction, an immunoaffinity column clean-up step and high-performance liquid chromatography with fluorescence detection. Mean recovery was 94% (RSD = 4.0%) with a detection limit of 0.4 ng g^-1 and quantification limit of 1.20 ng g^-1. Repeatability (r) and reproducibility (R) were 1.17 and 1.34, respectively. OTA determinations were applied to 50 grape samples (23 different varieties) originating from representative regions of Greece. Results showed the presence of OTA in 86% of samples tested (n = 50). Traces were found in 56% of samples but OTA was not detectable in 14% of samples. Traces were also found in 4% of red, organically grown samples. The most contaminated were three samples of red grapes, two from Central Greece (2.69 and 1.41 ng g^-1), both table and wine-making grapes. The third sample (1.46 ng g^-1), originating from the island of Samos, was used only in wine-making. Mean (1.06 ng g^-1) and median (0.76 ng g^-1) OTA concentrations in red grapes were slightly higher compared to the mean (0.82 ng g^-1) and median (0.65 ng g^-1) concentrations in white grape samples. The study shows that the potential risk for a person of 60 kg ranged from 0.9 to 9 ng kg^-1 bw day^-1 and is dependent on the quantity of grapes consumed daily.     

Occurrence of fumonisins B1 and B2 in asparagus from Shandong province, P.R. China

Thirty samples of asparagus spears were collected from the fields in Shandong province, China, in July 2004, and were analysed for the occurrence of fumonisins B₁ and B₂ (FB₁ and FB₂) by HPLC coupled with electrospray ionization tandem mass spectrometry. Twenty-four samples (80%) contained fumonisins, ranging from 24 to 670 ng g^-1 (average 123 ng g^-1) and 17 to 138 ng g^-1(average 35 ng g^-1) for FB₁ and FB₂, respectively. The total amount of fumonisins (FB₁ and FB₂) in all samples ranged from 47 to 714 ng g^-1 (average 158 ng g^-1) (based on dry weight). This is the first report on the natural occurrence of FB₁ and FB₂ in asparagus spears in China.     

Oestrogenicity of paper and cardboard extracts used as food containers

Bisphenol-A (BPA), dibutyl phthalate (DBP), and di-2-ethylhexyl phthalate (DEHP), which are common chemical residues in food-packaging materials, were investigated in paper and cardboard containers used for take-away food. The oestrogenicity of aqueous extracts was tested in E-Screen bioassay and analysis carried out by high-performance liquid chromatography (HPLC) and gas chromatography-mass spectrometry (GC/MS). Oestrogenicity was demonstrated in 90% of extracts (geometric mean [GM] = 11.97 pM oestradiol equivalents g^-1). DEHP, DBP, and BPA (GM = 341.74, 37.59, and 2.38 ng g^-1 of material) were present in 77.50, 67.50, and 47.50% of samples, respectively. In bivariate analyses, no significant association was found between the levels of these chemicals and oestrogenicity in cardboard/paper extracts. A close-to-significant association was found between oestrogenicity and DBP (β = 1.25; p = 0.06) in paper extracts, which reached statistical significance in multivariate analysis (β = 1.61; p = 0.03). Paper and cardboard used in food packaging may contribute to the inadvertent exposure of consumers to endocrine-disrupting chemicals.     

Variability in captan residues in apples from a Canadian orchard

Apple trees in an orchard in Quebec, Canada were treated, following label directions, with the fungicide captan (1,2,3,6-tetrahydro-N-(trichloromethylthio)phthalimide) during the 2003 agricultural season. A total of 142 apples from three rows of trees were selected for determination of captan by GC/MS. Individual apples were found to contain captan levels ranging from 16.9 to 6350 ng g^-1. Only two individual apple samples exceeded the Canadian maximum residue limit (5000 ng g^-1) for captan in apples. Six composite samples, comprising half portions of eight individual apples, were analysed from each of the three experimental rows. Composite samples ranged in concentration from 166 to 2620 ng g^-1. The greatest uncertainty associated with the measured concentrations was due to variability among apples rather than the measurement of residue levels.     

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.     

Analysis of vinylidene chloride and 1-chlorobutane in foods packaged with polyvinylidene chloride casing films by headspace gas chromatography/mass spectrometry (GC/MS)

A headspace gas chromatography/mass spectrometry method was developed for the simultaneous determination of vinylidene chloride and 1-chlorobutane in foods packaged with polyvinylidene chloride casing films. The solid foodstuff was homogenized with an equal mass of distilled water. The homogenate was incubated for 1 h at 90°C in a sealed headspace vial, and the headspace gas was then analysed by gas chromatography/mass spectrometry in selected ion-monitoring mode using a bonded porous polymer-coated capillary column. The recovery rates of vinylidene chloride and 1-chlorobutane in foodstuffs were 94.5-103.9 and 85.8-120.3%, respectively. Among 13 samples tested, vinylidene chloride was detected at 0.001-0.020 µg g^-1 in 11 foodstuffs, and 1-chlorobutane was detected at 0.004-0.040 µg g^-1 in all 13 foodstuffs. Furthermore, vinylidene chloride was detected at 0.04 µg g^-1 in one casing film, and 1-chlorobutane was detected in all casing films. The results indicate that these compounds migrated from the casing films into the foodstuffs.     

A sensitive solid-phase microextraction/gas chromatography-based procedure for determining pentachlorophenol in food

A new method for the determination of pentachlorophenol (PCP) in different foods was developed using capillary gas chromatography (GC) and microwave induced-plasma atomic emission spectrometry (MIP-AED). The analyte is first derivatized and then extracted and pre-concentrated by solid-phase microextraction (SPME) in headspace (HS) mode. A clear matrix effect was found for the different samples investigated, so that standard addition was required for quantification. Detection limits of 0.03-6.0 ng g^-1 were obtained, depending on the sample analysed. The method gave recoveries of 81-109% from spiked samples. Concentration levels of PCP ranged from 0.3 to 1.5 ng g^-1 were found in honey, but no PCP was detected in other samples.     

Ochratoxin A in dried vine fruits on the Canadian retail market

Between 1998 and 2000, 151 samples of raisins and sultanas and two samples of currants were collected from retail outlets across Canada and analysed for ochratoxin A. Samples were extracted with methanol-sodium bicarbonate, and the extracts were cleaned-up by immunoaffinity column chromatography. Ochratoxin A was quantified by liquid chromatography with fluorescence detection. The minimum quantifiable level was 0.1 ng g^-1. Ochratoxin A was present, above the minimum quantifiable level, in 67 (79%) of 85 samples of raisins, in 39 (59%) of 66 samples of sultanas, and in both samples of currants. The overall mean level of ochratoxin A was 1.8 ng g^-1 in both the raisins and sultanas, and 2.8 ng g^-1 in the currants.     

Determination of 1,3-dichloropropanol in soy and related sauces by using gas chromatography/mass spectrometry

A gas chromatography/mass spectrometry method for 3-MCPD in foods and food ingredients was modified for the determination of 1,3-DCP in soy and related sauces. The method was validated by using a blank soy sauce. The detection limit, quantitation limit and recoveries were determined, and identities were confirmed by mass spectrometry on the basis of analyses of test portions spiked with 1,3-DCP at 10, 25, 50 and 100 ng g^-1. The spiked test portions were quantitated by using an internal standard calibration curve. For the spiked test portions, the mean internal standard-corrected recovery for 1,3-DCP was 100% with a relative standard deviation of 1.32%. The limits of detection and quantitation were determined as 0.055 and 0.185 ng g^-1, respectively. The method also was compared with a headspace GC/MS method recently developed by the UK's Central Science Laboratory. Results from the method comparison showed that the recoveries for the spiked test portions, as well as the amounts of 1,3-DCP found in the retail products, were comparable.     

Dietary exposure assessment of infants to bisphenol A from the use of polycarbonate baby milk bottles

The residual bisphenol A (BPA) levels in 28 different brands of polycarbonate (PC) baby milk bottles available in the Singapore market were measured. With a detection limit of 3 mg/kg, BPA residues were detected in 19 out of the 28 PC baby milk bottles at levels between 4.01 and 141 mg/kg, with a mean of 28.1 ± 31.4 mg/kg and a median of 17.2 mg/kg. The potential migration of BPA from each of the 28 PC milk bottles was also measured using food-simulating solvents and time conditions recommended by the US Food and Drug Administration (US FDA), but using temperatures more severe than actual use. The highest upper-bound mean BPA migration levels of 0.64 ± 0.48 µg/in² in 10% ethanol at 70°C and 0.43 ± 1.25 µg/in² in corn oil at 100°C were observed after incubating cut portions of the milk bottles for 240 h. With this migration data and using US FDA's procedure for estimation of dietary exposure, the worst-case dietary exposure assessment for the intake of BPA by infants between birth and three months of age was below the oral Reference Dose of 0.05 mg/kg bw/day established by the US Environmental Protection Agency. This study showed that the dietary exposure to BPA from actual uses of PC milk bottles is unlikely to pose a health risk in infants.     

Development and application of a simplified clean-up procedure for the determination of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in horse fat by gas chromatography-tandem mass spectrometry (GC-MS/MS)

A simplified clean-up procedure was developed in combination with gas chromatography-tandem mass spectrometry (GC-MS/MS) for the determination of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in adipose tissue. Clean-up was performed by the successive application of a Mega Bond Elut® silica column and a Bond Elut® PCB column. Validation of the method was conducted according to European Union Commission Decision 2002/657/EC. In order to evaluate the applicability of the method, 44 horse fat samples were analysed. The total PCB concentration (sum of PCBs 28, 52, 101, 118, 138, 153 and 180) ranged from 5.35 to 140 ng g^-1 lipid weight. The total PBDE concentration (sum of BDEs 28, 47, 99, 100, 153, 154 and 183) ranged from below the decision limit to 6.34 ng g^-1 lipid weight.     

Occurrence of aflatoxin M1 in randomly selected North African milk and cheese samples

Forty-nine samples of raw cow's milk and 20 samples of fresh white soft cheese were collected directly from 20 local dairy factories in the north-west of Libya and analysed for the presence of aflatoxin M₁ (AFM₁). The samples were analysed using a high-performance liquid chromatography technique for toxin detection and quantification. Thirty-five of the 49 milk samples (71.4%) showed AFM₁ levels between 0.03 and 3.13 ng ml^-1 milk. Multiple analyses of five milk samples free of AFM₁ artificially contaminated with concentrations of AFM₁ at 0.01, 0.05, 0.1, 1.0 and 3.0 ng ml^-1 showed average recoveries of 66.85, 72.41, 83.29, 97.94 and 98.25%, with coefficients of variations of 3.77, 4.11, 1.57, 1.29 and 0.54%, respectively. Fifteen of 20 white soft cheese samples (75.0%) showed the presence of AFM₁ in concentrations between 0.11 and 0.52 ng g^-1 of cheese. Multiple assays of five cheese samples free of AFM₁ spiked with different concentration of AFM₁ (0.1, 0.5, 1.0 and 3.0 ng g^-1) showed average recoveries of 63.23, 78.14, 83.29 and 88.68%, with coefficients of variation of 1.53, 9.90, 4.87 and 3.79%, respectively. The concentrations of AFM₁ were lower in the cheese products than in the raw milk samples.     

Pattern of ivermectin (sheep) and doramectin (cattle) residues in muscular tissue from various anatomical locations

This trial reports comparative drug residual concentrations in muscular tissue obtained from various anatomical locations after subcutaneous administration of ivermectin (IVM) to sheep and topical treatment with doramectin (DRM) to calves at recommended therapeutic dose rates. Seven muscle samples from different anatomical locations (rhomboideus, supraspinatus, semitendinosus, gluteus medius, longissimus dorsi thoracis, intercostales and diaphragma) were collected at several post-treatment sampling times. Samples were frozen at-20°C until analyzed by HPLC. The highest IVM residual concentrations in muscular tissue from the different locations were found at 15 days post-treatment in sheep. Although the highest IVM mean concentrations were measured at 15 (16.8 ± 5.17 ng g^-1) and 20 (10.5 ± 4.06 ng g^-1) days post-administration in the intercostales muscles, at 30 days post-administration, the IVM concentration in this location was similar to that measured in the rhomboideus and diaphragma muscles. DRM residual concentrations were quantified in muscular tissue from all anatomical locations after topical administration to calves. Maximum residue level was observed at 10 days post-treatment in all anatomical sites. The diaphragma muscle showed the highest DRM residue levels at 2 (22.0 ± 4.35 ng g^-1), 5 (45.2 ± 3.78 ng g^-1) and 10 (57.9 ± 9.57 ng g^-1) days post-treatment in calves. These results demonstrated that the pattern of residue depletion from muscular tissue may differ according to its anatomical locations and/or physiological role. This should be considered in implementing residue control strategies in meat safety assurance for human consumption.     

食品金属罐中14种双酚类物质迁移量的同时测定及杀菌过程对其迁移的影响

为了调查国内食品金属罐中双酚类物质的迁移水平,本文建立了同时测定食品金属罐中14种双酚类物质迁移量的高效液相色谱法,并研究了杀菌过程对双酚类物质迁移的影响及食品金属罐中双酚类物质的迁移规律.结果表明,14种双酚类物质在4种食品模拟物(4％体积乙酸、10％体积乙醇、50％体积乙醇和异辛烷)中线性关系良好,加标回收率为83...