B.T.P. Chan

Validation and use of a fast sample preparation method and liquid chromatography-tandem mass spectrometry in analysis of ultra-trace levels of 98 organophosphorus pesticide and carbamate residues in a total diet study involving diversified food types.

This paper reports a comprehensive sensitive multi-residue liquid chromatography-tandem mass spectrometry (LC-MS/MS) method for detection, identification and quantitation of 73 pesticides and their related products, a total of 98 analytes, belonging to organophosphorus pesticides (OPPs) and carbamates, in foods. The proposed method makes use of a modified QuEChERS (quick, easy, cheap, effective, rigged, and safe) procedure that combines isolation of the pesticides and sample clean-up in a single step. Analysis is performed by liquid chromatography-electrospray ionization-tandem mass spectrometry operated in the multiple reaction monitoring (MRM) mode, acquiring two specific precursor-product ion transitions per target compound. Two main fragment ions for each pesticide were obtained to achieve the identification according to the SANCO guidelines 10684/2009. The method was validated with various food samples, including edible oil, meat, egg, cheese, chocolate, coffee, rice, tree nuts, citric fruits, vegetables, etc. No significant matrix effect was observed for tested pesticides, therefore, matrix-matched calibration was not necessary. Calibration curves were linear and covered from 1 to 20 microg L(-1) for all compounds studied. The average recoveries, measured at 10 microg kg(-1), were in the range 70-120% for all of the compounds tested with relative standard deviations below 20%, while a value of 10 microg kg(-1) has been established as the method limit of quantitation (MLOQ) for all target analytes. Similar trueness and precision results were also obtained for spiking at 200 microg kg(-1). Expanded uncertainty values were in the range 21-27% while the HorRat ratios were below 1. The method has been successfully applied to the analysis of 700 food samples in the course of a baseline monitoring study of OPPs and carbamates.

Trimethylamine oxide, dimethylamine, trimethylamine and formaldehyde levels in main traded fish species in Hong Kong.

Levels of trimethylamine oxide (TMAO), dimethylamine (DMA), trimethylamine (TMA) and formaldehyde (FA) were studied in 266 different fishes, including fresh/frozen raw whole fishes of 89 different species that traded in Hong Kong, China. Determination of TMAO can confirm the source of DMA and FA if present in the sample. These samples were purchased from different commercial outlets between April and August 2007. All samples of raw whole fish were identified for their species by the Agriculture, Fisheries and Conservation Department. The content of TMAO was determined by high-performance liquid chromatography (HPLC) coupled with a chemiluminescent nitrogen detector. The possible decomposition products of TMAO, DMA and TMA were analysed by headspace solid-phase micro-extraction gas chromatography-mass spectrometry (HS-SPME-GC-MS), while FA was conducted by steam distillation then quantified by a HPLC. The range for TMAO of all samples was <5–3800 mg kg−1 with median of 970 mg kg−1, while the endogenous enzymatic cleavage products DMA, TMA and FA were in the range of <2–320, <1–190 and <1–160 mg kg−1, respectively. These cleavage products were mainly found in three fish species, Harpadon nehereus, Saurida elongata and Saurida tumbil, that belong to the family Synodontidae (Lizardfishes) and subfamily Harpadontinae. Besides, freshwater fish species, namely, Micropterus salmoides, Oreochromis niloticus niloticus and Siniperca chuatsi, were found to contain TMAO in the range of 510–760, 85–720 and 400–640 mg kg−1, respectively.

A reliable method to determine methylmercury and ethylmercury simultaneously in foods by gas chromatography with inductively coupled plasma mass spectrometry after enzymatic and acid digestion

A reliable and sensitive method for determination simultaneously of monomethylmercury (MeHg) and monoethylmercury (EtHg) in various types of foods by gas chromatography inductively coupled plasma mass spectrometry (GC-ICP/MS) was developed and validated. Samples were digested with pancreatin and then hydrochloric acid. MeHg and EtHg in the extract were derivatized in an aqueous buffer with sodium tetraphenylborate. After phase separation, the extract was directly transferred to analysis. The analyses were conducted by GC-ICP/MS with monopropylmercury chloride (PrHgCl) as surrogate standard. Concentrations of 254±5.1, 13.7±0.69 and 162±6.2 μg Hg kg(-1) (one standard deviation, n=3) were obtained for MeHg in NIST SRM 1947 (Superior Lake fish), SRM 1566b (oyster tissue) and NRC Tort-2 (lobster Hepatopancreas), respectively. These are in good agreement with the certified values of 233±10, 13.2±0.7 and 152±13 μg Hg kg(-1) (as 95% confidence interval), respectively. The method detection limits (3σ) for MeHg and EtHg are 0.3 μg Hg kg(-1). The method detection limit was estimated by using a 0.5 g of subsample, sufficiently low for the risk assessment of MeHg and EtHg in foods. The spiked recoveries of MeHg and EtHg in different food matrices were between 87 and 117% and the RSDs were less than 15%. When isotopic dilution mass spectrometry (IDMS) analysis was performed with a commercial available (201)Hg-enriched monomethylmercury (Me(201)Hg) solution as internal standard, concentrations of 244±13.4, 13.9±0.25 and 161±1.3 μg Hg kg(-1) were obtained for MeHg in NIST SRM 1947, SRM 1566b and NRC Tort-2, respectively. It shown clearly that IDMS analysis got improvement in precision and accuracy, however, EtHg cannot be analyze simultaneously and the cost of analysis is higher.

Quantitative risk–benefit analysis of fish consumption for women of child-bearing age in Hong Kong

Maternal fish consumption is associated with both risks from methylmercury (MeHg) and beneficial effects from omega-3 fatty acids to the developing foetal brain. This paper assessed the dietary exposure to MeHg of women of child-bearing age (20–49 years) in Hong Kong, and conducted risk–benefit analysis in terms of the effects in children’s intelligent quotient (IQ) based on local data and the quantitative method derived by the expert consultation of FAO/WHO. Results showed that average and high consumers consume 450 and 1500 g of fish (including seafood) per week, respectively. About 11% of women of child-bearing age had a dietary exposure to MeHg exceeding the PTWI of 1.6 µg kg–1 bw. In pregnant women MeHg intake may pose health risks to the developing foetuses. For average consumers, eating any of the 19 types of the most commonly consumed fish and seafood during pregnancy would result in 0.79–5.7 IQ points gain by their children. For high consumers, if they only ate tuna during pregnancy, it would cause 2.3 IQ points reduction in their children. The results indicated that for pregnant women the benefit outweighed the risk associated with eating fish if they consume different varieties of fish in moderation.

Dietary exposures to eight metallic contaminants of the Hong Kong adult population from a total diet study

Dietary exposures to eight metallic contaminants, aluminium (Al), antimony (Sb), cadmium (Cd), lead (Pb), methylmercury (MeHg), nickel (Ni), tin (Sn) and vanadium (V), of the Hong Kong adult population were estimated using the total diet study (TDS) approach. The estimated mean exposures of Al (0.60 mg kg–1 bw week–1), Sb (0.016–0.039 µg kg–1 bw day–1), Cd (8.3 µg kg–1 bw month–1), Pb (0.21 µg kg–1 bw day–1), MeHg (0.74 µg kg–1 bw week–1), Ni (3.1 µg kg–1 bw day–1), Sn (0.029–0.031 mg kg–1 bw week–1) and V (0.13 µg kg–1 bw day–1) were well below the relevant health-based guidance values (HBGVs) where available. However, dietary exposures to MeHg of women aged 20–49 years (child-bearing age) accounted for 150% of the provisional tolerable weekly intake (PTWI) and to Al and Cd of some high consumers were found exceeding or approaching the HBGVs. The major food contributors of MeHg were fish and seafood (90%), of Al were non-alcoholic beverages including tea (33%), and of Cd were vegetables (36%). MeHg exposure during pregnancy was a public health concern in Hong Kong due to potential health risks to the foetus. Results suggest that there is a need to continue monitoring the exposures to metallic contaminants, especially Al, Cd and MeHg, of the Hong Kong population.

Total and inorganic arsenic in foods of the first Hong Kong total diet study.

Arsenic (As) is a metalloid that occurs in different inorganic and organic forms, which are found in the environment from both natural occurrence and anthropogenic activity. The inorganic forms of As (iAs) are more toxic as compared with the organic As, but so far most of the occurrence data in food collected in the framework of official food control are still reported as total As without differentiating the various As species. In this paper, total As and iAs contents of 600 total diet study (TDS) samples, subdivided into 15 different food groups, were quantified by high-resolution inductively coupled plasma mass spectrometry (HR-ICP/MS) and hydride generation (HG) ICP/MS respectively. The method detection limits for both total As and iAs were 3 μg As kg−1. As the samples were prepared for TDS, food items were purchased directly from the market or prepared as for normal consumption, i.e. table ready, in the manner most representative of and consistent with cultural habits in Hong Kong as far as practicable. The highest total As and iAs content were found in ‘fish, seafood and their products’ and ‘vegetables and their products’ respectively. Besides, this paper also presents the ratios of iAs and total As content in different ready-to-eat food items. The highest ratio of iAs to total As was found in ‘vegetables and their products’. It is likely that iAs in vegetables maintained its status even after cooking.

Dietary exposure of Hong Kong adults to fatty acid esters of 3-monochloropropane-1,2-diol

A total of 290 individual food samples were collected in Hong Kong, China, for 3-monochloropropane-1,2-diol (3-MCPD) fatty acid esters analysis. Most samples were processed food and in ready-to-eat form. The results show that the levels of 3-MCPD fatty acid esters were high in biscuits, fats and oils, snacks and Chinese pastry with mean bound 3-MCPD levels of 440, 390, 270 and 270 μg kg−1, respectively. The dietary exposures to bound 3-MCPD of average and high adult consumers were estimated to be 0.20 and 0.53 μg kg bw−1 day−1, respectively. The primary toxicological concern of 3-MCPD fatty acid esters is its potential to release 3-MCPD in vivo during digestion in the gastrointestinal tract. 3-MCPD would affect the kidney, the central nervous system and the male reproductive system of rats. Assuming that 100% of the 3-MCPD was released from 3-MCPD fatty acid esters by hydrolysis in the digestive system, the dietary exposures to 3-MCPD for average and high adult consumers were only 10% and 26% of the provisional maximum tolerable daily intake (PMTDI) of 3-MCPD established by the Joint Food and Agriculture Organization/World Health Organization Expert Committee on Food Additives (JECFA) (2 μg kg bw−1 day−1), respectively. The results suggest that both average and high adult consumers are unlikely to experience major toxicological effects of 3-MCPD.

Occurrence of bound 3-monochloropropan-1,2-diol content in commonly consumed foods in Hong Kong analysed by enzymatic hydrolysis and GC-MS detection.

The aim of this study was to determine the level of bound 3-monochloropropan-1,2-diol in foodstuffs commonly consumed in Hong Kong, China, by an enzymatic hydrolysis indirect method which proved to be free from interferences. A total of 290 samples were picked up randomly from the local market and analysed. About 73% of these samples were found to contain detectable amounts of bound 3-MCPD. Amongst the 73 food items, bound 3-MCPD was not detected in 13 food items, including extra virgin olive oil, beef ball/salami, beef flank, ham/Chinese ham, nuts, seeds, soy sauce, oyster sauce, butter, yoghurt, cream, cheese and milk. For those found to contain detectable bound 3-MCPD, the content ranged up to 2500 µg kg−1. The highest mean bound 3-MCPD content among the 14 food groups was in biscuits (440 [50–860] µg kg−1), followed by fats and oils (390 [n.d.–2500] µg kg−1), snacks (270 [9–1000] µg kg−1), and Chinese pastry (270 [n.d.–1200] µg kg−1). Among the samples, the highest bound 3-MCPD content was in a grape seed oil (2500 µg kg−1), followed by a walnut flaky pastry (1200 µg kg−1) and a grilled corn (1000 µg kg−1). Basically, the results of this study agreed well with other published results in peer-reviewed journals, except for cheese, cream, ham, nuts and seeds.