Wing-Fung Sun

Residues of polychlorinated biphenyls (PCB) in fatty foods of the Canadian diet

Market basket samples representative of food from six Canadian cities were surveyed from 1992 to 1996. Fifty composites of fatty foods, prepared for consumption were analysed for 40 PCB congeners by gas chromatography-mass spectrometry. Fish and butter contained the highest total PCB concentrations, while milk and infant foods contained the lowest. The dairy and meat composites were major contributors to the total PCB intake of 5.7 ng/kg/day, and to the TEQ (2,3,7,8-tetrachloro-p-dibenzodioxin equivalent) intake of 0.11 pg/kg/day. The pattern of congeners was similar for the different food groups with the exception of fish, which contained less tri- and tetra-chlorinated biphenyls and more of the hexachlorinated congener No. 153.

Canadian Total Diet Study in 1998: Pesticide levels in foods from Whitehorse, Yukon, Canada, and corresponding dietary intake estimates

The Canadian Total Diet Study is a national survey to determine the level of chemical contaminants in the Canadian food supply. Food samples were collected from Whitehorse, Yukon, supermarkets as part of the study in 1998. Whitehorse was chosen as a sampling centre, despite its small population (n = 19 000), to determine if residue levels were different in foods available in northern communities relative to levels observed in previous studies in the more populated south. Foods were prepared as for consumption before pesticide residue analysis. Residue levels observed in most foods were similar to levels observed in samples from previous surveys from southern Canadian cities. Malathion and DDE (1,1-dichloro-2,2-bis(p-chlorophenyl)ethylene), a transformation product of DDT (1,1,1-trichloro-2,2-bis(p-chlorophenyl(ethane), were the two most frequently detected compounds (26.4 and 25.8%, respectively). The majority of pesticides, however, had a detection frequency of <5%. In general, pesticides in food composites were well below maximum residue limits established in the Canadian Food and Drug Regulations. Chlorpropham and captan had the highest dietary intakes (2.16 and 1.94 µg (kg body weight-day)−1, respectively), based on the results from Whitehorse. No dietary intakes above the acceptable daily intakes, however, were observed for any of the 39 pesticides investigated in any age–sex category, where an acceptable daily intake has been proposed.

Brominated flame retardant concentrations in sera from the Canadian Health Measures Survey (CHMS) from 2007 to 2009.

Pooling of surplus serum from individual samples, collected between 2007 and 2009 during Cycle 1 of the Canadian Health Measures Survey (CHMS), was performed to develop a national baseline estimate of brominated flame retardants in Canadians. Serum samples were categorized by sex and distributed by five age groups ranging from 6 to 79years. Nearly 5000 (4583) serum samples were used to form 59 composite pools. Serum pools were created to ensure a high detection frequency of these analytes in serum because low volume samples had previously resulted in non-detectable concentrations. The analytes of interest in these serum pools included 23 polybrominated diphenyl ethers (PBDEs) and three hexabromocyclododecane (HBCD) isomers (α-, β- and γ-HBCD). PBDEs were observed in all samples tested and total PBDE concentrations ranged from 27ngg(-1) lipid to 130ngg(-1) lipid (geometric mean [GM] 46ngg(-1) lipid). ∑PBDE concentrations were significantly elevated in samples representing the 6-11year old age group (GM 65ngg(-1) lipid) relative to ages above 40years, although no difference in concentration was observed between the sexes. PBDE concentrations in Canadian sera from the general population were higher than reported in Europe and Asia, but a little lower than observed in the US. PBDE 47 was the greatest contributor to ∑PBDE concentrations and the GM concentration for this congener was 22ngg(-1) lipid. The other dominant contributors to ∑PBDE concentrations were in descending order: 153 [GM 9.4ngg(-1) lipid]>99 [GM 4.6ngg(-1) lipid]≅100 [GM 4.1ngg(-1) lipid]>209 [GM 1.1ngg(-1) lipid] and 183 [GM 0.42ngg(-1) lipid]. ∑HBCD was detected in all samples analysed, although most samples were observed at concentrations <1ngg(-1) lipid, similar to global concentrations. α-HBCD was the dominant contributor to ∑HBCD concentrations in Canadians although β- and γ-HBCD were detected in 23% and 35% of the samples, respectively. No differences in ∑HBCD concentration were associated with age or sex. This dataset represents the first national data describing HBCD isomers and some PBDEs (e.g., 183, 209) in Canadians.

Captan residue reduction in apples as a result of rinsing and peeling

Apples, treated with captan for disease control in a commercial orchard in Quebec, Canada, were collected and sorted into post-harvest preparation types (no preparation; rinse; rinse and peel). Captan residues were greatest (25.5-5100ng/g) in apples with no post-harvest preparation and lowest (0.146-136ng/g) in apples that had been rinsed and peeled prior to extraction and analysis. Residues were significantly lower (p=0.003) in apples that had been rinsed prior to extraction than in apples with no post-harvest preparation. Similarly, apples subjected to rinsing and peeling had significantly lower captan residues than had apples that had been rinsed alone (p<0.0001). Although captan residues in rinsed apples were approximately 50% lower than those in apples that received no post-harvest preparation, the reduction associated with peeling of apples was much greater (98%). Estimated mean captan intakes resulting from consumption of raw apples were established and single day intakes, based on apples with no preparation, ranged from 2.58μg/kg in females >70 years to 9.48μg/kg for individuals aged three years (at this age no distinction is made between males and females). Mean intakes estimated using rinsed and peeled apples were approximately two orders of magnitude lower than intakes estimated using apples with no post-harvest preparation, demonstrating the effect of post-harvest preparation on captan intakes. Mean captan intake estimates from all post-harvest preparation types were well below the World Health Organization acceptable daily intake of 100μg/kg/day, based on raw apple consumption.

Pesticide residues in the Canadian Market Basket Survey 1992 to 1996

Market basket food samples from six Canadian cities collected from 1992 to 1996 were analysed for pesticide residues. One hundred and thirty-six composites were prepared for each city, representing 99% of the Canadian diet. Residues were found most frequently in peanut butter and butter. DDE, malathion and captan occurred most frequently, while the fungicides chlorothalonil, dicloran and captan were present in the highest concentrations. Processed commodities contained fewer residues and at lower concentrations than the raw products. No residues were detected in either milk or soy-based infant formula. Of the infant foods sampled, fruit contained both the greatest number and highest concentrations of pesticides.

PCDD/F and PCB concentrations in sera from the Canadian Health Measures Survey (CHMS) from 2007 to 2009

In order to establish a national baseline estimate of the concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs) in Canadians, pooling of individual human sera was performed to ensure that a high frequency of detectable concentrations of analytes would be achieved. Nearly 5000 (4583) sera samples from Cycle 1 of the Canadian Health Measures Survey (CHMS) collected between 2007 and 2009 were used to form 59 composite pools of approximately 25 mL each. Pools were categorized by sex and age with participants ranging from 6 to 79 years. The pooled samples were analysed for 17 PCDD/Fs and 36 PCB congeners, and from these data, total toxic equivalent concentrations (TEQ(2005 PCDD/F+Dioxin-like [DL]-PCB)) were estimated. The average 2,3,7,8 tetrachlorodibenzodioxin (TCDD) concentration was <1 pg g⁻¹ on a lipid extractable basis. The average total TEQ(2005 PCDD/F+DL-PCB) was 11 pg TEQ g⁻¹ lipid and average ΣPCB concentrations were about 100 ng g⁻¹ lipid. Sex did not affect the concentrations, while PCB and PCDD/F concentrations were positively correlated with age (p<0.001). It appeared in some cases that the age group 6-11 years had higher concentrations of these persistent organic pollutants (POPs) than the concentrations observed in 12-19 year olds, however, the results were not statistically significant based on pair-wise comparisons. Concentration levels and patterns observed in this study of Canadians were similar to those reported in the US and European populations.

Brominated flame retardants in Canadian chicken egg yolks

Chicken eggs categorised as conventional, omega-3 enriched, free range and organic were collected at grading stations in three regions of Canada between 2005 and 2006. Free run eggs, which were only available for collection from two regions, were also sampled during this time frame. Egg yolks from each of these egg types (n = 162) were analysed to determine brominated flame retardant levels, specifically polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD). PBDEs were detected in 100% of the 162 samples tested, while HBCD was observed in 85% of the egg yolks. Total PBDE concentrations in egg yolks ranged from 0.018 to 20.9 ng g−1 lipid (median = 3.03 ng g−1 lipid), with PBDE 209 identified as being the major contributor to ΣPBDE concentrations. In addition to PBDE 209, PBDE 99, 47, 100, 183 and 153 were important contributors to ΣPBDE concentrations. Total HBCD concentrations ranged from below the limit of detection to a maximum concentration of 71.9 ng g−1 lipid (median = 0.053 ng g−1 lipid). The α-isomer was the dominant contributor to ΣHBCD levels in Canadian egg yolks and was the most frequently detected HBCD isomer. ΣPBDE levels exhibited large differences in variability between combinations of region and type. ΣHBCD concentrations were not significantly different among regions, although differences were observed between the different types of egg yolks analysed in the present study.

Survey of organotin compounds in blended wines

An extraction method for butyltin, cyclohexyltin, octyltin and phenyltin compounds in wines was developed using 0.05% tropolone in 75% diethyl ether/pentane. Recoveries averaged 96.8% (range 78-121%). Methyl derivatives made by Grignard reaction were quantitated by gas chromatography (GC)-atomic absorption spectrometry (AAS). Twenty-nine of the 90 samples (32.2%) tested contained at least one of the analytes. Mono- and diocyltin were found in one sample only, at levels of 2.41 and 0.12 ng/ml respectively. Dibutyltin levels ranged from < 0.08 to 1.44 ng/ml. Monobutyl and tributyltin were found less frequently and at lower levels than dibutyltin. GC/mass spectrometric analysis confirmed the presence of butyl- and octyltins. No other organotin compounds were detected by either GC-AAS or GC-MS.

The impact of production type and region on polychlorinated biphenyl (PCB), polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/F) concentrations in Canadian chicken egg yolks

Chicken eggs from five different production types (conventional, omega-3 enriched, free range, organic and free run) were collected, when available, from three regions (west, central and east) of Canada to determine persistent organic pollutant (POP) concentrations. Total polychlorinated biphenyl (PCB) concentrations (∑37 congeners) in yolks from the eggs ranged from 0.162 ng g(-1) lipid to 24.8 ng g(-1) lipid (median 1.25 ng g(-1) lipid) while the concentration of the sum of the 6 indicator PCBs ranged from 0.100 ng g(-1) lipid to 9.33 ng g(-1) lipid (median 0.495 ng g(-1) lipid). Total polychlorinated dibenzo-p-dioxin/dibenzofuran (PCDD/F) concentrations ranged from 2.37 pg g(-1) lipid to 382 pg g(-1) lipid (median 9.53 pg g(-1) lipid). The 2005 WHO toxic equivalency (TEQ) ranged from 0.089 pg TEQ(PCDD/F+dioxin-like[DL]-PCB) g(-1) lipid to 12.8 pg TEQ(PCDD/F+DL-PCB) g(-1) lipid (median 0.342 pg TEQ(PCDD/F+DL-PCB) g(-1) lipid). PCB and PCDD/F concentrations were significantly different (p<0.001) in egg yolks from different regions of collection. In contrast to observations in Europe, PCB and PCDD/F concentrations in Canadian egg yolks were not impacted solely by the production type (e.g., conventional, free range, organic, etc.) used to maintain the laying chickens. Additionally, only one Canadian free range yolk from western Canada (12.8 pg TEQ(PCDD/F+DL-PCB) g(-1) lipid) exceeded the European toxic equivalent concentration limits for eggs (5 pg TEQ(PCDD/F+DL-PCB) g(-1) lipid). This differs from observations in Europe where free range/home produced eggs frequently have higher POP concentrations than eggs from other production types. Median PCB dietary intake estimates based on consumption of eggs were less than 10 ng d(-1) while median PCDD/F intakes were less than 45 pg d(-1).

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.