Environment International 73 (2014) 259–269

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Concentrations of phthalates and bisphenol A in Norwegian foods and beverages and estimated dietary exposure in adults Amrit K. Sakhi a,⁎, Inger Therese L. Lillegaard b, Stefan Voorspoels c, Monica H. Carlsen d, Elin B. Løken d, Anne L. Brantsæter a, Margaretha Haugen a, Helle M. Meltzer a, Cathrine Thomsen a a

Division of Environmental Medicine, Norwegian Institute of Public Health, P.O. Box 4404, Nydalen, 0403 Oslo, Norway Norwegian Scientific Committee for Food Safety, Oslo, Norway Flemish Institute for Technological Research (Vito NV), 2400 Mol, Belgium d Department of Nutrition, University of Oslo, 0317 Oslo, Norway b c

a r t i c l e

i n f o

Article history: Received 17 February 2014 Accepted 6 August 2014 Available online xxxx Keywords: Phthalate Bisphenol A Food Beverages Dietary exposure Norway

a b s t r a c t Phthalates and bisphenol A (BPA) are ubiquitous in our environment. These chemicals have been characterized as endocrine disruptors that can cause functional impairment of development and reproduction. Processed and packaged foods are among the major sources of human exposure to these chemicals. No previous report showing the levels of these chemicals in food items purchased in Norway is available. The aim of the present study was to determine the concentration of ten different phthalates and BPA in foods and beverages purchased on the Norwegian market and estimate the daily dietary exposure in the Norwegian adult population. Commonly consumed foods and beverages in Norway were purchased in a grocery store and analysed using gas- and liquid chromatography coupled with mass spectrometry. Daily dietary exposures to these chemicals in the Norwegian adult population were estimated using the latest National dietary survey, Norkost 3 (2010–2011). This study showed that phthalates and BPA are found in all foods and beverages that are common to consume in Norway. The detection frequency of phthalates in the food items varied from 11% for dicyclohexyl phthalate (DCHP) to 84% for di-isononyl phthalate (DiNP), one of the substitutes for bis(2-ethylhexyl) phthalate (DEHP). BPA was found in 54% of the food items analysed. Among the different phthalates, the highest concentrations were found for DEHP and DiNP in the food items. Estimated dietary exposures were also equally high and dominated by DEHP and DiNP (400–500 ng/kg body weight (bw)/day), followed by di-iso-butyl phthalate (DiBP), di-n-butyl phthalate (DnBP), di-n-octyl phthalate (DnOP) and di-iso-decyl phthalate (DiDP) (30–40 ng/kg bw/day). Dimethyl phthalate (DMP), diethylphthalate (DEP) and DCHP had the lowest concentrations and the exposures were around 10– 20 ng/kg bw/day. Estimated dietary exposure to BPA was 5 ng/kg bw/day. In general, levels of phthalates and BPA in foods and beverages from the Norwegian market are comparable to other countries worldwide. Grain and meat products were the major contributors of exposure to these chemicals in the Norwegian adult population. The estimated dietary exposures to these chemicals were considerably lower than their respective tolerable daily intake (TDI) values established by the European Food Safety Authority (EFSA). © 2014 Elsevier Ltd. All rights reserved.

1. Introduction Abbreviations: APCI, atmospheric pressure chemical ionization; bw, body weight; BBzP, butyl benzyl phthalate; BEH, bridged ethylsiloxane hybrid; BPA, bisphenol A; EFSA, European Food Safety Authority; EPA, Environmental Protection Agency; EU, European Union; DCHP, dicyclohexyl phthalate; DEHP, bis(2-ethylhexyl) phthalate; DEP, diethylphthalate; DiBP, di-iso-butyl phthalate; DiDP, di-iso-decyl phthalate; DiNP, di-isononyl phthalate; DMP, dimethyl phthalate; DnBP, di-n-butyl phthalate; DnOP, di-n-octyl phthalate; ESI, electrospray ionization; GC, gas chromatography; GPC, gel permeation chromatography; LB, lower bound; MB, middle bound; UB, upper bound; KBS, Kost Beregnings System i.e., diet calculation system; LOQs, limits of quantification; LC, liquid chromatography; MRM, multiple reaction monitoring; MS, mass spectrometry; NA, not applicable; ND, not detected; PVC, polyvinyl chloride; TDI, tolerable daily intake; UPLC, ultra performance liquid chromatography. ⁎ Corresponding author. Tel.: +47 21076320; fax: +47 21076686. E-mail address: [email protected] (A.K. Sakhi).

http://dx.doi.org/10.1016/j.envint.2014.08.005 0160-4120/© 2014 Elsevier Ltd. All rights reserved.

Phthalates and bisphenol A (BPA) are high volume industrial chemicals used in a wide variety of plastic products. Phthalates are esters of phthalic acid and are mainly used as plasticizers in numerous consumer products (Cao, 2010; Wormuth et al., 2006). The major use of phthalates is to impart flexibility and durability to plastics such as polyvinyl chloride (PVC) (Cao, 2010; Wormuth et al., 2006). Short side chained/low-molecular weight phthalates like dimethyl phthalate (DMP), diethyl phthalate (DEP), di-iso-butyl phthalate (DiBP) and din-butyl phthalate (DnBP) are mainly used in personal care products, certain dietary supplements, medications, printing inks, lacquers and adhesives (Aurela et al., 1999; Cao, 2010; Wormuth et al., 2006). Long side chained/high-molecular weight phthalates like butyl benzyl

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phthalate (BBzP), bis(2-ethylhexyl) phthalate (DEHP), di-iso-nonyl phthalate (DiNP) and di-iso-decyl phthalate (DiDP) are mainly found in flexible PVC used in consumer products like food packaging, floorings, home furnishings, other building materials and medical equipment (Cao, 2010; Wormuth et al., 2006). BPA is an industrial chemical used mainly in the production of polycarbonate plastics and epoxy resins that are used as protective coating inside food cans (Koch and Calafat, 2009). Polycarbonate is a transparent, hard plastic mainly used in the manufacture of water- and infant feeding bottles. BPA-derived products are also used in thermal papers and as composites and sealants in dentistry (Koch and Calafat, 2009). Neither phthalates nor BPA are chemically bound to the products and can thus leach, migrate or evaporate into indoor air and dust, the atmosphere or foods (Koch and Calafat, 2009). Because of widespread use of these chemicals, human exposure is unavoidable. Biomonitoring studies reveal that both phthalates and BPA are found in more than 95% of urine samples worldwide (Koch and Calafat, 2009). BPA and phthalates have been identified as endocrine disruptors and are categorized as chemicals of concern, among others, by the United States Environmental Protection Agency (EPA). Epidemiological and animal studies have shown that exposure to these chemicals may cause functional impairment of development and reproduction (Bergman et al., 2013; Lyche et al., 2009; Martino-Andrade and Chahoud, 2010; Meeker, 2012), and also increase the risk of allergy/asthma (Bertelsen et al., 2013; Hoppin et al., 2004, 2013). Due to their reproductive and developmental toxicity in animal studies, phthalates like DnBP, BBzP and DEHP have been banned in toys in the European Union (EU) since 2007. BPA has been prohibited in the manufacture of infant feeding bottles in EU since 2011. Additionally, the European Food Safety Authority (EFSA) has specified tolerable daily intakes (TDIs) for these restricted chemicals. The TDIs for DnBP, BBzP and DEHP specified by EFSA are 10, 500 and 50 μg/kg body weight (bw)/day, respectively (Anon, 2006, 2013; EFSA, 2005a,b,c). A new TDI for BPA of 5 μg/kg bw/day was proposed by EFSA in a draft scientific opinion published for public consultation 17 January 2014 (Anon, 2014). For the phthalates, DiNP and DiDP, a group TDI of 150 μg/kg bw/day has been specified by EFSA (EFSA, 2005d,e). Diet is one of the major sources of human exposure to BPA and certain phthalates like DnBP, DEHP, DiNP and DiDP (Cao, 2010; Wormuth et al., 2006). For short side chained phthalates like DMP, DEP and DnBP, use of personal care products, air and dust ingestion also contribute significantly to human body burdens (Wormuth et al., 2006). Foodstuffs are likely to get contaminated with these chemicals during processing, packaging/storage and transport. Data on concentrations of BPA and phthalates in foodstuffs are limited. This may be related to methodological challenges in the chemical analysis, e.g. to maintain low procedural contamination from the laboratory during analysis because of the ubiquitous presence of these chemicals. Large variations in the concentration and occurrence profiles of these chemicals within food categories and among different geographical locations are observed. For instance, DMP has frequently been found in foods in China but not in European countries (Guo et al., 2012). Moreover, the occurrences of different phthalates also change over time, and the restricted phthalates like DEHP are gradually being replaced by substitutes like DiNP and DiDP. For exposure estimations it is thus, quite important to use recent data from the particular country for which the exposure estimates are to be calculated. To our knowledge, there is neither new nor old data available showing the levels of phthalates and BPA in Norwegian food items. The aim of the present study was to analyse common Norwegian foods and beverages for phthalates and BPA and estimate dietary exposure to these chemicals in the Norwegian adult population using the latest national dietary survey (Myhre et al., 2013; Totland et al., 2012).

2. Materials and methods 2.1. Samples Thirty seven different food items and beverages, grouped into appropriate food categories, were included in the study as shown in Table 1. The selection of food items and beverages was based on two criteria: (i) basic food items that are commonly consumed in a typical Norwegian diet (Johansson et al., 1997; Meltzer et al., 2008), (ii) foods and beverages that are likely to contain these chemicals (e.g. canned dinners and canned mackerel fillet in tomato sauce to assess possible BPA contamination; soft drinks both in plastic bottles and cans to assess both BPA and phthalate contamination) (Casajuana and Lacorte, 2003; Liao and Kannan, 2013). For most of the food items and beverages, the three most sold brands were purchased and a composite sample (pool) was made as shown in Table 1. The selection of the three most sold brands for a particular food item was based on the sales statistics of that food item (personal communication). All the food items and beverages were purchased in a regular grocery store in Oslo in April 2012 and stored in a refrigerator or a freezer according to specifications written on the label until analysed. The analyses were done at the Flemish Institute for Technological Research (VITO NV, Belgium). In order to avoid any contamination from the environment, the pooling of the samples was performed at the laboratory responsible for the analysis. The samples were shipped in their original packaging within 6 days after their purchase to the analysis laboratory (VITO). The phthalate analyses were finished by July 2012 and BPA analysis by September 2012. 2.2. Chemicals DMP, DEP, DiBP, DiDP, DiNP, DnBP, BBzP, DEHP, dicyclohexyl phthalate (DCHP), di-n-octyl phthalate (DnOP) and BPA were supplied by Sigma-Aldrich (Bornem, Belgium). Dichloromethane, isopropanol, acetone, n-hexane and sodium sulphate were bought from Merck (Overijse, Belgium). Deuterium labelled phthalate compounds (d4-DMP, d4-DEP, d4-DiBP, d4-DnBP, d4-BBzP, d4-DEHP, d4-DnOP and d16-BPA) were bought from Sigma-Aldrich (Bornem, Belgium). 2.3. Standards and blanks Both standards and internal standards were prepared as described elsewhere (Fierens et al., 2012). In brief, stock solutions of native phthalate compounds were prepared both in dichloromethane (1 μg/mL; for analytes analysed by gas chromatography (GC), i.e. DMP, DEP, DiBP, DnBP, BBzP, DEHP, DCHP and DnOP) and iso-propanol (0.85 μg/mL; for analytes analysed by liquid chromatography (LC), i.e. DiNP, DiDP and BPA). Calibration solutions (0.05, 0.1, 0.5 and 1.15 μg/mL) were prepared by serial dilutions of stock solutions in dichloromethane. Standard solutions of internal standards (deuterium labelled standards) were prepared in dichloromethane at the concentration of 16 μg/mL. The calibration curves were prepared by spiking 1 mL of every standard with 25 μL of the internal standard solution. In order to maintain lowest possible blank concentrations, a strict protocol was made and followed during the sample preparation and analysis (Fierens et al., 2012). According to the protocol described in Fierens et al. (2012), all the glassware used in the analysis was heated at 450 °C for at least 4 h and covered with aluminium foil prior to use. Furthermore, all glassware, syringes and spatula were rinsed carefully with dichloromethane prior to use and no laboratory gloves were used during sample preparation. Dedicated rooms and instruments for phthalate analysis were used. 2.4. Sample preparation and analysis Out of 10 ten phthalates measured, eight (DMP, DEP, DiBP, DnBP, BBzP, DEHP, DCHP and DnOP) were prepared and determined as

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Table 1 Overview of the analysed food items, number of brands per food item, fat percent and the type of packaging. Food category

Number of brands for each food item that is pooled to one sample

Grain and grain products 1 Bread 2 Pasta (dry) 3 Buns 4 Breakfast cereals 5 Flour

3 3 3 3 2

Milk and dairy products 6 Milk 7 Hard cheese 8 Cheese spreads 9 Norwegian brown cheese

3 3 2 3

Meat and meat products 10 Minced meat 11 Chicken fillet 12 Sausages 13 Hamburgers 14 Sliced salami 15 Liver paté 16 Sliced ham 17 Sliced turkey

2 2 3 2 3 3 1 1

13 1 21 11 35 18 4 1.5

Fish and fish products 18 Fish balls 19 Fish pudding 20 Mackerel fillet in tomato sauce 21 Caviar spread, cod roe 22 Frozen fish

3 3 3 2 2

0.6–2 2.3 23 20 10–13

Fats 23 24

Margarine Butter

3 2

80 82

Fruits and vegetables 25 Jam 26 Frozen vegetables

2 2

0.5 0.2–0.5

Glass with metal or plastic screw cap Plastic

3 2

9 4.5–4.7

Plastic Canned

1 3

20–26 10–20

Plastic Plastic

Beverages 31 Soft drinks 32 Soft drinks 33 Bottled water 34 Juice

3 3 2 3

0 0 0 0

Condiments 35 Mayonnaise 36 Crushed tomatoes

2 3

80 0–1

Others 37 Whole egg

1

10

Ready to eat 27 Frozen pizza 28 Canned dinners Snacks 29 Chocolate spreads 30 Biscuits

described in Fierens et al. (2012). In brief, the samples were divided into three groups: high fat (fat content N 5% on a fresh weight basis), low fat (fat content b 5% on a fresh weight basis) and beverages. For both high and low-fat samples, the samples were homogenized by shaking, stirring or cutting into pieces. The samples with high amount of water were chemically dried with sodium sulphate, extracted with acetone/ n-hexane (1:1; v:v) and centrifuged. The supernatant was evaporated, reconstituted in dichloromethane and injected into a GC coupled to mass spectrometry (MS) (Fierens et al., 2012). For high fat and some low-fat samples, an extra fat removing purification step was performed by gel permeation chromatography (GPC) as described in Fierens et al. (2012). The extract was further evaporated to approximately 1 mL prior to injection into the GC–MS (Fierens et al., 2012). To determine the two phthalates DiNP and DiDP, 5 g of the sample was weighed and 10 ng of internal standards was added. The samples were extracted with a solution of acetone/n-hexane (1:1; v:v). After

% Fat

Packaging 1.5 2 8 2.5–15 2

1.5–3.5 28 28 29

Plastic and paper bag Plastic Plastic Plastic and paper Paper

Cardboard box Plastic Plastic and metal foil Plastic

Plastic Plastic Plastic Plastic Plastic Plastic and metal foil Plastic Plastic

Canned Plastic and paper Canned Metal tube Plastic

Plastic and metal/aluminium foil Plastic and metal/aluminium foil

Plastic Canned Plastic Cardboard box with plastic cap and metal foil

Plastic Canned

Cardboard box

shaking for 30 min, the mixture was centrifuged and the supernatant was collected. The residue was re-extracted with n-hexane (1:1; v:v), shaken for 30 min, centrifuged and the collected supernatant was combined with the previous one. The total supernatant was evaporated to dryness, reconstituted in acetonitrile and 10 μL injected into a LC-MS/ MS system. The phthalates (DiNP and DiDP) were separated on an Acquity ultra performance liquid chromatography (UPLC) bridged ethylsiloxane hybrid (BEH) Phenyl column (2.1 × 100 mm, 1.7 μm particle size) using a gradient between mobile phase A (0.1% formic acid in water) and mobile phase B (0.1% formic acid in methanol). The gradient elution programme was: 0–0.5 min: 50% B; 0.5–0.75 min: 50–75% B; 0.75–2 min: 75% B; 2–4 min: 100% B; 4–4.1 min: 100–50% B (return to initial conditions); and 4.1–6 min: equilibration of the column. The phthalates were detected and quantified using atmospheric pressure chemical ionization (APCI)–MS/MS. Identification of DiNP and DiDP was based on retention times and their specific multiple reaction

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monitoring (MRM) transitions. Retention time and MRM transitions for DiNP were 2.92 min, 419 → 127 (quantifier), 419 → 275 (qualifier), respectively. Retention time and MRM transitions for DiDP were 3.00 min, 447 → 177 (quantifier), 447 → 289 (qualifier), respectively. Since labelled internal standards were not available for these two phthalates, quantification was based on the standard addition approach (Miller and Miller, 2005). For BPA, the extraction was performed as described by Yoshida et al. (2001) with some modifications. To 5 g of the solid sample (both high and low-fat content), 25 mL of acetonitrile, 5 g of sodium sulphate and 100 ng of internal standard (d16-BPA) were added. The mixture was filtered and the residue rinsed with another 25 mL of acetonitrile. The filtrate was evaporated to 20 mL of acetonitrile and 20 mL of n-hexane was added. Phase separation was induced and the acetonitrile phase was collected. The n-hexane phase was re-extracted with 20 mL of acetonitrile. All the acetonitrile phases were combined, added 10 mL of isopropanol, evaporated to dryness and reconstituted in 10 mL acetone/ heptane (2.5:97.5; v:v). To remove fats, the extract was purified by using a Florisil column conditioned with 10 mL of acetone/heptane (5:95; v:v). The extract was applied to the conditioned column and BPA was eluted with 20 mL of acetone/heptane (20:80; v:v). The extract was evaporated to dryness and reconstituted in 1 mL of methanol/water (50:50; v:v). For beverages, 100 ng of internal standard (d16-BPA) was added to an aliquot of 300 mL of the sample. The sample was liquid–liquid extracted with 50 mL of dichloromethane. The dichloromethane phase was collected, evaporated to dryness and reconstituted in 1 mL methanol/water (50:50; v:v). The liquid–liquid extractions gave poor results for milk and juice and these matrices were treated as solid samples after thickening the samples in an oven at 70 °C. The dry matter content was used to convert the concentration from μg/kg product to μg/L. BPA was determined using UPLC–MS-MS in electrospray ionization (ESI) negative mode. Fifty microliters of the extract was injected into an Acquity UPLC BEH C 18 column (100 mm × 2.1 mm, 1.7 μm particle size) and BPA was separated from other compounds using a gradient between mobile phase A (2 mM ammonium acetate in water) and mobile phase B (acetonitrile). The gradient elution programme was: 0.–0.5 min: 20% B; 0.5–8 min: 20–95% B; 8–10 min: 95% B; 10– 10.10 min 95–20% B (return to initial conditions); and 10.10–12 min: equilibration of the column. The column temperature was held at 40 °C and the retention time for BPA under the described conditions was 4.63 min. The identification of BPA was based on retention times and the specific MRM transitions. MRM transitions for BPA and its internal standard (d16-BPA) were 227 → 212 (quantifier), 227 → 133 (qualifier) and 241 → 142, respectively. 2.5. Method performance characteristics Procedural blanks and reference samples were analysed along with the food samples in each analytical series. The composition of the procedural blanks was dependent upon the sample matrix (beverages, lowfat and high-fat food samples). For beverages, dichloromethane (30 mL) with 400 ng of each of the internal standards was brought into a separating funnel and extracted as described for beverages in Fierens et al. (2012). For high-fat food samples, dichloromethane (2 mL) containing 400 ng of each of the internal standards was treated through GPC and the extract was evaporated to approximately 1 mL prior to injection (Fierens et al., 2012). For low-fat food samples, 40 mL of acetone/n-hexane (1:1; v:v) was exchanged and evaporated to 1 mL of dichloromethane (Fierens et al., 2012). Limits of quantification (LOQs) were calculated based on the phthalate concentrations detected in the various procedural blanks for each type of sample preparation (beverages, high-fat and low-fat food samples). The LOQ for high-fat samples was calculated as the average blank concentration plus 6 times the standard deviation of replicate procedural blank measurements (Fierens et al., 2012). For low-fat samples and beverages, limited number of procedural blanks (b 3) were available and thus the

LOQs were calculated as two times the average blank concentrations. For DiNP, DiDP and BPA, LOQ was based on the signal-to-noise ratio in the chromatogram of real samples. The LOQs of phthalates and BPA are shown in Table S1 of Supplemental material. Recovery and intralaboratory reproducibility was determined on the basis of replicate determinations of the reference samples. The reference samples used were also defined according to the sample matrix (beverages, low-fat and high-fat food samples) (Fierens et al., 2012). For beverages, phthalates were added to tap water in a concentration of 0.25 μg/L. For high-fat food samples, sunflower oil was fortified with phthalates in a concentration of 250 μg/kg. Sunflower oil without addition of phthalates was also analysed. For low-fat food samples, the phthalates were added to one of the selected products in a concentration of 15 μg/kg fresh weight. The samples were prepared and analysed as described in Section 2.4. For BPA, the recovery was determined by fortifying 5 different food samples (bread, sliced salami, hard cheese, caviar and sliced turkey) at a concentration of 1 μg/kg fresh weight. Each food sample was prepared and analysed (as described in Section 2.4) in duplicate and on two different days. The recoveries and intralaboratory reproducibilities of phthalates and BPA are shown in Table S1 of the Supplementary material. 2.6. National dietary survey Norkost 3 A nationally representative sample (n = 5000) of the Norwegian population aged 18–70 years was selected from the National register and invited to participate in the Norkost 3 survey in 2010–2011 (Myhre et al., 2013; Totland et al., 2012). In total, the survey included 1787 participants (862 men and 925 women) resulting in a participation rate of 37%. The food consumption was assessed by two telephone-administered 24-hour recalls approximately four weeks apart. The first recall also included self-reported height and weight. Details of all food brands were not systematically collected in Norkost 3 study. Thus, in order to calculate representative dietary exposure to these chemicals, we bought up to three most sold brands and pooled them together as one sample as shown in Table 1. The survey was conducted by the Department of Nutrition, University of Oslo in collaboration with the Directorate of Health and the Norwegian Food Safety Authority (Myhre et al., 2013; Totland et al., 2012). 2.7. Statistical methods IBM SPSS version 20 was used for the statistical analyses. Mann– Whitney U test was used to compare the median concentrations of short-chained phthalates (sum of DMP, DEP, DiBP and DnBP), longchained phthalates (sum of BBzP, DCHP, DEHP, DnOP, DiNP and DiDP) and BPA in different packaging materials. The test was done twotailed and the p-value b 0.05 was considered significant. The plastic food packaging may be one of the sources of phthalate contamination in foods and beverages (Cirillo et al., 2011). Thus, phthalate concentrations in food items packed in plastic were compared to other packaging materials (metal, paper, cardboard and glass). For BPA, the epoxy lining in the metal containers may be one of the sources of its contamination in food items (Liao and Kannan, 2013; Noonan et al., 2011). Thus, BPA concentration in food items packed in metal were compared to other packaging materials (plastic, paper, cardboard and glass). The exposure to BPA and ten different phthalates was calculated in three different scenarios where the concentrations below LOQ were treated differently; i.e. by using LOQ, ½ LOQ and 0 μg/kg referred to as upper, middle and lower bound, respectively. The dietary exposures to phthalates and BPA were estimated from the 24 hour recalls using the diet calculation system Kost Beregnings System (KBS) version 7.0 (Rimestad et al., 2000). The exposure was calculated for each participant by multiplying the amount of different food items consumed with the respective phthalate and BPA concentrations in the food items. In order to use KBS for calculating the exposure to

Table 2 Concentrations of the phthalates and BPA in 37 food items. Values in bold and italics show median concentrations in different food categories [median lower bound (minimum, maximum)]. Values were given in μg/kg fresh weight. Values less than the LOQ are written as “bspecific LOQ value”. DMP

DEP

DiBP

DnBP

BBzP

DEHP

DCHP

DnOP

DiNP

DiDP

BPA

12/37

7/37

25/37

23/37

11/37

24/37

4/37

19/37

31/37

14/37

20/37

Grain and grain products

0.26 (ND, 2.8) 1.2 b0.10 2.8 b1.0 0.26 ND

ND (ND, 2.1) b1.5 b1.5 2.1 b1.0 b1.5 ND (ND, 9.3) b1.5 b3.0 b3.0 9.3 ND

3.0 (1.3, 16) 2.8 1.3 5.1 16 3.0 ND (ND, 31) b0.50 b5.0 b5.0 31 0.55 (ND, 5.8) 2.9 b0.50 5.2 b2.0 5.8 b5.0 b12 1.1 0.78 (ND, 12) 0.78 3.0 12 b5.0 b1.5 ND

0.82 (ND, 3.5)

b1.5 b1.5 1.75 (1.7, 1.8) 1.7 1.8 ND

b0.50 b0.50 4.1 (2.7, 5.4) 2.7 5.4 6.9 (6.2, 7.7) 7.7 6.2 0.18 (0.060, 0.88) 0.059 0.28 0.079 0.88 1.5 (0.79, 2.2) 2.2 0.79 b1.0

b12 b12 0.46 (ND, 0.92) 0.92 b0.50 3. 6 (2.9, 4.2) 2.9 4.2 3.6 (ND, 7.1) 7.1 b5.0 0.41 (0.34, 0.95) 0.35 0.95 0.34 0.46 0.60 (ND, 1.2) b12 1.2 b2.0

7.1 (ND, 734) 74 7.1 734 3.9 b1.0 49 (6.8, 166) 17 81 166 6.8 47 (3.0, 275) 41 4.0 275 52 153 16 3.0 76 38 (2.0, 55) 6.5 38 55 2.0 54 7.5 (ND, 15) b8.0 15 3.5 (2.9, 4.0) 4.0 2.9 70 (45, 94) 45 94 225 (88, 362) 362 88 ND (ND, 3.2) 3.2 b0.80 b0.80 b0.80 12 (9.4, 14) 14 9.4 b1.0

0.11(ND, 0.24)

b4.0 b4.0 ND

1.3 (ND, 3.3) 1.3 b0.50 1.9 b1.0 3.3 3.9 (ND, 24) b0.50 1.5 24 6.3 ND (ND, 29) 19 b0.50 b3.0 b1.5 29 18 b8.0 b0.50 ND (ND, 14) b0.50 b0.50 14 b3.0 12 14 (ND, 27) 27 b8.0 ND

6.2 (ND, 11) 6.2 b0.90 11 6.4 b0.90 ND

b8.0 b8.0 ND

43 (ND, 60) 46 18 61 43 b10 126 (19, 173) 19 173 128 124 ND (ND, 117) 64 b10 b25 b15 117 b25 b70 15 ND (ND, 35) b10 b10 35 b25 10 221 (118, 323) 323 118 4.8 (ND, 9.5) 9.5 b10 136 (37, 235) 37 235 66 (56, 76) 56 76 0.66 (0.17, 0.74) 0.67 0.74 0.17 0.65 17 (ND, 33) b70 33 b15

ND (ND, 5.2) b0.50 b0.50 5.2 b3.0 3.6 ND

b1.5 b1.5 b3.0 b3.0 b1.0 ND

6.9 (1.0, 24) 6.9 1.0 9.8 24 4.7 3.1 (ND, 5.4) b0.50 3.3 3.0 5.4 0.47 (ND, 12) 12 b0.50 b1.5 2.7 4.2 b1.5 b4.0 0.93 0.72 (ND, 3.2) 0.52 0.72 3.2 1.7 b0.50 ND

Bread Pasta (dry) Buns Breakfast cereals Flour Milk and dairy products Milk Hard cheese Cheese spreads Norwegian brown cheese Meat and meat products Minced meat Chicken fillet Sausages Hamburgers Sliced salami Liver paté Sliced ham Sliced turkey Fish and fish products Fish balls Fish pudding Mackerel fillet in tomato sauce (canned) Caviar spread, cod roe Frozen fish packed in plastic Fats Margarine Butter Fruits and vegetables Jam Frozen vegetables packed in plastic Ready to eat Frozen pizza Canned dinners Snacks

b0.10 b3.0 b3.0 b3.0 ND (ND, 20) b1.5 b0.10 18 b1.5 20 b3.0 b8.0 b0.10 ND (ND, 0.53) 0.41 0.53 b3.0 b3.0 b1.0 ND b8.0 b8.0 2.6 (0.30, 4.9) 4.9 0.30 1.6

b1.5 b1.5 b3.0 b1.5 b3.5 b3.0 b8.0 b1.5 ND

b3.0 b3.0 0.040 (ND, 0.070) 0.067 0.051 0.037 b0.025 ND

Mayonnaise Canned tomatoes Whole egg

b8.0 b0.10 b1.5

b8.0 b1.5 b1.5

Chocolate spreads Biscuits Beverages

ND = not detected.

ND b0.50 b7.5 b7.5 b7.5 ND (ND, 78) 78 1.6 b7.5 b4.0 Interference 11 b20 b0.5 ND (ND, 32) b0.50 b0.50 b7.5 32 4.0 ND b20 b20 ND b0.50 b0.50 2.9 (ND, 5.7) b2.5 5.7 ND b7.5 b7.5 ND (ND, 0.19) b0.030 b0.030 b0.030 0.19 ND b20 b0.50 b4.0

b0.50 b10 b10 b10 ND b5.0 b0.50 b10 b5.0 b10 b10 b25 b0.50 ND (ND, 30) b0.50 b0.50 b10 30 b3.0 ND b25 b25 ND b0.50 b0.50 ND b3.0 b3.0 ND b10 b10 ND (ND, 0.070) b0.040 b0.040 b0.040 0.073 ND b25 b0.50 b5.0

b0.50 b0.50 4.2 (3.1, 5.2) 5.2 3.1 6.8 (5.7, 7.9) 7.9 5.7 0.040 (ND, 0.12) 0.024 0.059 b0.020 0.12 8.8 (ND, 18) 18 b0.50 b1.5

b0.90 b5.0 b5.0 b5.0 ND (ND, 13) b2.0 b0.90 6.8 13 b5.0 b2.0 b0.90 b0.90 1.7 (ND, 3.7) 1.7 3.7 b5.0 b2.0 2.6 ND b6.0 b6.0 1.8 (ND, 3.6) 3.6 b0.60 5.1 (5.0, 5.1) 5.1 5.0 9.9 (9.7, 10) 9.7 10 ND b0.60 b0.60 b0.60 b0.60 0.43 (ND, 0.86) b6.0 0.86 b1.3

0.24 b0.10 0.19 b0.10 0.11 ND (ND, 0.72) b0.02 0.72 b0.10 b0.10 0.24 (ND, 3.2) 0.19 b0.10 2.1 0.17 0.29 3.2 b0.10 0.88 1.2 (ND, 7.3) 7.3 1.3 1.2 0.42 b0.10 ND b0.10 b0.10 0.19 (ND, 0.38) 0.38 b0.10 5.8 (2.9, 8.7) 2.9 8.7 ND b0.10 b0.10 ND (ND, 0.37) b0.020 0.37 b0.020 b0.020 2.7 (ND, 5.4) b0.10 5.4 1.2

263

Soft drinks (plastic bottle) Soft drinks (cans) Bottled water Juice Condiments

1.6 1.6 0.75 (ND, 1.5) 1.5 b3.0 ND (ND, 0.060) b0.025 b0.025 b0.025 0.060 ND

1.3 0.82 b2.5 b2.5 3.5

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Food category Quantitation frequency (all products)

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these chemicals, the analysed concentrations from the 37 food items were assigned to the reported food items and also to similar food items. For instance, the pooled bread sample consisted of three different bread types, and these three bread types were assigned the pooled bread concentration. Additionally, all the other types of breads were

(a)

also assigned the pooled bread concentration. In cases where the analysed food item was also an ingredient, the total exposure included concentrations calculated from recipes where the ingredient is present e.g. amount of milk in white sauce or amount of minced meat in lasagne. Furthermore, for the food items in the KBS database that did not have any concentration data, the most similar alternative of the food items analysed was chosen. For instance, the values for milk are also used for yoghurt since type of packaging and fat content were similar. The 37 pooled food items were assigned to approximately 35% of the food codes used in Norkost 3, and these food codes accounted for around 70–80% of the energy and total food intake (weight based) in the Norkost 3 study. Although, the major contributing food items have been assigned phthalate and BPA concentrations, there are some food items with missing values. For instance, wine and beer were not analysed in the present study and none of the analysed beverages were similar to them. Thus, wine and beer were given no values.

3. Results

(b)

(c)

Fig. 1. (a) Concentration of short-chained phthalates (sum of DMP, DEP, DiBP and DnBP) in food items packed in plastic compared to other packaging materials, (b) concentration of long-chained phthalates (sum of BBzP, DCHP, DEHP, DnOP, DiNP and DiDP) in food items packed in plastic compared to other packaging materials, and (c) concentration of BPA in food items in metal containers compared to other packaging materials.

The concentrations of 10 different phthalates and BPA in 37 food items bought from the Norwegian market are shown in Table 2. Five phthalates (DiBP, DnBP, DEHP, DnOP and DiNP) and BPA were found in concentrations above the LOQ in more than 50% of the samples. DiNP, one of the substitutes of the restricted phthalate DEHP, was detected in 31 out of 37 (84%) of the food items followed by DEHP in 24 out of 37 (65%) food items. The highest phthalate concentrations in most of the food items were also measured for these two compounds. The least detected phthalates were DCHP and DEP with concentrations above the LOQ in only 11% and 19% of the samples, respectively. The food items with the highest concentrations of total phthalates were buns, chocolate spreads, margarine, canned dinners, sliced salami, cheese spreads, sausages and hard cheese. Among the food categories, grain and grain products and ready to eat dinners had the highest number of phthalates with median concentration above the LOQ. For BPA, the food items with the highest concentrations were canned dinners, fish balls and canned tomatoes. Plastic food packaging may be one of the sources of phthalate contamination in foods and beverages (Cirillo et al., 2011). Fig. 1(a) shows that the concentration of short-chained phthalates (sum of DMP, DEP, DiBP and DnBP) in food items packed in plastic was not significantly different (Mann–Whitney U test, p-value for MB = 0.075) than other packaging materials (paper, cardboard, metal and glass). Fig. 1(b) shows that the concentration of longchained phthalates (sum of BBzP, DCHP, DEHP, DnOP, DiNP and DiDP) in food items packed in plastic was significantly higher (Mann–Whitney U test, p-value for MB = 0.024) than other packaging materials (paper, cardboard, metal and glass). The epoxy lining in the metal containers may be one of the sources of BPA contamination in food items (Liao and Kannan, 2013; Noonan et al., 2011). Fig. 1(c) shows that the concentration of BPA in foods and beverages in metal containers was significantly higher (Mann–Whitney U test, p-value for MB = 0.002) compared to other packaging materials (plastic, paper, cardboard and glass). Estimated daily dietary exposure is based upon the information on food consumption frequency and the measured concentrations of the contaminants in the food. Estimated exposures to phthalates and BPA in the Norwegian adult population are shown in Table 3. Mean, median, minimum, maximum and 95th percentiles are shown for the three different scenarios (lower, middle and upper bounds). Estimated daily dietary exposure to DEHP and DiNP was almost equal (mean MB 416 and 486 ng/bw/day) and was followed by DiBP, DnBP and DiDP. Estimated daily dietary exposure to BPA was 10–100 times lower than phthalates and was 4.6 ng/bw/day (mean MB).

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Table 3 Estimated daily dietary exposure to 10 different phthalates and BPA in the Norwegian adult population and current TDIs of phthalates and BPA. All values are given in ng/kg bw/day. Chemicals

Scenario

Mean

Median

Minimum

Maximum

95th percentile

TDI

DMP

LB MB UB LB MB UB LB MB UB LB MB UB LB MB UB LB MB UB LB MB UB LB MB UB LB MB UB LB MB UB LB MB UB

8.58 12.5 16.6 2.38 12.1 21.8 34.5 37.1 39.6 26.4 32.1 37.8 30.0 40.8 51.4 396 416 436 1.75 16.8 31.9 23.8 27.2 30.5 477 486 494 23.5 35.0 46.4 4.26 4.59 4.93

5.84 9.94 14.0 1.51 11.2 20.3 30.6 33.1 35.7 24.0 29.6 35.2 5.81 18.4 30.8 366 384 406 0.556 15.5 29.4 18.9 22.1 25.6 392 402 412 21.3 32.7 43.8 3.08 3.40 3.73

5.49 × 10−2 1.48 2.33 0.00 2.31 3.73 3.29 4.46 5.54 3.23 5.89 8.39 0.00 2.41 3.62 36.6 51.4 59.1 0.00 1.72 3.45 0.435 1.89 2.84 13.6 27.2 32.7 0.00 6.79 11.7 0.00 0.34 0.46

81.6 91.5 102 33.2 46.5 73.3 183 185 187 101 107 118 1.04 1.05 1.06 1.29 1.29 1.29 26.2 62.3 109 276 277 279 3.77 3.78 3.79 157 174 190 47.8 48.3 48.7

26.8 30.6 35.1 7.11 22.0 39.5 71.1 73.8 77.3 52.0 59.3 67.8 150 160 173 751 780 809 7.47 31.2 58.6 59.8 63.3 66.8 1.08 × 103 1.09 × 103 1.10 × 103 47.6 62.6 79.5 11.4 11.7 12.0

NA

DEP

DiBP

DnBP

BBzP

DEHP

DCHP

DnOP

DiNP

DiDP

BPA

× × × × × ×

103 103 103 103 103 103

× 103 × 103 × 103

NA

10 × 03

10 × 103

500 × 103

50 × 103

NA

NA

150 × 103a

5 × 103

LB = values below the LOQ are replaced by 0. MB = values below the LOQ are replaced by LOQ/2. UB = values below the LOQ are replaced by LOQ. NA = not applicable. a Group TDI.

Table 4 shows the four major food groups that contribute to more than 50% of the exposure to phthalates and BPA in the Norwegian adult population. Among the food groups, bread was the most important contributor to the exposure to different phthalates, except for BBzP and DnOP. For BBzP, meat and meat products alone contributed 68% to the dietary exposure. Other food groups with significant impact on phthalate exposure were milk, cheese and biscuits. For BPA, the major contributors to the estimated dietary exposure were grain and meat products and beverages.

4 . Discussion 4.1 . Concentration of phthalates and BPA in food items Our study is the first to investigate the occurrence of phthalates and BPA in foods and beverages bought from the Norwegian market. Additionally, we present comprehensive data on the occurrence of the DEHP replacements DiNP and DiDP in food items. Our main findings were that phthalates and BPA were present in most of the food items that constitute an important part of the average Norwegian

Table 4 Top four food groups contributing to more than 50% of the dietary exposure to phthalates and BPA in the Norwegian adult population. First

Second

Third

Fourth

% contribution of top four

DMP DEP DiBP

Meat and meat products (37%) Milk and milk products (25%) Bread (42%)

Fats and oils (10%) Meat and meat products (11%) Meat and meat products (14%)

Fruits and berries (7%) Cheese (11%) Cakes and biscuits (5%)

75 61 81

DnBP

Beverages (21%)

Bread (21%) Bread (14%) Grain and grain products other than bread (20%) Bread (19%)

Cheese (11%)

68

BBzP DEHP DCHP DnOP

Meat and meat products (68%) Bread (24%) Meat and meat products (23%) Meat and meat products (36%)

Fats and oils (8%) Milk and milk products (19%) Fats and oils (23%) Fats and oils (21%)

Grain and grain products other than bread (17%) Bread (7%) Cheese (17%) Cheese (12%) Bread (11%)

87 76 67 76

DiNP DiDP

Bread (34%) Bread (40%)

Cakes and biscuits (20%) Beverages (15%)

Meat and meat products (16%) Meat and meat products (12%)

BPA

Grain and grain products other than bread (23%)

Meat and meat products (14%)

Beverages (14%)

Cheese (4%) Fats and oils (16%) Cakes and biscuits (9%) Grain and grain products other than bread (8%) Milk and milk products (14%) Grain and grain products other than bread (10%) Bread (11%)

84 77 62

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diet. DEHP and one of its substitutes, DiNP were the two chemicals found at the highest concentrations in most of the food items. As a consequence, estimated dietary exposures were also highest for

these two phthalates in the Norwegian adult population. For BPA, the estimated dietary exposure was 10–100 times lower than for the phthalates.

Table 5 Concentration of phthalates (median) and BPA (mean) in different food categories worldwide. All the values are given as μg/kg fresh weight. Food categories

Country, food sampling year

DEHP

DnBP

DiBP

DnOP

DiNP

BPA

Grain and grain products including bread

Norway, 2012a United States, 2011b Belgium, 2009–2010c United Kingdom, 2008d China, 2011e EFSA, canned, 2006–2012 EFSA, non-canned, 2006–2012 Norway, 2012a United States, 2011b Belgium, 2009–2010c United Kingdom, 2008d China, 2011e EFSA, canned, 2006–2012 EFSA, non-canned, 2006–2012 Norway, 2012a United States, 2011b Belgium, 2009–2010c United Kingdom, 2008d China, 2011e EFSA, canned, 2006–2012 EFSA, non-canned, 2006–2012 Norway, 2012a United States, 2011b Belgium, 2009–2010c United Kingdom, 2008d China, 2011e EFSA, canned, 2006–2012 EFSA, non-canned, 2006–2012 Norway, 2012a United States, 2011b Belgium, 2009–2010c United Kingdom, 2008d China, 2011e EFSA, canned, 2006–2012 EFSA, non-canned, 2006–2012 Norway, 2012a United States, 2011b Belgium, 2009–2010c United Kingdom, 2008d China, 2011e EFSA, canned, 2006–2012+ EFSA, non-canned, 2006–2012+ Norway, 2012a United States, 2011b Belgium, 2009–2010c United Kingdom, 2008d China, 2011e EFSA, canned, 2006–2012 EFSA, non-canned, 2006–2012 Norway, 2012a United States, 2011b Belgium, 2009–2010c United Kingdom, 2008d China, 2011e EFSA, canned, 2006–2012+ EFSA, non-canned, 2006–2012+ Norway, 2012a United States, 2011b Belgium, 2009–2010c United Kingdom, 2008d China, 2011e EFSA, canned, 2006–2012 EFSA, non-canned, 2006–2012 Norway, 2012a United States, 2011b Belgium, 2009–2010c United Kingdom, 2008d China, 2011e EFSA, canned, 2006–2012 EFSA, non–canned, 2006–2012

43 51 63 ND 9.2 NA NA 126 71 28 78 77 NA NA ND 7 45 ND 90 NA NA nd 40 86 ND 96 NA NA 221 49 102 ND 62 NA NA 4.8 ND ND NA NA NA NA 136 NA 16 NA NA NA NA 0.66 ND 0.1 NA 0.8 NA NA 66 NA 35 42 86 NA NA 17 21 44 NA 0.14 NA NA

3 5.1 4.6 ND 7.2 NA NA ND 3.0 2 ND 27 NA NA 0.55 ND 1.5 ND 6.8 NA NA 0.78 ND ND ND 4.4 NA NA ND ND ND ND 6.2 NA NA 0.46 ND 1.7 NA NA NA NA 3.6 NA 3.4 NA NA NA NA 0.41 ND 0.1 NA 0.41 NA NA 3.6 NA 3.2 ND 58 NA NA 0.6 1.3 2.8 NA 9.5 NA NA

6.9 1.6 8.7 ND 6.2 NA NA 3.1 0.47 2.4 ND 34 NA NA 0.47 ND 2 ND 9.9 NA NA 0.72 ND ND ND 9.6 NA NA ND 0.25 ND ND 4.7 NA NA ND 0.48 1 NA NA NA NA 4.1 NA 3.3 NA NA NA NA 0.18 ND 0.1 NA 0.56 NA NA 6.9 NA 4.3 ND 56 NA NA 1.5 0.81 ND NA 5.1 NA NA

1.3 ND ND ND ND NA NA 3.9 0.63 ND ND ND NA NA ND ND ND ND 2.4 NA NA ND ND ND ND ND NA NA 14 ND ND ND 1.3 NA NA ND ND ND NA NA NA NA 4.2 NA ND NA NA NA NA 0.04 ND ND NA ND NA NA 6.8 NA ND ND ND NA NA 8.8 ND ND NA ND NA NA

7.1 NA NA ND NA NA NA 49 NA NA ND NA NA NA 47 NA NA ND NA NA NA 38 NA NA ND NA NA NA 7.5 NA NA ND NA NA NA 3.5 NA NA NA NA NA NA 70 NA NA NA NA NA NA ND NA NA NA NA NA NA 225 NA NA ND NA NA NA 12 NA NA NA NA NA NA

0.11 NA NA NA NA 37 0.8 0.18 NA NA NA NA 4.4 0.2 0.85 NA NA NA NA 28 9.4 2.0 NA NA NA NA 35 7.4 0.05 NA NA NA NA NA 0.3 0.19 NA NA NA NA 18 0.7 5.8 NA NA NA NA 35 2.3 0.09 NA NA NA NA 0.98 0.28 0.05 NA NA NA NA 52 0.1 2.7 NA NA NA NA 41 0.2

Milk and dairy products

Meat and meat products

Fish and fish products

Fats

Fruits and vegetables

Ready to eat (frozen pizza and canned dinners)

Beverages

Snacks

Condiments

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267

Table 6 Estimated dietary exposures to phthalates (median) and BPA (mean) in adult populations worldwide (country, year of dietary survey). All values are given in ng/kg bw/day. Chemicals

Present study (Norway, 2010–2011)a

Schecter et al. (2013) (United States, 2003–2006)a

Sioen et al. (2012) (Belgium, 2004)a

Guo et al. (2012) (China, 2006)b

Fromme et al. (2007) (Germany, 2005)a

EFSA report (Anon, 2013) (2006–2012)a only adults

DMP DEP DiBP DnBP BBzP DEHP DCHP DnOP DiNP DiDP BPA

10 11 33 30 18 384 16 22 402 33 3

3 7 8 34 16 416 2 17 NA NA NA

14 46 174 85 55 1.59 × 103 19 15 NA NA NA

17 14 245 243 10 620 NA NA NA NA NA

110 130 570 260 230 2.43 × 103 110 NA * NA NA

NA NA NA NA NA NA NA NA NA NA 29–59

NA = not applicable. * = not estimated. a MB. b LB.

A comprehensive review by Cao (2010) presented concentrations of phthalates in different food items worldwide. Their study clearly showed that there is a large variation in phthalate concentrations among different countries, even within similar food groups. In the past years, the use of phthalates like DnBP, BBzP and DEHP in consumer products has been restricted and some are replaced by substitutes. This substitution may affect the pattern of phthalates measured in different consumer products and hence also in food. Although the detection frequencies are dependent on the LOQ used in the respective studies, comparisons with other countries can still be informative. The detection frequencies and patterns of the different phthalates in our study were comparable with what was observed in a Belgian study (Fierens et al., 2012) and in a study from United States (Schecter et al., 2013), except for DEHP. In our study, DEHP was detected in 65% of the samples in contrast to the above mentioned studies where the detection rates were 74–81%. None of these studies determined the substitutes of DEHP, namely DiNP and DiDP. We observed a higher detection rate for DiNP (84%) confirming that there is a shift in use of phthalates from the restricted compounds to their substitutes. The detection patterns of phthalates in Chinese food samples (Guo et al., 2012) were slightly different from our study. The food samples in China had higher detection rates of low-molecular weight phthalates like DMP (82%), DEP and BBzP (both N 60%) and lower detection rates for DnOP (b 16%). However, our study and other studies in Europe had detection rates below 50% for DMP and DEP in the food samples. The median concentrations of different phthalates in the Norwegian food items were in general comparable to concentrations in other studies as shown in Table 5. However, the maximum levels of phthalates in our study were 10– 500 times lower than maximum values in the Belgian study (Fierens et al., 2012). The major differences were observed in food categories containing meat and fish. Median values of DEHP both in meat and

fish products from Norway were below the LOQ compared to 45 and 86 μg/kg fresh weight in the Belgian study (Fierens et al., 2012). For both these products, the DiNP concentrations in the present study were comparable to the DEHP concentrations in the other studies (Fierens et al., 2012; Guo et al., 2011; Schecter et al., 2013). DEHP in ready to eat dinners was 10 times higher in our study compared to the Belgian study (Fierens et al., 2012), which may be due to differences in food items included in this food category. Food can be contaminated with these chemicals from the packaging material during storage and/or during processing (Cirillo et al., 2011; Tsumura et al., 2001). The present study also showed that food packed in plastic containers contained significantly higher concentration of long-chained phthalates compared to other types of packaging materials like glass and cardboard. This is expected since the long-chained phthalates are mainly used in food packaging (Cao, 2010; Wormuth et al., 2006). Differences in phthalate concentrations observed between studies, in general, may be due to differences in materials used for food packaging, differences in analytical methods and choice of food samples. EFSA recently issued a comprehensive report on the concentration of BPA in food items in Europe, assessing canned and non-canned foods separately. The difference between canned and non-canned foods varied from 3 to 500 times for the different food categories as shown in Table 5. The higher levels of BPA in canned foods are probably due to leakage from the protective epoxy lining in the storage containers (Liao and Kannan, 2013; Noonan et al., 2011). In the present study, food packed in cans contained eight times higher concentration of BPA compared to other types of packaging materials like plastic, glass and cardboard. Similar results were reported in other studies (Geens et al., 2010; Liao and Kannan, 2013). Nonetheless, BPA concentrations in the canned food bought in Norway were much lower than observed in other

Notes to Table 5: + Mean of individual food items were taken to be included in the particular food category NA = not applicable. ND = not detected. a Present study. b Schecter et al. (2013). Data for milk and other dairy products were given separately in Schecter et al. (2013) and median of these two was taken to be presented under food category “milk and other dairy products” in the above table. c Fierens et al. (2012). d Bradley et al., Food Service Agency report (Bradley, 2012). In the Food Services Agency report (Bradley, 2012), phthalate concentrations in individual food items under each food category were reported. Median of individual food items under each food category was taken and presented in the table above apart from two food categories. The food category “miscellaneous cereal products” in the report include 26 food items (Bradley, 2012). Twelve food items from this reported food category were included under the food category “grain and grain products” and the remaining fourteen food items under the food category “snacks” for the above table. Details of food items included in these two food categories are shown in Table S2 of Supplementary material. e Guo et al. (2012). The food category “cereals or soy” (Guo et al., 2012) had 5 food items and the median of 3 cereal food items (rice, flour and instant noodles) was taken to be presented under food category “grain and grain products” in the above table. The food categories “milk and milk products”, “meat and meat products” and “beverages” had sub-categories (Guo et al., 2012). The median of these sub-categories for each food category was taken and presented in the above table. The concentration of phthalates in “cookies and cakes” (Guo et al., 2012) was presented under food category “snacks” in the above table.

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European countries and in general comparable or lower than the concentrations of non-canned food in the EFSA report. One of the reasons could be the strong focus in media of potential adverse health effects of BPA resulting in local manufacturers deliberately shifting to BPAfree cans and food packaging.

For both phthalates and BPA, the food items with highest concentrations of these chemicals were not always among the major contributors to their exposure showing that for exposure estimations both food consumption and food concentration play an important role. 4.3. Strengths and limitations

4.2. Estimated daily dietary exposure to phthalates and BPA in the Norwegian adult population The variation in the concentrations of phthalates and BPA in different food categories increases the importance of using country specific data for dietary exposure calculations. Variations are also observed between similar food groups and might be due to the different origin and/or difference in production methods between brands. The food items selected in our study covered about 70–80% of energy and food intake (weight based) in the Norkost 3 study, indicating that our selection of food items was representative for a typical Norwegian diet. Estimated daily dietary exposures to phthalates in our study were comparable with other studies worldwide except from a German study (Fromme et al., 2007) where the intakes were estimated to be 10 times higher (Table 6). In contrast to the present study, DiNP was detected in only 1% of the food samples analysed in the German study (Fromme et al., 2007), and no exposure estimate was made. One of the possible reasons could be the 100 times higher LOD for DiNP in the German study (Fromme et al., 2007) as compared to the present study, that will decrease the detection rates of DiNP in their food samples and hence affect the exposure calculations. The DEHP exposure was 4 times lower in the present study compared to the relatively new Belgian study (Fierens et al., 2012). However, the present study shows an equally high exposure to one of the substitutes of DEHP, DiNP. The total exposure to DEHP and both of its substitutes DiNP and DiDP was around 0.8 μg/kg bw/day which is comparable to the Belgian study (Fierens et al., 2012). Another difference between the present and the Belgian study (Fierens et al., 2012) was the dietary exposure to DiBP. In the present study, dietary exposures to DnBP and its substitute DiBP were equally high and were 2–5 times less than the Belgian study (Fierens et al., 2012). In the present study, bread, meat, grain and dairy (including cheese) products were among the major contributing food categories to the exposure to phthalates in the Norwegian adult population. Similar results have been observed by Sioen et al. (2012) and Schecter et al. (2013). Bread and other grain products are important in the Norwegian diet and are the food groups with the largest contribution to total energy intake, with bread contributing on average 19% and other grain products contributing 9% of all calories (Totland et al., 2012). Estimated dietary exposure to BPA in the Norwegian adult population was 10–20 times lower than in other European countries (Anon, 2013), which is in accordance with the low BPA concentrations measured in the food samples from Norway. Comparable exposures of 15 and 8 ng/kg bw/day from the canned foods have been reported in Belgium (Geens et al., 2010) and New Zealand (Thomson and Grounds, 2005), respectively. In the present study where both canned and non-canned foods were included, grain products including bread were the major contributors to the BPA exposure. This is in contrast to a study by Cao et al. (2011) where the canned foods contributed highest to the BPA exposure in the Canadian population and white bread contributed only to 0.6% of the total dietary exposure. One possible reason for this difference could be that the dietary estimates in the Canadian study were based on survey data from 1970 and that consumption patterns might have changed over the past 40 years. Another reason could be the actual differences in food intakes between different countries. The estimated dietary exposure to phthalates and BPA in the Norwegian adult population is far below the current tolerable daily intakes (TDI) of these chemicals (Table 2), also when considering the upper bound scenario and the 95th percentiles.

One of the strengths of this study is that both the food collection and the dietary survey were performed in the same time period making our dietary exposure estimates more accurate. Concentrations of phthalates and BPA were only assessed in 37 food items, which is deficient compared to the total number of food items available on the Norwegian market. This might lead to underestimation in dietary exposures to these chemicals. Since food items selected in the present study covered about 70–80% of energy and weight intake in the Norwegian population, this bias is probably minor. The participants in the Norkost dietary survey self-reported their weight and height. Since it has been shown earlier that weight is usually under reported (Dekkers et al., 2008), this may lead to an overestimation in the dietary exposure. This study has not considered the effect of food preparation on the dietary exposure to these chemicals. Sioen et al. (2012) found a slight decline in the estimated exposure to most of the phthalates after food preparation. 5. Conclusion This is the first study to present comprehensive data on 10 phthalates including the substitutes of DEHP, namely DiNP and DiDP, and BPA in foods and beverages sold in Norway, and to further estimate the daily dietary exposure in the adult population. Mean estimated dietary exposure to phthalates (DnBP, BBzP, DEHP, DiNP and DiDP) and BPA in the Norwegian adult population was considerably lower than their respective current TDI values established by EFSA. Equally high concentrations of DiNP and DEHP in foods and beverages indicate a shift in exposure from a restricted phthalate (DEHP) to one of its substitutes. Grain and meat products were the major contributors to the dietary exposure to phthalates in the Norwegian adult population. For BPA, grain and meat products and beverages were the most important contributors to the estimated dietary exposure. Acknowledgements This study was funded by a grant from the Norwegian Research Council (NFR project number: ES445160) and the Norwegian Food Safety Authority (2011/169237). Appendix A. Supplementary data Supplementary data to this article can be found online at http://dx. doi.org/10.1016/j.envint.2014.08.005. References Aurela B, Kulmala H, Soderhjelm L. Phthalates in paper and board packaging and their migration into Tenax and sugar. Food Addit Contam 1999;16(12):571–7. Bergman Å, Heindel JJ, Jobling S, Kidd KA, Zoeller RT. State of the science of endocrine disrupting chemicals 2012; 2013. Bertelsen RJ, Carlsen KC, Calafat AM, Hoppin JA, Haland G, Mowinckel P, et al. Urinary biomarkers for phthalates associated with asthma in Norwegian children. Environ Health Perspect 2013;121(2):251–6. Bradley EL. Determination of phthalates in foods and establishing methodology to distinguish their source; 2012 [FD 10/05]. Cao XL. Phthalate esters in foods: sources, occurrence, and analytical methods. Compr Rev Food Sci Food Saf 2010;9(1):21–43. Cao XL, Perez-Locas C, Dufresne G, Clement G, Popovic S, Beraldin F, et al. Concentrations of bisphenol A in the composite food samples from the 2008 Canadian total diet study in Quebec City and dietary intake estimates. Food Addit Contam Part A Chem Anal Control Expo Risk Assess 2011;28(6):791–8. Casajuana N, Lacorte S. Presence and release of phthalic esters and other endocrine disrupting compounds in drinking water. Chromatographia 2003;57(9–10):649–55.

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