**3.4 Brominated flame retardants**

Brominated flame retardants (BFRs) are widely used in electronic household equipment, plastics, textile and polyurethane foam in furniture and cars for safety reasons. Of the brominated products, about one-third contain tetrabromobisphenol-A (TBBPA) and derivatives, another third contains various bromines, including hexabromocyclododecane (HBCD) and the last third contains polybrominated diphenylethers (PBDEs). All three types of BFRs are determined in this study. The PBDEs are commercial mixtures with different degrees of bromination and used as additives to fireproof polymers. HBCD is a cycloaliphatic brominated chemical introduced as a replacement for the PBDEs and with the same applications. TBBPA is mainly used as a reactive (chemically bound) flame retardant in epoxy polymers such as printed circuit boards in electronic equipment. The structure of BDE-209 (better known as deca-BDE), HBCD and TBBPA is shown below. In a study by the Dutch National Institute for Public Health and the Environment the levels of various PBDEs, HBCD and TBBPA in 84 food products were determined (de Winter-Sorkina et al., 2003, 2006). With the exception of fish products PBDEs were absent or present in low concentrations (<0.1 ng/g) in food products. For the fish products the concentrations of the congeners BDE-28, -47, -99, -100, -153 and -154 ranged from 0.1 to 14 ng/g. BDE-209 was found in none of the 84 products while TBBPA was found in 7 products in concentrations ranging from 0.1 to 3.4 ng/g. Surprisingly, HBCD was found in 28 of the 84 samples in concentrations ranging from 0.1 to 8.9 ng/g product. TBBPA and HBCD were predominantly found in fish products, especially in eel.

Industrial Contaminants and Pesticides in Food Products 77

Perfluorinated compounds (PFCs) are synthetic compounds characterised by an alkyl chain in which the hydrogen atoms are completely replaced by fluorine atoms. PFCs are heat stable, very resistant to degradation and environmental breakdown and have an amphiphilic nature (they repel water as well as oil). Because of these properties PFCs are used a myriad of applications, such as non-stick pans, stain and water repelling coatings for clothing, furniture and paper with typical brand names as Teflon, Gortex, Stainmaster and Scotchguard (3M-company, 1999). PFCs accumulate in the environment and they have been detected far from manufacturing plants in birds, marine plants and mammals from the Arctic to the Pacific and Indian Oceans and in land creatures in Europe and the USA (Kannan et al., 2002; Martin et al., 2003, 2004). In addition PFCs have been found in human blood (Kannan et al., 2004; Peters, 2005). The structures of the two most common PFCs,

 Many studies focus on biota such as fish and birds and only limited information about levels of PFCs in food seem to be available. In 2001 the Centre Analytical Laboratory performed a study for the 3M-company as part of a Multi-City Study. PFCs were found in a limited number of samples. PFOS was found in five samples, four whole milk samples and a ground beef sample in concentrations up to 0.85 ng/g. PFOA was found in seven samples, two ground beef samples, two bread samples, two apple samples and one green been sample in concentrations up to 2.35 ng/g (Centre Analytical Laboratory, 2001). The results for PFCs are given in table 3 at the end of this section. PFOS and PFOSA are found in only one of the five samples that were analysed. The concentrations found in the sample of pickled herring, are 1.3 ng/g for PFOS and 0.2 ng/g for PFOSA. PFOS is widely detected in the environment, animals and humans and therefore expected. Surprisingly, Schecter et al. did not find PFOS, but do find PFOA in 50% of the analysed samples in concentrations

Phthalates are one of the most ubiquitous classes of chemical contaminants in our everyday environment as a consequence of their high volume uses in open applications. They are used as plasticizers to increase the flexibility of high molecular weight polymers (mainly in PVC), as heat-transfer fluids and as carriers, and can be found in ink, paint, adhesives, pesticides, vinyl flooring (Vethaak et al., 2002), but also in cosmetics and personal care products. Consequently, the potential for human exposure is very high. Di-(2-ethylhexyl) phthalate (DEHP) and di-ethyl phthalate (DEP) are two of the most common used plasticizers. DEHP is nowadays gradually replaced by iso-alkyl phthalate mixtures like diisononyl phthalate (DINP). The chemical structure of DEP and DEHP is shown below.

**3.5 Perfluorinated compounds** 

PFOA and PFOS are given below.

ranging from 0.02 to 1.8 ng/g (Schecter et al., 2010).

**3.6 Phthalates** 

 A recent report on the results of a round robin exercise for BFRs in environmental, human and food samples gives some results for herring and salmon. The highest concentrations are found for BDE-47, up to 9.3 ng/g in herring and 0.89 ng/g in salmon. Those for the BDE-28, -99, -100, -153, -154 and -183 are in the range of 0.1 to 1.3 ng/g. BDE-209 and HBCD were not detected in these samples. The results for PBDEs in typical market basket studies show some differences, while studies in Spain (Bocio et al., 2003) and Japan (Ohta et al., 2002, 2008) show a predominance of the tetra- and penta-BDE with maximum concentrations up to 0.34 ng/g, an American study reports PBDE levels up to 3.1 ng/g product with surprisingly a predominance of BDE-209 which comprised as much as 50% of the total PBDE content in some of the samples (Schecter et al., 2004). The results for the BFRs in this study are reported in table 3 at the end of this section, and graphically in figure 3. PBDEs were found in 19 of the 24 samples. BDE-209, TBBPA and HBCD were found in none of the samples. BDE-47, -32 and -99 seem to be the predominant and the highest concentration for an individual PBDE was 0.65 ng/g found for BDE-47 in the sample of Scottish Cheese. Surprisingly, and different from other studies, only a limited number of BFRs were found in the fish products, in salmon no BFRs were found at all. The total PBDE concentrations ranged from 0.15 to 1.2 ng/g with the highest concentration in the sample of minced beef. The concentrations found in this study are therefore comparable with those found in the Spanish and Japanese study and much lower than those found in the American food study.

Fig. 3. Graphic presentation of the total-BFRs concentration in 24 food samples

#### **3.5 Perfluorinated compounds**

76 Pesticides in the Modern World - Risks and Benefits

 A recent report on the results of a round robin exercise for BFRs in environmental, human and food samples gives some results for herring and salmon. The highest concentrations are found for BDE-47, up to 9.3 ng/g in herring and 0.89 ng/g in salmon. Those for the BDE-28, -99, -100, -153, -154 and -183 are in the range of 0.1 to 1.3 ng/g. BDE-209 and HBCD were not detected in these samples. The results for PBDEs in typical market basket studies show some differences, while studies in Spain (Bocio et al., 2003) and Japan (Ohta et al., 2002, 2008) show a predominance of the tetra- and penta-BDE with maximum concentrations up to 0.34 ng/g, an American study reports PBDE levels up to 3.1 ng/g product with surprisingly a predominance of BDE-209 which comprised as much as 50% of the total PBDE content in some of the samples (Schecter et al., 2004). The results for the BFRs in this study are reported in table 3 at the end of this section, and graphically in figure 3. PBDEs were found in 19 of the 24 samples. BDE-209, TBBPA and HBCD were found in none of the samples. BDE-47, -32 and -99 seem to be the predominant and the highest concentration for an individual PBDE was 0.65 ng/g found for BDE-47 in the sample of Scottish Cheese. Surprisingly, and different from other studies, only a limited number of BFRs were found in the fish products, in salmon no BFRs were found at all. The total PBDE concentrations ranged from 0.15 to 1.2 ng/g with the highest concentration in the sample of minced beef. The concentrations found in this study are therefore comparable with those found in the Spanish and Japanese

study and much lower than those found in the American food study.

0.0

Butter

Cheese

Bacon

Sausages

Eggs

Milk

Olive oil

Chicken

Fish fingers

Fig. 3. Graphic presentation of the total-BFRs concentration in 24 food samples

Salmon

Honey

Tuna

Brown bread

Frankfurter sausages

Reindeer meat

Pickled herring

Minced beef

Pork chops

Cottage cheese

Salami

Cheese

Ham

Cheese

Scottish cheese

0.2

0.4

0.6

0.8

**total-BFR (ng/g)**

1.0

1.2

1.4

Perfluorinated compounds (PFCs) are synthetic compounds characterised by an alkyl chain in which the hydrogen atoms are completely replaced by fluorine atoms. PFCs are heat stable, very resistant to degradation and environmental breakdown and have an amphiphilic nature (they repel water as well as oil). Because of these properties PFCs are used a myriad of applications, such as non-stick pans, stain and water repelling coatings for clothing, furniture and paper with typical brand names as Teflon, Gortex, Stainmaster and Scotchguard (3M-company, 1999). PFCs accumulate in the environment and they have been detected far from manufacturing plants in birds, marine plants and mammals from the Arctic to the Pacific and Indian Oceans and in land creatures in Europe and the USA (Kannan et al., 2002; Martin et al., 2003, 2004). In addition PFCs have been found in human blood (Kannan et al., 2004; Peters, 2005). The structures of the two most common PFCs, PFOA and PFOS are given below.

 Many studies focus on biota such as fish and birds and only limited information about levels of PFCs in food seem to be available. In 2001 the Centre Analytical Laboratory performed a study for the 3M-company as part of a Multi-City Study. PFCs were found in a limited number of samples. PFOS was found in five samples, four whole milk samples and a ground beef sample in concentrations up to 0.85 ng/g. PFOA was found in seven samples, two ground beef samples, two bread samples, two apple samples and one green been sample in concentrations up to 2.35 ng/g (Centre Analytical Laboratory, 2001). The results for PFCs are given in table 3 at the end of this section. PFOS and PFOSA are found in only one of the five samples that were analysed. The concentrations found in the sample of pickled herring, are 1.3 ng/g for PFOS and 0.2 ng/g for PFOSA. PFOS is widely detected in the environment, animals and humans and therefore expected. Surprisingly, Schecter et al. did not find PFOS, but do find PFOA in 50% of the analysed samples in concentrations ranging from 0.02 to 1.8 ng/g (Schecter et al., 2010).

#### **3.6 Phthalates**

Phthalates are one of the most ubiquitous classes of chemical contaminants in our everyday environment as a consequence of their high volume uses in open applications. They are used as plasticizers to increase the flexibility of high molecular weight polymers (mainly in PVC), as heat-transfer fluids and as carriers, and can be found in ink, paint, adhesives, pesticides, vinyl flooring (Vethaak et al., 2002), but also in cosmetics and personal care products. Consequently, the potential for human exposure is very high. Di-(2-ethylhexyl) phthalate (DEHP) and di-ethyl phthalate (DEP) are two of the most common used plasticizers. DEHP is nowadays gradually replaced by iso-alkyl phthalate mixtures like diisononyl phthalate (DINP). The chemical structure of DEP and DEHP is shown below.

Industrial Contaminants and Pesticides in Food Products 79

Alkylphenols, but primarily alkylphenol ethoxylates are used as additives in plastics and as surface-active ingredients in industrial detergents and emulsifiers. The ethoxylates are produced by a condensation reaction of alkylphenols with ethylene oxide. Alkylphenols commonly used are nonylphenol (NP) and to a lesser extent octylphenol (OP), in both cases pre-dominantly the para-substituted isomers (>90%). Alkylphenols are the common products of bio- or chemical degradation of the ethoxylates. The chemical structure of n-NP

As with the phthalates only little information seems to be available about levels of alkylphenols in food. Guenther et al. determined NPs in 60 different commercially available foodstuffs and concluded that NPs are ubiquitous in food (Guenther et al., 2002). The concentrations of NPs (sum of the isomers) varied between 0.1 and 19.4 ng/g product and were found in all samples. Despite the lipophilic properties of NPs, high concentrations of NPs were not only found in fatty foods but also in non-fatty food products. In another study OP and NP were determined in composite foods (Fernandes et al., 2003). OP was found in only one sample in a concentration of 8.7 ng/g while NP was found in concentrations up to 25 ng/g. In a previous TNO study alkylphenols were determined in wrapped fresh meat and cheese products (Geenen, 2003). Since the alkylphenols were determined in slices of the product collected directly below the foil or wrapper, the results are not representative for the entire product. OP was detected in none of the samples while NPs were found in five of the eight sub-samples in concentrations ranging from 9 to 590 ng/g. For one sample the whole food item was analysed resulting in a much lower concentrations in the order of 1 ng/g for NP. The results for alkylphenols in this study are given in table 3 at the end of this section. NP was found in 2 of the 19 samples, the samples of butter and bacon in concentrations around 5 ng/g. OP was found in none of the samples. Although the concentrations are in the range of what Guenther found, the results are different because the frequency of detection in this study is far lower. Perhaps this is a result of the way sub-samples are collected since higher

In nature, musk is a compound produced by a gland in male deer which has been used in perfumes, but the increasing demand resulted in the production of artificial musk compounds. The most well-known are nitro musks like MX and MK that are nowadays replaced by polycyclic musks like AHTN and HHCB. Musks are used as additives for perfumes, in detergents and soaps, in body lotions and deodorizers. The structure of MK

concentration may be found in top-layers beneath the packaging foil.

**3.7 Alkylphenols** 

is shown below.

**3.8 Musk compounds** 

and HHCB is presented below.

 There is not much information about concentrations of phthalates in food. Most attention has been focused on phthalates in plastic wrapping materials for food products. An older study dating from 1994 deals with the determination of DEHP in milk, cream, butter and cheese (Sharman et al., 1994). DEHP was found in all these products in concentrations ranging from 330 to 980 ng/g. More recent information is available from the UK Food Standard Agency and is concerned with the presence of phthalates in infant formulae (Joint Food Safety and Standards Group, 1998). Seven phthalates including DEHP were determined in 39 samples of infant formulae. In 12 of the 39 samples none of the phthalates were found. In the remaining samples di-butyl phthalate (DBP), benzylbutyl phthalate (BBP) and DEHP were found. DEHP was the most abundant individual phthalate in concentrations ranging from 50 to 440 ng/g product. DBP was found in concentrations up to 90 ng/g and BBP up to 15 ng/g product. Concentrations of other phthalates were less than 10 ng/g. The results for phthalates in this study are presented in table 3 at the end of this section, and graphically in figure 4. 16 of the 19 samples analysed for phthalates did contain one or more of these compounds. In eggs, milk and orange juice no phthalates were detected. DIDP was the only phthalate that was not found in any of the samples. As expected DEHP is the predominant phthalate found in 16 of the 19 samples with concentrations ranging from 20 to 24,000 ng/g. It should be mentioned that the latter concentration is an exception and was found in the sample of olive oil. The neck of the olive oil bottle contains a polymer spout that may be responsible for the high DEHP concentration in the olive oil. Other phthalates that are frequently found (>50% of the samples) are DBP and BBP, be it in lower concentrations than DEHP.

Fig. 4. Graphic presentation of the sum of the eight phthalates in 19 food items

#### **3.7 Alkylphenols**

78 Pesticides in the Modern World - Risks and Benefits

 There is not much information about concentrations of phthalates in food. Most attention has been focused on phthalates in plastic wrapping materials for food products. An older study dating from 1994 deals with the determination of DEHP in milk, cream, butter and cheese (Sharman et al., 1994). DEHP was found in all these products in concentrations ranging from 330 to 980 ng/g. More recent information is available from the UK Food Standard Agency and is concerned with the presence of phthalates in infant formulae (Joint Food Safety and Standards Group, 1998). Seven phthalates including DEHP were determined in 39 samples of infant formulae. In 12 of the 39 samples none of the phthalates were found. In the remaining samples di-butyl phthalate (DBP), benzylbutyl phthalate (BBP) and DEHP were found. DEHP was the most abundant individual phthalate in concentrations ranging from 50 to 440 ng/g product. DBP was found in concentrations up to 90 ng/g and BBP up to 15 ng/g product. Concentrations of other phthalates were less than 10 ng/g. The results for phthalates in this study are presented in table 3 at the end of this section, and graphically in figure 4. 16 of the 19 samples analysed for phthalates did contain one or more of these compounds. In eggs, milk and orange juice no phthalates were detected. DIDP was the only phthalate that was not found in any of the samples. As expected DEHP is the predominant phthalate found in 16 of the 19 samples with concentrations ranging from 20 to 24,000 ng/g. It should be mentioned that the latter concentration is an exception and was found in the sample of olive oil. The neck of the olive oil bottle contains a polymer spout that may be responsible for the high DEHP concentration in the olive oil. Other phthalates that are frequently found (>50% of the samples)

are DBP and BBP, be it in lower concentrations than DEHP.

0

Butter

Cheese

Bacon

Sausages

Eggs

Milk

Olive oil

Chicken

Fig. 4. Graphic presentation of the sum of the eight phthalates in 19 food items

Orange juice

Frankfurter

sausages

Reindeer meat

Minced beef

Pork chops

Cottage cheese

Salami

Cheese

Ham

Cheese

Scottish cheese

1000

2000

3000

sum of phthalates (ng/g)

4000

5000

24000

Alkylphenols, but primarily alkylphenol ethoxylates are used as additives in plastics and as surface-active ingredients in industrial detergents and emulsifiers. The ethoxylates are produced by a condensation reaction of alkylphenols with ethylene oxide. Alkylphenols commonly used are nonylphenol (NP) and to a lesser extent octylphenol (OP), in both cases pre-dominantly the para-substituted isomers (>90%). Alkylphenols are the common products of bio- or chemical degradation of the ethoxylates. The chemical structure of n-NP is shown below.

As with the phthalates only little information seems to be available about levels of alkylphenols in food. Guenther et al. determined NPs in 60 different commercially available foodstuffs and concluded that NPs are ubiquitous in food (Guenther et al., 2002). The concentrations of NPs (sum of the isomers) varied between 0.1 and 19.4 ng/g product and were found in all samples. Despite the lipophilic properties of NPs, high concentrations of NPs were not only found in fatty foods but also in non-fatty food products. In another study OP and NP were determined in composite foods (Fernandes et al., 2003). OP was found in only one sample in a concentration of 8.7 ng/g while NP was found in concentrations up to 25 ng/g. In a previous TNO study alkylphenols were determined in wrapped fresh meat and cheese products (Geenen, 2003). Since the alkylphenols were determined in slices of the product collected directly below the foil or wrapper, the results are not representative for the entire product. OP was detected in none of the samples while NPs were found in five of the eight sub-samples in concentrations ranging from 9 to 590 ng/g. For one sample the whole food item was analysed resulting in a much lower concentrations in the order of 1 ng/g for NP. The results for alkylphenols in this study are given in table 3 at the end of this section. NP was found in 2 of the 19 samples, the samples of butter and bacon in concentrations around 5 ng/g. OP was found in none of the samples. Although the concentrations are in the range of what Guenther found, the results are different because the frequency of detection in this study is far lower. Perhaps this is a result of the way sub-samples are collected since higher concentration may be found in top-layers beneath the packaging foil.

#### **3.8 Musk compounds**

In nature, musk is a compound produced by a gland in male deer which has been used in perfumes, but the increasing demand resulted in the production of artificial musk compounds. The most well-known are nitro musks like MX and MK that are nowadays replaced by polycyclic musks like AHTN and HHCB. Musks are used as additives for perfumes, in detergents and soaps, in body lotions and deodorizers. The structure of MK and HHCB is presented below.

Industrial Contaminants and Pesticides in Food Products 81

butter

ng/g ng/g ng/g ng/g ng/g ng/g ng/g ng/g ng/g ng/g ng/g ng/g ng/g ng/g

eggs milk bacon sausages chicken breast

frankfurthers reindeer beef

cottage cheese

α-HCH 0.1 < < < < < < < < < < < < < β-HCH 0.1 < < < < < < < < < < < < < γ-HCH 0.1 < < < < < < < < < < < < < HCB 0.1 0.12 0.22 0.26 0.18 0.10 0.34 < < < 0.10 < 0.10 0.83 α-chlordane 0.1 < < < < < < < < < < < < < β-chlordane 0.1 < < < < < < < < < < < < < o,p'-DDE 0.1 < < < < < < < < < < < < < p,p'-DDE 0.1 0.18 0.48 1.6 0.43 1.3 0.79 < < < 0.25 < < < o,p'-DDD 0.1 < < < < < < < < < < < < < p,p'-DDD 0.1 < < < < < < < < < < < < < o,p'-DDT 0.1 < < < < < < < < < < < < < p,p'-DDT 0.1 < < < < < < < < < < < < <

PCB 18 0.1 0.13 0.15 0.22 0.16 0.24 0.25 < 0.12 0.19 0.16 0.20 0.26 0.14 PCB 28/31 0.1 0.31 0.22 0.37 0.36 0.49 0.56 0.16 0.36 0.32 0.35 0.40 0.44 0.26 PCB 22 0.1 < < 0.11 < 0.14 < < < < < < < < PCB 41/64 0.1 < < < < < 0.27 < < < < < < < PCB 44 0.1 < < < 0.18 < 0.27 < < 0.18 0.24 < 0.18 0.14 PCB 49 0.1 < < < < 0.14 0.18 < < 0.19 0.13 0.13 0.16 0.13 PCB 52 0.1 0.16 < < 0.15 0.29 0.40 < 0.21 0.21 0.16 0.17 0.27 0.15 PCB 54 0.1 < < < < < < < < < < < < < PCB 56/60 0.1 < < < < < < < < < < < < < PCB 70 0.1 < < < 0.12 0.16 0.20 < < 0.21 0.12 < 0.17 0.11 PCB 74 0.1 < < < < 0.14 0.22 < < 0.11 < < < 0.12 PCB 87 0.1 < < < < < < < < < < < < < PCB 90/101 0.1 < < < < < < < < < 0.11 < < < PCB 99 0.1 < < < < < 0.14 < < < < < < < PCB 104 0.1 < < < < < < < < < < < < < PCB 105 0.1 < < < < < < < < < < < < < PCB 110 0.1 < < < < < < < < < < < < < PCB 114 0.1 < < < < < < < < < < < < < PCB 118 0.1 < < < < < 0.23 < < < < < < < PCB 123 0.1 < < < < < < < < < < < < < PCB 138 0.1 < < < < < < < < < < < < < PCB 141 0.1 < < < < < < < < < < < < < PCB 149 0.1 < < < < < < < < < < < < < PCB 151 0.1 < < < < < < < < < < < < < PCB 153/168 0.1 < 0.22 0.31 0.16 < 0.29 < < < 0.12 < 0.14 0.11 PCB 156 0.1 < < < < < < < < < < < < < PCB 157 0.1 < < < < < < < < < < < < < PCB 158 0.1 < < 0.12 0.10 < < < < < < < < < PCB 167 0.1 < < < < < < < < < < < < < PCB 170 0.2 < < < < < < < < < < < < < PCB 177 0.2 < < < < < < < < < < < < < PCB 180 0.2 < < < < < < < < < < < < < PCB 183 0.2 < < < < < < < < < < < < < PCB 187 0.2 < < < < < < < < < < < < < PCB 188 0.2 < < < < < < < < < < < < < PCB 189 0.2 < < < < < < < < < < < < < PCB 194 0.2 < < < < < < < < < < < < < PCB 199 0.2 < < < < < < < < < < < < < PCB 203 0.2 < < < < < < < < < < < < < Table 2. Results for organochlorine pesticides and polychlorobipenyls expressed in ng/g

compound

**Organochlorine pesticides**

**Polychlorinated biphenyls** 

product.

limit of detection

cheese 1 cheese 2 cheese 3 scottisch cheese

As far as we know there are no reports or studies concerning the presence of artificial musks in food or food products. However, since 1981 it is known that artificial musks can be found in fish (Yamagishi et al., 1981, 1983; Rimkus & Wolf, 1995; Fromme et al., 2001; Gatermann et al., 2002), and as a results artificial musks may be present in fish products. The results for musks in this study are given in table 3 at the end of this section. The nitro-musks MK and MX are not found in the four fish products analysed for artificial musks. The polycyclic musks AHTN and HHCB are found in two of the samples, the samples tuna and pickled herring in a maximum concentration of 0.56 ng/g for the latter sample. As in other environmental matrices and human blood the HHCB concentrations are about twice that of the AHTN concentrations. That the concentrations are lower than those reported for fish in the literature is probably because most literature studies report results for fish in waterways connected to sewer effluents and not for typical marine fish species.

#### **3.9 Organotin compounds**

The main OTCs to be found in food are likely to be tri-substituted compounds, tributyltin (TBT) and triphenyltin (TPT), which have been used extensively as biocides in wood preservatives, in antifouling paints for boats and as pesticides. Mono- and di-substituted OTC's (dibutyltin, mono-n-octyltin and di-n-octyltin) are used as stabilizers in PVC plastics, and di-alkyltins have been approved as PVC stabilizers for food contact materials. OTC's tend to accumulate in fish and other aquatic organisms and tri-alkyltins are bio-degraded to di- and mono-alkyltin compounds and therefore these may be found also in addition to the tri-substituted OTCs. The structures of TBT and TPT are presented below.

 Based on an EU SCOOP report the European Food Safety Authority estimated that the median concentrations of TBT, DBT and TPT in fish and fishery products are 7.0, 2.5 and 4.0 ng/g product (EC, 2003; EFSA, 2004). The EU SCOOP report contains very few data on DOT, which were always below the limit of detection. The results for organotin in this study are given in table 3 at the end of this section. Organotin were found in three of the four samples that were analysed. The highest concentration of 9.0 ng/g was found for mono-butyl tin (MBT), a degradation product of TBT in the sample of tuna. Di-butyl tin (DBT) and TBT were also found in this sample. The pickled herring and the fish fingers contained butyl-tin as well as octyl-tin compounds.

#### **3.10 Result tables of the concentrations of determined parameters in 25 samples of food**

Tables 2 and 3 contain the full results of the study. Note that not all parameters are measured in all samples. In those cases the positions in the table are left blank. If concentrations of the parameters in a sample were below the detection limit, this is indicated with a "<" sign. The limits of detection for each parameter are printed directly after the compound name of the parameter. All results are expressed in ng/g product.

As far as we know there are no reports or studies concerning the presence of artificial musks in food or food products. However, since 1981 it is known that artificial musks can be found in fish (Yamagishi et al., 1981, 1983; Rimkus & Wolf, 1995; Fromme et al., 2001; Gatermann et al., 2002), and as a results artificial musks may be present in fish products. The results for musks in this study are given in table 3 at the end of this section. The nitro-musks MK and MX are not found in the four fish products analysed for artificial musks. The polycyclic musks AHTN and HHCB are found in two of the samples, the samples tuna and pickled herring in a maximum concentration of 0.56 ng/g for the latter sample. As in other environmental matrices and human blood the HHCB concentrations are about twice that of the AHTN concentrations. That the concentrations are lower than those reported for fish in the literature is probably because most literature studies report results for fish in waterways

The main OTCs to be found in food are likely to be tri-substituted compounds, tributyltin (TBT) and triphenyltin (TPT), which have been used extensively as biocides in wood preservatives, in antifouling paints for boats and as pesticides. Mono- and di-substituted OTC's (dibutyltin, mono-n-octyltin and di-n-octyltin) are used as stabilizers in PVC plastics, and di-alkyltins have been approved as PVC stabilizers for food contact materials. OTC's tend to accumulate in fish and other aquatic organisms and tri-alkyltins are bio-degraded to di- and mono-alkyltin compounds and therefore these may be found also in addition to the

 Based on an EU SCOOP report the European Food Safety Authority estimated that the median concentrations of TBT, DBT and TPT in fish and fishery products are 7.0, 2.5 and 4.0 ng/g product (EC, 2003; EFSA, 2004). The EU SCOOP report contains very few data on DOT, which were always below the limit of detection. The results for organotin in this study are given in table 3 at the end of this section. Organotin were found in three of the four samples that were analysed. The highest concentration of 9.0 ng/g was found for mono-butyl tin (MBT), a degradation product of TBT in the sample of tuna. Di-butyl tin (DBT) and TBT were also found in this sample. The pickled herring and the fish fingers

**3.10 Result tables of the concentrations of determined parameters in 25 samples of** 

compound name of the parameter. All results are expressed in ng/g product.

Tables 2 and 3 contain the full results of the study. Note that not all parameters are measured in all samples. In those cases the positions in the table are left blank. If concentrations of the parameters in a sample were below the detection limit, this is indicated with a "<" sign. The limits of detection for each parameter are printed directly after the

connected to sewer effluents and not for typical marine fish species.

tri-substituted OTCs. The structures of TBT and TPT are presented below.

contained butyl-tin as well as octyl-tin compounds.

**food** 

**3.9 Organotin compounds** 


Table 2. Results for organochlorine pesticides and polychlorobipenyls expressed in ng/g product.

Industrial Contaminants and Pesticides in Food Products 83

butter eggs milk bacon sausages chicken breast

ng/g ng/g ng/g ng/g ng/g ng/g ng/g ng/g ng/g ng/g ng/g ng/g ng/g ng/g

frankfurthers reindeer beef

cottage cheese

BDE-17 0.1 < < < < < < < < < < < < < BDE-28 0.1 < < < < < < < < < < < < < BDE-32 0.05 < 0.07 < 0.06 < < < < 0.06 < 0.08 0.06 0.06 BDE-35 0.05 < < < < < < < < < < < < < BDE-37 0.05 < < < < < < < < < < < < < BDE-47 0.05 0.75 0.3 0.43 0.82 0.29 < < < 0.27 0.41 0.26 0.33 0.26 BDE-49-71 0.05 < < < < < < < < < < < < < BDE-66 0.05 < < < < < < < < < < < < < BDE-75 0.05 < < < < < < < < < < < < < BDE-77 0.05 < < < < < < < < < < < < < BDE-85 0.05 < < < < < < < < < < < < < BDE-99 0.05 0.10 < < 0.15 < 0.15 < < < < < 0.05 0.06 BDE-100 0.05 < < < 0.12 < < < < < < < < < BDE-119 0.05 < < < < < < < < < < < < < BDE-126 0.05 < < < < < 0.21 < < < < < < < BDE-138 0.05 < < < < < < < < < < < < < BDE-153 0.05 < < < < < < < < < < < < < BDE-154 0.05 < < < < < < < < < < < < < BDE-156 0.05 < < < < < < < < < < < < < BDE-166 0.05 < < < < < < < < < < < < < BDE-181 0.05 < < < < < < < < < < < < < BDE-183 0.05 < < < < < < < < < < < < < BDE-184 0.05 < < < < < < < < < < < < < BDE-190 0.1 < < < < < < < < < < < < < BDE-191 0.1 < < < < < < < < < < < < < BDE-196 0.2 < < < < < < < < < < < < < BDE-197 0.2 < < < < < < < < < < < < < BDE-206 1 < < < < < < < < < < < < < BDE-207 1 < < < < < < < < < < < < < BDE-209 5 < < < < < < < < < < < < <

DMP 1 < < < < < < < < < < 4.9 < < DEP 1 < < < < < 5.6 < < < < 24 < < DIBP 10 < < 4400 < 1500 < < < < < 2300 < < DBP 10 < 76 190 200 780 132 < < < < 760 < < BBP 1 21 32 50 9.9 25 17 < < 2 < 11 < < DEHP 20 910 3000 210 130 890 770 < < 1320 640 670 20 210 DINP 20 31 26 59 < 660 < < < < < 390 < < DIDP 20 < < < < < < < < < < < < <

NP 2 < < < < < 5.1 < < 5.5 < < < < OP 2 < < < < < < < < < < < < <

Table 3. Results for brominated flame retardants, perfluorinated chemicals, phthalates, alkylphenols, artificial musks and organotin compounds expressed in ng/g product. Empty spaces, as for the artificial musks, indicate that the parameter was not determined in this

compound

**Brominated flame retardents**

**Perfluorinated chemicals** PFOA 0.2 PFNA 0.2 PFDA 0.2 PFUnA 0.2 PFDoA 0.2 PFTrA 0.2 PFOS 0.2 PFOSA 0.2 **Phthalates**

**Alkylphenols**

**Artificial musks** AHTN 0.1 HHCB 0.1 MK 0.1 MX 0.1 **Organotin compounds** MBT 0.2 DBT 0.2 TBT 0.2 MOT 0.2 DOT 0.2

sample.

limit of detection

cheese 1 cheese 2 cheese 3 scottisch cheese


Table 2. (continued) Results for organochlorine pesticides and polychlorobipenyls expressed in ng/g product. Empty spaces, as PCBs in orange juice, indicate that the parameter was not determined in this sample.

salmon

ng/g ng/g ng/g ng/g ng/g ng/g ng/g ng/g ng/g ng/g ng/g ng/g ng/g

tuna pickled hering

honey orange juice brown bread

olive oil

fish fingers

α-HCH 0.1 < < < < < < < < < < < < β-HCH 0.1 < < < < < < < < < < < < γ-HCH 0.1 < < < < < < < < < < < < HCB 0.1 0.14 < 0.10 0.10 < 0.22 < 0.7 < < < 0.10 α-chlordane 0.1 < < < < < 0.13 < 0.2 < < < < β-chlordane 0.1 < < < < < < < < < < < < o,p'-DDE 0.1 < < < < < < < < < 0.65 < < p,p'-DDE 0.1 0.33 0.17 0.21 0.17 < 0.83 < 5.6 < 1.5 < 0.40 o,p'-DDD 0.1 < < < < < < < < < < < < p,p'-DDD 0.1 < < < < < < < < < < < < o,p'-DDT 0.1 < < < < < < < < < < < < p,p'-DDT 0.1 < < < < < < < < < < < <

PCB 18 0.1 0.14 0.16 0.22 0.24 0.45 0.19 0.20 0.23 0.38 0.29 < PCB 28/31 0.1 0.36 0.23 0.59 0.43 0.63 0.49 0.38 0.76 0.55 0.61 0.19 PCB 22 0.1 < < 0.14 < 0.13 0.11 < 0.13 0.11 0.16 < PCB 41/64 0.1 < < 0.14 < < < < 0.38 < < < PCB 44 0.1 0.24 < 0.29 0.17 0.22 0.24 0.19 0.33 0.19 0.21 < PCB 49 0.1 < 0.12 0.19 0.11 0.21 0.23 < 0.22 0.15 0.19 < PCB 52 0.1 0.25 0.20 0.28 0.24 0.27 0.36 < 0.74 0.19 0.35 < PCB 54 0.1 < < < < < < < < < < < PCB 56/60 0.1 < < < < < 0.18 < 0.31 < 0.14 < PCB 70 0.1 0.13 < < < 0.14 0.38 < 0.71 0.16 0.17 < PCB 74 0.1 < < < < < 0.19 < 0.37 < 0.11 < PCB 87 0.1 < < < < < 0.12 < 0.41 < < < PCB 90/101 0.1 < < 0.13 < < 0.47 0.14 2.4 < 0.15 < PCB 99 0.1 < < < < < 0.24 < 0.95 < < < PCB 104 0.1 < < < < < < < < < < < PCB 105 0.1 < < < < < 0.14 < 0.59 < < < PCB 110 0.1 < < < < < 0.30 0.14 1.6 < < < PCB 114 0.1 < < < < < < < < < < < PCB 118 0.1 0.11 < < < < 0.40 0.11 1.8 < < < PCB 123 0.1 < < < < < < < 0.27 < < < PCB 138 0.1 < < 0.10 < < 0.24 0.20 1.5 < < < PCB 141 0.1 < < < < < < < 0.30 < < < PCB 149 0.1 < < < < < 0.49 < 2.8 < < < PCB 151 0.1 < < < < < 0.17 < 0.92 < < < PCB 153/168 0.1 0.26 < 0.13 < < 1.0 0.12 5.5 < 0.13 < PCB 156 0.1 < < < < < < < 0.22 < < < PCB 157 0.1 < < < < < < < < < < < PCB 158 0.1 < < < < < 0.50 0.16 3.2 < < < PCB 167 0.1 < < < < < < < 0.19 < < < PCB 170 0.2 < < < < < < < 0.56 < < < PCB 177 0.2 < < < < < < < 0.56 < < < PCB 180 0.2 < < < < < 0.32 < 0.90 < < < PCB 183 0.2 < < < < < < < 0.43 < < < PCB 187 0.2 < < < < < < < 1.6 < < < PCB 188 0.2 < < < < < < < < < < < PCB 189 0.2 < < < < < < < < < < < PCB 194 0.2 < < < < < < < < < < < PCB 199 0.2 < < < < < < < < < < < PCB 203 0.2 < < < < < < < < < < <

Table 2. (continued) Results for organochlorine pesticides and polychlorobipenyls expressed in ng/g product. Empty spaces, as PCBs in orange juice, indicate that the parameter was not

compound

**Organochlorine pesticides**

**Polychlorinated biphenyls** 

determined in this sample.

limit of detection

minced beef

pork chops

salami

ham


Table 3. Results for brominated flame retardants, perfluorinated chemicals, phthalates, alkylphenols, artificial musks and organotin compounds expressed in ng/g product. Empty spaces, as for the artificial musks, indicate that the parameter was not determined in this sample.

Industrial Contaminants and Pesticides in Food Products 85

In this study the concentrations of a number of typical man-made chemicals in food or food products were determined. The compound groups of interest were organochlorine pesticides, polychlorinated biphenyls, brominated flame retardants, phthalates, alkylphenols, artificial musks, perfluorinated compounds and organitin compounds. The results show that many of these compounds are present food in the range of 0.1 to 10 ng/g with the exception of phthalates for which the typical concentrations are two orders of magnitude higher. Organochlorine pesticides were found in the 17 of the 25 samples. The main organochlorine pesticides found in food are p,p'-DDE, a metabolite of DDT, and HCB in concentrations up to 5.6 ng/g. Polychlorinated biphenyls were found in all samples with predominance for PCB-18, -28 and -52. The sum of the indicator-PCBs ranged from 0.16 to 13 ng/g and total PCBs up to 32 ng/g. The highest concentrations were found in fish. Brominated flame retardants were found in 19 of the 24 samples with predominance for the tetra- and penta-PBDEs, especially BDE-47, -32 and -99. Total PBDE concentrations ranged from 0.15 to 1.2 ng/g with the highest concentration found in meat and not in fish as in other studies. BDE-209, HBCD and TBBPA were not found in any of the samples. The prefluorinated compounds PFOS and PFOSA were found in one of the four samples analysed, a fish sample, in concentrations of 1.3 and 0.2 ng/g. The predominant phthalates in food were DEHP, DBP and BBP. Phthalates were found in 12 of the 19 samples. DEHP concentrations ranged from 20 to 24,000 ng/g, the latter for a sample of olive oil, with a median concentration of 640 ng/g. Median concentrations for DBP and BBP were 200 and 17 ng/g. Alkylphenols were detected in 2 of the 19 samples, in both cases nonylphenol in concentrations around 5 ng/g. Of the artificial musks the polycyclic musks HHCB and AHTN were found 2 of the 4 samples in concentrations up to 0.56 ng/g for HHCB. As in other matrices the AHTN concentrations are about half those of HHCB. Organotin compounds were found in three of the five samples. Apart from TBT and its metabolites

DBT and MBT, two samples also contained octyltin compounds.

We kindly acknowledge the support of the WWF in the execution of this study.

3M-company (1999). Fluorochemical Use, Distribution and Release Overview. EPA docket

Bocio, A.; Llobet, J.M.; Domingo, J.L.; Corbella, J.; Teixido, A.; Casa, C. (2003). Human

CDC report (2003). National Report on Human Exposure to Environmental Chemicals.

Centre Analytical Laboratory (2001). Analysis of PFOS, PFOSA and PFOA from various

*Journal of Agricultural and Food Chemistry,* Vol.51, (2003), pp. 3191-3195. CDC report (2001). National Report on Human Exposure to Environmental Chemicals.

exposure to polybrominated diphenyl ethers through th diet in Catalonia, Spain.

food matrices using HPLC electrospray/mass spectrometry. Study number 023-

**4. Conclusions** 

**5. Acknowledgement** 

AR226-0550 (1999).

057, (June 2001).

CDC, Atlanta, Georgia, (March 2001).

CDC, Atlanta, Georgia, (January 2003).

**6. References** 


Table 3. (continued) Results for brominated flame retardants, perfluorinated chemicals, phthalates, alkylphenols, artificial musks and organotin compounds expressed in ng/g product. Empty spaces, as for the brominated flame retardants in orange juice, indicate that the parameter was not determined in this sample.

#### **4. Conclusions**

84 Pesticides in the Modern World - Risks and Benefits

salmon tuna

ng/g ng/g ng/g ng/g ng/g ng/g ng/g ng/g ng/g ng/g ng/g ng/g ng/g

BDE-17 0.1 < < < < < < < < < < < BDE-28 0.1 < < < < < < < < < < < BDE-32 0.05 0.07 0.05 0.06 0.09 < < < 0.08 0.15 < < BDE-35 0.05 < < < < < < < < < < < BDE-37 0.05 < < < < < < < < < < < BDE-47 0.05 0.78 0.52 0.81 0.78 < < 0.39 0.35 < 0.55 < BDE-49-71 0.05 < < < < < < < < < < < BDE-66 0.05 < < < < < < < < < < < BDE-75 0.05 < < < < < < < < < < < BDE-77 0.05 < < < < < < < < < < < BDE-85 0.05 < 0.32 < < < < < < < < < BDE-99 0.05 0.12 < < 0.10 < < < < < 0.19 < BDE-100 0.05 0.11 < < < < < < < < < < BDE-119 0.05 < < < < < < < < < < < BDE-126 0.05 0.08 < < < < < < < < < < BDE-138 0.05 < < < < < < < < < < < BDE-153 0.05 < < < < < < < < < < < BDE-154 0.05 < < < < < < < < < < < BDE-156 0.05 < < < < < < < < < < < BDE-166 0.05 < < < < < < < < < < < BDE-181 0.05 0.18 < < < < < < 0.10 < < < BDE-183 0.05 < < < < < < < < < < < BDE-184 0.05 < < < < < < < < < < < BDE-190 0.1 < < < < < < < < < < < BDE-191 0.1 < < < < < < < < < < < BDE-196 0.2 < < < < < < < < < < < BDE-197 0.2 < < < < < < < < < < < BDE-206 1 < < < < < < < < < < < BDE-207 1 < < < < < < < < < < < BDE-209 5 < < < < < < < < < < <

PFOA 0.2 <<<< < PFNA 0.2 <<<< < PFDA 0.2 <<<< < PFUnA 0.2 <<<< < PFDoA 0.2 <<<< < PFTrA 0.2 <<<< < PFOS 0.2 < < < 1.3 < PFOSA 0.2 < < < 0.2 <

DMP 1 < < < 1.1 < < DEP 1 < < < < < < DIBP 10 < < 165 400 < < DBP 10 < 170 183 260 < < BBP 1 < 13 12 17 < 340 DEHP 20 290 140 160 3300 < 24000 DINP 20 < 470 < 230 < 72 DIDP 20 < < < < < <

NP 2 < < < < < < OP 2 < < < < < <

Table 3. (continued) Results for brominated flame retardants, perfluorinated chemicals, phthalates, alkylphenols, artificial musks and organotin compounds expressed in ng/g product. Empty spaces, as for the brominated flame retardants in orange juice, indicate that

AHTN 0.1 < < 0.18 0.29 HHCB 0.1 < < 0.27 0.56 MK 0.1 <<<< MX 0.1 <<<<

MBT 0.2 0.5 < 9 < DBT 0.2 < < 1.1 0.6 TBT 0.2 < < 0.2 0.8 MOT 0.2 0.3 < < 0.8 DOT 0.2 < < < 1.2

the parameter was not determined in this sample.

pickled hering

honey orange juice brown bread

olive oil

compound

**Brominated flame retardents**

**Perfluorinated chemicals**

**Phthalates**

**Alkylphenols**

**Artificial musks**

**Organotin compounds**

limit of detection

minced beef

pork chops salami ham fish fingers

In this study the concentrations of a number of typical man-made chemicals in food or food products were determined. The compound groups of interest were organochlorine pesticides, polychlorinated biphenyls, brominated flame retardants, phthalates, alkylphenols, artificial musks, perfluorinated compounds and organitin compounds. The results show that many of these compounds are present food in the range of 0.1 to 10 ng/g with the exception of phthalates for which the typical concentrations are two orders of magnitude higher. Organochlorine pesticides were found in the 17 of the 25 samples. The main organochlorine pesticides found in food are p,p'-DDE, a metabolite of DDT, and HCB in concentrations up to 5.6 ng/g. Polychlorinated biphenyls were found in all samples with predominance for PCB-18, -28 and -52. The sum of the indicator-PCBs ranged from 0.16 to 13 ng/g and total PCBs up to 32 ng/g. The highest concentrations were found in fish. Brominated flame retardants were found in 19 of the 24 samples with predominance for the tetra- and penta-PBDEs, especially BDE-47, -32 and -99. Total PBDE concentrations ranged from 0.15 to 1.2 ng/g with the highest concentration found in meat and not in fish as in other studies. BDE-209, HBCD and TBBPA were not found in any of the samples. The prefluorinated compounds PFOS and PFOSA were found in one of the four samples analysed, a fish sample, in concentrations of 1.3 and 0.2 ng/g. The predominant phthalates in food were DEHP, DBP and BBP. Phthalates were found in 12 of the 19 samples. DEHP concentrations ranged from 20 to 24,000 ng/g, the latter for a sample of olive oil, with a median concentration of 640 ng/g. Median concentrations for DBP and BBP were 200 and 17 ng/g. Alkylphenols were detected in 2 of the 19 samples, in both cases nonylphenol in concentrations around 5 ng/g. Of the artificial musks the polycyclic musks HHCB and AHTN were found 2 of the 4 samples in concentrations up to 0.56 ng/g for HHCB. As in other matrices the AHTN concentrations are about half those of HHCB. Organotin compounds were found in three of the five samples. Apart from TBT and its metabolites DBT and MBT, two samples also contained octyltin compounds.
