FLAME RETARDANTS: SCREENING OF PRODUCTS ON THE MARKET IN THE CZECH REPUBLIC by International Educational Scientific Research Journal

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SERVICES, INC., PRAGUE, CZECH REPUBLIC - 110 00. (*Corresponding Author) NATIONAL INSTITUTE OF PUBLIC HEALTH, PRAGUE, CZECH REPUBLIC - 100 42. 3 DEPARTMENT OF ORGANIC TECHNOLOGY, UNIVERSITY OF CHEMISTRY AND TECHNOLOGY, PRAGUE, CZECH REPUBLIC 166 28. 4 NORWEGIAN INSTITUTE FOR WATER RESEARCH, OSLO, NORWAY - NO-0349. 5 NATIONAL INSTITUTE OF MENTAL HEALTH, KLECANY, CZECH REPUBLIC - 250 67. 2

ABSTRACT Flame retardants (FR) are substances added to materials to reduce their ignition and slow down the burning process. This study presents a series of screening data for different types of FRs occurring in the Czech Republic. A total of 80 different samples were taken, from which mostly organophosphates (PFR), polybrominated diphenylethers (PBDE), hexabromocyclododecane (HBCDD), polybrominated biphenyls (PBB), were found. Positive detections of PFR were measured in the following range: TCPP – 47 times (levels 0.2 to 9.9 µg/g for fabrics, clothes, carpets and some isolations, car interiors, 0.85-2.1 µg/g for children toys, 0.12-2.1 µg/g for mattress, 130-370 µg/g for thermocups, 0.034-27 µg/g for polycarbonate sheet, windowsills, and beach shoes), TPP – 33 times (levels 190-690 µg/g in mineral wools, polyurethane foams, polystyrene EPS and IPS, 150-760 µg/g in clothes, 55 ng/g in carpets, 330-970 µg/g in some electronic devices), TnBP – 3 times (levels 5.7 µg/g in PUFs, 0.8 µg/g in PP carpet, 0.098 µg/g in car interior, TDCPP – 6 times (levels 0.044-1.2 µg/g in PUFs, clothes, seatbelts and car interiors). For TCPP, no samples were found which exceeded regulatory levels set to 5 mg/kg. Compared to brominated flame retardants (BFRs) and PFRs, higher concentrations of PFRs were found. In these cases future efforts should therefore be focused towards these compounds rather than BFRs. One alarming result was the presence of both, BFR and PFR, in children’s clothes and PFR in children’s toys. Keywords: Flame Retardants; Organophosphates; TCPP; PBDE; POP; Czech Republic

1. Introduction Flame retardants (FR) are substances added to various materials to slow their burning or prevent the combustion process, and thus increase safety. Brominated flame retardants (BFR) and organic substances containing phosphorus, e. g. organophosphates (PFR) belong to the group of the most widely studied FR when considering their occurrence and effects on the environment. FR reduce flammability of many common products which are in daily use, such as plastics in electronics and vehicles, printed circuit boards, textiles, building materials and a wide ranging series of other industrial products (de Wit et al. 2002). These compounds often contribute greatly to the weight of the products, for example plastics may contain up to 15 % of polybrominated diphenylethers (PBDE) and polyurethane foam (PUF) up to 30 % of these compounds (EFRA 2004). As stated the main purpose of FR is for fire prevention or to slow its spread, and thus to protect damage to property and ultimately to prevent deaths. The literature indicates that at the beginning of this millennium more than 75 different types of BFR have

been used commercially (Alaee et al. 2003). Given their persistent properties, possible toxicity, and their ability to accumulate in the human body, there have been worldwide efforts for their measurement carried out in all environment compartments (Hites et al. 2004). In the 80’s contamination by BFR was documented (Wilford et al. 2005). Subsequently PBDEs have been detected in both, abiotic samples (air, dust, sediment basins, sludge) and biotic samples (fish, mammals, birds) (Chen et al. 2007). PBDEs have also been shown to be present in human adipose tissue, breast milk and blood (Kazda et al. 2004). It is believed that the main sources of PBDEs and other types of FR is in inhalation of the dust in homes, workplaces or in cars, and from the consumption of fish and other fatty meat products (Cequier et al. 2015). Other widely used BFR includes polybrominated biphenyls (PBB), hexabromocyclododecane and its isomers (HBCDD) and tetrabromobisphenol-A (TBBPA). Global production of these substances is in the tens of thousands of tonnes per year. The Stockholm Convention on Persistent Organic Pollutants, includes several FR for regulatory

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consideration, HBCDD, hexabromobiphenyl (HBB) and tetra to heptaBDE have been listed as persistent organic pollutants (POPs) in the Stockholm Convention (Stockholm Convention 2001). As the Czech Republic, ratified the Convention in 2001, it is legally committed to several actions concerning these compounds. These actions include a regularly updated National Implementation Plan (NIP) of the Convention. The NIP including national inventories summarizes manufacturing, import, trade, usage in manufacturing and agriculture of these substances, and concentrations in the environment, or whether their presence may lead to accumulation in biological, and particularly human tissues. Thus PBDEs, HBB and other new listed POPs like PFOS and HBCDD are now listed in the Stockholm Convention together with the initially listed 12 POPs which included organochloride pesticides, PCBs and PCDDs/PCDFs. With the inclusion of new POPs substances, it is necessary to update the information for them. It is also strategically and economically advantageous to gain information about other groups of substances whose inclusion in the Annexes to the Stockholm Convention is being discussed, or substances that industry uses as a substitute for those controlled compounds. Other legislative measures apart from the Stockholm Convention are also in place. In the European Union for example a list of substances of very high concern, are subject to authorization for import, manufacture and use. This list is regularly updated and supplemented in Annex XIV of the European Parliament and Council Regulation (EC) no. 1907/2006 concerning the Registration, Evaluation, Authorization and Restriction of Chemicals (REACH). The REACH database has included Deca-BDE and HBCDD since 2010. The main goal of this publication is to present a series of screening data for different types of FR in current consumer products in the Czech Republic. More precisely in which matrixes, which compounds and at what concentrations. For this purpose, a series of products were sampled and a wide range of flame retardants were measured in the respective samples.

1. Materials and Methods

Product selection From the available literature on the occurrence of FR, 80 sample types were selected, of which 10 samples were from building insulaion, 10 samples of fabrics, 10 samples of floor coverings, 20 samples of electronics and 30 samples of other materials. Several criteria for samples choosing were considered including; expectation of high FR content in each material, exposure routes into the human body, and whether these exposure routes were inhalation, ingestion or passage through skin. For some of the products, the

type and quantity of FR is declared on the material safety data sheet from the producer, for example for PUF which has a requirement for fire class B1 (heavily inflammable), it can be found declared tris-(2-chloro-1-methylethyl)phosphate amounting to 25 % of the product weight. For fabrics, research shows (Rauert et al. 2014) that the FR is often added to textiles in the EN, so clothes used by children and adults were also selected, mostly from second-hand importing goods solely from Great Britain. Floor coverings carpets and PVC samples were also selected and typically were made from polypropylene and polyamide. In addition 30 samples of other materials products that are in direct contact with people or near to them were selected, e.g. car interior materials in the vicinity of the driver (seat belts, headrest, dashboard), bed mattress from PUF, since it is in direct contact with people for longer period of time during sleep, and finally toys, because of the potential for adverse effects towards a critical group, young children. All the samples were either bought at the regular store or obtained by other means, e.g. the older unused products granted by a person or company. Product selection was conducted so that the resulting products were manufactured before 2000’s. There were only a few exceptions (e.g. curtains) for comparison. It is essential that from the 80 sample types selected the relevant FR were never commercially produced in Czech Republic. Their primary sources are mainly imported products, to which FR are added before the importation. The FR release to the environment during production and/or final disposal processes was not considered in the current study and so is not included in the presented environmental risk.

Sample work up and extraction The amount of material for each sample was always at least 150 grams. Samples were homogenized using a high speed grind in a high-speed homogenizer type “Total Blender” with stainless steel vessel and high resistance materials, milling for 1 minute to achieve complete homogenization of the sample. After collection, samples were stored in a laboratory freezer (-18 °C) until they were analysed.

Chemical analysis and instrumentation Two main groups of FR were analyzed: 

PFR, substances containing phosphorus,



BFR, this group contains congeners PBDE, PBB and three isomers of HBCDD, which are involved in commercially produced mixtures of FR.

Given the diverse behavior and structure of the analytes which were analyzed, the following analytical

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techniques were applied for their analysis: GC-HRMS, LC-HRMS, or alternative techniques with a lower resolution but still adequate techniques, e.g. GC-MS/MS, LC-MS/MS. The instrumentation Thermoquest Finnigan, San Jose, USA was: Quantum LC-MS/MS, GC-HRMS MAT95, GC-MS/MS Polaris Q. For 10 samples the LC-HRMS-TOF technique in the Norwegian Institute for Water Research was used for polar substances like PFR and HBCDD.

TBEP

Method for determination of PBDE and PBB: Analyses were performed on GC-MS/MS or GC-HRMS MAT95 with these chromatographic conditions: column Thermo Scientific TG-XLBMS, 30 m, ID 0.25 mm, film 0.25 m, flow rate of helium 1.2 ml/min, temperature programme: 150 °C for 1 min, rate 20 °C/min to 220, rate 3 °C/min to 286 holding 1 min, rate 10 °C to 310 °C holding 20 min, total analysis 50 minutes; MS transfer line 275 °C, inlet temperature 270 °C.

TBPP

Method for determination of BFR and HBCDD: Analyses were performed on LC-MS/MS with these chromatographic conditions in MS/MS regime: HBCDD (column Phenomenex Kinetex 50x2.1 mm 2.6 m, mobile phase: A=water, B=methanol, isocratic elution 0-15 min, 20 % A and 80 % B, flow rate 0.3 ml/min) BFR (column Phenomenex Kinetex 50x2.1 mm 2.6 m, mobile phase: A=water+0.1 % formic acid, B=methanol+0.1 % formic acid, gradient elution 0-18 min, 0-4 min 80 % A and 20 % B, 4-9 min 30 % A and 70 % B, 9-18 min 80 % A and 20 % B flow rate 0.2 ml/min. In following table 1 all the measured substances are divided into two groups: polar substances (organophosphates, HBCDD and TBBA) and nonpolar substances (PBDE and PBB):

Table 1 FR analytes and methods of analysis

TCP EHDP TEHP DCP T35DMP P TBBA

Tritolylphosphates (cresyl) o,m,p mix

1330-78-5

2-Ethylhexyl diphenyl phosphate

1241-94-7

Tris(2-ethylhexyl) phosphate

78-42-2

Diphenylcresyl phosphate

26444-495

Tris(3,5-dimethylphenyl) phosphate

25653-161

Tris(2,3-dibromopropyl)phosphate

126-72-7

3,3′,5,5′-Tetrabromobisphenol A

79-94-7

(analytical methods: LC-HRMS, LC-MS/MS, LC-HRMS-TOF) αHBCDD alpha-1,2,5,6,9,10-hexabromocyclodod 134237-50 ecane -6 βHBCDD beta-1,2,5,6,9,10-hexabromocyclodode 134237-51 cane -7 γHBCDD gama-1,2,5,6,9,10-hexabromocyclodod 134237-52 ecane -8 Brominated flame retardants (analytical methods: GC-HRMS, GC-MS/MS) PBB3 4-Bromobiphenyl PBB15 4,4′-Dibromobiphenyl PBB18 2,2′,5-Tribromobiphenyl PBDE28 PBB52 HBB PBDE47 PBB101 PBDE10 0

CAS RN

(analytical methods: LC-HRMS, LC-MS/MS, LC-HRMS-TOF) TCEP Tris(2-chloroethyl)phosphate 115-96-8 TPrP Tripropylphosphate 513-08-6 TCPP Tris(2-chloro-1-methylethyl)phosphat 13674-84e 5 TiBP Triisobutyl phosphate 126-71-6 BdPhP Butyl diphenyl phosphate 2752-95-6 TPP Triphenylphosphate 115-86-6 DBPhP Dibutylphenyl phosphate 2528-36-1 TnBP Tributylphosphate 126-73-8 TDCPP Tris(1,3-dichloro-2-propyl)phosphate 13674-878

78-51-3

HBCDD

PBDE99 Compound Organophosphates

Tris(2-butoxyethyl) phosphate

PBDE15 4 PBB153 PBDE15 3 PBDE18 3 PBB180 PBB194 PBB206

92-66-0 92-86-4 95080-341

2,4,4′-Tribromodiphenyl ether

41318-756

2,2′,5,5´-Tetrabromobiphenyl

59080-374

Hexabromobenzene

87-82-1

2,2′,4,4′-Tetrabromodiphenyl ether

5436-43-1

2,2′,4,5,5´-Pentabromobiphenyl

67888-964

2,2′,4,4′,6-Pentabromodiphenyl ether

189084-64 -8

2,2′,4,4′,5-Pentabromodiphenyl ether

60348-609

2,2′,4,4′,5,6′-Hexabromodiphenyl ether

207122-15 -4

2,2′,4,4´,5,5´-Hexabromobiphenyl

59080-409

2,2′,4,4′,5,5′-Hexabromodiphenyl ether

68631-492

2,2′,3,4,4′,5′,6-Heptabromodiphenyl ether

207122-16 -5

2,2′,3,4,4′,5,5´-Heptabromobiphenyl

67733-522

2,2′,3,3′,4,4′,5,5´-Octabromobiphenyl

67889-003

2,2′,3,3′,4,4′,5,5′,6-Nonabromobipheny l

69278-622

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Research Paper PBDE20 9 PBB209

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Decabromodiphenyl ether

1163-19-5

Decabromobiphenyl

13654-096

Extraction with organic solvents (mixture of hexane/acetone – 3:1) was used at the first step of sample processing. In case of PFR and BFR, aliquots of 13C labelled PBDE, 13C labelled PBB, 13C labelled HBB, 13C labelled TBBA, deuterated gamma HBCDD, deuterated TBP were spiked. PFR were clean-up by using column with silicagel and hexane/ethyl-acetate eluting system and were concentrated to 200 µl of methanol. For BFR, aliquots were purified using acidic and basic columns filled with silicagel, alumina and charcoal and final volume of the sample ranges from 40 to 100 µl of nonane. Samples prepared by these procedures were measured using GC-HRMS or GC-ITQ (ion trap) analytical method or LC-MS/MS with similar conditions (van der Veen et al. 2012; McGoldick et al. 2014; Eede 2012; Martínez-Carballo et al. 2007).

1. Results and discussions In the following table (table 2), samples with positive detections are shown (66 out of 80). In the first column the total amount of PFR is given whereas in the second column the concentration of TCPP is shown, as the main representative of the PFR group of FR. The third column shows the sum of all 7 congeners of PBDE, as the only group of BFR which was detected (with exception of one sample of HBCDD, see note in the description of table 2). The last column is filled with percentage of most frequently detected congener – BDE209. In the case of PBB, of the 11 compounds analysed for, none were detected in any of the samples. In the subsequent text the results for each individual compound group are considered separately.

Expanded polystyrene Extruded polystyrene OSB board Facade plastic net – “perlinka” Cardboard IPA T-shirts - import EN Infant clothes import EN Women’s T-shirts – CZ Children’s T-shirts Beddings Terry towels Children’s sweatshirts Carpet, polyamide – new Carpet, polypropylene – new Carpet, polyamide – aged PVC new Carpet aged Keyboard new LAN cord A LAN cord B Extension cord – outdoor Extension cord – indoor Micro USB cord

Table 2 Concentrations of PFR and PBR measured in series of materials (HBCDD is not depicted, since it was determined only in infant clothes, see chapter about HBCDD)

Printed connections 2 Mouse for PC

Material

Keyboard – used

PUF 1, fire class B1 PUF 2, fire class B1 PUF, regular Mineral wool

Sum of PFR

TCPP (most frequent PFR)

Sum of PBDE

BDE209 (most frequent PBDE)

µg/g

ng/g

% from sum of PBDE

2.3 x 10-5

6.2 x 10-4

0.56 0.63

Stereo headphones Printing server Power cables to the PC Cables to the PC screen Monitor CRT

0.80 0.69

Jug kettle Thermocup 1

100

140

460

100

0.19 1.3

1.3

9.9

0.76

1.8

1.3

0.22 0.51

0.36

2.6

6.4

1.5

0.50

0.21

0.33

0.52

3.2

0.071

78000

100

0.27

0.59

6.0

1.1

1000

3.5

0.15

2.4

100

0.060

1.5

0.23

100

330

0.097

100

2.9 3.7

0.47

100

2.6

0.29

970

0.46

100

Monitor LCD Printed connections PC Vacuum cleaner

1.2 0.19

0.19

0.13

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Research Paper Thermocup 2 Car interior – safety belt Car interior – headrest Plastic from car interior 1 Plastic from car interior 2 Disposable containers–plates Plastic spoons Upholstered seat Upholstered chair Nightstand Kitchen countertop Wardrobe Plastic pipe PET bottle Cuddly toy Cuddly toy 2 Cuddly toy – sun Plastic plate for children Mattress 1 Mattress 2 – for children Mattress 3 Mattress 4 Mattress 5 Polycarbonate sheet Plastic beach shoes Crocs Windowsill

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0.37

0.49

0.25

1.1

100

2.4

0.51

130

100

250

100

0.16 1.9 0.90

0.39

1.7

0.066

0.39 0.49

0.34

0.13

0.65

0.94

2.1

0.4

0.85

0.082

2.1

0.79

0.52

1.1

1.0

0.14

0.12

0.23

2.7

1.3

100

Organophosphates (PFR) FRs containing phosphorus have been used for more than 150 years and they are suitable alternative to BFRs. In comparison to bromine, phosphorus is more efficient retardant and it was proved that using phosphorus as a part of FR is also less harmful to the environment (van der Veen et al. 2012). At least in 1 of the 80 samples contained the following substances belonging to the group of PFR; 1. TCPP – 47 times, 2. TPP – 33 times, 3. TnBP – 3 times, 4. TDCPP – 6 times. Production and import of these 4 compounds are subject to supervision (guidance) of the European

Chemical Agency (ECHA) regarding their safe use (ECHA 2016). In general, the highest concentrations of FR were expected at the samples of antifire PUF, where PFRs are added in large amount during production. In case of TCPP, for the first purchased sample of PUF with safety class B the measured amount was 23 % of the product mass (safety sheet from producer declared 25 %). In another producer’s sample, the amount of TCPP was defined as 6.2 % of mass. TCPP is colorless liquid mostly used in PUF, PVC, EVA plastic, phenolic and epoxydic resins. Firstly, TCPP was introduced to the market at 1960’s, since when its consumption increased along with the growing demand for polyurethane and other plastic materials. It is sparingly soluble in water, but well soluble in organic solvents. TCPP is produced by reacting propylene oxide and phosphoryl trichloride with subsequent purification. TCPP is a mixture of 4 isomers. Although, there is no difference in use of these isomers as a PFR. TCPP is halogenated analogue of tris(-2-chloroethyl)phosphate, which is identified as a human carcinogen, mutagen and a substance with negative impact on reproduction process. Since 2001, it is produced on EU territory and imported to the Czech Republic. According to the risk Classification Societies working for ECHA this substance is harmful by ingestion and also for water environment with long-term consequences. Since the end of 2015, values for TCPP along with TCEP and TDCP are regulated in children’s toys by European Commission Regulation 2014/79/EU. The limit of the content for these substances is set to 5 mg/kg. In the samples of building material, TCPP was measured only at the sample of cardboard IPA – 1.3 µg/g. For fabrics in infant clothes for children from 0 to 2 years of age purchased in second-hand with clothing from EN the measured amount was 9.9 µg/g. Also, the compound TDCCP (1.2 µg/g) was detected in the same sample as well as in samples of beddings and a children’s sweatshirt. Also, TCPP was detected in 4 samples of carpets, from which 3 were newly produced and in one sample of new PVC – measured concentrations were ranged from 0.2 to 2.6 µg/g. In the case of electronic devices, TCPP was detected in 12 samples out of 20. It appears mostly in electric cords with maximum value of 2.4 µg/g in isolation of a 240 V conductor. In the plastic of electronic devices TCPP was detected sporadically. In samples of thermocups, the measured amount was from 130 to 370 µg/g. TCPP was detected in all samples from car interior – from 0.25 to 3.1 µg/g, with maximum values found in the headrest sample. TCPP was further evaluated in seat upholstery chairs, a kitchen countertop, wardrobe, plastic pipes, PET bottles, polycarbonate sheet, beach shoes and windowsill with concentrations ranging from 34 to 2700 ng/g. Maximal concentration was measured in plastic beach shoes.

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TCPP was measured in all articles which are intended for children, in three samples of cuddly toys – from 0.85 to 2.1 µg/g, similarly in a children’s plastic plate (82 ng/g). TCPP was also presented in all of 5 samples of mattresses, with concentration ranging from 0.12 to 2.1 µg/g. The results from this study show that this compound is not present only in products where it is expected e.g. PUF and electric conductors, but is also found in products where there is much closer contact to the human body – children’s clothes, toys, plate for children and mattresses made from PUF. However, measured concentrations at subjects intended for children lies below the EU limit for toys 5 mg/kg.

TPP – triphenylphosphate According to the classification of risks by ECHA, TPP is very toxic compound for water environment with long-term consequences. This compound is produced and/or imported into European Economic Area in an amount between 1,000 to 10,000 tons a year. Above the limit of determination, we measured TPP in certain building materials. In five of the ten selected: in ordinary PUF, mineral wool, in insulation polystyrene EPS and IPS and facade plastic net – so-called “perlinka” in the Czech Republic. The values ranged from 190 to 690 ng/g. In textiles, 4 of the samples contained measurable amounts: women’s t-shirt from CZ, in beddings, terry towels and children’s sweatshirt, with defined concentrations from 150 to 760 ng/g. In floor coverings, TPP was detected only in old carpet with concentrations just above the detection limit – 55 ng/g. Conversely, TPP was present in electronics (13 out of 20 samples): in both keyboards, 6 times in samples of cords, stereo headphones, CRT monitor, printer server, printed circuit board and a vacuum cleaner. The highest values were detected in print server (330 µg/g) and the CRT monitor (970 µg/g). In cords, TPP concentration was in the order of tens of µg/g. TPP was also detected in other products including seatbelts and headrests from car interiors, in one of the car interior plastics, and in disposable plates, plastic spoons, an upholstered seat, a chair, and in the nightstand. Interestingly, the highest concentration was in the car headrest – 30 µg/g.

TnBP – tributylphosphate and TCDPP – tris(1,3-dichloro-2-propyl)phosphate According to the classification of risks by ECHA, TnBP is harmful by ingestion, it is assumed to cause cancer and irritate the skin. It is also dangerous to aquatic life with long-term consequences. This substance is produced and/or imported into the European Economic Area in the amount of 1,000 to 10,000 tons per year.

µg/g) and in headrest of a car interior (0.098 µg/g). TCDPP was found in 6 samples: in PUF (44 µg/g), in the infant clothes from EN (1.2 µg/g), in outdoor extension cord (0.098 µg/g) and in seatbelts in car interior (0.091 µg/g) as well as in headrest (1.3 µg/g).

HBCDD – hexabromocyclododecane HBCDD is one of the hazardous persistent organic pollutants under the Stockholm convention (Stockholm Convention 2001) and its use is given special attention. This substance was labeled by ECHA in 2008 as a substance of very high concern (so-called SVHC). In 2009, ECHA recommended placing HBCDD on the REACH authorization certificate, which was carried out in September 2010. In October 2010, HBCDD was included in the POP list of Stockholm Convention, and the Convention Committee has recommended a worldwide ban on its use. In addition, Annex XIV Regulation EC/1970/2006 (REACH) from February 2011 with effect from 17th of February 2011, includes this compound leading to its ban from use without permission since 2015. When considering the effects the ECHA has classified HBCDD as very toxic to aquatic organisms with possible long-term effects on the water environment, since 2009. In December 2010, ECHA has proposed to classify HBCDD in accordance with EU Directive 67/548/EEC as a substance causing reproductive toxicity with possible effects to unborn fetuses and possible effects on infants. In the current study isomers of HBCDD were found in one sample, in infant clothing for children from 0 to 2 years of age, with a concentration of 330 ng/g: αHBCDD – 100 ng/g, βHBCDD – 64 ng/g, γHBCDD – 170 ng/g. Commercially produced HBCDD mixtures usually contain 10 – 20 % of α, 1 – 10 % β and 70 – 90 % of γ isomer. However, according to the literature, the ratio of isomers can be different in real samples. Although, we analyzed 80 samples of both new and older generation and even in building materials, HBCDD was only found in infant clothes. The presence of HBCDD in children’s textiles is striking, especially if we consider that its possible effects on the infant body are explicitly mentioned as one of the side effects of HBCDD. The literature indicates that the EN is one of countries where the most HBCDD is added into the clothes (Rauert et al. 2014).

Brominated flame retardants (BFR) Within the group of BFR, these compounds were detected: 1. HBB – 4 samples of electronics, 2. PBDE 47, 100, 99, 154, 153, 183, 209 – at least one of these congeners in 31 samples.

TnBP were found only in 3 samples: in one of PUFs (5.7 µg/g), in new carpet made from polypropylene (0.80

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HBB – hexabromobiphenyl HBB is a synthetic compound belonging to PBB. Since 2009, HBB is written on a sheet of banned substances of Stockholm convention. In Czech Republic, this substance has never been produced or used. Under normal conditions, HBB is white crystalline substance poorly soluble in water, but soluble in fats and oils. Generally, PBB (including HBB) are not firmly bound into the matrix of the compound in which they are contained and are relatively easy to release into the environment. PBB is subject to UV degradation. PBB found its application in a variety of electronics, cabling, mounting foams and textiles. PBB has been in electronic devices since 2006 and are regulated by European directive RoHS (Restriction of the use of Hazardous substances). Also, is present on computers where FRs are mainly used as a component of printed circuit boards, connectors, cords and plastic covers. HBB was detected in 4 samples of electronics: LAN cords A and B, in outdoor extension cord and in micro USB cord in concentrations from 10 to 72 ng/g.

PBDE – polybrominated diphenylethers Legislation according to the Directive of the European Parliament and Council Directive 2002/95/EC on the restriction of use of certain hazardous substances in electrical and electronic devices valid from 1st of July 2011 states that all new electronic equipment put on the market must not contain some heavy metals, PBB and PBDE. The maximum tolerated value of PBDE concentration is therefore set to 0.1 % by weight in homogeneous materials. Although, usage of some BFR within the European Union is prohibited or restricted, these compounds already exist and were used so they can get into the environment during disposal process. In terms of adverse effects on humans and the environment PBDE’s have been addressed for a long period of time. Given the structural similarity, PBDE (particularly tetra- and penta- congeners) and their hydroxylated derivates have been shown to mimic the actions of thyroid hormones (thyroxine and triiodothyronine) (Petterson et al. 2001). PBDEs may also act as endocrine disruptors and neurotoxins (Meironyté et al. 1999; Sjödin et al. 1999). PBDEs are supposed to cause damage to reproductive function and the growth of aquatic organisms (Dishaw et al. 2014). Chronic BFR exposure is people has been associated with fatigue, headache, dizziness and irritability. These symptoms are often accompanied by gastrointestinal problems such as loss of appetite, weight loss, diarrhea and abdominal pain (Kharlyngdoh et al. 2015). In electronics, the maximum tolerated sum of concentration of all PBDE congeners is set to 0.1 % by weight. In our analyzed samples of electrical products, the content of PBDEs was much lower. The sum of all

PBDEs did not exceed 1 µg/g, which is about three orders of magnitude lower than the limit for electronic devices, except for the plastic sample from the keyboard, which reached 78 µg/g. In 29 of the 31 positive samples, the highest representation of a single compound belongs to the congener BDE 209. A notable exception is the sample of plastic spoon, where the concentration of BDE 47 and BDE 99 was in both cases 110 ng/g and in case of BDE 209 only 4.5 ng/g. From the building materials PBDEs were measured in extruded polystyrene and oriented strand board. In textiles, PBDEs were detected in three samples of T-shirts, in an infant’s clothing obtained from the EN and children’s sweatshirts. Regarding the floor coverings, PBDEs were detected in the carpet of polypropylene. In electronics, PBDEs were identified in the aforementioned keyboard and other 15 samples out of 20. In other materials, PBDEs were detected in 3 samples from the car interior, plastic spoon and in one of the mattress as well as in the sample of windowsill.

Summary of PFRs and BFRs When compared with data from the literature around the world, we can ascertain that the PFRs were found where they were expected the most. Also, we can generally say that there was no difference in concentration depending on the time of production of the material – whether the product was newly purchased or used for many years. The obtained results confirmed the expectation of high PFR’s concentrations in PUF, electronics, and in materials used in car interiors. In electronics, the most dominant was TPP. In other subjects, it was mostly TCPP. The presence of PFRs in toys was below the regulatory limit (5 mg/kg), with the highest concentration in cuddly toys (2.1 mg/kg). In the children’s clothing from the EN we found a significant amount of TCPP and TDCCP (9.9 mg/kg and 1.2 mg/kg, respectively).From the limited number of observed samples, it can be assumed that the higher concentrations of FR used in materials in the Czech Republic belongs mainly to PFRs rather than BFRs. The reason for this is probably the legal restriction for BFRs which have come into force. The only exception is the sample of PC keyboard with higher concentration of PBDE. Also, the rest of the materials with relatively higher PBDEs values belong to the group of electronics. The most frequent BDE congener is by far BDE 209, followed by BDE 183 and 153. The most alarming result is the presence of all 3 groups (PFRs, HBCDD and PBDE) in a sample of infant’s textile.

4. Conclusion This screening study mapped the presence of the FR in various commonly available consumer products. The results confirmed the expected high levels of

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organophosphates in polyurethane foams, electronics, and in materials used in car interiors. From the group of PFRs the most widely used substance is TCPP. The measured concentrations of BFR were generally lower, which can be attributed to legislative measures already undertaken. One alarming find was the presence of FR in children’s toys and clothes. Although, these concentrations did not exceed the regulatory limit valid in the Czech Republic, continued attention should be paid to these products in future monitoring programs, together with consideration of human samples (namely breast milk, fat tissue, blood) to examine their potential to accumulate.

Science & Technology. 38:945-956.

Acknowledgement

11. Martínez-Carballo, E., et al. (2007) Determination of selected organophosphate esters in the aquatic environment of Austria. Science of the Total Environment. 388:290-299.

This paper was written as a part of the contract “Flame retardants in products and in an indoor environment in the Czech Republic” – TB030MZP003 supported by Technical Agency of Czech Republic in BETA program. We would also like to acknowledge the National Program of Sustainability NPU I (LO1611) for partially funding the study.

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