No. 10 June Polybrominated Flame Retardants in Food and the Environment

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1 No. 10 June 2014 By Carsten Schaffors, GBA Laboratory Group Polybrominated Flame Retardants in Food and the Environment The term "flame retardants" is used to describe a variety of organic and inorganic chemicals that when utilized in specific products have the property of reducing the flammability of those objects or delaying the spread of a fire. These are often used in the production of cases for electronic devices, circuit boards, cables, for coating the underside of carpets, for special textiles, insulating material, and expanding foam. Organic flame retardants not only include brominated compounds, but also organophosphorus compounds (with or without halogens), as well as chloroparaffins. The most commonly utilized inorganic flame retardants are aluminum hydroxide (AI(OH) 3), magnesium hydroxide (Mg(OH) 2), and antimony trioxide (Sb 2O 3). The positive properties of flame retardants have to be compared with the characteristics which are hazardous to our health and environment, especially in the case of organic compounds containing halogens. These are classified as persistent in the environment and can also accumulate within organisms (i.e. bioaccumulation). If there is a fire, corrosive or highly toxic gasses can be generated, or in the case of polybrominated diphenyl ethers (PBDE), it may also lead to the formation of polybrominated dibenzo-p-dioxins and furans.,[2] However, not all compounds in the group of brominated flame retardants have a hazardous effect on the environment and/or our health. Even some alternative compounds that are already in use, such as chloroparaffins or certain halogenated phosphorus compounds, can be harmful to the environment. [2] The most commonly produced brominated flame retardants worldwide belong to the following groups: decabromodiphenyl ether (DecaBDE), tetrabromobisphenol A (TBBPA), and hexabromocyclododoecane (HBCD or HBCDD). At 145,000 t per year, the brominated compound with the highest production worldwide is TBBPA. The consumption within the EU is approximately 7,000 t per year. The main usage for TBBPA is in circuit boards (approx. 90%) and sometimes also in casing materials. DecaBDE has the second largest production rate worldwide, at approximately 54,400 tons per year (about 8,3000 t per year in Europe). It is mainly used as a flame retardant in the plastic cases of electrical and electronic devices, as well as in textiles. About 22,000 tons of HBCD are used per year worldwide (about 9,600 [2] - 12,000 t [3] per year in Europe). HBCD is mainly utilized for polystyrene insulating materials for buildings. To a small extent, HBCD is also used in textiles [2], [3], [4] and synthetic materials. TBBPA has been classified as non-toxic for humans, but toxic for aquatic organisms. The compound is very persistent in the environment and remains in the food chain even to the point of being detected in breast milk. Due to the catalytic effect of the copper contained in circuit boards, dioxins and furans can be generated if there is a fire or when not properly disposed of. DecaBDE is very persistent, bioaccumulative, and furthermore, it is very mobile. Elevated concentrations can be detected in sediment samples near production facilities, but also at the top of the food chain in distant regions. It is not considered toxic to humans or the environment. However, even at low doses, neurological or endocrine effects cannot be completely ruled out with certainty. Presumably, it may decompose into less brominated compounds that are more toxic or bioaccumulating, such as PentaBDE and Octa BDE, which even today may neither be utilized nor sold in Europe. [2] In this case as well, dioxins and furans can be generated if burned or disposed of improperly. HBCD has similarly negative characteristics too. Furthermore, this has already been detected in fish, marine mammals, and birds of prey from the arctic region and therefore it was listed as a persistent organic pollutant (POP) according to the criteria of the European chemical regulations, REACH. In animal tests, it was shown that the development of embryos and infants was impaired by the

2 influence of HBCD. Additionally, there is the suspicion that reproduction is also hindered. In humans, the compound has only been found in trace amounts, however this could also be due to the lack of adequate methods for testing thus far. [3] In March 2014, based on the results of six appraisals of the health risks associated with brominated flame retardants in food products, which the European Food Safety Authority (EFSA) released between 2010 and 2012, the European Commission recommended that the EU member states should at first monitor the occurrence of brominated flame retardants in food products in 2014 and A wide spectrum of food products, aligned with consumer habits, should be integrated into the monitoring program, and different food products should be selected for different classes of brominated flame retardants. [5] They recommend analyzing eggs, egg products, milk and milk products, meat and meat products, plant-based and animalbased fats and oils, fish and seafood products, food products for babies and infants, among other products. The analytical methods should at least be capable of obtaining a limit of quantification of 0.01 ng/g fresh weight for the PBDE and HBCD classes, and 0.1 ng/g fresh weight for the TBBPA and brominated phenols classes. Newly arising and new kinds of brominated flame retardants should be analyzed with a limit of quantification of 1 ng/g fresh weight or better. Even if these groups of substances do not have acute toxic effects on humans, there is still the possibility of a harmful effect after a long period of time and over a long distance due to their widespread distribution and accumulative properties, if harmful concentration levels are exceeded. HBCD may continue to be used as before in the EU up until August However, according to the Stockholm-Convention, a worldwide ban on usage is planned as of November [3] It is still unclear whether or not the substance may be used in insulating materials under these strict conditions after August After renovating or demolishing buildings, polystyrene insulating materials are burnt. That's why they should always be collected separately, since there is no recycling process for them at this time nor in the foreseeable future. [3] The HBCD is then destroyed and the resulting exhaust is then refined. In the future, the requirements for the destruction of HBCD in disposal will also be strictly defined when HBCD is added to the EU-POP regulations, which will be valid for all textiles and casing materials that contain HBCD. This is in contrast to the USA, where construction debris generally still end up in municipal solid waste landfill sites or construction and demolition landfill sites and are subject to the effects of UV rays, as well as microbiological and physical loads, which lead to the release of HBCD. [4] More and more halogen-free, organophosphorus compounds are being used in synthetic materials for electrical and electronic devices as alternatives to TBBPA, DecaBDE, and HBCD. In order to do so, low-cost mass-produced materials such as acrylonitrile butadiene styrene (ABS) and high impact polystyrene (HIPS) must be replaced by more expensive synthetic mixtures with polycarbonate (PC) or polyphenyl ether (PPE). Magnesium hydroxide, microencapsulated red phosphorus, melamines, or organic phosphinates should be used as fire-inhibitor for polyester materials (PBT, PET) or polyamide (PA). [2] It is possible to use cellulose fibers with a phosphor-based reactive flame retardant as a replacement for DecaBDE and HBCD in textiles. Another alternative is fabric made of flame-resistant materials such as polyaramids or fiberglass. The density and structure of a material also influence the combustibility of a material decisively. [2] At the moment, there is only one brominated polymer known to be used in polystyrene insulating materials, which is added to the polystyrene. The German Federal Environment Agency recommends avoiding the use of mineral insulating materials, cellular glass, or expanded concrete. It is also possible to use natural insulating materials based on wood chips, cellulose, or hemp. For years, the GBA Laboratory Group has been analyzing flame retardants in all kinds of matrices as part of its portfolio, including a diverse range of isomers from various polybrominated diphenyl ethers, chloroparaffins, and organophosphorus compounds. Besides trace analyses of sediments, water, soil, and biota, also the determination of those substances in electronic devices, such as circuit boards and cables are part of it. Additionally, we always follow the latest market developments in order to stand by your side providing you with expert advice and assistance. Feel free to contact us about this topic: Mr. Ralf Murzen Flensburger Straße Pinneberg Tel.: +49 (0) 4101 / Fax: +49 (0) 4101 / pinneberg@gba-laborgruppe.de

3 References: Flammschutzmittel in Produkten, Schadstoffe in Produkten, Umweltbundesamt, May 28, 2013 [2] Bromierte Flammschutzmittel Schutzengel mit schlechten Eigenschaften?, Umweltbundesamt, April 2008 [3] Hexabromcyclododecan (HBCD) Antworten auf häufig gestellte Fragen Umweltbundesamt, Fachgebiet IV 1.1 Internationales [4] [5] Chemikalienmanagement, February 2014 Flame Retardant Alternatives for Hexabromocyclododecane (HBCD) EPA United States Environmental Protection Agency, Final Report, June /118/EU: Commission Recommendation of 3 March 2014 on the monitoring of traces of brominated flame retardants in food Text with EEA relevance Official Journal L 065, 05/03/2014 P General Decree According to 54 of German Food and Consumer Goods Law: Consumers Protected From EU Law By Carsten Schaffors, GBA Laboratory Group In the European free trade agreement, the principle of the free exchange of goods was established between the member states. That also means food products which do not necessarily adhere to the national regulations may be imported as long as they are legally in distribution within an EU member state. In order to protect the consumers here in Germany, constraints to the free trade agreement have been defined in 54, para. 1, sent. 2, no. 2 of the German Foodstuffs and Consumer Goods Law (LFGB). Products that do not meet the requirements of the German consumer health protection laws are only able to be traded if announced by a general decree in the Federal Gazette. This kind of general decree must be requested from the Federal Office for Consumer Protection and Food Safety (BVL), which then works together with other agencies to check if there are any objections to the product based on health risks. When one general decree is issued, it is valid for all similar products from other importers that already circulate these products in other EU member states. In certain cases, there may be conditions in the general decree that must be observed when this product is imported into Germany. If the food monitoring program in Germany determines that a food product from another EU member state poses health risks or otherwise fails to adhere to the legal requirements, the objections will be forwarded to the agency responsible in its country of origin, along with the relevant appraisals, laboratory results, etc. The resulting measures will then be forwarded via the BVL to the individual federal states. The same procedure is also valid conversely, if there are objections to a German product in another member state. [2] Feel free to contact us about this topic: Dr. Roland Bernerth Goldtschmidtstraße Hamburg Tel.: +49 (0) 40 / Fax: +49 (0) 40 / service@gba-laborgruppe.de References: Allgemeinverfügung nach 54 LFGB Bundesamt für Verbraucherschutz und Lebensmittelsicherheit, 2014 [2] Grenzüberschreitender Handel Bundesamt für Verbraucherschutz und Lebensmittelsicherheit, 2014

4 The GBA Laboratory Group Supports the Day of Social Action by Sabine Gerkau, GBA Laborgruppe On June 12, 2014, the GBA Laboratory Group took part in the "Sozialen Tag" (Social Day). This is an initiative carried out by the organization called "Schüler Helfen Leben," a nonprofit association that has been sponsoring projects for children and adolescents since With a charitable fund of over 22 million euros and the participation of up to 80,000 schoolchildren nationwide, it is the largest school initiative in Germany. At this event, school children had the opportunity to try out a profession for one day. The salary they earned was then donated to the youth and educational programs in southern Europe and Germany. The students themselves decided which programs to sponsor. This year, the GBA laboratory group offered an interested student an inside look at the sample preparation department for food analysis. GBA also supports this initiative in the interest of promoting the field of laboratory analysis to future generations. References: (accessed: ) The GBA Laboratory Group on the Move at the HSH Nordbank Run By Sabine Gerkau and Carsten Schaffors, GBA Laboratory Group On Saturday, June 21, 2014, at 1:13 p.m., the time had finally come. 30 employees of the GBA Laboratory Group from the Pinneberg and Hamburg locations, along with their family members, took part in the HSH Nordbank Run. The company run, which has now taken place for the thirteenth time, included 812 teams and over 23,000 participants this year. The four-kilometer route straight through the Hafen- City provided a special atmosphere unique to Hamburg, and all participants had the same goal: Run for a good cause! The GBA Laboratory Group covered both the individual registration fees for each of its runners as well as the team fee. Like every year, this money was donated to the initiative called "Kinder helfen Kindern" (Kids Help Kids), which is organized by the newspaper the Hamburger Abendblatt. In total, the (Highly motivated and in good spirits: the GBA-team before the start) team "ran up" a donation of 150,000.

5 By taking part in this event, we not only want to show the team spirit that we have at GBA, but we'd also like to support social projects in the various areas of daily life. (The starting shot was fired at 1:13 p.m. and the runners went straight through the Hafen-City along the lines of We analyse even faster as we run!.) Inquiries or orders can be directly placed at this or any other of our locations: Hamburg: Pinneberg: Hameln: Goldtschmidtstraße 5 Flensburger Straße 15 Brekelbaumstraße Hamburg Pinneberg Hameln Tel.: +49 (0) 40 / Tel.: +49 (0) 4101 / Tel.: +49 (0) 5151 / Fax: +49 (0) 40 / Fax: +49 (0) 4101 / Fax: +49 (0) 5151 / service@gba-laborgruppe.de pinneberg@gba-laborgruppe.de hameln@gba-laborgruppe.de Gelsenkirchen: Hildesheim: Freiberg: Wiedehopfstraße 30 Daimlerring 37 Meißner Ring Gelsenkirchen Hildesheim Freiberg Tel.: +49 (0) 209 / Tel.: +49 (0) 5121 / Tel.: +49 (0) 3731 / Fax: +49 (0) 209 / Fax: +49 (0) 5121 / Fax: +49 (0) 3731 / gelsenkirchen@gba-laborgruppe.de hildesheim@gba-laborgruppe.de freiberg@gba-laborgruppe.de Publisher of this Newsletter: GBA Laboratory Group. All rights reserved. Please send questions and comments to newsletter@gba-laborgruppe.de. We try to research the content of our newsletters without errors and as thoroughly as possible for your benefit. If the statements contained within are nevertheless incomplete or contain errors, then we bear no liability.