|Approaches for better information and monitoring of POPs in articles|
|Monitoring of POPs in articles and products|
|Alternative assessment approaches for chemical alternatives|
|Screening of potential POPs in chemical databases|
|Tools for the assessment of POPs properties of chemicals|
|Toxicity assessment of alternatives|
|Case study: Scientific assessment of a PFOS alternatives in chromium plating|
Since products and articles containing POPs are not labelled as such, a certain extent of monitoring is needed. In addition to articles/products on the market, this includes the monitoring and management of articles in use, stockpiles, and at end-of-life including recycling. A range of these articles/products can return to the market either as used goods (e.g. electronics, cars, carpets, furniture) or as material in the recycling flow (e.g. polymers from electronics; polyurethane foam from furniture; material recycling of textiles, paper, or synthetic carpets). Therefore, information on monitoring data from these materials is also crucial to get an overall picture of POPs in the material flows including product/article and related recycling flows.
In order to help countries overcome the challenges regarding monitoring of new listed POPs in products and articles, as well as in the recycling streams, the Secretariat of the Stockholm Convention, with financial support from Norway has developing a “Guidance on Sampling, Screening and Analysis of Persistent Organic Pollutants in Products and Articles” (Draft).
This document provides guidance on monitoring (sampling, screening and analysis) of the POPs content in articles and products in use and in the recycling streams for those POPs listed in 2009 and 2011.
Guidance is provided on:
The guidance addresses to the types of major articles, products and other material, which may contain POPs listed in 2009 and 2011 (Annex 1).
The guidance is to:
New analytical standard procedures for specific matrices and other case studies can be considered in the finalization and updating of the draft guidance.
There has already has been a range of activities of monitoring of POPs in articles and products by research institutions or by governmental entities in different countries/regions. An overview of existing studies gives an insight on the current presence of POPs in articles. Some of the case studies reveal that many former applications of PFOS are no longer relevant. Recent surveys detected no PFOS or related substances in coated paper in Germany, for example (Schlummer et al. 2011) . Also for PBDE only specific categories of plastics from E-waste appear to contain POP-PBDEs at significant levels (Wäger et al. 2010) .
Case studies provide information on methodologies and approaches for monitoring POPs in articles and products and how such monitoring could be performed. These case studies can therefore be assessed with the view of selecting the most appropriate approaches and methodologies (sampling and analysis).
Monitoring project of PFOS/PFAS in consumer products in Norway and Sweden
The Norwegian Pollution Control Authority (SFT) has commissioned a survey on PFOS/PFCs in consumer products (Herzke et al. 2009). It was carried out by Swerea IVF (Sweden) together with Norwegian Institute for Air Research (NILU) and aimed to identify and quantify possible sources of PFAS in Norway in industrial manufacturing and applications used by the Norwegian population in daily life.
The study included waterproofing agents (5), paint and inks (5), impregnated products: paper, textiles, leather and carpets (2/2/2/2), non-stick ware (6), electronics (5) and fire fighting agents (5).
PFOS has been banned in Norway since 2007 but was still detected in 47% of samples in low concentrations. However, concentrations in only 4 of the 34 products analysed were close to or exceeding the regulations. These products were all within the leather or carpet product groups: The two leather samples had the highest concentrations of PFAS: Office furniture leather; (pool of 3) and black shoe, leather, showed PFOS levels of 38 and 21 μg/m2, exceeding the EU regulation of 1 μg/m2. Carpets were around the regulation of 1 μg/m2. The relatively low levels detected indicate that PFOS were not applied as major performance chemical but rather as by-product or contaminant of other PFAS or treatment procedure. Only five of the 34 analysed industrial materials and consumer products contained none of the 29 polyfluorinated substances for which the samples were tested.
Case study: PFOS/PFAS monitoring Baking and Muffin papers
As a contribution to the European Perfood project (http://www.perfood.eu/; KBBE-227525), 154 paper-based food contact materials (Baking papers and Muffin cups) were collected and screened for fluorinated contaminants (Schlummer et al. 2011) . 47 fluorine-positive samples were identified und subjected to a detailed analysis for PFOS and other perfluorinated sulfonates (PFSA), fluorotelomer alcohols (FTOH), and perfluorinated carboxylates (PFCA). In this study, PFOS and other perfluorinated sulfonates (PFSA) were not detected in any sample at levels above 1 ng/g. Instead 6:2 FTOH, 8:2 FTOH and 10:2 FTOH were identified in all fluorine-positive samples at levels ranging from 9 to 39,500 ng/g. Concentrations of PFCA were considerably lower and ranged from LOD (<1) to 619 ng/g PFOA, LOD (<1) to 1,500 ng/g PFNA, and LOD (<1) to 390 ng/g PFDA  . This strongly indicates a switch from PFOS/FOSE-based coatings for paper to FTOH containing macromolecules in industrial practise.
It needs to be highlighted that in the first phase of the study performed in 2009/2010, most baking paper and muffin cups purchased in super markets were fluorine positive and had significant FTOH and PFCA levels (no PFOS). However, in a second screening in 2010/11 of baking and muffin papers newly purchased in super markets, most samples were fluorine negative in the screening (detection limit approx. 0.1%), meaning that most of the investigated brand marks had changed for the European market their coating in recent years towards non-organofluorine coatings and already some years earlier moved away from PFOS precursor based coatings.
Monitoring of paper packaging for food (Denmark)
PFOS and related chemicals in food packaging are of particular concern due to possible direct human exposure. In an (on-going) survey for the Danish Food Administration approximately 85 food packaging samples were taken by food inspectors in food packaging businesses (samples with no previous contact with food) and by DTU-Food in retail stores (samples in contact with foods). Only four samples contained perfluorinated sulfonates (PFSAs), and only two of these contained PFOS but in low levels (< 10 ppb). The other samples contained FTOH based PFAS in 57 % of the samples. Also this study revealed/conformed with the pattern of detected PFAS that industry for the European market already have shifted away from PFOS-derived coatings to diPAPs and now towards FTOH containing coatings. PFCA impurities/breakdown products were often seen in the paper extracts/migrates.
Non-analytical screening of PFOS/PFAS in products on the Danish market
In the first steps of monitoring of newly listed POPs in a country other approaches (including) import statistics, product registers, company survey and audits should be considered and compiled before any instrumental screening and analysis is done. One documented survey on of PFOS/PFAS in consumer products in the Danish market with non-analytical means has been conducted and published from the Danish Ministry of Environment (2008).
Approaches of the Danish market survey of PFOS/PFAS on the national market were:
Monitoring of PBDEs in WEEE plastic in EU
The largest and most relevant transboundary substance flow of POP-PBDEs and BFR containing materials are plastic fractions from WEEE recycling, followed by polyurethane foam in car/transport, furniture, construction, mattresses or baby products,. The Swiss national material testing institute EMPA developed a standardized methodology for sampling of WEEE for a survey of RoHS regulated substances in WEEE plastic in Europe including c-OctaBDE (Wäger et al. 2010) .
Specific features of EMPA’s case study on PBDE and other RoHS relevant substance screening in WEEE plastics are:
Determination of POPs-PBDE and BFRs in WEEE plastics in Nigeria
The largest POP-PBDE share within EEE/WEEE is casings of Cathode Ray Tubes (CRTs) (see PBDE Inventory Guidance3). In a monitoring study of POP-PBDEs in Nigeria the two major CRT categories (TVs and computers) were monitored (Sindiku et al. 2011 and 2012). In this case study 382 single housings of computer and TV Cathode Ray Tubes (CRTs) were sampled at WEEE storage sites in Nigeria (Sindiku et al. 2011, 2012). Furthermore the recycling of the plastic of these appliances is of interest from an economic perspective.
The samples were specifically selected from waste storages, electronics workshops, roadsides, dumpsites and dismantling sites. The labels on the TVs and computer monitor plastic housings were examined for information on the manufacturer, brand, model, serial number, year and origin (production or assembly). About 250 cm2 sizes were cut from each sample.
Small parts of these sub-samples were subjected to a screening with EDXRGF aiming at the semi-quantification of bromine, chlorine but also of inorganic compounds listed in the RoHS directive. Bromine positive samples were then selected for GC/ECD and GC/MS analysis and the type and amount of PBDE and other major BFR determined.
Monitoring of BFRs in polymers of electronics on Swiss market
The Swiss competent authorities monitored brominated flame retardants in 2000 in consumer products currently in sale including electrical devices, building materials and lighting equipment (Bantelmann et al. 2010). The aim of the survey was to evaluate the compliance of commercial articles with the provisions of the Swiss restrictions on BFRs: In Switzerland, the placing on the market and use of c-PentaBDE, c-OctaBDE and PBBs in preparations with contents of each of these BFRs equal to or exceeding 0.1% by mass is prohibited. Also placing of articles on the market of articles that contain these substances in concentrations equal to or exceeding 0.1% by mass is banned as well.
Only 2 of the approximately 2000 samples contained c-OctaBDE above the 0.1% RoHS threshold. The study gives an insight on POP-PBDE and other BFRs used in electronic products present/imported to the European market. The study shows that the POP-PBDE content in current products on the Swiss (and therefore European) market is small.
The results of the third screening level of unknown BFRs in the samples by EMPA revealed that some of these samples contained e.g. hexabromobenzene or pentabromobenzene where the chlorinated analogues (HCB & PeCBz) are prohibited by the Stockholm Convention.
Monitoring POP-PBDEs in carpet rebond from recycled PUR foam
PUR foam is recycled to carpet rebond in some regions in particular North America. In a monitoring project of POP-PBDEs in recycled carpet padding samples from different word regions have been screening with XRF for bromine content and 26 samples were analysed for PBDE content by GC/MS analysis (DiGangi et al. 2011).
The study showed that carpet padding/rebond in the US and Canada was impacted with high levels of PBDEs but that the levels in samples from developing countries were low.
Monitoring of POP-PBDEs and other flame retardants in baby products
For the first time a wide range of polyurethane baby products were sampled, screened and analysed for POP-PBDEs and other flame retardants. In total 101 commonly used baby products from the United States containing polyurethane foam were monitored for POP-PBDEs and other flame retardants (Stapleton et al. 2011). The study combined bromine screening methodology with confirmation analysis (as suggested in this guidance document). A portable X-ray fluorescence (XRF) analyser was used to estimate the bromine and chlorine content of the foams.
From these products:
The study revealed that flammability standard in a country can result in high levels of flame retardant in sensitive products with critical exposure to vulnerable groups like infants. Based on exposure estimates conducted by the US Consumer Product Safety Commission, the study predict that infants may receive TDCPP from these products higher than acceptable daily intake levels of TDCPP set by the US Consumer Product Safety Commission (Stapleton et al. 2011). This highlights that the selection of alternative flame retardants is crucial for the safety of vulnerable groups and that in monitoring studies the alternative flame retardants used should be measured and assessed for their risk and toxic flame retardants excluded from the substitution process.
Monitoring of POP-PBDE in children’s toys
A Chinese research group assessed the presence of PBDEs and other BFRs in children’s toys in South China (Chen et al. 2009). In all samples PBDE or other BFRs were detected. The median BFR concentrations in the hard plastic toys were notably higher than values in other toys. The PBDE concentrations were below the threshold limit (1000 ppm) required by the European Commission’s Restriction of Hazardous Substances (RoHS) and Waste Electrical and Electronic Equipment (WEEE) directives in all of the toys, except for one hard plastic toy with a total PBDE concentration of 5,344 ppm. Several samples made from hard plastic were above POP-PBDE concentrations of 50 ppm, while the major contaminant was DecaBDE responsible for exceedance of RoHS limit for some samples. The BFR profiles in the toys were therefore consistent with the patterns of their current production and consumption in China, where PBDEs, specifically DecaBDE, were the dominant BFR, followed by the emerging DBDPE used as alternative for commercial DecaBDE and commercial OctaBDE (Chen et al. 2009).
The study revealed the broad use of recycled WEEE plastic in sensitive use areas like children toys and that recycling of polymers seems uncontrolled and that monitoring of polymers in these sensitive uses for POP-PBDEs and other BFRs are important to control the recycling flow and control exposure.
Monitoring of PBDEs/BFRs in thermo cups and selected kitchen utensils
A market survey on black plastic food-contact articles (FCA) was conducted in order to screen for the presence of recycled polymer from waste electric and electronic equipment (WEEE) (Samsonek & Puype 2013). Thermo cups and selected kitchen utensils where screened with XRF spectrometry to discover bromine-containing samples. In a second step the bromine-positive samples were analysed by thermal desorption GC-MS. A large share of thermo-cups contained brominated compounds. The flame retardants detected contained mainly commercial decabromodiphenyl ether (decaBDE) currently evaluated from the POPs review committee. Also tetrabromobisphenol A (TBBPA), tetrabromobisphenol A bis(2,3-dibromopropyl), ether (TBBPA-BDBPE) and decabromodiphenylethane (DBDPE) were detected. However the samples did not contain POP-PBDEs. The results indicate that polypropylene–polyethylene copolymers (PP-PE) and mainly styrene-based food-contact materials, such as acrylonitrile-butadiene-styrene (ABS) have the highest risk of containing BFRs.
 Wäger P, Schluep M, Müller E. 2010. RoHS substances in mixed plastics from Waste Electrical and Electronic Equipment. Final Report September 17, 2010.
Waeger P, Schluep M, Müller E. (2010) . Final Report September 17, 2010.
 Recommendation for further reading on PFAS analysis::Trace analysis of per- and polyfluorinated alkyl substances in various matrices-How do current methods perform? Journal of Chromatography, A 2009, 1216, (3), 410-421. Challenges in perfluorocarboxylic acid measurements. Analytical Chemistry 2007, 79, (11), 3966-3973.
 Herzke D, Posner S, Olsson E (2009) Survey, screening and analyses of PFCs in consumer products. TA‐2578/2009; Swerea IVF Project report 09/47.
 Regulation EC No 552/2009 of 22 June 2009 amending Regulation (EC) No 1907/2006 of the European Parliament and of the Council on the Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH) as regards Annex XVII , p.53.
 Danish Veterinary and Food Administration (2012) Danish Technical University Report (not published).
 Danish Ministry of Environment (2008) Survey and environmental/health assessment of fluorinated substances in impregnated consumer products and impregnating agents. Survey of Chemical Substances in Consumer Products, No. 99, 2008.
 Stockholm Convention (2011) Work programmes on new persistent organic pollutants. 5th Conference of Parties meeting. UNEP/POPS/COP5/15.
 Stapleton MH, Klosterhaus S, Keller A, Ferguson PL, van Bergen S, Cooper E, Webster TF, Blum A (2011) Identification of Flame Retardants in Polyurethane Foam Collected from Baby Products. Env. Sci. Technol. 45. 5323-5331.
 Bantelmann E, Ammann A, Näf U, Tremp J. (2010) Brominated flame retardants in products: Results of the Swiss market survey 2008. BFR 2010, April 7-9, Kyoto, Japan.
 Baby products containing PUR foam must meet California state furniture flammability standards, which likely affects the use of flame retardants in baby products throughout the U.S and possibly North America.
 Chen S-J, Ma Y-J, Wang J, Chen D, Luo X-J, Mai B-X (2009) Brominated Flame Retardants in Children's Toys: Concentration, Composition, and Children's Exposure & Risk Assessment. Environ Sci Technol 43, 4200- 4206.
 Samsonek J., Puype F. (2013): Occurrence of brominated flame retardants in black thermo cups and selected kitchen utensils purchased on the European market, Food Additives & Contaminants: Part A, DOI: 10.1080/19440049.2013.829246