Document EvV32KL5Z3vyL1L8X0J3n9rnx

PFOS used in Paper Production Consequences on drinking water and agricultural land in Germany, Holland, Denmark and Sweden -- 2017-08-12 EE -- 2 Abstract The chemical PFOS was forbidden in 2008. A ruthless chemical manufacturer uses a method where PFOS can be marketed as a "green chemical". The manufacturer manipulates the product so that its actual content of PFOS is impossible to measure using the certified and standardized measurement method commonly used by government agencies and accredited institutes. The purpose is similar to Volkswagens Dieselgate; the product is manipulated in order to avoid government control and government regulations. The pulp and paper industry use hundreds of tons yearly of this "green chemical" and where PFOS remains in the produced paper. Paper end up in waste and which is burned in incineration plants. PFOS is not destroyed in the burning process. The result is that PFOS is spread with the flue gas to surface- ground- and drinking water as well as to agricultural land. The supply of non toxic water and food belongs to basic infrastructure. This basic infrastructure has been destroyed beyond repair in parts of Germany, Holland, Denmark and Sweden. 3 1. Introduction This report displays that a ruthless chemical manufacturer sells hundreds of tons yearly of the forbidden chemical PFOS in a way where the users, the pulp and paper industry, believe they purchase a "green chemical". This report shows that Swedish pulp and paper industry use approximately hundred tons PFOS yearly. All used PFOS end up in the environment. This report shows that PFOS is not destroyed in incineration plants and therefore spread with the flue gas to surface- ground- and drinking water as well as to agricultural land. Incineration plants operate according to the EU directive 2010/75/EU. Consequently, there is a serious fault in the EU directive. PFOS was measured in sewage and in produced paper from Swedish paper manufacturers. Furthermore, PFOS was measured in tap water in 40 cities in Germany, Holland, Denmark and Sweden. PFOS was also measured in vegetables produced in Holland and Sweden. Water samples and vegetables were collected during April-June 2017 and analyzed in June 2017. 2. Use of PFAS/PFOS in papermaking Paper is produced using the Fourdrinier process. Slurry of fibers, containing 98 % water, is spread on a rotating and perforated plastic mesh conveyor and where the water must be removed fast. This is achieved by adding a surfactant which reduces the water surface tension. Since 2015 a mix of four PFAS is used in Sweden: PFOS (C8F17SO3), PFDS (C10F21SO3), PFDoDS (C12F25SO3) and PFTeDS (C14F29SO3). The mix contains equal amount of the molecules PFOS, PFDS, PFDoDS and PFTeDS; hence, all four PFAS have the same concentration (measured in mol). A part of these four PFAS remain in the produced paper. Paper produced in Sweden was analyzed. In all cases the paper displayed the same concentration (measured in mol) of PFOS, PFDS, PFDoDS and PFTeDS; therefore only the concentration of PFOS is shown. The measurement accuracy is moderate and therefore the approximate concentration is displayed (400 mg/kg); however, results could vary between 300-500 mg/kg. Producer and city Unknown Unknown Mets Tissue AB, Paulistrm Mets AB, Mariestad SCA hygiene products, Edet SCA hygiene products, unknown Type of paper Dagens Nyheter, newspaper Svenska Dagbladet, newspaper Lambi, toilet paper Serla, kitchen paper Edet Torky, kitchen paper Libero Newborn, diaper PFOS concentration, mg/kg Approx. 400 Approx. 400 Approx. 400 Approx. 400 Approx. 400 Approx. 400 Sewage from 4 paper mills was analyzed. All samples displayed the same concentration (measured in mol) of PFOS, PFDS, PFDoDS and PFTeDS; therefore only the concentration of PFOS is shown. Paper Mill Stora Enso Fors (Avesta) Artic Paper Grycksbo AB Grycksbo Stora Enso Kvarnsveden (Borlnge) Waggeryd Cell AB (Vaggeryd) 4 Place were sample was taken In river Forsn, 1 km downstream of the paper mill In lake Grycken, 1 km downstream of the paper mill In river Dallven, 1 km downstream of the paper mill Tap water (ground water) in nearby city Vaggeryd PFOS concentration, mg/l 40 20 0.002 (2 g/l) 2 Note that river Dallven is very large. Hence, the concentration is low although the total amount of PFOS, PFDS, PFDoDS and PFTeDS is high. The results prove that Swedish paper making industry use a mix of PFOS, PFDS, PFDoDS and PFTeDS as surfactant and where PFOS was forbidden in 2008. Analyses of produced paper from 2014, 2015 and 2016, display that the Swedish paper making industry introduced PFOS, PFDS, PFDoDS and PFTeDS, as surfactant, during the third quarter 2015. 3. A method to mask PFOS and PFAS The pulp and paper industry has used different types of PFAS as surfactants since the 1960ies. During 50 years a surfactant consisted of only one type of PFAS; often C16F33SO3. From 2015, one surfactant dominates the market and it consists of a mix of four PFAS (PFOS, PFDS, PFDoDS and PFTeDS). Why? The reason is that the chemical industry is now able to mask the presence of PFAS, including PFOS. The chemical industry uses a method where PFOS, PFDS, PFDoDS and PFTeDS are mixed in a way where they form clusters. The state of the art method used when analyzing PFOS, PFDS, PFDoDS and PFTeDS is mass spectrometry (LC-MS/MS). This method analyzes single or solitary molecules; however, not PFOS, PFDS, PFDoDS and PFTeDS which are part of a cluster. The consequence is that it is impossible to measure presence of these chemicals and the product can be promoted as a "green" surfactant. Swedish companies must register import/use of chemicals to the Swedish Chemical Agency. The following paper manufacturers in Sweden use PFOS, PFDS, PFDoDS and PFTeDS and the total import is hundreds of tons yearly (wherein approximately hundred ton is PFOS): Artic Paper Grycksbo AB, BillerudKorsns, Mets AB, SCA, Stora Enso and Waggeryd Cell AB. According to the Swedish Chemical Agency their database contains no registration of PFOS, PFDS, PFDoDS and PFTeDS imported/used by these companies or by the pulp and paper industry as a whole. It is common knowledge within the pulp and paper business that the manufacturing process used since the 1960ies demands use of surfactants and where the dominating surfactant has been PFAS. 4. A novel method to measure PFAS/PFOS The above clusters of PFOS, PFDS, PFDoDS and PFTeDS disintegrate at very low concentration. Consequently, the method is to mix the sample with MQ-water (distilled water). This report displays 5 that tap water often contain 3-100 mg/l PFOS and which is a very high concentration. The method used is to mix the sample with 1000 times water, often 100 000 times water and sometimes with 1 million times water. That reduces the concentration to 30-1000 ng/l and which is the normal measurement range of state of the art methods. 5. Incineration plants In Europe incineration plants operate according to the EU directive 2010/75/EU. In short, waste containing less than 1 % halogen compounds is burned in a process where the flue gas temperature must be increased to at least 850 OC during at least 2 seconds. PFAS are known to be extremely persistent and there is reason to believe that they can sustain temperature up to approximately 1100 OC. The result is that PFOS, PFDS, PFDoDS and PFTeDS are spread with the flue gas to lakes, groundwater and drinking water as well as to agricultural land which contaminates produced food. Many reports display contamination of lakes, groundwater, drinking water and agricultural land by PFOS and PFDS caused by historic use of these chemicals in e.g. fire fighting foam (AFFF). The concentration is normally very low. The concentration of PFOS and PFDS in Stockholm tap water (lake Mlaren) has been approximately 4-5 ng/l of each of these chemicals. Water samples from Stockholm tap water (Norsborg water plant) have been collected and stored since 2015. The table below displays concentration of PFOS, PFDS, PFDoDS and PFTeDS during 2015 to 2017. Time when sample was collected 2015-01-01 2015-10-20 2016-02-23 2016-04-13 2016-05-18 2016-06-27 2016-08-01 2016-10-01 2016-12-22 2017-02-27 2017-03-20 2017-05-01 PFOS, g/l 0.005 4 15 42 160 300 480 610 2200 5200 8100 20000 PFDS, g/l 0.004 0.020 13 46 190 360 580 530 2600 6200 9700 24000 PFDoDS, g/l 0 0.017 15 53 210 420 670 850 3010 7300 11000 28000 PFTeDS, g/l 0 0.02 18 60 240 470 750 950 3500 8200 13000 31000 The sample from 2015-01-01 shows the historic contamination from AFFF; the concentration of PFOS and PFDS is very low (4-5 ng/l). The sample from 2015-10-20 shows the first sign of novel contamination from PFOS, PFDS, PFDoDS and PFTeDS. Samples from 2016-02-23 display very large increase of PFOS, PFDS, PFDoDS and PFTeDS. In all samples the four PFAS have the same concentration, measured in mol. However, they have different molecular weight and hence, e.g. PFTeDS has higher concentration measured in g/l compared to PFOS. The conclusion is that Stockholm tap water (lake Mlaren) started to contain increasing concentration of PFOS, PFDS, PFDoDS and PFTeDS at the same time as these chemicals were introduced as surfactant by the Swedish paper making industry. All samples from 2016-02-23 to 2017-05-01 contain the same concentration (in mol) of all four PFAS; i.e. exactly the same mix as in produced paper and 6 in paper mill sewage. There is no paper making industry in the lake Mlaren region; consequently this contamination originates from burning of paper in incineration plants primarily in the Stockholm region. 6. PFOS in Sweden Tap water from 13 Swedish cities, with incineration plants, has been analyzed with respect of PFOS, PFDS, PFDoDS and PFTeDS. In all cases the water in a city displayed approx. the same concentration (measured in mol) of each of these four PFAS; therefore only the concentration of PFOS is shown. City and type of water Avesta, ground water Borlnge, ground water Gteborg, lakes Delsjarna Halmstad Linkping, river Motala strm Ljungby, ground water Norrkping, lake Glan Nykping, lake Yngaren Stockholm Norrvatten, northern part of lake Mlaren Stockholm Vatten, southern part of lake Mlaren Sdertlje, ground water Uppsala, ground water, Grnby waterplant rebro, ground water PFOS concentration, mg/l 6 80 5 10 6 100 10 2 8 20 40 40 4 In Sweden water is unsuitable for consumption when the sum of PFOS and PFDS exceeds 900 ng/l. Consequently, the drinking water in these cities exceeds this level with 4 000 to 200 000 times. Tap water from the cities Sala and Hedemora were analyzed as reference. Sala and Hedemora have no incineration plant and both reside approximately 50 km from the nearest incineration plant. The PFOS concentration was 3 g/l in Sala and 4 g/l in Hedemora, i.e. significantly lower than in cities with incineration plants. However, the PFOS and PFDS concentration was 6 to 8 times above the recommended level for unsuitable water. 7 different vegetables and root vegetables were randomly selected from two grocery stores (COOP and Hemkp). Wheat from farmland was also analyzed. Each vegetable displayed approx. the same concentration (measured in mol) of PFOS, PFDS, PFDoDS and PFTeDS; therefore only PFOS is shown in the table. Type of vegetable Potato Wheat Broccoli Jerusalem artichoke Onion Carrot Cucumber Cucumber Producer, city Unknown, Vsters Grown outside Gnesta Horna Grd, hus Mariannes Farm, Strvelstorp Dalbo Grd, Oxie Steglinge Grden, Hgans Unknown, Jrna Vxtkraft AB, Hlsingborg PFOS concentration, g/kg 30 6 2 8 10 20 40 60 Some of these vegetables were grown close to incineration plants. These vegetables display high concentration of PFOS, PFDS, PFDoDS and PFTeDS (potato/Vsters, cucumber/Hlsingborg, 7 cucumber/Jrna and carrot/Hgans). The city hus is situated far away from incineration plants in Hssleholm and Malm and consequently, broccoli produced there has lower PFOS, PFDS, PFDoDS and PFTeDS concentration. The results display correlation between concentration and distance to incineration plants. 7. PFOS in Germany Tap water in 10 German cities, with incineration plants, has been analyzed with respect of PFOS, PFDS, PFDoDS and PFTeDS. In all cases the water in a city displayed approx. the same concentration (measured in mol) of each of these four PFAS; therefore only the concentration of PFOS is shown. City and place where sample was taken Bielefeld, Ost Bremen, Zentrum Dortmund, Westfalenhalle Dsseldorf, Zentrum Hannover, Langenhage Hamburg, Stillhorn Krefeld, Zentrum Neustadt, Zentrum Remscheid, Zentrum Wuppertal, Zentrum PFOS concentration, mg/l 10 8 6 9 20 100 20 70 40 50 Note that the concentration is mg/l, i.e. extremely high. The recommended PFOS level for drinking water in Germany is 300 ng/l. Hence, this level is exceeded with 10 000 to 300 000 times. Tap water from the cities Lbeck (Stockelsdorf) and Neumnster (Brokenlande) were analyzed as reference. Lbeck and Neumnster do not have incineration plants. The PFOS concentration was 1 respectively 6 g/l, i.e. significantly lower than in cities with incineration plants. However, the PFOS concentration was 3 respectively 20 times above recommended level. 8. PFOS in Holland Tap water in 7 Dutch cities close to incineration plants has been analyzed with respect of PFOS, PFDS, PFDoDS and PFTeDS. In all cases the water in a city displayed approx. the same concentration (measured in mol) of each of these four PFAS; therefore only the concentration of PFOS is shown. City and place where sample was taken Amsterdam, city centre Arnhem, city centre Dordrecht, city centre Enschede, city centre Hengelo, city centre Roosendaal, city centre Rotterdam, city centre PFOS concentration, mg/l 40 10 8 60 20 100 60 Note that the concentration is mg/l, i.e. extremely high. 8 Vegetables from Holland, bought in Sweden, have been analyzed with respect of PFOS, PFDS, PFDoDS and PFTeDS. In all cases the vegetable displayed approx. the same concentration (measured in mol) of each of these four PFAS; therefore only the concentration of PFOS is shown. Type of vegetable Bell pepper (paprika) Egg plant (aubergine) Leek Tomato PFOS concentration, g/kg 240 140 200 120 9. PFOS in Denmark Tap water in 5 Danish cities with incineration plants has been analyzed with respect of PFOS, PFDS, PFDoDS and PFTeDS. In all cases the water in a city displayed approx. the same concentration (measured in mol) of each of these four PFAS; therefore only the concentration of PFOS is shown. City and place where sample was taken Copenhagen, Kastrup Kolding, city centre Odense, city centre Nstved, city centre Slagelse, city centre PFOS concentration, mg/l 10 20 90 10 30 Tap water from the city Greve was analyzed as reference. Greve has no incineration plant and resides 30 km south of Copenhagen. The PFOS concentration was 30 g/l, i.e. significantly lower than in cities with incineration plants. However, the PFOS concentration is far above recommended level. 10. PFOS in China Tap water from Chinese cities was collected 2013, 2014, 2015 and 2016. Tap water from Beijing Xidan 2013-06 and from Tianjin 2014-04 contains very small concentration of PFOS, PFDS and no measurable PFDoDS and PFTeDS. The table below displays PFOS, PFDS, PFDoDS and PFTeDS in tap water collected 2015-04. City where sample was collected Beijing, north Beijing, Xidan Kenli Tianjin Tiantongguan PFOS, g/l 65 84 36 12 8 PFDS, g/l 75 100 40 14 9 PFDoDS, g/l 84 110 46 14 10 PFTeDS, g/l 95 120 52 16 11 The results display that the all water samples contain approx. equal amount of the four PFAS (PFOS, PFDS, PFDoDS and PFTeDS) measured in mol. 9 The table below displays PFOS, PFDS, PFDoDS and PFTeDS in tap water collected 2016-11. City where sample was collected Beijing, north Beijing, Xidan Suqian Kenli Nanjing Yang Zhou PFOS, g/l 52000 26000 70000 36000 21000 28000 PFDS, g/l 62000 31000 84000 43000 25000 33000 PFDoDS, g/l 73000 36000 98000 50000 29000 39000 PFTeDS, g/l 82000 41000 110000 57000 33000 44000 The results display that all water samples contain equal amount of the four PFAS (PFOS, PFDS, PFDoDS and PFTeDS) measured in mol. The news paper "China Daily" from 2015-04 and 2016-11 contains PFOS, PFDS, PFDoDS and PFTeDS and where these four PFAS have the same concentration measured in mol. Analyses made on newspaper and water samples from 2015-04 and 2016-11 prove that a surfactant, consisting of a mix of equal amount of PFOS, PFDS, PFDoDS and PFTeDS, is used in China; i.e. exactly the same surfactant which used in Sweden and described in section 2. However, this surfactant was introduced large scale in China late 2014 or early 2015, i.e. approx. one year earlier than in Sweden. It is reasonable to assume that this surfactant originates from China. The rapid increase of PFOS, PFDS, PFDoDS and PFTeDS in Chinese tap water during 2016 indicates that the launch was successful and that the chemical manufacturer gained large market share during relatively short time. Subsequently, this surfactant was marketed in EU where it rapidly gained large market share. 11. Action levels As far as the author understands the recommended level for PFOS in drinking water in Germany is 300 ng/l. As far as the author understands TDI for PFOS in food in Germany is 150 ng/kg/day. Sweden has two levels for drinking water. Action must be taken when the sum of 11 PFAS (including PFOS and PFDS) exceeds 90 ng/l and water is unsuitable for consumption when the sum of 11 PFAS exceeds 900 ng/l. There is no recommended level for food in Sweden. The directive 2013/39/EU sets the PFOS limit in inland water to 0.65 ng/l. Lake Mlaren and lake Grycken exceeds this value by 30 million times and Dallven exceeds the limit by 3 000 times. 12. Swedish government and science Swedish scientists and government agencies are convinced that contamination of PFOS is primarily caused by historic use of PFOS in fire fighting foam (AFFF) and leakage of PFOS from e.g. military airfields. That is what they look for and that is what they find. 10 The chemical industry knows how to "package" PFAS (including PFOS) where its presence is masked and can be marketed as "green chemicals". Government agencies must adapt to this and learn how to measure in a way where PFAS, including PFOS, can be analyzed. 13. Conclusions The study provides evidence that Swedish paper manufacturers use a mix of PFOS, PFDS, PFDoDS and PFTeDS as surfactant in paper production. PFOS was forbidden 2008. The study provides evidence that PFOS, PFDS, PFDoDS and PFTeDS are spread by incineration plants to drinking water reservoirs and to agricultural land and where the result is huge contamination of tap water and food. The study provides evidence that incineration plants do not operate as expected and hence, the EU directive 2010/75/EU must be changed accordingly. Illegal import of surfactants containing PFOS must stop immediately. PFDS, PFDoDS and PFTeDS are not forbidden; however, it is highly questionable to use them in a way where they pollute paper mill sewage and the produced paper. The study displays that a chemical manufacturer manipulates its product in a way where it is impossible to measure its contents of PFOS, PFDS, PFDoDS and PFTeDS, using state of the art methods. The result is a devastating environment catastrophe. The origin of this surfactant is probably China.