Document n9ab72rvoByXdkXgpmX8Ypw6m

Intended for European Chemicals Agency Document type Report Date 28.05.2021 PFAS IN FIREFIGHTING FOAMS (PART 3)PFAS IN FIREFIGHTING [TITLE] PFAS IN FIREFIGHTING FOAMS (PART 3)PFAS IN FIREFIGHTING FOAMS (PART 3) Project name REACH RESTRICTION SUPPORT PFAS IN FIREFIGHTING FOAMS (PART 3) Project no. ECHA/2020/876 Recipient European Chemicals Agency Document type Report Version 1 Date 28/05/2021 Prepared by Checked by Approved by Ramboll Werinherstrae 79 Gebude 32a 81541 Mnchen Germany T +49 89 978970-100 https://de.ramboll.com Ramboll Deutschland GmbH Werinherstrae 79 81541 Mnchen Germany District Court Mnchen, HRB 126430 Managing Directors: Jens-Peter Saul, Stefan Wallmann BNP Paribas S.A. Branch Germany IBAN: DE40512106004223034010 BIC: BNPADEFFXXX Ramboll - [Title] CONTENTS 1. Introduction 7 Background 7 Project Aim 7 2. Material and methods 8 Literature search 8 2.1.1 Disposal methods 8 2.1.2 Equipment cleaning 8 Stakeholder consultation and interviews 9 3. Disposal methods for PFAS in AFFF 11 Description of the problem 11 Disposal of PFAS-containing AFFF concentrates 12 3.2.1 Physical destruction Incineration in HWI plants 12 3.2.2 Physical destruction Incineration in cement kilns 16 Final conclusion on the disposal of PFAS-containing AFFF concentrates 18 4. Disposal of PFAS-contaminated (fire run off and Cleaning) water 21 Description of the problem 21 Non-destructive: Granular activated carbon (GAC) treatment 28 Non-destructive: Ion exchange (IX) 30 Non-destructive: Precipitation - PerfluorAd 32 Non-destructive: Foam fractionation and ozofractionation 36 Destructive approaches 39 4.6.1 Incineration 39 Final Conclusion on the Disposal of PFAS-contaminated (fire run off and cleaning) water 39 5. Cleaning of stationary or mobile PFAS firefighting foam equipment 45 Description of the problem 45 Non cleaning 46 Cleaning procedure by BIOEX 46 171 by Arcadis 47 Cleaning procedure with PerfluorAd by Cornelsen 48 Cleaning protocol by the Bavarian State Ministry for the Environment and Consumer Protection (LfU) 52 Cleaning protocol by Fire Rescue Victoria (FRV) - Appliance PFAS Decontamination Project 53 Cleaning protocol by FPA Australia 57 Cleaning protocol by the Australian DoD 58 Cleaning protocol by Werkfeuerwehrverband Deutschland (WFVD) 59 1/80 Ramboll - [Title] Final Conclusion on available cleaning procedures for firefighting equipment 62 6. References 67 7. Appendix 1 71 Information submitted by Fire Rescue Victoria - FRV Appliance PFAS Decontamination Project 71 2/80 Ramboll - [Title] TABLE OF FIGURES Figure 1: The HWI process taken from Eurits homepage......................................... 13 Figure 2: Availability of HWI across the EU taken from Eurits homepage ................... 15 Figure 3: PFAS treatment technologies for water, ranged according to their practicality (taken from (UBA 2020)). ............................................................................. 21 Figure 4: Conceptual impact of volume on the relevance of currently available non- destructive and destructive treatment approaches for PFAS contaminated water (taken from (Horst et al. 2020)) .................................................................... 22 Figure 5: PFAS treatment technologies for water, ranged according to their practicality (taken from (UBA 2020)). ............................................................................. 23 Figure 6: Outline of the entry of firefighting water into the subsurface if no retention facilities are available taken from (Cornelsen 2021). ......................................... 24 Figure 7: On the left, a representation of a soil excavation after successful infiltration of extinguishing water into the subsoil. On the right the pump and treat procedure is shown (Cornelsen 2021). .............................................................................. 25 Figure 8: PFAS-contents of a 1% AFFF Premix, measured using different analytical techniques. ................................................................................................. 26 Figure 9: PFAS flow diagram for adsorption filtration with IEX /taken from (Concawe 2020)). ...................................................................................................... 31 Figure 10: Schematic overview of an Activated Carbon Plant (GAC) with PerfluorAd Pretreatment Stage (taken from Cornelsen) ......................................................... 33 Figure 11: The interaction between the PFAS molecule (below shown for the example of 6:2 FTS) and the added cation (taken from Maga et al 2020) ............................. 34 Figure 12: left) Residual concentration total PFASs [mg/l] and right) elimination rate total PFASs [%] for 1% AFFF premix after addition of PerfluorAd (taken from (Cornelsen 2020)). ...................................................................................... 35 Figure 13: Elimination rates for different parameters [%] at an optimal dosing rate of 2.0 g/l PerfluorAd for this application (taken from (Cornelsen 2020)). ................. 35 Figure 14: Illustrative Concept of foam fractionation (taken from (UBA 2020)) .......... 37 Figure 15: Ozofractionation process concept (taken from (UBA 2020)). .................... 37 Figure 16: Picture showing the GHS hazard statements of Arcadis solvent V171 (taken from a presentation of Arcadis at NEWEA, 2019 see here). ................................ 38 Figure 17: Sum of PFAS Concentrations during decontamination of AFFF- Impacted sewer system and of a 20-m concentrate tank. ............................................... 48 Figure 18: Schematic overview on the three individual steps of the cleaning procedure are shown schematically. The cleaning of stationary equipment is shown at the left and the cleaning of fire brigade machines is shown at the right (no illustration available for the first step). ........................................................................... 50 Figure 19: Results of the Cleaning of Fire Trucks using PerfluorAd. .......................... 51 Figure 20: The Decontamination Process in pictures (taken from (Fire-Rescue-Victoria 2021)). ...................................................................................................... 55 Figure 21: Achieved PFAS levels after decontamination according to the protocol by FVR, before (blue) and after (red) (taken from (Fire-Rescue-Victoria 2021))................ 56 Figure 22: Overview on the Aircraft Rescue & Firefighting (ARFF) foam transition project (DoD-AUS 2020a)........................................................................................ 58 Figure 23: Cleaning procedure phases in accordance to the Queensland DoD (DoD-AUS 2020c) ....................................................................................................... 59 Figure 24: PFAS Analysis of rinsing water from apparatus "TMB" from step 4 of tank cleaning procedure (note, that the detection limit is lower as this is an analysis for PFAS in water as opposed to PFAS in foam concentrate in other figures).............. 61 3/80 Ramboll - [Title] Figure 25: PFAS Analysis of rinsing water from apparatus "PTLF II" from step 4 of tank cleaning procedure (Note 1: The detection limit is lower as this is an analysis for PFAS in water as opposed to PFAS in foam concentrate in other figures. Note 2: This apparatus is also referred to as "TroTSLF 2" or PTLF 2)................................... 61 Figure 26: Estimated costs for the cleaning of a 1 m foam concentrate tank with the described cleaning procedure ........................................................................ 62 TABLE OF TABLES Table 1: Contacted stakeholders who submitted relevant information ......................... 9 Table 2: Comparison between incineration techniques for PFAS-based AFFF in HWI (hazardous waste incinerators and cement kilns).............................................. 20 Table 3: Comparison of disposal techniques for PFAS-contaminated (fire run off and cleaning) for PFAS-based AFFF in HWI (hazardous waste incinerators and cement kilns) ......................................................................................................... 42 Table 4: PFAS residual thresholds (taken from (Fire-Rescue-Victoria 2021)).............. 56 Table 5: Comparison between cleaning procedures ................................................ 64 4/80 Ramboll - [Title] ABBREVIATIONS AFFF AOB BDSAV CaF CAS CFA CMC CMR DoD EC ECHA EEA EPA ESTCP EU EURITS FFFC FFFC FOSA FPA FRV FTA GAC GRP GSB HF HMCS HWI IBC IED IPEN ITRC JOIFF LANUV LfU LRRL MCB MFB MLB MS NATA NGO O&M PBT PFAA PFAS PFC PFCA Aqueous Film Forming Foam Any Other Business Federal Association of German Hazardous Waste Incineration Plants e.V. Calcium Fluoride Chemical Abstracts Service Country Fire Authority Critical Micelle Concentration Carcinogenic, Mutagenic, Reprotoxic US Department of Defence European Commission European Chemicals Agency European Environment Agency Environmental Protection Agency Environmental Security Technology Certification Program European Union European Union for Responsible Treatment of Special Waste Film-forming Fluoroprotein Foam Fire Fighting Foam Coalition Perfluorooctane Sulfonamide Fire Protection Association Fire Rescue Viktoria Fire Training Areas Granulated Activated Carbon Glass-fibre Reinforced Plastic Hazardous Waste Disposal Bavaria Hydrogen Fluoride Harmonised Mandatory Control System Hazardous Waste Incinerators Intermediate Bulk Containers Industrial Emissions Directive International Pesticides Elimination Network Interstate Technology & Regulatory Council International Organisation for Industrial Emergency Services Management The Ministry for Environment, Agriculture, Conservation and Consumer Protection of the State of North Rhine-Westphalia Bavarian State Ministry for the Environment and Consumer Protection Extinguishing Water Retention Directive Mechanochemical Ball Milling Metropolitan Fire & Emergency Services Board Mobile Extinguishing Water Treatment Plant Mass Spectrometry National Association of Testing Authorities Nongovernmental Organization Operation and Maintenance Persistent, Bioaccumulative and Toxic Perfluoroalkyl Acids Perfluoroalkyl Substances Perfluorinated Hydrocarbon Perlfuorocarboxylic Acids 5/80 Ramboll - [Title] PFHxA PFHxS PFOA PFOS PFSA PFT PIC POP PTFE QLD REACH SAFF SERDP TEA TOF TOP TP UBA UVCB VwVwS WFVD WWTP Perfluorohexanoic Acid Perfluorohexane Sulfonic Acid Perfluorooctanoic Acid Perfluorooctane Aulfonic Acid Perfluorosulfonic Acids Polyfluoroalkyl Substances Products of Incomplete Combustion Persistent Organic Pollutant Polytetrafluoroethylene Queensland Policy Regulation concerning the Registration, Evaluation, Authorisation and Restriction of Chemicals. Surface Active Foam Fractionation Strategic Environmental Research and Development Program Triethanolamine Quats Total Organic Fluorine Total Oxidisable Precursor Transitional Periods German Environment Agency Unknown or Variable composition, Complex reaction products or Biological materials Regulation of Substances Hazardous to Water Plant Fire Brigade Association Germany Waster-Water Treatment Plant 6/80 Ramboll - [Title] 1. INTRODUCTION Background Polyfluoroalkyl and perfluoroalkyl substances (PFAS) are a large group of substances that have been widely used in articles and products since many years. Because of their properties (e.g. very thermally stable, oil- and water repellents, film-forming) PFASs were and are used in fire-fighting foams intentionally and are present as process impurities. A project has recently been carried out by WOOD and Ramboll to assess the use of PFASs and their fluorine-free alternatives in fire-fighting foams, looking specifically at their volumes, functions, and emissions. The analysis of alternatives for fire-fighting foams and the socio-economic impacts of substituting PFAS-based fire-fighting foams with fluorine-free alternatives were elaborated in this context as well. The respective report was published in June 2020. In order to limit the risks to the environment and human health from the manufacture and use of all PFAS, five EU countries (DE, NL, NO, SE and DK) are currently preparing a broad PFAS restriction proposal. For this a call for evidence was organised in May 2020. In October 2020, ECHA has announced its intention to propose a REACH restriction on the use of PFAS in firefighting foams, in a move that extends regulatory measures on the controversial substances. Also related to fire-fighting foams is the intentioned restriction of Perfluorohexanoic acid (PFHxA), its salts and related substances as many PFAS (e.g. 6:2 fluorotelomers) used in firefighting foams are precursors of PFHxA. For this restriction of PFAS in firefighting foams, ECHA has called for information on the status of PFAS waste disposal methods and equipment cleaning methods for firefighting foams. Project Aim This project aims to obtain current information on the disposal methods for PFAS-containing firefighting foam, as well as methods for the cleaning of stationary or mobile PFAS-containing firefighting equipment. This includes information about: their availability across the EEA, including (for waste disposal) their availability at industrial scale to handle large amounts of PFAS firefighting foams, their technical performance (i.e. percentage of PFAS reduction/residual PFAS concentrations) and conditions of uses/constrains, their costs (per kg or litre of PFAS waste to dispose of or per equipment to be cleaned), identity and concentrations or ratios of the substances generated by the process and their estimated emissions in the environment, available case studies, overall evaluation of pros and cons of the technique, references to the sources of information, and any other information of interest. The first section of this report discusses the methods for the disposal of PFAS-containing firefighting foam. This also includes methods for run-off water from fire incidents in which PFAS-containing foams have been used. The aim is to point to best practice methods with a prioritization on methods with complete or maximised defluorination. As such the focus lies on large scale established methods and not on small scale laboratory methods. However, if new promising techniques not available yet at large industrial these should be mentioned as well since they could be implemented in a near future for waste disposal of smaller foam users. For the identified treatment methods, the substances which can potentially be released (for example F-gases) will be highlighted. It should ultimately be guided to a technique related to low/no F-gas releases. 7/80 Ramboll - [Title] The second part of the report contains the cleaning methods of stationary or mobile PFAS-containing firefighting equipment. As a PFAS-concentrations threshold for the cleaning methods 10.000 to 50.000 ppb should be considered. Additionally, any considered technique from other countries should be also available in the EU. 2. MATERIAL AND METHODS In order to obtain information on the disposal and cleaning methods a desktop study was performed. This study was based on: Literature databases (Europe PMC, PubMed) Reports from environmental agencies Case studies/Projects Reports from NGOs Available online data from associations and manufacturers Additionally, expert interviews were performed in order to obtain unpublished information. Literature search 2.1.1 Disposal methods The chosen literature databases were Europe PMC and PubMed. For the search the following search term was chosen: Europe PMC: ABSTRACT:(per- and polyfluoroalkyl OR PFAS OR perfluoroalkyl OR polyfluoroalkyl OR fluorinated OR fluor*) AND ABSTRACT:(firefighting foam OR fire fighting foam OR fire-fighting foam OR Aqueous film forming foam OR Aqueous film-forming foam OR AFFF) AND ABSTRACT:(disposal OR destruction OR waste water OR WWT OR sewage OR incinerat* OR combust* OR landfill OR waste OR removal) The abstract function was chosen due to a higher chance of finding a relevant publication. As of 19.01.2021 this resulted in 42 hits. PUBMED: (PFAS OR perfluoroalkyl OR polyfluoroalkyl OR fluorinated OR fluor*) AND ("firefighting foam" OR "fire fighting foam" OR "fire-fighting foam" OR "Aqueous film forming foam" OR "Aqueous filmforming foam" OR AFFF) AND (disposal OR destruction OR "waste water" OR WWT OR sewage OR incinerat* OR combust* OR landfill OR waste OR removal) As of 19.01.2021 this resulted in 38 hits. After combining the results from both searches and the removal of duplicates 61 papers were found. From these 61 papers nine were found to be relevant for the disposal or removal of PFAS-containing AFFF. EPAs, NGOs, case studies and industry websites were also screened for information on disposal methods for firefighting foams. All found sources were compiled in an excel sheet for better overview. 2.1.2 Equipment cleaning The following search string was used in PUBMED: 8/80 Ramboll - [Title] 3. DISPOSAL METHODS FOR PFAS IN AFFF Description of the problem The strength of the C-F-bond provides the PFAS with a high thermal and chemical stability. This gives PFAS unique physiochemical properties which make them an ideal substances group to use as a surfactant in firefighting applications. PFAS are added to aqueous film-forming foams (AFFF) as a fluorosurfactant. These AFFF create a gas impermeable layer of water on the surface of flammable liquids and as such surpass the mixture of fuel in the foam. This way the extinguishing effect of the foam can be enhanced. AFFF are commonly used in military and civilian applications such as airports and industrial sites with a concentration of up to 6 % of PFAS. They are also used for fire protection of large tank farms, road accidents, as well as in the railway industry. Commonly used in AFFF, as surfactants were perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA). These two substances have already been restricted due to their persistent, bioaccumulative and toxic properties. As such shorter chained homologues as well as fluorotelomers have been used, which are suspected to have comparable properties as PFOS and PFOA. Due to their open application and high PFAS concentration, firefighting foams have a high potential to contribute to the spill of PFAS into the environment. As such the containing PFAS contaminate the surrounding soil and water. Once in the environment they persist for long time. For this reason, ECHA announced the aforementioned intention to restrict the use of PFAS in firefighting foams. For this a disposal plan for the remaining stock of PFAS-containing AFFF needs to be developed in order to safely dispose of the PFAS in AFFF in an environmentally friendly matter. In this chapter the identified disposal methods are described. A differentiation is made between the disposal of AFFF concentrate and run-off water. The AFFF concentrate is mostly composed of water with smaller concentrations of solvents, surfactants and stabilisers with PFAS-concentrations ranging from 0.1 45 % with an average PFAS concentration between 2 3 %. This concentrate is then mixed with water to form the applied firefighting foam. Typical mixing rates of the concentrate with water ranges between 1 % and 6 % (Wood et al. 2020). From this information it can be derived that the typical PFAS concentration in the applied firefighting foam is in the range between 0,02 0,18 %. Only methods with a complete or maximised defluorination or mineralisation were considered. This excludes the treatment of AFFF concentrates and run-off water in typical municipal and industrial waste water treatment plants and the disposal on landfills as these methods do not effectively destroy the containing PFAS (Houtz et al. 2018). Furthermore, only large scale established, and financially feasible methods were looked at. If a promising technique was identified which is not yet available at the industrial level it is mentioned in the chapter on emerging techniques. 11/80 Ramboll - [Title] Disposal of PFAS-containing AFFF concentrates The incineration of PFAS is according to recent literature and stakeholder input the most reliable method for their destruction. Several authorities and associations also recommend the incineration of AFFF concentrate and run-off water as the most efficient method for destruction (AU-EPA 2021; CA-EPA 2021; FFFC 2016). Also the collected input from stakeholders shows that the only available adequate disposal option for PFAS-containing AFFF is incineration at high temperatures. Based on available literature, the incineration is performed either in hazardous waste incinerators or cement kilns. According to literature, some manufacturers and downstream companies offer to take PFAS-based foams back (sometimes only if new fluorine-free foams are purchased). For example, Bio-Ex offered in the past (year 2018-2019) to take back PFAS based AFFF when the same amount of fluorine-free foam was purchased1. 3.2.1 Physical destruction Incineration in HWI plants Background The strongest bond in a PFAS-molecule is the carbon-fluorine bond with a bond strength of 485 kJ/mol (Roesch et al. 2020). This bond needs to be broken in order to completely destroy a PFAS molecule. The breaking of only the carbon-carbon bonds may lead to the formation of shorter fluorinated molecules, such as ultra-short chain PFAS like trifluoroacetic acid and fluorinated gases like hexafluoro ethane (C2F6) and tetrafluoro methane (CF4). The complete thermal destruction, meaning mineralisation, of a PFAS molecule leads to hydrogen fluoride, water, and CO2. Technical performance The main principle of waste incineration lies in the thermal breaking of the chemical bonds in a molecule. For this the IED requires European waste incinerators to operate at a minimum temperature of 850C with a residence time of at least two seconds. In Europe, for hazardous waste with more than 1 % of halogenated organic substances (what would also apply to PFAS-based AFFF run-off and cleaning water) the incinerator needs to reach temperatures of at least 1,100C (2010/75/EU 2010). The respective incinerators are commonly called hazardous waste incinerators (HWI). To current knowledge, the conditions can break the chemical bonds of a molecule and transform the waste into CO2, water, salt, and ash. Hazardous waste incinerators are designed to handle and destroy the most difficult hazardous (explosive and/or toxic) substances. Hazardous waste incinerators have specialized systems for the input of waste material, depending on the type of waste being handled. This is particularly important for some of the most hazardous and toxic wastes. Options include a solid waste bunker, a tank farm for liquid and pasty wastes, drum storage and transportation facilities. For certain (highly reactive) wastes, a dedicated direct injection system is necessary. The decomposition temperatures for PFAS vary depending on chain length and functional group. PFOA decomposes already at around 100 C, FOSA at 150 C, PFHxS and PFOS around 350 C and PTFE at around 500 C. At these temperatures the bonds inside the compounds are broken and gaseous fragments are formed. During the decomposition of PTFE fragments such as CF, CF3, C2F4 and C3F5 can be found which indicates, that not all carbon-fluorine bonds were broken (Wang et al. 2015). To completely mineralise PFAS to hydrogen fluoride, water and CO2 higher temperatures are needed. According to current literature the temperatures should reach at least 1,100 C to degrade PFAS to carbon dioxide and hydrogen fluoride (KEMI 2016). The Danish Ministry of Environment published a report on the incineration of persistent organic pollutants (POPs) including PFOS. It is stated, that PFOS will be destroyed to more than 99 % by co-incineration and that other studies 1 For more informat on see here accessed at 01.04.2021 12/80 Ramboll - [Title] have shown a destruction efficiency of more than 99.97 % for fluorotelomers, chlorofluorocarbons and PTFE in conventional waste incineration. It is however also stated, that during the decomposition of PFOS at 900 C simple fluorocarbons such as CF4, C2F6, CHF3 and C2H2F2 will be formed (Lundin & Jansson 2017). Among the fluorinated gases tetrafluoro methane (CF4) is the hardest to destroy, as it only contains carbon-fluorine bonds. Figure 1: The HWI process taken from Eurits homepage Side products and emissions A study performed in 2014 analysed the ash and waters arising from multiple waste incinerators in Sweden. The incinerators generally operated at temperatures above 850 C and employed a flue gas cleaning process where the flue gas is first pumped through an acidic solution and then through a neutral step where sulphur dioxides are separated through the addition of lye. While multiple PFAS could be found in all sampled media the authors conclude that as the amounts were so low that waste incineration plants in Sweden are unlikely to contribute significantly to environmental emissions of PFAA (Sandblom 2014). According to data from the US, the end product of the complete combustion of any organic compound will lead to carbon dioxide and water which will be emitted to the air. In the case of PFAS, hydrogen fluoride will also be formed if the compound is completely destroyed. It can be found in the bottom ash as well as the flue gas. In order to remove the HF from the gas a gas scrubber is applied. For this the hot flue gas is cooled in a quenching unit filled with water whereby the HF dissolves in the water. This step is then repeated with a multistep scrubbing tower where the flue gas is scrubbed with a sodium hydroxide solution to remove all remaining HF. The resulting effluent is then quenched in a calcium hydroxide solution where the dissolved fluorine precipitates as calcium fluoride. As this method employs an alkaline solution it may also remove any airborne charged PFAS such as PFCA and PFSA but can however not remove fluorinated gases(US-EPA 2020a). If the temperature is too low products of incomplete destruction will be formed. These include for example CF4, C2F6, CHF3, C2H2F2 and C3F8(DK-EPA 2019; US-EPA 2020a). 13/80 Ramboll - [Title] A quantitative analysis of the formation of these fluorinated gases during the combustion of PFAS has not yet been performed. In general, these gases have a high greenhouse gas potential and should be avoided. As the PFAS destruction efficiency of the thermal treatment is not 100 %, small amounts of PFAS will not be destroyed and as such can be emitted to air or be found in the fly and bottom ash. The ashes are often landfilled and the contained PFAS can thus be washed out and emitted into the water and ground. However, based on data from Sweden, PFAS concentrations in fly and bottom ash are very low (26 748.3 pg/g) (Wohlin 2020). Another study concluded that in total less than 10 kg of PFAA are deposited on Swedish landfills per year from ash from waste incinerators (Sandblom 2014). Data from stakeholder interviews indicate that there is a need for standardisation and future scientific investigations: One stakeholder from Germany made it clear that there is still a need for research with regard to the incineration of PFAS-containing wastes and the associated issues, particularly with regard to the required minimum temperatures and possible products of incomplete incineration. In the past, investigations have already been carried out, for example at household waste incineration plants, but these often focused on individual substances such as PFOA and PFOS or long-chain compounds. Although it can be assumed that these compounds break down at sufficiently high temperatures and long residence times, the extent to which short-chain compounds or products of incomplete combustion (PICs) are formed or emitted and how these are to be evaluated has not yet been sufficiently researched according to current knowledge (LASTFIRE-Interview 2021). Another stakeholder from Germany stated that currently measured background levels of PFAS substances must come via incineration. According to measurements in Bavaria, when PFAS is measured in soil 50% of taken samples would be over current threshold levels as defined by the Bavarian PFC assessment guidelines (measurements based on DIN 3841414) (LfU-Gierig-Interview 2021). The same stakeholder also indicated that so far, there are no validated measurement methods for the determination of PFAS in exhaust air. However, a DIN-standard for the determination of PFAS in exhaust air is drafted right now. The stakeholder guessed it will take approx. 2-3 years to publish it (LfU-Gierig-Interview 2021). Availability across the EU According to the Nordics Council of Ministers there are 808 incineration facilities in Europe, including hazardous and municipal waste incinerators (NordicCouncil 2019). The Confederation of European Waste-of-Energy Plants reported in 2018 that there are 492 waste to energy plants operating in Europe. This number does not include the hazardous waste incineration plants. In total the 492 plants treated 96 million tonnes of waste in 2018 (CEWEP 2018)2. Hazardous Waste Europe represents 155 hazardous waste treatment installations in Europe with a total treatment capacity of 4.6 million tonnes per year. These facilities however also include non-incineration processes such as biological treatment and landfills3. Another association, the European Union for Responsible Treatment of Special Waste EURITS, shows on its homepage the availability of HWI across the EU (see Figure 2). Of course, this overview only includes member companies of this respective association. Based on the overview it can be assumed, that HWI availability differs across Europe. This is in line with a stakeholder comment from Norway who reported that there is no HWI available in Norway, thus PFAS-based AFFF was sent to cement kilns (see also next chapter) (Equinor-Ystanes-Interview 2021). Another stakeholder from the Netherlands indicated that there would be no such incineration 2 Assuming that the difference between the 808 incineration facilities and the 492 waste to energy plants are hazardous waste incinerators t could be assumed, that there are 316 hazardous waste incinerators in Europe. However, the exact numbers are not known. 3 Numbers are taken from the respective homepage, see here accessed at 01.04.2021 14/80 Ramboll - [Title] plant in the Netherlands. Neighbouring countries Belgium and Germany would have these (LECBrandweerBRZO-Submission 2021). Figure 2: Availability of HWI across the EU taken from Eurits homepage According to the German Federal Environmental Agency there are 29 hazardous waste incinerators in Germany with a total capacity of 1,520,490 million tonnes per year4. The WI BREF reported 121 hazardous waste incinerators in Europe in 2019 with a total capacity of 6.75 million tonnes of waste per year however the exact incineration conditions are unknown. Costs5 According to the EC/ECHA report the cost to incinerate one PFAS-containing AFFF litre range between 0.3 1.5 /l (Wood et al. 2020). This range is in accordance to the data gathered in the stakeholder engagement and literature review of this project: On their website, the Rosenbauer Group reports a price of 200 400 /m for the high temperature disposal of PFAS-containing AFFF, which corresponds to 0.2 0.4 /l6. Also, another company from Germany offers to take back foams for 1 2 /l7. A stakeholder from Germany named a price of 700 /t for the incineration of PFAS- containing AFFF which corresponds to 0.7 /l (DUS-Valentin-Interview 2021). Another stakeholder from Germany named a price of about 400 - 600 /t, which corresponds to 0.4-0.6 /l (LfU-Gierig-Interview 2021). Another stakeholder from Germany named prices between 700-1000 /t, which corresponds to 0.7-1 /l. The specification of the fluorine content before incineration is obligatory (Cornelsen-Interview 2021). Higher prices are reported for the US and Australia. The US EPA published an interim guide on the destruction of PFAS where a price for liquid halogenated hazardous waste of 1,218 1,770 $/ton is 4 Numbers are taken from the respective homepage, see here accessed at 01.04.2021 5 The following assumptions have been cons dered: dens ty of PFAS-containing AFFF is approximated to be 1 kg/m3 and exchange rate Euro to US dollar of around 1,2:1 (as of 01st of April 2021) 6 Numbers are taken from the respective homepage, see here accessed at 01.04.2021 7 Numbers are taken from the respective homepage, see here accessed at 01.04.2021 15/80 Ramboll - [Title] stated. This corresponds to roughly 1 1.46 /l (US-EPA 2020b). For Australia 2,000 per m are reported, which corresponds to 2 /l8. Additional information and available case studies According to one stakeholder from Germany, incineration plans often do not accept PFAS-based AFFF, because of its foaming capacities (the liquid waste is fed into the combustion chamber through a nozzle) and the formation of HF-acid (corrodes the tiling). This could lead to the fact that the prices for AFFF-incinerations will increase in the future (Cornelsen-Interview 2021). On stakeholder from Germany stated that the only publicly accessible plant for a thermal treatment of waste containing PFCs in Bavaria is GSB - Sonderabfall-Entsorgung Bayern GmbH in Ebenhausen near Ingolstadt. The incineration plant consists of 2 lines with a total annual throughput of approximately 220,000 tons. In 2020, GSB thermally disposed of about 834 t of waste from the segment of extinguishing foam, extinguishing water, extinguishing agents, for which at least a PFC contamination could not be excluded in principle; only 23.88 t of foam extinguishing agents, extinguishing foam, extinguishing water contain a specific reference to PFC or PFT in the waste designation. Since the exhaust gas cleaning technology used in Ebenhausen consists, among other things, of various scrubber stages, which generally ensured a high separation of halogenated pollutant compounds such as HF, the emission of HF is far below the legal limit. Combustion temperatures average 1080C in the rotary kiln and 1000C in the afterburner chamber. Thermal destruction of components containing PFC/PFT can therefore be assumed with a high degree of probability (LfU-Gierig-Interview 2021). A stakeholder from the Netherlands brought up the idea to set up consortia in different regions in Europe for the destruction of foam concentrates. Many parties (public and private) will soon have foam concentrates that may no longer be used. Tackling this together seems a good option for cost-efficient and environmentally friendly solutions (LEC-BrandweerBRZO-Submission 2021). 3.2.2 Physical destruction Incineration in cement kilns Background According to (Lundin & Jansson 2017), cement kilns typically consist of a long cylinder of 50150 meters in length, inclined slightly from the horizontal (3% to 4% gradient), which is rotated at about 1-4 revolutions per minute. Raw materials such as limestone, silica, alumina, and iron oxides are fed into the upper or cold end of the rotary kiln. The slope and rotation cause the materials to move toward the lower or hot end of the kiln. The kiln is fired at the lower end, where material temperatures reach 1,400C1,500C. The fuel used to heat the rotary kiln has traditionally been coal, but lately different kinds of waste fractions have been utilized in some plants. Wang et al. published a paper in 2015 indicating, that the addition of calcium hydroxide can catalyse the defluorination process of PFAS. At temperatures of 900 C this method showed high transformation rates, indicated by the formation of calcium fluoride. For PFOS a transformation rate of 90 % was achieved with even better results for PFHxS. PFOA and FOSA however only reached transformation ratios of around 50 % suggesting, that the functional group has an influence on the efficacy of the method. PTFE reached transformation ratios of 80 % already at a temperature of 400 C (Wang et al. 2015). Comparing this to the decomposition temperature of 500 C for PTFE, the calcium salts can lower the needed reaction temperature by 100 C. This research suggests that the addition of these salts to the incineration process can lower the formation of fluorinated gases. According to data from Australia, the advantage of adding PFAS waste to the production of clinker in cement kilns, is that no extra energy is required to destroy the PFAS and additionally the quality of the clinker can be enhanced through the addition of fluorine (Holmes & Queensland 2020b). 8 See comment on Rosenbauer homepage, see here accessed at 01.04.2021 16/80 Ramboll - [Title] Fluorinated substances react in the cement production process as mineralizers, which can promote the formation of a specific phase altering the thermodynamic equilibrium of reactions. Mineralizers are more efficient in the presence of a liquid phase and can contribute to the flux activity. Next to fluor other examples are: Zinc, Manganese, Sulphur, among others (Cemex 2013). The addition of fluoride has proven to increase the reactivity of clinker used in cement as well as reducing the amount of clinker needed. Typical fluorine addition rates are 0.2 % by weight of clinker to achieve mineralisation without adverse effects (Cooper 2014). Fluorine is often added in the form of calcium fluoride to the cement kiln but can also be added in the form of PFAS, however the calcium fluoride content should not be lower than 40%. The inclusion of calcium fluoride can decrease the burning temperature by 100 C (Cemex 2013). As limestone (calcium and magnesium carbonate) is an ingredient for the production of clinker PFAS could be added to form in situ calcium fluoride (CaF2) in the cement kiln. The preferred method of introduction of PFAS wastes is by blending the foam concentrate or any other liquid wastes into the alternative fuels (waste oils) so as to control and minimise the water content that would otherwise disturb the temperature of the burner flame. Solid wastes such as PFAS contaminated GAC and resins can also be introduced packaged in 20L buckets at a suitable point in the kiln as is currently done for clinical and drug wastes. Overall, it is considered that the use of cement kilns for PFAS destruction represents the best option based on the very large safety margins in the normal production conditions for complete destruction (calcium, high temperature, long residence times), permanent capture of the fluorine as inert, insoluble, non-toxic minerals, no need to modify kiln equipment, and no need for additional fuel/energy costs (Holmes & Queensland 2020a). Technical performance The cement kiln generally operates at temperatures between 800 1,800 C depending on which process step with a total residence time of about 25 minutes. At the hottest point the residence time at ~17 21 seconds at 1,800 C (Holmes & Queensland 2020b), which according to recent literature is hot enough to even destroy CF4. As such this technology can be used to effectively destroy PFAS and at the same time produce cement clinker. The Queensland government in Australia has already conducted a trial run with a total fluorine input of 325kg/h from which 5kg/h was from PFAS. As a result, no PFAS and only minimal amounts of hydrogen fluoride could be detected after the burning process. The quality of the clinker was unaffected (Holmes & Queensland 2020b). Also, according to US-EPA, the temperature at which the cement kilns operate (usually around 1400C-2000 C) allows for full destruction of PFAS compounds and the residence time (6-10 sec) is believed to be sufficient (Patterson & Dastgheib 2020). For conventional waste incinerators on average ~354 534 kWh/m of energy is needed at 1,100 C for the burning of waste (Holmes & Queensland 2020b). Maga et al. state an energy demand for the high temperature incineration of AFFF containing spent fire-extinguishing water at 1,100 C of 1,312 kWh/m (Maga et al. 2021a). This value is higher due to the added energy needed to vaporise the water. Side products and emissions According to stakeholder knowledge, cement kilns do not possess the same filter techniques as incinerators handling hazardous waste (HWI). This needs to be considered when emissions are discussed (DUS-Valentin-Interview 2021). However, there are no standardized methods to monitor PFAS in exhaust air from incinerators as discussed above. Other Stakeholders also indicated, that there is no knowledge about a possible PFAS-contamination (or other fluorinated side products) of the end product (cement) (LASTFIRE-Interview 2021). Data from Australia however, indicate that when PFAS introduced to both the main burner and the calciner produced results of very high destruction efficiencies with no PFAS in flue gases and no 17/80 Ramboll - [Title] change to the usual emissions of very low levels of HF in normal clinker production. A significant point to note is that the trial runs of destruction of PFAS at 5kg/hr (as F) were done with and without the input of aluminium smelter cell waste materials with fluorine throughput of 325kg/hr (as F). The destruction of the fluorine-containing (~15%) spent cell carbon and refractory waste has been common practice in cement kilns for decades with low HF emissions demonstrating the very high efficiency of fluorine capture by calcium and the failure of the carbon and fluorine to recombine into PFAS. The Cement Australia kiln at Gladstone is licensed to destroy up to 5kg/hr PFAS (as F) based on the maximum throughput rate in the trials (at ~4.50/L). However, the other larger fluorine inputs with no significant HF or PFAS outputs suggest that greater throughputs of PFAS wastes could be destroyed just as effectively as the 5kg/hr (as F) in the licence (Holmes & Queensland 2020a).. Availability across the EU According to the best available techniques reference document for the production of cement, lime and magnesium oxide, there are 268 cement kilns in Europe. In 2004 6.1 million tonnes of waste was used as fuel in cement kilns from which one million tonnes were hazardous waste. It is also stated that in 2007 17% of fuels was sourced from waste (CLM-BREF 2013). German authorities are not aware that the incineration of PFAS-based foams in cement kilns are taking place in Germany (DUS-Valentin-Interview 2021; LASTFIRE-Interview 2021; LfU-GierigInterview 2021). According to other stakeholders this is a developing field in the EU (LASTFIREInterview 2021). Based on desktop search, also no other cases are reported. However, in Australia calcium catalysed destruction in cement kilns is currently best practice (Holmes 2020) . Costs One stakeholder indicated costs for incineration in cement kiln in Norway of 1-2$/litre, what would correspond to 0.85 to 1.7 /l (Equinor-Ystanes-Interview 2021). Australian Stakeholder indicate a cost of 4.50/L (Holmes & Queensland 2020a). This price (EU-based) is comparable to the prices reported for HWIs (0.2 2 /l). Additional information and available case studies One stakeholder sent its waste to a cement kiln (Norcem in Brevik) in Norway, which uses temperatures of 2,000 C. To his knowledge this would be the only waste disposal option in Norway, as most municipal waste incinerators operate at lower temperatures (800 C) (Equinor-Ystanes-Interview 2021). Final conclusion on the disposal of PFAS-containing AFFF concentrates The incineration of PFAS-containing AFFF is the most used disposal method. Literature indicates that waste incinerators at temperatures of 900 C are able to destroy PFOS at more than 99%. A destruction efficiency of more than 99.97 % for fluorotelomers, chlorofluorocarbons and PTFE in conventional waste incineration was also reported. However, this process might not lead to the complete mineralisation of the PFAS i.e. the decomposition of the PFAS to CO2, water, and hydrogen fluoride. At these temperatures short chain fluorinated compounds such as CF4, C2F6, CHF3, C2H2F2 and C3F8 can be formed and released to the air. Literature indicates that temperatures of at least 1,400 C are needed to destroy CF4 and as such completely mineralise the PFAS. Literature indicates, that 1,100 C is sufficiently hot and feasible for the destruction of PFAS, however no study has provided quantitative results on possible fluorinated gas emissions. The average cost of approximately 1/l (range is 0.2-2 /l) is comparatively cheap but the process requires high amounts of energy as the water needs to be vapourised. No actual data has been found that would indicate that the cost for incineration increased recently or will increase in the future. However, based on input of a stakeholder, the capacity is an issue for some hazardous waste incinerators, as not all of them can handle large amounts of liquid waste and foaming can cause 18/80 Ramboll - [Title] issues, when it is stored intermediately with other liquid waste (WFVD & Peltzer 2021). Also, according to another stakeholder from Germany, incineration plans often do not accept PFAS-based AFFF, because of its foaming capacities (the liquid waste is fed into the combustion chamber through a nozzle) and the formation of HF-acid (corrodes the tiling). This could lead to the fact that the prices for AFFF-incinerations will increase in the future (Cornelsen-Interview 2021). The co-incineration of PFAS waste in cement kilns is a viable alternative to incineration in HWI, as these kilns reach temperatures of up to 1,800 C with residence times of ~20 seconds. It has been shown that the addition of calcium fluoride can increase the quality of the clinker. Additionally, calcium salts can decrease the decomposition temperature of PFAS and increase the mineralisation rate by forming calcium fluoride. Through the addition of PFAS-containing waste to the clinker production in-situ calcium fluoride can be formed, which can increase the clinker quality and destroy the PFAS. The applicability of liquid AFFF concentrate in the cement kilns in the EU is rather unclear. German authorities are not aware that the incineration of PFAS-based foams in cement kilns are taking place in Germany (DUS-Valentin-Interview 2021; LfU-Gierig-Interview 2021). One stakeholder from Norway indicated that his company sent PFAS-based firefighting foams to a cement kiln as there in no HWI available in Norway (Equinor-Ystanes-Interview 2021). No costs have been reported for this case. In Australia calcium catalysed destruction in cement kilns is well established and currently best practice (Holmes 2020). Australian Stakeholder indicate a cost of 4.50/L (Holmes & Queensland 2020a). However, stakeholders from Germany indicated, that cement kilns dont have the same filter techniques as HWIs (DUS-Valentin-Interview 2021). In addition, stakeholders from Germany are concerned that the cement could also be contaminated (DUS-Valentin-Interview 2021). However, data from Australia indicate no contamination of the cement and a very high destruction efficiencies with no PFAS in flue gases and no change to the usual emissions of very low levels of HF in normal clinker production (Holmes & Queensland 2020a). According to German federal environmental authorities the degree of destruction of PFASs (e.g. related to the input concentration) during incineration is not well understood. In general, there is still a need for research concerning the incineration of PFAS-containing wastes and thus also of AFFF concentrates (LANUV-Voland-Response 2021). 19/80 Ramboll - [Title] 4. DISPOSAL OF PFAS-CONTAMINATED (FIRE RUN OFF AND CLEANING) WATER Description of the problem General Treatment of PFAS-contaminated water As shown above, the current go-to technique for the disposal of PFAS-containing firefighting foam is incineration either in incineration plants and/or cement kilns. Incineration at high temperatures is a destructive technique and leads to the mineralisation of PFAS. For PFAS-containing fire run of water (and any other PFAS contaminated water), the treatment methods and successive disposal methods can be distinguished between non-destructive and destructive techniques, whereby the final destruction of PFAS is in most cases also a succeeding incineration at high temperatures. Generally, it is not well known, what happens to run off water after a fire incident. Based on stakeholder input, it is known, that companies (at least in Germany) which are regulated by the LRRL contain run off water. Other fire run off water from fires that happen outside these facilities (municipal fires) is not well contained. This is also true for marine applications. This will be again highlighted in the a sperate section of this report (see What happens to fire-run off water?) According to JOIFF, from a waste management perspective, treating foam concentrates and spent foam mixtures resulting from AFFF and fluoroprotein foams used in fire incidents is not possible using biological treatment processes. Conventional wastewater treatment plants will not breakdown non-biodegradable PFASs. Discharge of these wastes to sewer is therefore not an effective treatment (JOIFFF 2020). In 2020, UBA together with Arcadis highlighted in a review article all available PFAS treatment technologies for groundwater and ranged them according to their practicality (UBA 2020). In Error! Reference source not found. a visual summary of this overview is shown. Figure 3: PFAS treatment technologies for water, ranged according to their practicality (taken from (UBA 2020)). 21/80 Ramboll - [Title] When PFAS treatment technologies for water are discussed the volume of the water and the proportional PFAS-concentration need to be considered. According to Horst et al., the current state of the practice for treating water contaminated with PFAS is to take extremely large volumes with low PFAS concentrations typically in the part per trillion range (ppt; i.e., nanogram per litre [ng/L]); and convert it into much smaller volumes of high PFAS concentration, which can then be more economically treated using technologies attempting to destroy PFAS (Horst et al. 2020). In Figure 4 the conceptual impact of volume on the relevance of currently available non-destructive and destructive treatment approaches for PFAS contaminated water is shown. Figure 4: Conceptual impact of volume on the relevance of currently available non-destructive and destructive treatment approaches for PFAS contaminated water (taken from (Horst et al. 2020)) Fire run off water and cleaning water In the context of this project, only feasible and mature techniques for the treatment of fire run off and cleaning water (shown in Figure 5 in the green box) have been analysed in detail. For both PFAS-contaminated water types it is assumed that a rather high PFAS-concentration is to be expected. For example, PerfluorAd is designed for treating water containing PFAS concentrations greater than 0.3 g/L (Ross et al. 2018). 22/80 Ramboll - [Title] Figure 5: PFAS treatment technologies for water, ranged according to their practicality (taken from (UBA 2020)). Available techniques focussing on in situ techniques for groundwater are not considered (e.g. activated carbon injection into aquifer9), as they lack market maturity and are not compatible with both types of water (Concawe 2020). In addition, those technique for which no references were available for treatment of fireextinguishing waters or water with PFAS concentrations within the range of fire-extinguishing waters have been also not analysed. According to Concawe, for the following techniques there are no reported case studies regarding fire-extinguishing water treatment: Electrochemical degradation Sono-chemistry UV-radiation Plasma treatment These non-destructive and destructive treatment techniques have therefore not been considered. The techniques have been analysed and updated based on current available literature (predominantly the ITRC-guideline (ITRC 2020) and a review of water treatment systems for PFAS removal from Concawe (Concawe 2020)) and finally stakeholder input. According to UBA, the treatment of high AFFF-contaminated water poses a challenge. With the help of electrocoagulation and filtration, the water was prepared to such an extent that it could be treated by reverse osmosis (degree of purification approx. 99.9%) (UBA 2020). What happens to fire-run off water? One stakeholder from Germany indicated, that PFAS-contaminated fire-run off waters mostly enter the environment (both via WWTP and directly) and (company-owned or municipal) WWTPs. Those who use chemical and physical treatment methods only are not suited to appropriately handle PFAS. In his opinion, a more suited way of handling the run-off water would be to collect it and store it in silos, where it can be treated. However, he observed this only in rare cases. Legally, in Germany, the run-off water after an incident is the responsibility of the company in which the fire occurred. Based on an article by Cornelsen, three cases are to be distinguished when the fate of run-off water is to be characterised (Cornelsen 2021): 1. If the fire event occurs on unsealed surfaces and/or grounds that do not have retention facilities or catchment areas for the extinguishing water, it must be assumed that the extinguishing water will infiltrate into the subsoil and possibly also into the groundwater (see Figure 6). Following infiltration, the contaminated soil material may have to be excavated and then disposed of (e.g. landfilled or incinerated), as shown in Figure 7 or the groundwater may have to be cleaned up over many years by means of a pump-and-treat measure (see Figure 7). 2. If the fire occurs on a paved area and the extinguishing water flows directly to the natural receiving water via the storm drain system, there is no possibility of intervention and the environmental impact is immediate. If, however, the water enters a sewage system, it might be possible to collect the PFAS-contaminated extinguishing water in the basin systems of the wastewater treatment plant. For this, the necessary space would have to be available, the "wave of pollutants" would have to be collected in a targeted manner and diverted into the buffer basins. If this is not possible - which is likely to be the more frequent case in practice - then it must be assumed that a significant share of the PFAS substances 99 According to the national geographic society an aquifer is an underground layer of water-bearing permeable rock, rock fractures or unconsol dated materials (gravel, sand, or silt). Groundwater can be extracted using a water well. The study of water flow in aquifers and the characterization of aquifers is called hydrogeology. See here, accessed at 02.04.2021. 23/80 Ramboll - [Title] will pass through the wastewater treatment plants without any targeted treatment of these non-biodegradable substances. 3. Companies that are subject to the Extinguishing Water Retention Directive (LRRL) have bunding areas in which the extinguishing water can be temporarily stored. In the case of intermediate storage on site, various options can be selected for the subsequent handling of PFAS-contaminated extinguishing water. a. Transport of the extinguishing water in silo vehicles to off-site water treatment plants: The so-called CP plants (chemical-physical water treatment plants) are mostly plants that accept process waters from trade and industry. In many cases, pre-treatment is carried out via a neutralization step in order to feed the water influenced in this way for subsequent treatment in the public wastewater system. As a rule, such plants do not have a purposefully equipped process stage for the treatment of PFAS. Under such marginal conditions, a noticeable reduction of the PFAS load cannot be assumed. b. Transport of the extinguishing water in silo vehicles to incineration plants: domestic waste incineration plants (850C), and hazardous waste or high-temperature incineration plants (1,100C). c. On-site treatment of firefighting water with activated carbon (GAC). Theoretically conceivable and already implemented in some practical cases is the use of largevolume activated carbon filters for the treatment of PFAS -contaminated firefighting water. Depending on the respective PFAS contamination and the so-called organic and inorganic background contamination of the extinguishing water, it may not be possible to achieve the treatment objective at all or the costs resulting from the treatment may assume considerable dimensions. d. On-site treatment with the PerfluorAd process, in order to enable on-site treatment of PFAS -contaminated extinguishing water and also the risk-free use of activated carbon for such and other applications, the PerfluorAd process was developed, which significantly reduces the content of PFAS as a pre-treatment stage, so that downstream process stages are significantly relieved and costs are reduced. Figure 6: Outline of the entry of firefighting water into the subsurface if no retention facilities are available taken from (Cornelsen 2021). 24/80 Ramboll - [Title] Figure 7: On the left, a representation of a soil excavation after successful infiltration of extinguishing water into the subsoil. On the right the pump and treat procedure is shown (Cornelsen 2021). Another stakeholder from Germany indicated that there is awareness about PFAS-contamination and that the water is treated with adequate responsibility. In Bavaria (and also Germany in general) fire water-containment measures are in place that need to follow the Lschwasser-RckhalteRichtlinie (LRRL in english: Extinguishing Water Retention Guideline, an English translation is not available). According to his knowledge the containment based on this guideline works (e.g. in industry plants), however, burning incidents involving large fires at facilities that are not covered by LRRi are more problematic. As an example, he named scrap tire storages (LfU-Gierig-Interview 2021). A stakeholder from the UK (LASTFIRE) informed that during/after fires the water run off containment has a lower priority than other concerns, at least this has been the case historically. However, adequate containment is possible in an industrial context but not followed in reality or not easy/cost effective to implement fully. In general, the containment of the water is not a problem for smaller fires, where the quantity of water is small, but can be for big fires. This is due to the fact, that the bunding might fail due to the high amount of water, or the bunding may not be sized to take account of the large amounts of water required. For the successful containment of PFAScontaminated fire-run off waters the type and architecture of bunding areas is of highest importance and should be based on the amount of foam and water (e.g. in fire-fighting ponds) stored in the facility or the amount of fire and water required for a particular scenario (this information should be retained in the site emergency response plan). Today, the size of bunding area is typically calculated to have a holding capacity of 110 % of the largest tank, or where there are multiple tanks in a single bund 25 % of the total capacity of the tanks, whichever is the greater. There are primary, secondary, and tertiary bunding types. The primary containment is the tank itself. The secondary containment is the bund and the tertiary containment is beyond the bund but is designed to either contain a spill or direct the flow to a designed catchment area where it can be managed. Some of LASTFIREs members have taken adequate measures to prevent overflow of water, by having tertiary containment often following reviews from the Buncefield incident. For jetty areas, the containment is even harder, and water would usually go nowadays directly to the sea. Another stakeholder from Germany explained that a complete containment of PFAS-containing runoff water is not in line with his real-life experience. In more detail, he explained that most of the run-off water is forfeit during the operations. Further, the stakeholder explained that there is almost always contamination of soil and water (DUS-Valentin-Interview 2021). 25/80 Ramboll - [Title] PFAS-contents of PFAS-based AFFF and what can be measured Safety data sheets of PFAS-based AFFF often indicate a content of <5 % for fluorosurfactants. According to (Wood et al. 2020) this number can be further narrowed to a concentration range of 2-3 %. In practice, the foam gets further diluted in concentrations between 1 and 6 % (mostly in 1 %, 3 %, and 6 %). In a very recent publication by (Cornelsen 2020) it is stated, that for waters with an undened PFAS composition, as is to be assumed especially when using current AFFF foaming agents, an evaluation of the water load as well as the achievable cleaning results is not possible if only the quantiable individual PFAS are evaluated. Held & Reinhard assume that AFFF foaming agents contain hundreds of precursor substances which include approx. 40 PFAS classes (Barzen-Hanson et al. 2017) and are highly complex and difcult to determine by classical analytical methods (Th. Held & Reinhard 2016). However, the precursors in such complex mixtures can be assessed by the Total Oxidisable Precursor (TOP) Assay (Mumtaz et al. 2019). In the same publication (Cornelsen 2020), the composition of re extinguishing water has been analysed using an exemplary product (not further specified) and various PFAS quantification techniques. In Figure 8 the results of this analysis are shown. Figure 8: PFAS-contents of a 1% AFFF Premix, measured using different analytical techniques. As shown in Figure 8, based on the analysis of 23 individual PFAS substances, as can be determined from parameter lists currently available on the market10, the foam had a total content of only 1.7 mg/l PFAS. It should be noted that precursor substances such as Capstone A and Capstone B are not yet included as parameters in the standard lists of environmental laboratories. In the example shown, these PFASs, which are often not yet quantiable by measurement technology, have a concentration of 59 mg/l alone, i.e. these substances are almost 35 times higher in concentration than the individual PFAS compounds that are quantied by PFAS standard analysis in laboratories. In order to address the total content of uorine-organic sub- stance in complex contaminated waters, the organically bound uorine was therefore used as an additional parameter for PFAS- contaminated waters that were contaminated due to exposure to AFFF foams. In the example in Fig. 3, the concentration of organically bound uorine is 100 mg/l. Assuming that the 10 DIN 38407e42 (status March 2011) served as the basis for the determination of PFASs. Methods using high-performance liqu d chromatography and mass spectrometr c detection (HPLC-MS/MS) after solid-liquid extract on (F42). W th a simple matrix, determination limits of 10 ng/l can be achieved w th this method for the individual congeners. However, in the case of complex matrix loads, the determination lim ts are often increased to several 100 ng/l. 26/80 Ramboll - [Title] average chain length and structure of the PFAS structures contained in current AFFF foams are signicantly similar to the structure of the 6:2 FTS (H4PFOS), a hypothetical total PFAS concentration of 173 mg/l can be calculated. The hypothetical total concentration of PFAS leads, on the basis of the example shown to the conclusion, that the uoro-organic substances in the water that cannot be detected as PFAS single substances can be a factor of 100 higher (or more) than actually measured PFAS by single substance analysis. This knowledge leads to the need to evaluate PFAS that are not known or quantiable as single substances by sum parameters. However (Cornelsen 2020), there is currently no normative standard for this. The above described results by (Cornelsen 2020) show, that there is an ongoing uncertainty about PFAS-substances in AFFF. Based on stakeholder input in the context of this project, it can be stated that PFAS substances based on <C6-chemistry have never been used as an active ingredient for firefighting foams, as the chemistry is not suitable. <C6-substances are unintended by-products of the synthesis process (telomerization process) (FFFC-Interview 2021). When does clean mean clean? Stakeholders have been indicated that there are uncertainties about what level are achievable when the success of cleaning procedures is to be judged. Concerning the wording: One stakeholder made the point that decontamination is to be distinguished from cleaning. Cleaning needs to be done when one foam type is replaced by another (e.g. PFAS-based to PFAS-based). Concerned about remaining PFAS-levels, Martin Cornelsen made the statement that by replacing the AFFF foam with a "truly" fluorine-free foam, there is already a positive effect for the environment. Also, if the PFAS-contaminated equipment of the fire departments would then be cleaned professionally in the course of this and the PFAS contamination remaining in the system were thus cleaned by 90, 95, possibly even 99 to 100%, this would be already a great accomplishment. But to prescribe a cleaning success of 100% bindingly, Martin Cornelsen considers as not goal-leading (Cornelsen-Interview 2021). The same stakeholder also raised that fire extinguishing systems do not release foams permanently. Only at incidents or trips, PFAS-foams are emitted. This happens, in general, every 30-40 years per fire extinguishing system (Cornelsen-Interview 2021). Judged from the reported remaining PFAS-levels, it can be observed that a variety of PFASdetermination techniques is used. There are methods which concentrate on single PFASsubstances and also sum parameters are used. One stakeholder from Australia, indicated that setting cleanout standards for fixed foam systems and fire appliances was a concern in the Queensland foam Policy development stage as there were almost no precedents available. The primary issue was limiting crosscontamination of new foam put into existing systems from residues. From industry inputs and existing limits for foam concentrates we arrived at limits for PFOS + PFHxS in foams of 10mg/kg (UK and EU limits at the time) and 50mg/kg for other long-chain PFAS (by TOP Assay as F) as being practical and achievable for manufacturers and end users in systems and foam manufacture. It is not practical to set goals for cleanout based on wash-water concentrations as every system is different. Since then, experience has shown that much lower levels can be achieved. We have not set any recommended methods as each system is different in age, foam and components but we initially suggested that combinations of aggressive surfactants, solvents such as glycol ethers and methanol may prove to be effective based on foam compositions and lab equipment cleaning techniques. Various fire engineer services have demonstrated that cleanout is achievable to those and lower levels depending on the circumstances, each has their own proprietary process and agents (Holmes 2020). 27/80 Ramboll - [Title] Non-destructive: Granular activated carbon (GAC) treatment Background The treatment of PFAS-contaminated water (or PFAS-containing AFFF) with activated carbon is based on the adsorption of a molecule on the surface of the activated carbon. This is facilitated by van-der-Waals interactions between the activated carbon and the target molecule. As these interactions can occur between any two molecules a broad variety of compounds may be adsorbed, including some PFAS (mainly PFOS, this will be discussed in the technical performance sub chapter). This means that if a high concentration of other organic substances is present, the activated carbon becomes quickly fully loaded and unable to adsorb more molecules. As such the PFAS compete with other contaminants for the adsorption on the activated carbon surface. The carbon is typically supplied as powdered activated carbon or as granulated activated carbon (GAC) carbon (Analytik 2019; US-EPA 2020a). For the treatment with activated carbon the to-be-treated water is first filtered by a sand or multilayered filter to filter out any non-solved contaminants and then sent through one or multiple activated carbon filters. By doing so the solved contaminants including PFAS adsorb to and saturate the surface of the activated carbon. If enough filters are installed in succession virtually all contaminants can be adsorbed out of the solution. The spent active carbon is either sent to reactivation or high temperature incineration. During reactivation high temperatures are used to thermally desorb the contaminants, which allows the reuse of the activated carbon. For this the spent carbon is heated up to 800 C for around 35 120 minutes. The conditions hereby range from a pyrolysis atmosphere (no oxygen) to a mild oxidative atmosphere (low oxygen) in order to restore the original carbon pore-structure. An afterburner with temperatures between 880 1,316 C and a minimum residence time of 1 second is used to achieve a destruction rate of >99.99 % of the remaining contaminants. To what extent PFAS are destroyed under these conditions needs to be evaluated. Not all spent activated carbon can be reactivated. If the levels of organic halogens or metals is too high or the base carbon type is not suitable, a reactivation may not be possible. Alternatively, the activated carbon can also be incinerated via high temperature incineration. A reuse is therefore not possible (US-EPA 2020a) Technical performance According to the ITRC-guideline, individual PFAS have different GAC loading capacities and corresponding breakthrough times (often defined as the number of bed volumes treated prior to detection in the effluent) (Eschauzier et al. 2012). GAC removal capacity for PFOS is greater than PFOA, but both can be effectively removed (McCleaf et al. 2017). In general, shorter chain PFAS have lower GAC loading capacities and faster breakthrough times but could be effectively treated if changeout frequency is increased. There are currently no published studies on the effectiveness of GAC in removing cationic, zwitterionic, and anionic precursor com- pounds; however, a recent theoretical study suggests some precursors are unlikely to be effectively removed by GAC ((Xiao et al. 2017) cited in (Ross et al. 2018). Furthermore, also the organic background of the water needs to be considered as this also lowers the efficacy as other organic substances can also bind to the GAC (Ross et al. 2018). Under optimal conditions i.e. using activated carbon with a high capacity potential, strongly absorbing PFAS, few competitive contaminants, low organic levels and a high concentration in the to-be-treated water loading rates of up to 0.1% can be achieved which corresponds to 1 g/kg of PFAS on the activated carbon. More realistic loading rates lie between 0,004 0,01 %(Analytik 2019; LANUV 2009; Maga et al. 2021a). According to Concawe, the US-EPA Health Advisory level for PFOS and PFOA (0.07 g/L) as well as the proposed EU drinking water threshold of 0.1 g/L for individual PFAS components (0.5 g/L for 28/80 Ramboll - [Title] total PFAS) are achievable by activated carbon treatment, but may require the use of several beds in series (Concawe 2020). A PFAS removal rate of 99.9% has been documented for a fireextinguishing water treated by granular activated carbon. However, this elimination rate has been determined after a very short operation time. The maximum operation time until material exhaustion has not been reported. While higher influent concentrations would lead to higher loadings of PFAS onto the carbon, the presence of numerous co-contaminants may lead to a reduction in the loading due to competitive sorption. According to ITRC, most GAC full-scale treatment system case studies to date are based on treatment of PFOA and PFOS in the impacted drinking water sources. As such, limited information is available regarding the treatment of other PFAS. The full-scale drinking water systems demonstrate that PFOA and PFOS can be removed to below analytical detection limits until breakthrough occurs. Treatment of groundwater impacted with PFAS from an AFFF release area contaminated with PFAS such as fire training areas (FTAs) may require complex pre-treatment and more frequent change-outs (higher influent concentrations compared to influent for drinking water treatment systems) and higher operation and maintenance (O&M) costs. Side products and emissions The adsorption removal mechanism of GAC is not expected to transform precursors (for example, telomer alcohols) to terminal PFAS as would be the case when using advanced oxidation/reduction technology (ITRC 2020). Emission may however arise when the GAC is reactivated or incinerated. For emissions from incineration see chapter 3.2.1. During the reactivation of GAC pyrolysis and gasification conditions are applied to restore the surface of the carbon. Hereby the carbon is heated to temperatures around 800 C under either a non-reactive (inert; no oxygen; pyrolysis) to mildly oxidising (steam and CO2; gasification) atmosphere. As the destruction of PFAS is achieved by completely oxidising all carbons of the PFAS molecule via the reaction with oxygen these processes may lead to different products. Especially under pyrolysis conditions where no oxygen is present small chain PFAS compounds and fluorinated gases may be formed. Typically, the facilities are equipped with afterburners operating between 885 1,316 C with a residence time of at least 1 seconds where all remaining contaminants are ought to be destroyed. As the formation of short chain fluorinated gases under the aforementioned conditions is likely it needs to be assessed whether the afterburner conditions can adequately destroy these compounds (US-EPA 2020b). According to (Ross et al. 2018) research indicates that some PFAAs can be destroyed on GAC surfaces at temperatures as low as 700 C during the reactivation process. Destruction of volatized PFAAs (in the air phase) requires 1,100 C; however, thermal reactivation kilns normally include after- burners for air pollution control, and these usually operate at temperatures above 1,100 C. Thus, a typical thermal reactivation process (800 C to 1,000 C reactivation temperature, plus an afterburner) seems to be well-suited for reactivating GAC that has exceeded its adsorption capacity for PFAAs. However, testing was not performed considering the wider range of PFASs, such as higher molecular weight (less volatile), polyfluorinated precursors reported to be associated with AFFF formulations. Data on whether these temperatures destroy all PFASs, including precursors potentially adsorbed to GAC, appears to be lacking. One stakeholder indicated that the activated carbon is mostly imported from China, used, and then re-activated in the EU. Reactivation is more profitable than buying virgin products. To his knowledge, the reactivation takes place at temperatures around 600 C, which could lead to incomplete destruction of PFAS and the formation of PFAS-side products. This could also lead to atmospheric deposition and contamination of soil and water (Cornelsen-Interview 2021). 29/80 Ramboll - [Title] Availability across the EU Temporary and permanent GAC systems can be rapidly deployed and require minimal operator attention, if intensive pre-treatment is not needed (ITRC 2020). Currently, GAC is a widely used water treatment technology for the removal of PFOS and PFOA, and, to a lesser extent, other PFAAs from water. Based on stakeholder input there is knowledge, that the activated carbon is mostly imported from China, used, and then re-activated in the EU. Reactivation is more profitable than buying virgin products (Cornelsen-Interview 2021). Costs According to a recent report by the German Umweltbundesamt and Arcadis, the cost for the remediation can vary considerably (UBA 2020), for example from 0.40 - 2.30 /m in a pilot test. In another case, costs of < 0.06/m to 0.68 /m were found. Another study indicates the costs of sorption on activated carbon in the range of 0.24 /m (10 g/L PFAS in raw water) to 0.78 (100 g/L PFAS in raw water) (Q = 25 m/h). This includes electrical energy, maintenance, and activated carbon consumption. Based on these numbers an average cost of 1.25 per m PFAScontaminated water is assumed, as calculated as the average of the respective highest reported cost value. Additional information and available case studies Maga et al 2020 published a life cycle assessment comparing three treatment options for spent AFFF. In this study the authors compared the incineration, the treatment with granulated activated carbon and the treatment with PerfluorAd and subsequent activated carbon with one another. The focus was on the environmental impacts of the individual treatment methods e.g. greenhouse gas potential, resource depletion and emission of ionising radiation. In this study the treatment with GAC showed adequate results. GAC treatment emits large amounts of ionising radiation as most GAC is sourced from fossil coal deposits (Analytik 2019). Additionally GAC treatment can deplete the ozone layer as during the disposal of GAC many short chain side products may arise (Maga et al. 2021a). Non-destructive: Ion exchange (IX) According to Concawe, no references were available for IEX treatment of fire-extinguishing waters or water with PFAS concentrations within the range of fire-extinguishing waters have been reported (Concawe 2020). However, as IX might be used as a secondary treatment after for example PerfluorAd, this method is shortly introduced as it is next to GAC the most established method. Background According to ITRC, IX is an effective sorbent for other contaminants and has historically been used for a variety of water treatment applications (for example, nitrate, perchlorate, arsenic). To date, IX for PFAS removal from water is limited to ex situ applications (ITRC 2020). IX resin options for removal of PFAS include single-use and regenerable resins. Single-use resins are used until breakthrough occurs at a pre-established threshold and are then removed from the vessel and currently disposed of by high temperature incineration or by landfilling, where permitted. Regenerable resins are used until breakthrough but are then regenerated on site using a regenerant solution capable of returning the full exchange capacity to the resin. Temporary and permanent IX systems can be rapidly deployed. 30/80 Ramboll - [Title] Figure 9: PFAS flow diagram for adsorption filtration with IEX /taken from (Concawe 2020)). There is a variety of IX resins available at the market. According to Dupont, the polymer matrix of an ion exchange resin generally falls into two categories gel or macroporous. A number of resins, both gel and macroporous type, developed for this market have similar chemical properties to allow for improved PFAS selectivity (Dupont 2020). Technical performance According to the Concawe report and the therein cited literature, various anion exchangers have been identified with a higher adsorption capacity towards PFAS than activated carbons. The selective PFAS removal from contaminated waters by anion exchange works at both high PFAS concentrations of hundreds of mg/L as well as at low concentrations in the ng/L and g/L range. Similar to the adsorption onto activated carbon, the affinity of per- and polyfluoroalkyl sulfonates (PFSA) to ion exchangers is higher than those of per- and polyfluoroalkyl carboxylates (PFCA), and long-chain PFAS are absorbed preferably compared to short-chain PFAS. Treating groundwater, operation times up to 80,000 to 150,000 BV can be reached for the elimination of long-chain PFAS. However, retention of short-chain PFAS is lower and breakthrough starts at 10,000 to 30,000 BV. For ion exchange, the sorption kinetics for PFAS are relatively slow but it is still faster than adsorption on activated carbon. Fast sorption kinetics will result in a smaller filter geometry and therefore less investment costs. US and EU threshold value for PFOS and PFOA (0.07 to 0.1 g/L) are achievable using ion exchange resins. Availability across the EU According to ITRC, Ion exchange technology has been used in the US since the late 1930s for common water treatment processes like softening, demineralization, and selective contaminant removal. The development and use of selective resins for PFAS removal is relatively new but already well established. As of 2019, a limited number of regenerable IX systems have been installed in full-scale applications after successful pilot testing. Collection of data on longer term treatment and on-site regeneration of the IX resin is ongoing at a case study site. Also, according to UBA, groundwater purification by means of ion exchangers is a common and widely used process. However, they have only rarely been used in Germany for the remediation of PFAS contamination. Accordingly, only limited experience is available from remediation on a 31/80 Ramboll - [Title] technical scale. Due to the growing experience with this process, especially in Australia, it can be expected that ion exchangers will be used more frequently in the future (UBA 2020). Side products and emission In single-use applications, the IEX resins are loaded with the PFAS and must be disposed for final destruction using high temperature incineration in HWI. It is noted that the IEX resin vendors normally cooperate with specialist licensed waste handling companies that can organize the resin disposal (ITRC 2020). Treatment costs might be lower when regenerating and re-using the ion exchanger resin. The binding of PFAS to ion exchangers is not only affected by the intended electrostatic interactions, but also by hydrophobic interactions with the backbone of the ion exchanger (UBA 2020). Therefore, a sufficient regeneration the use of an organic solvent such as methanol or ethanol is required adding to the complexity and cost. Also, these solvents would also need to be treated (ITRC 2020). Costs The material costs of ion exchangers are about 12 /kg and thus about 3 times higher than the average costs of activated carbon. Using the above information, it is estimated that groundwater treatment costs for long-chain PFAS of 0.05 to 0.1 per m PFAS-contaminated water and for short-chain PFAS of 0.25 to 0.8 per m PFAS-contaminated water respectively (Concawe 2020). Based on these numbers an average cost of 0.45 per m PFAS-contaminated water (for both longand short-chain PFAS) is assumed. According to UBA, the total costs for ion exchangers compete with the costs for the sorption of the PFAS on activated carbon. Even if the activated carbon process is less efficient and requires more sorption material, in the end it could be cheaper (UBA 2020). However, there are no actual costs cited. Additional information and available case studies Treatment of PFAS with anion exchange resins has been demonstrated in numerous small- and large-scale applications. The following collection is a sample of published examples for PFAS removal using ion exchange resin. Non-destructive: Precipitation - PerfluorAd Background The principle behind the precipitation of PFAS is to introduce a molecule which can bind to the charged moiety (e.g. sulfonic acids). By doing so the PFAS molecule interacts with added cations via electrostatic and intermolecular interaction and becomes insoluble and as such precipitates. The affinity to bind to this cation depends on many factors such as molar mass, functional groups, amount of charges etc. The precipitate can be mechanically filtered and as such be removed from the PFAS solution. Cornelsen Umwelttechnologie GmbH is a specialist supplier of systems, technologies, products and services for the remediation, water filtration and landfill leachate sectors located in Essen, Germany. Cornelsen together with the Fraunhofer-Institute UMSICHT developed a technology based on this principle called PerfluorAd (in the following called PerfluorAd). At the homepage of Cornelsen GmbH (available in German and English) a lot of information is accessible. In addition to that, the technique is also described in scientific literature and Mr. Cornelsen has been also interviewed in the context of this project. Based on the information provided by Mr. Cornelsen during the interview, the technique is used mainly for highly PFAS-contaminated water (also with an optional organic background level). Highly PFAS-contaminated water means here values in the higher range of g/l. Containing PFAS can be removed of PFAS with efficacies of 80-90 % and can be then subjected to further treatment 32/80 Ramboll - [Title] like GAC and ion exchange. In Figure 10 a schematic overview of an GAC with PerfluorAd Pretreatment stage is given. Figure 10: Schematic overview of an Activated Carbon Plant (GAC) with PerfluorAd Pre-treatment Stage (taken from Cornelsen) Highly PFAS-contaminated water can be for example fire run-off water or water from PFAS-related cleaning from technical equipment. According to the stakeholder, low PFAS-contaminated water is not the primary subject to PerfluorAd. Therefore, most groundwater contamination is not suited to be treated by PerfluorAd. GAC and techniques using ion exchanger (and combinations) are better suited. Also, AFFF-concentrates are not suited for PerfluorAd and would, theoretically, need to be diluted. The concentration of PFASand non-fluoride organic surfactants would be too high. Direct Incineration is the preferred option (Cornelsen-Interview 2021). PerfluorAd changes the solution equilibrium of PFAS in water. The reaction modes are precipitation and flocculation, mainly based on ion ionic interaction. The reaction is non-destructive meaning that the chemical composition of the PFAS substance is not changed (Cornelsen-Interview 2021). In addition to PFAS, PerfluorAd also removes other non-fluorinated surfactants. Those are used together with PFAS-surfactants in AFFF-products (Cornelsen-Interview 2021). For this a cationic compound mix consisting of different di- or triethanolamine quats (TEA) based vegetable fatty acids is added to the PFAS-containing water These fatty acids have the advantage of being biodegradable and synthesised from sustainable sources(Maga et al. 2021b) . The charged PFAS molecules interact with the positively charged head of the ethanolamine quats and precipitate (see Figure 11Error! Reference source not found.). The combination ratio thereby is not always 1:1 (Maga et al. 2021b). 33/80 Ramboll - [Title] Figure 11: The interaction between the PFAS molecule (below shown for the example of 6:2 FTS) and the added cation (taken from Maga et al 2020) Depending on the PFAS-concentration precipitant is added and is as such scalable. After precipitation the precipitated flakes can be filtered out (sand filter) and sent to high temperature incineration. Technical performance In general, the removal efficiency of PerfluorAd is depending on the chain length and the polarity of the PFAS. The long-chain sulfonic acids (PFSAs) show the best removal efficacy. The same effect is also observed when using GAC (Cornelsen-Interview 2021). According to the Cornelsen the treatment with PerfluorAd can effectively remove a wide range of PFAS with an efficiency of up to 99.3 % for PFSA and PFCA. Other PFAS such as Capstone A and B11 only reach removal efficiency of 81 %. Substances like 6:2 fluorotelomer sulfonate (6:2 FTS) can reach a removal efficiency of 97 % and other non-PFAS surfactants can even be removed with up to 99,8 % efficiency (Cornelsen 2020). The dosage ranges from 25 mg/L to 2 g/L and can be optimised for different PFAS concentrations and the water matrix to obtain higher elimination rates. In Figure 12 residual concentration total PFASs [mg/l] and right) elimination rate total PFASs [%] for 1% AFFF premix after addition of PerfluorAd are highlighted. 11According to UBA, The AFFF fire-extinguishing foams of products frequently used in Germany contain, in addition to some perfluorocarboxylic and sulfonic ac ds, the compound 6:2 FTS in low concentrat ons and, above all, in high proport ons the two betaines (CAS: 80475-32-7 and 34455-293). 34/80 Ramboll - [Title] Figure 12: left) Residual concentration total PFASs [mg/l] and right) elimination rate total PFASs [%] for 1% AFFF premix after addition of PerfluorAd (taken from (Cornelsen 2020)). Principally, it is designed for treating water containing PFAS concentrations greater than 0.3 g/L (Ross et al. 2018). PerfluorAd is used as the first PFAS treatment step within a treatment train. Thus, this process is not intended to achieve final target threshold values (e. g. 0.1 g/L) as it is recognised that a further polishing step is required (Ross et al. 2018). The added PerfluorAd is specific for charged molecules so that in a recent experiment with diluted AFFF only 1.1 % of the dissolved organic carbon was precipitated. In this experiment 99.3 % of the total PFAS (23 substance) could be removed with the PerfluorAd treatment. 80.5 % of the Capstones and 87 % of the organically bound fluorine (precursors) were also removed with this process (Cornelsen 2020). In Figure 13 elimination rates for different parameters [%] at an optimal dosing rate of 2.0 g/l are shown. Figure 13: Elimination rates for different parameters [%] at an optimal dosing rate of 2.0 g/l PerfluorAd for this application (taken from (Cornelsen 2020)). The time to precipitate the containing PFAS ranges from 10 30 minutes depending on the water matrix and containing pollutants (WVF 2019). These values represent optimal removal efficiencies and are however dependent on the correct amount of PerfluorAd based on the PFAS-concentration in the solution. Too high or too low amounts of PerfluorAd can negatively affect the efficiency of the process. Additionally, the precipitate shows a higher selectivity toward longer chain PFAS and has lower efficiencies for short chain PFAS (Cornelsen 2020; Maga et al. 2021a). 35/80 Ramboll - [Title] The precipitate (sludge) can then be treated by high temperature incineration. The advantage with this is, that only the precipitated PFAS including cationic counterpart need to be incinerated instead of incineration the whole AFFF solution/ run-off water, including its water content. This decrease in volume of PFAS-contaminated water is more economically. Side products and emissions The precipitation techniques cannot destroy or mineralise any PFAS. It instead enables the removal of the PFAS from a watery solution by precipitation. According to Martin Cornelsen, measurements/ calculations of mass balance show that there are no side reactions and/or loss of reaction partners (PFAS & PerfluorAd substance). The incineration of the precipitate or spent activated carbon may however lead to the formation of products of incomplete combustion. For these products see chapter 3.2.1. Availability across the EU The active ingredient is produced in the EU and according to Mr. Cornelsen, there are no limitations regarding its availability. Costs The substance costs around 10-25 /kg, depending on the purchased quantity. However, the active ingredient is not the only limitation criteria. According to Mr. Cornelsen, the costs are more related to the manpower and material (including for example the activated carbon). For the entire PerfluorAd/activated carbon system, operating costs (depending on the activated carbon used) amounted to < 0.055 - 0.68 per m of treated water, of which approx. 0.04 /m is attributable to the PerfluorAd requirement (UBA 2020). Additional information and available case studies Maga et al 2020 published a life cycle assessment comparing three treatment options for spent AFFF. In this study the authors compared (1) the incineration, (2) the treatment with granulated activated carbon and (3) the treatment with PerfluorAd and subsequent activated carbon. The focus was on the environmental impacts of the individual treatment methods e.g. greenhouse gas potential, resource depletion and emission of ionising radiation. In this study the PerfluorAd technology with subsequent active carbon treatment performed the best of the analysed treatment methods in nearly all investigated impact categories. Remediation of PFAS-contaminated groundwater under the Nuremberg Airport Fire Department's firefighting training area: the groundwater underneath the firefighting training area at Nuremberg Airport has been contaminated by PFAS due to the use of fluorine-containing firefighting agents over many years. A mobile groundwater remediation system based on the PerfluorAd principle was made available, thereby remediating the groundwater. The initial PFAS concentration in the groundwater was more than 600 g/l for the sum of the PFAS. With the PerfluorAd treatment alone, the PFAS load is reduced to 41 g/l (i.e., by 93.5%). After the final activated carbon stage (GAC for granulated activated carbon), PFAS contamination is no longer measurable. Non-destructive: Foam fractionation and ozofractionation Background Foam fractionation and ozofractionation are technologies that take advantage of the foam-forming properties of PFAS. The process selectively separates PFAS from water by injecting compressed air (foam fractionation) or ozone (ozone fractionation) into the water in the form of air bubbles. PFAS surfactants adhere to the bubble walls and are thus transported to the surface. The PFAS-enriched 36/80 Ramboll - [Title] foam is collected at the water surface for further destruction-based treatment. The treated water typically goes through a polishing step (e.g. GAC)(Concawe 2020). In the case of ozofractionation, precursors (also PFAS) are transformed to the perfluoroalkyl carboxylic (PFAA) and sulfonic acids (PFSA). Those PFAS remain in the system and are concentrated and discharged in the gas bubbles. Ozone can also promote the degradation of accompanying organic contaminants. Due to the small size of the gas bubbles (diameter < 200m), the total mass of the ozone bubbles has a large gas-water interface. At the surface of the water phase in the reactor, the PFAS are therefore concentrated in a small, separable volume. Figure 14: Illustrative Concept of foam fractionation (taken from (UBA 2020)) Technical performance On a technical scale (Figure 15), the ozone fractionation consists of several reactors connected in series with continuous flow, into which ozone is introduced as bubbles. The PFAS concentrate as highly PFAS-contaminated foam on the liquid surface of the reactors. From the surface the bubbles get extracted via vacuum, further concentrated and can be fed to a further destructive treatment. The volume of the concentrate is 0.5 2 % of the inflow volume. According to literature the ozofractionation process alone mostly cannot achieve required PFAS concentrations and a supplementary process stage is needed. The gas phase is released into the atmosphere via an activated carbon absorber. As a rule, the last process stage of the water phase is an activated carbon absorber, with which the residues of the PFAS that have not yet been removed can be retained in order to achieve the required discharge values. If impurities are present, the process can be extended by further process stages if required. Figure 15: Ozofractionation process concept (taken from (UBA 2020)). For long-chain PFAS such as PFOS and PFOA, a purification level of 99.9% has been achieved (Evocra 2017). For the ozofractionation stages alone, a purification level of >98.7% was always achieved. The short-chain PFAS can be removed better with ozone than with air (Ross et al. 2018). 37/80 Ramboll - [Title] The results further indicate that, for PFAS concentration levels below 0.3 g/L, high elimination down to a few ng/L could still be achieved (Evocra 2017). Similar to the precipitation with PerfluorAd, ozonofraction has an economic advantage at very high PFAS concentrations (which would be the case in PFAS-contaminated fire run off water and water from cleaning processes). The process is not only suitable for the treatment of water, but also for sludge with a solids content of up to 20%. The fractionation reactors separate the liquid from the solid phase. Small particles get into the foam concentrate and are removed with it. Coarse particles sediment at the bottom of the reactors and are removed there. Unlike many other processes, the degradation of an accompanying organic contamination does not significantly affect the PFAS removal level. The disadvantage is that a waste product (PFAS zone foam concentrate) is produced which must be disposed of separately (UBA 2020). Based on desktop research, it seems that the ozone is introduced to the reaction by adding of Arcadis Solvent V171. The liquid has the following hazard statements: H227 (combustible liquid), H319 (causes serious eye irritation), H336 (may cause drowsiness or dizziness) and AUH019 (May form explosive peroxides). AUH019 is an Australian-specific H-statement and equals the European EUH019 (also may form explosive peroxides). Figure 16: Picture showing the GHS hazard statements of Arcadis solvent V171 (taken from a presentation of Arcadis at NEWEA, 2019 see here). Foam fractionation uses compressed air and is commercialized by the Australian company OPEC systems, allowing a continuous on-site treatment process in a containerized system. The treatment system is called Surface Active Foam Fractionation (SAFF). The operation mode of the system can be adjusted to manage a broad range of total detectable PFAS influent concentrations (0.1 to 100,000 g/L). The residence time per reactor vessel ranges from 5 to 30 minutes. PFAS-enriched foam is removed with a vacuum extraction system (Concawe 2020). According to the Concawe report and therein cited literature, for both methods , depending on influent concentrations, the US-EPA Health Advisory levels for PFOS and PFOA (0.07 g/L) as well as the proposed EU drinking water threshold of 0.1 g/L for individual PFAS compounds (0.5 g/L for total PFAS) are achievable without polishing. However, bboth technologies usually include a final polishing step, resulting in removal efficiencies of 99.9% to 99.99%. Very high influent concentrations might be managed via a multi-stage fractionation process (Concawe 2020). Side products and emission Foam fractionation and ozofractionation are non-destructive techniques. In the case of ozofractionation, the PFAS-ozone bubbles are drawn off (vacuum extraction) and further concentrated and can be fed to a further destructive treatment. The volume of the concentrate is 0.5 - 2% of the inflow volume (UBA 2020). 38/80 Ramboll - [Title] Availability across the EU According to UBA/Arcadis, the ozofractionation process has already been tested on a technical scale in Australia. According to the available documentation, the process appears to be ready for the market. However, as is the case with most newer technologies, there is a lack of supplierindependent studies to verify its effectiveness. The supplier in Australia is a company called Evocra12, which signed a strategic exclusive agreement in 2019 with Arcadis. Based on research undertaken in this project, it seems that Arcadis promotes nowadays the usage of a V171 cleaning agent, which is most likely the same substances and related systems as the Evocra process. Foam fractionation is not available on a technical scale. However, limited field trials show promising results (OPEC-Systems 2020). Costs Ozofractionation is a relatively complex technology whose operating costs are significantly higher than those of alternative market-ready technologies (e.g. GAC) but this cannot be assessed due to lacking data (UBA 2020). Additional information and available case studies The technique has been used in several cases in Australia and one in the UK, this involved (based on the results of the desktop search within this project): A large-scale implementation of ozofractionation at an airport in Australia using a NF unit for polishing to treat PFAS affected surface water and wastewater achieved a removal efficiency of 97% for the sum of 28 PFAS with inlet concentrations of 100 to 5,400 g/L13. Water remediation at a fire training site14 Containing of 22,000 liters of escaped PFAS contaminated waste from a failed deluge system within an airport hangar15. Contamination stemming from an airport in the UK (Guernsey island)16 US-Department of Defence (DoD) concerning the Demonstration and Validation of Environmentally Sustainable Methods to Effectively Remove PFAS from Fire Suppression Systems Destructive approaches 4.6.1 Incineration The details of PFAS-based incineration are explained in detail in chapter 3.2.1 (hazardous waste incinerators) and 3.2.2 (cement kilns). For the incineration of PFAS-contaminated water, the same information applies as in those chapters. However, as the concentration of PFAS-contaminated fire run off water and cleaning water are considerably lower, literature indicates that in some cases non-destructive techniques are used in order to lower the to be incinerated volume and related costs. Final Conclusion on the Disposal of PFAS-contaminated (fire run off and cleaning) water The following conclusions can be made for available disposal options for PFAS-contaminated (fire run off and cleaning) water: 12 See Evocras internet s te here, last accessed 01.04.2021 13 See s te here, last accessed 01.04.2021 14 See presentation here, last accessed 01.04.2021 15 See presentation here, last accessed 01.04.2021 1616 See presentation here, last accessed 01.04.2021 39/80 Ramboll - [Title] Fire run off and cleaning water are highly PFAS-contaminated compared to for example groundwater contaminations. Based on this not all available remediation techniques for groundwater can be used also for run off and cleaning water. GAC can be also used for all PFAS-contaminated for run off and cleaning water. However, the efficiency is lower for PFAAs (carboxylic acid) in general and short chain PFAS. For other PFAS (e.g. zwitterionic) no data is available. One stakeholder brought up that when GAC is reactivated (using 800 C) PFAS could be emitted (Cornelsen-Interview 2021). Ion exchange (IX) is generally suited for PFAS-contaminated run off and cleaning water. However, no caste studies are available. Based on the type of PFAS various IX-matrices are available. IX is believed to be 4 times more expensive that GAC, when only the material is considered. According to UBA, the total costs for ion exchangers compete with the costs for the sorption of the PFAS on activated carbon. Even if the activated carbon process is less efficient and requires more sorption material, in the end it could be cheaper (UBA 2020). However, there are no actual costs cited. GAC and IX are generally based on column beds to which PFAS absorb. To achieve certain PFAS-levels several beds in series must be used. With both techniques proposed EU drinking water threshold of 0.1 g/L (0.001 ppm) for individual PFAS components (0.5 g/L for total PFAS) are achievable but may require the use of several beds in series. The material cost for GAC is around 0,41 3,68 /kg. According to a recent report by the German Umweltbundesamt and Arcadis, the cost for the remediation can vary considerably (UBA 2020), for example from 0.40 - 2.30 /m in a pilot test. In another case, costs of < 0.06/m to 0.68 /m were found. Another study indicates the costs of sorption on activated carbon in the range of 0.24 /m (10 g/L PFAS in raw water) to 0.78 (100 g/L PFAS in raw water) (Q = 25 m/h). This includes electrical energy, maintenance, and activated carbon consumption. Based on these numbers an average cost of 0,85 per m PFAS-contaminated water is assumed, as calculated as the average of the respective cost values. For IX, material cost is about 12 /kg and treatment costs for long-chain PFAS of 0.05 to 0.1 /m and for short-chain PFAS of 0.25 to 0.8 /m respectively. Based on these numbers an average cost of 0.45 per m PFAS-contaminated water (for both long- and short-chain PFAS) is assumed. To minimize the load (and therefore costs) of GAC/IX, precipitating agents like PerfluorAd can be used. The active ingredient changes the solubility of PFAS. PFAS-PerfluorAd sludge can be incinerated. The water then is then further treated with GAC/IX (treatment train). For the entire PerfluorAd/activated carbon system, operating costs (depending on the activated carbon used) amounted to < 0.055 - 0.68 per m of treated water, of which approx. 0.04 /m is attributable to the PerfluorAd requirement. Ozonofraction uses the fact that PFAS remain the air-water interface and creates ozonebubbles which are considerably smaller than regular air-bubbles. Bubbles then can be physically removed. The water then is then further treated with GAC/IX (treatment train). For PFAS concentration levels below 0.3 g/L, high elimination down to a few ng/L could still be achieved. No information is available for the costs of this technique, however, ozonofraction is a complex technology whose operating costs are significantly higher than those of alternative market-ready technologies (e.g. GAC), but this cannot be assessed due to lacking data. PFAS-contaminated fire run off and cleaning water can also be directly subjected to incineration. The cost for the disposal of 1 liter of PFAS-based AFFF are currently in the range of 0.2-2 /l (around 200-2000 /m3), it can be assumed that the same costs apply to fire runoff water. Based on the available data, the direct incineration of PFAS-contaminated run-off water would be the most expensive disposal alternative (200-2000 /m3). According to (UBA 40/80 Ramboll - [Title] 2020)GAC and IX are comparable in costs (although material costs differ). For GAC an average cost of 0,85 per m PFAS-contaminated water is assumed (three projects considered). For IX an average cost of 0.45 per m PFAS-contaminated water (for both long- and short-chain PFAS) is assumed. Based on available data, the combination of PerfluorAd and GAC is the cheapest technique with an average reported cost of < 0.055 0.68 per m of treated water, of which approx. 0.04 /m is attributable to the PerfluorAd requirement. The cost depends on the activated carbon used. Based on these numbers an average cost of 0.37 per m PFAS-contaminated water (for both longand short-chain PFAS) is assumed. 41/80 Ramboll - [Title] 5. CLEANING OF STATIONARY OR MOBILE PFAS FIREFIGHTING FOAM EQUIPMENT Description of the problem PFAS are known to settle and accumulate on vessels and equipment, which, if not taken care properly, leads to the contamination of new fluorine-free foam. In more detail, PFAS adhere to surfaces and are known to self-assemble in multiple layers to coat surfaces forming a waterproof coating (JOIFFF 2020). Thus, PFAS chemicals would continue to be released into the environment during operations. Therefore, before using any stationary or mobile equipment, that has already been used for the PFAS foam, it is necessary to clean or dispose and replace the equipment that cannot be cleaned (JOIFFF 2020). According to Arcadis, there is a common misconception that repeat washing of fire suppression systems with water can effectively remove PFAS, as for example after a few rinses, less PFOS may be detected in rinse water. However, PFASs can as explained above form a waterproof coating on surfaces, so PFAS concentration in the rinse water will not be representative of that still remaining entrained within fire suppression systems (JOIFFF 2020). According to Arcadis fluorine free foams (F3) foams used to replace C8/C6 foams become contaminated with PFASs over time. After years of holding AFFF concentrate, the surfaces of piping system components including pipe, fittings, valves, and tanks are coated with self-assembled PFAS which slowly dissolve into the replacement F3 foam. In addition to the replacement and cleaning of PFAS and PFAS-contaminated equipment, it is current knowledge and has been raised also during interviews, that minor modifications to existing fire protection systems are commonly required with foam replacements to ensure appropriate standards for proportioning and flow requirements are achieved, and often to maintain accreditation for insurance coverage (Cornelsen-Interview 2021; Equinor-Ystanes-Interview 2021; JOIFFF 2020). To ensure proper performance, it is now common practice for existing foam proportioners to be replaced with units tested and accredited with the replacement foam. For most cases, performance requirements cannot be achieved without the tested and certified proportioner. Foam application rate and discharge duration are often impacted by the differing physiochemical properties of the replacement foam. One clear example is kinematic viscosity, which will affect the performance of pumps and storage volumes of concentrate. The switch to aspirated discharge devices typically increases replacement foam performance and reduces the need for more extensive system modifications. Different institutions (manufacturers, remediation companies, public authorities) define guidelines and instructions for the cleaning process, which fire departments and companies can make use of. Based on current literature and stakeholder input, the following passages encompasses current goto techniques. In some cases, the described techniques are the same as described in chapter 4, when the disposal of PFAS-contaminated fire run-off or cleaning water have been described. Thus, in this chapter information specific only for the cleaning will be highlighted this includes for example the step-by-step instructions. 45/80 Ramboll - [Title] Non cleaning There is no official guideline that lays out the practical details the transition from PFAS-based foam to fluorine free foam, describing for example cleaning procedures and accepted remaining levels. Thus, companies and fire brigades have been developed their own replacement strategy. Based on the input of stakeholder this included, in comparison to cleaning techniques, no washing steps with water. Background One stakeholder from Germany shared their experiences after transition from C8-based foam (3M Lightwater which is supposed to be based on PFOS) to C6-based foam without a cleaning procedure. After the replacement, the C6-based foam was tested for its PFAS content and high concentration of PFOS were found. In the end this observation led to the development of a cleaning procedure specialized on foam concentrate tank located at industrial fire brigades. This procedure is explained in detail in chapter 5.10. Also, another stakeholder from Norway stated that when a first round of replacement of PFAS to non-fluorine foam took place, no official cleaning protocol has been used. The PFAS-foam was simply drained and new foam (fluorine free) was filled in. However, follow-up measurements then showed that PFAS were still detectable. Replacement Procedure According to one stakeholder, the PFAS-foam was simply drained and new foam (fluorine free) was filled in. No more information available (Equinor-Ystanes-Interview 2021). Remaining PFAS concentrations Legacy C8-contamination levels as measured by the PFOS-concentration are reported to be 28.000 g/kg(which is higher than the threshold of 10,000 g/kg according to the POP-regulation (10 ppm)). The stakeholder from Norway used a limit is 0,001% (10 ppm) PFAS and had to refill tanks twice in a couple of cases to get below this limit. Costs No information on costs of the actual replacement strategy is available. Secondary costs are due to the incineration of the replaced foam. As highlighted above, both stakeholders have been faced with contamination of the new foams with legacy PFAS-substances (like PFOS). Based on this contamination both stakeholders decided to develop cleaning strategies and had to start the process again. Additional information and available case studies See above. Cleaning procedure by BIOEX According to their homepage17, BIOEX launched 2002 the first Fluorine-Free Foam on the market: ECOPOL. The BIOEX customer support services provide customer assistance in case of urgent need of foam concentrate, foam sample analysis and testing. BIOEX provides a foam calculation tool defining foam concentrate needs. BIOEX also supports companies in their transition to FluorineFree Foam (F3). 46/80 17 See here, last accessed at 05th February 2021 Ramboll - [Title] Background According to the BIOEX homepage, BIOEX F3 foams are compatible with existing proportioning equipment. We must define appropriate foam application rate and discharge duration. It may induce minor system modifications. Cleaning Procedure PFAS cleanout with replacement costs and time. BIOEX recommends the following cleanout protocol, in case downstream users dont want to replace pump and storage tank: 1. Drain all foam from tank 2. Flush tank and pipes with hot water and scrub where possible 3. Rinse water analysis at lab to confirm PFAS cleanout 4. F3 Foam replacement: tank refilling with F3 5. Test/commissioning with the concentrate: the finished foam quality is highly dependent on the hardware (foam proportioning system, distribution system and discharge device) 6. Fluorinated foam disposal Based on this protocol and the fact that the disposal of the cleaning water is not discussed, it can be assumed that water stemming from the cleaning itself are not disposed as hazardous waste. Remaining PFAS concentrations There is no information available on remaining PFAS concentrations. Costs There is no information available on costs for this technique. Additional information and available case studies There is no information available on available case studies. V171 by Arcadis Background According to the JOIFF-article (which has been authored by Ian Ross and Peter Storch from Arcadis), decontamination of firefighting and fire suppression equipment is essential to limit carryover of PFASs from old foam usage. Triple rinse with water is not sufficient and leads to a significant volume of decontamination water that requires treatment. Arcadis recommends using specialized biodegradable cleaning agents such as V171 to effectively remove PFAS residuals from fire suppression systems to limit future liabilities and cost associated with PFAS contaminating F3 foams as a result of inadequate decontamination (JOIFFF 2020). Arcadis has developed methods for PFAS decontamination of piping and tank systems including the use of a proprietary biodegradable cleaning agent, V171. These methods and the cleaning agent have been successfully applied in foam transition projects to remove PFASs from steel and PVC piping systems, stainless-steel concentrate tanks, and underground wastewater tanks (JOIFFF 2020). Also application in foam suppression systems, emergency response vehicles, and concrete sewer distribution systems are described (Anderson 2021). In chapter 4.5, the technical performance and other details of this technique has been described. The following information concentrate on the actual cleaning procedure. Cleaning Procedure The initial PFAS cleanout project in 2017 used a sequential series of aqueous rinses, high- pH flushes and application of the cleaning agent as shown in Figure 17. presenting Sum of PFAS (28) TOP 47/80 Ramboll - [Title] Assay results. The results demonstrated that water and high pH are ineffective for removal of PFASs from surfaces, as demonstrated by the relatively low concentrations of PFASs measured in these flush solutions. The elevated concentration in the cleaning agent demonstrated significantly greater PFAS mass removal even after multiple flushes of water and caustic solution. Further work to clean PFASs out of a 20- m foam concentrate tank was conducted, and results are presented in Figure 17. This application demonstrated that soaking with the cleaning agent, followed by high-pressure washing can be effective. The importance of using TOP assay for analysis of PFASs was revealed. Figure 17: Sum of PFAS Concentrations during decontamination of AFFF- Impacted sewer system and of a 20-m concentrate tank. Remaining PFAS concentrations As shown above in the diagrams of Figure 17, the final water flush/rinse contained around 0.1 g/l PFAS as measured for the sum of 28 PFAS (according to TOP 4 g/l). Costs There is no information available on costs for this technique. Additional information and available case studies Available case studies has been already discussed in chapter 4.5 under Additional information and available case studies. In addition, Arcadis claims that the technique has been successfully applied in foam transition projects to remove PFASs from steel and PVC piping systems, stainless-steel concentrate tanks, and underground wastewater tanks (JOIFFF 2020). Also application in foam suppression systems, emergency response vehicles, and concrete sewer distribution systems are described (Anderson 2021). For these projects, no documentation has been found via desktop search. One ongoing study for the DoD focuses on Fire Suppression Systems. US-Department of Defence (DoD) concerning the Demonstration and Validation of Environmentally Sustainable Methods to Effectively Remove PFAS from Fire Suppression Systems. Cleaning procedure with PerfluorAd by Cornelsen Background Detailed information on the background of this technique has been already given in chapter 4.2. 48/80 Ramboll - [Title] Cleaning Procedure Cleaning of PFAS Contaminated Fire Fighting Trucks and Equipment as well as Stationary Fire Extinguishing Systems in the Transition Process from AFFF Foams to Fluorine-free Foams with Cornelsen's PerfluorAd Technology is executed in 3 Steps (Cornelsen 2021): 1. Complete and careful emptying of all System Components (possibly even with partial replacement of Components): Pipes, Hose Lines, Seals, Valves, Pumps, Fittings, Tanks including Partitions and hidden Areas, 2. Performing a Flushing of all individual Pipelines with a PerfluorAd Dilution. The last Flushing is carried out with Fresh Water. The visually recognizable Foam Formation serves as an Indicator for the Degree of Cleaning. 3. Treatment of the collected Rinse Water directly on site with a further PerfluorAd application. Off-site Disposal of Rinse Water does not take Place. The PFAS Content of the Rinse Water can already be significantly reduced when using the PerfluorAd Technology exclusively. The steps are identical for the cleaning of equipment of fire brigades and for stationary fire extinguishing systems. In Figure 18 the three individual steps of the cleaning procedure are shown schematically. The cleaning of stationary equipment is shown at the left and the cleaning of fire brigade machines is shown at the right (no illustration available for the first step). 49/80 Ramboll - [Title] Figure 18: Schematic overview on the three individual steps of the cleaning procedure are shown schematically. The cleaning of stationary equipment is shown at the left and the cleaning of fire brigade machines is shown at the right (no illustration available for the first step). Remaining PFAS concentrations According to Cornelsen, the achievable PFAS residual concentrations in the system depend on several factors: Degree of emptying of the entire system (do PFAS deposits still remain in the system after emptying has been completed?) Materials present in the system (plastic, GFK, rubber, ...) Are all components accessible for mechanical cleaning (steam jet, brush, ...) or can adhesions remain in places that cannot be seen? What is the effort involved in replacing "critical components" (e.g. are all seals and plastic parts replaced before cleaning?) If complete emptying is possible and subsequent "bleeding" of PFAS from individual components is impossible, and at least 3 (better 5) rinses with a PerfluorAd dilution and a 50/80 Ramboll - [Title] final rinse with fresh water are performed (Depending on the boundary conditions described before, flushing water volumes of >15 to <30 m/vehicle are often required in practice), Considering all of these factors, using the PerfluorAd technology final residual concentration (measured in the final rinse with fresh water) of less than 1.0 g/l total PFAS, very often less than 0.3 g/l to 0.0 g/l can be achieved. Figure 19: Results of the Cleaning of Fire Trucks using PerfluorAd. Costs According to Cornelsen, several parameters flow into the pricing, such as size, type, age ... of the vehicle, disposal of the AFFF concentrate to our extent (y/N?), place of cleaning (in our approved installation in Essen or at the customer's?), etc. Depending on these boundary conditions, the costs are usually between 20,000-25,000 Euro/vehicle. These figures include the treatment of all rinsing water and all disposal costs (Cornelsen-Interview 2021). Additional information and available case studies A typical PerfluorAd application is the cleaning of fire brigade trucks. For this Cornelsen GmbH is accredited by a German environmental authority. The process takes approx. one working week (Monday to Friday). However, a longer time is needed if components need to be replaced. Cornelsen GmbH is providing the plant and needed personnel. According to MC, several parameters flow into the pricing, such as size, type, age ... of the vehicle, disposal of the AFFF concentrate to our extent (Y/N?), place of cleaning (in our approved installation in Essen or at the customer's?), etc. Depending on these boundary conditions, the costs are usually between 20,000-25,000 Euro/vehicle. These figures include the treatment of all rinsing water and all disposal costs. In the last 6-12 months Cornelsen GmbH is receiving more inquiries from companies with large fire extinguishing systems. MC mentioned that the costs for systems are very hard to extrapolate, as they differ based on the needs of the company. In large fire extinguishing systems, the PFAS-concentrates normally are contained in the tank, tank to mixer pipes, and finally the mixer. Based on the knowledge of MC, PFAS-contamination is not to be expected after the mixer. However, if there have been incidents/training with PFAS-foams then also these systems are expected to be contaminated. In MC's understanding, cleaning of all systems is not required, thus, only PFAS-containing systems (as described before) would need to be cleaned. Based on MCs opinion, a replacement of critical components (plastics, etc.) is advisable to remove PFAS-substances and to prevent future bleeding of PFAS-substances. The state of North Rhine-Westphalia has funded the production of a mobile extinguishing water treatment plant (MLB) using the PerfluorAd process. This plant will be made available to the market in July 2019 and will be kept by Cornelsen Umwelttechnologie GmbH at the company's site in Essen and, if required, "mobilized" at short notice, i.e. transported to the site of the fire, 51/80 Ramboll - [Title] so that the collected PFC-contaminated firefighting water can be purified directly on site. With the approval of the responsible authority, the cleaned water is discharged into the sewer system. Alternatively, the MLB can also be used directly at sites with the consent of the responsible authority. authorities, the MLB can also be used directly at locations where collected extinguishing water is temporarily buffered, e.g. at waste disposal companies, sewage treatment plants, etc. The operation of the MLB and the cleaning process of the collected extinguishing waters are carried out by Cornelsen as services. Cleaning protocol by the Bavarian State Ministry for the Environment and Consumer Protection (LfU) Background The Bavarian State Ministry of the Interior, Sports and Integration and the Bavarian State Ministry for the Environment and Consumer Protection in cooperation with state fire department schools, working group of professional fire departments, state fire department association , plant fire brigade association, Bavarian insurance chamber and VdS Loss Prevention GmbH published a document about the environmentally friendly use of firefighting foams in September 2019. Topics are environmental relevance of foam extinguishing agents, distinguishing between fluorinecontaining and fluorine-free foam extinguishing agents. Also, the evaluation of the environmental compatibility of foam agents. Furthermore, the basics of extinguishing foam, as well as procurement, use and disposal. In the following it is focused on the cleaning instructions of equipment when replacing fluorinecontaining with fluorine-free foam extinguishing agents. The main goal, as described in the guideline is to prevent contamination of fluorine-free foam concentrate with PFAS. In general, the guideline recommends not to reuse used foam concentrate canisters and intermediate bulk containers (IBCs) that have contained fluorosurfactant foam concentrate. Furthermore, in the case of smaller tanks and IBCs, the guideline states that removing those might be more efficient compared to a time-consuming cleaning procedure. Permanently installed foam concentrate tanks in vehicles must be thoroughly cleaned before refilling with fluorosurfactant-free foam concentrate. During the course of this project, Dr. Michael Gierig from LfU has been interviewed and important information was collected. Cleaning Procedure Good cleaning results can be achieved with stainless steel tanks and tanks made of polyethylene or glass-fiber reinforced plastic (GRP), on condition that the tank cleaning is carried out very carefully. In detail, the LfU-GL is recommending the following cleaning procedure for stainless steel tanks, GRP and polyethylene tanks: 1. Complete draining of the foam concentrate (dispose of foam concentrate) 2. Remove foam concentrate residues mechanically and by rinsing with hot (50-60 C) water. All pipes and fittings carrying foam concentrate must also be rinsed during this process. The rinsing process is sufficient when the draining water no longer foams. The flushing water must be disposed of18. 3. The tank, the lines and fittings carrying the foaming agent must be completely filled with water that is as hot as possible. The water must remain in the tank for at least 24 hours. After that, the water must be completely drained and disposed of. 52/80 18 Referring to the Lfu-guideline foaming agents containing fluorine surfactants must be disposed of by suitable disposal companies (German waste code number usually 16 10 01* = aqueous liquid waste containing hazardous substances). Certified disposal companies can be researched at www.lfu.bayern.de/abfall/entsorgerfachbetriebe/recherche/index.htm . Ramboll - [Title] 4. The tank, the pipes carrying the foaming agent and the fittings must be completely filled with hot water three more times. The water must remain in the tank for at least 24 hours each time. The rinsing water from these rinsing processes can - if careful procedures are followed - be discharged via the sewage system into the sewage treatment plant. After this cleaning procedure, the tank can be filled with fluorosurfactant-free foam concentrate. The complex cleaning process ensures that the new, fluorosurfactant-free foam concentrate is not contaminated with fluorosurfactants from the tank wall. Remaining PFAS concentrations According to stakeholder knowledge, the effectiveness of the cleaning is monitored by measurements. A foam concentrate tank can then be released for further use if sufficient cleaning success is guaranteed. As a rule, concentrations below 10 ng/l of each of the 13 standard PFAS19 can be achieved with the cleaning procedure described in the guide and, if necessary, replacement of all accessible seals (LfU-Gierig-Interview 2021). The stakeholder reported, that usually < 10 ng/l, i.e. 10 ppt, related to foam concentrate tanks in fire engines are achievable. LfU does not have any figures for stationary extinguishing systems. LfU also sometimes accepts cleaning efficiencies the range of 100 ng, when special circumstances are to be considered (PFAS-emitting gaskets cannot be replaced). Costs Costs are available for tank fire engines. Costs are approx.- 100.000-200.000 per engine, when a permanently installed foam concentrate tank is cleaned before refilling with fluorosurfactant-free foam concentrate. Additional information and available case studies According to stakeholder knowledge, the Munich Fire Department has cleaned its permanently installed foam concentrate tanks according to this guideline. Likewise, other fire departments in Bavaria are likely to have successfully cleaned their foam concentrate tanks according to this procedure (LfU-Gierig-Interview 2021). According to stakeholder knowledge, In Bavaria, there are approximately 1,000 fire engines with permanently installed foam concentrate tanks. Most of these tanks can be sufficiently cleaned with the recommended flushing procedure. The residual quantities are tolerable, especially since a large number of fire extinguisher fills containing PFAS are still in circulation. It would be completely uneconomical to completely replace the vehicle tanks as long as significantly higher inputs of PFAS are present in other areas (LfU-Gierig-Interview 2021). Cleaning protocol by Fire Rescue Victoria (FRV) - Appliance PFAS Decontamination Project Fire Rescue Victoria and the United Firefighters Union developed a decontaminate procedure for appliances (fire trucks). According to their own knowledge, FRV are the only firefighting authority in the world that has achieved this. Due to the verified success of this PFAS decontamination work, FRV have assisted many other emergency service agencies, to either advise or provide similar decontamination processes and applied safe threshold limits for their respective firefighting appliances. FRV are considered national leaders in the successful implementation of measurable PFAS mitigation work. 53/80 19 Measurements based on DIN 38414-14 the German standard methods for the examination of water, waste water and sludge - Sludge and sediments (group S) - Part 14: Determinat on of selected polyfluorinated compounds (PFC) in sludge, compost and soil - Method using high performance liquid chromatography and mass spectrometr c detection Ramboll - [Title] Background The MFB previously used PFAS containing Aqueous film forming foams (AFFF) as firefighting foam, based on 3Ms earlier recommendation of it being safe. Global use of PFAS containing AFFF firefighting foam is the source of approximately 30% of the worlds PFAS contamination. In 2007, MFB made a decision to replace existing firefighting foam with fluorine-free firefighting foam. This decision was on the basis of concerns relating to firefighter health and environmental issues. MFB then phased out the use of persistent PFAS-containing firefighting foams across its operations. MFB engaged expert independent environmental consultants to analyse PFAS exposure pathways for MFB firefighters on the job. This report was used to inform and develop MFB PFAS threshold limits and prioritise PFAS mitigation work. The MFB (FRV) developed and formally endorsed an Operational Use of Firefighting Foam Policy and the use of fluorine free foam. Victorian Environmental Protection Authority (Vic EPA), and Victorian WorkSafe played a part to formalise this policy. By 2014, all MFB firefighting appliances had been converted to only carry fluorine free B Class foam in their foam tanks. Following the MFB establishment of the safe PFAS thresholds, in 2016, MFB embarked on a process to test and decontaminate the MFB firefighting fleet. Further work is currently being done to PFAS decontaminate more recently introduced FRV appliances and monitoring the previous PFAS decontamination work on the earlier MFB appliances. Cleaning Procedure FRV used independent environmental consultants and our industrial cleaning partners, to develop a 32-stage decontamination and verification process targeted at ensuring that the appliances, after decontamination, can be safely returned to service. A detailed description of all steps is shown in the annex (see chapter 7.1). In the following each of the steps will be shortly introduced (information taken from a presentation submitted by a stakeholder (Fire-Rescue-Victoria 2021)): 1. Suitable Facility for the PFAS Decontamination process: Fire trucks are taken to a specially constructed decontamination facility, where the removable components (hoses, connectors, ladders etc.) are stripped off for separate decontamination. The trucks are then put into a bund system, where the raw foam is carefully pumped out and the tanks prepared to be flushed and cleaned. 2. Flushing of the tanks: The tanks are carefully flushed with slowly introduced, temperature controlled, water to maximise raw-product foam removal whilst minimising foam creation. Wastewater is collected for future processing and disposal. After removal of the majority of foam product, agitation is introduced to break down and dissolve solidified foam product. Separate, colour-coded pumps and pipelines-lines are maintained to ensure that crosscontamination is avoided. Filters, strainers and breathers are carefully dismantled to allow removal of solidified foam product, found to have built-up inside on-board components, wherever there are gaps, welds, connectors, or in joints and gaskets. 3. Cleaning of truck internals: The on-board water pumps are fed by, and feed, an intricate series of pipes, lines and injectors. Cross contamination has been found to be common, and the pumps and feed lines internal to the truck need to be cleaned. 4. Cleaning of delivery systems: Delivery of foam/water mix can be through on-board hose reels, direct to hose systems from the main delivery panels on the side of the trucks, or from what is termed the monitor, a roof-mounted delivery system. Each of these also needs to be decontaminated. 5. Purging of truck internal lines: A specially designed multi-part manifold is connected to the truck and the internal pump systems. Lines and foam injectors are purged. 6. Cleaning of Onboard components: Truck-mounted hose reels and monitor are decontaminated by flushing with clean water. Ground-spray systems are also flushed. Detachable components are decontaminated separately. Finally, the whole appliance is 54/80 Ramboll - [Title] pressure washed. The interior voids on the truck, where the tanks and pumps sit, is also pressure washed. All washings are collected using a wet-vac system, for subsequent treatment. 7. Cleaning of Removable components: Each truck also has a series of removable components such as fire-fighting hoses, connectors, uptake and transfer hoses that need to be decontaminated. 8. Hose Decontamination: Fire-fighting hoses are decontaminated both externally and internally using a series of specially design hose-washing units. Several lengths of hose are connected to a high-pressure water recycling unit for internal decontamination. This device has a 5,000 litre water tank and a pump capable of high pressure delivery According to FRV, the key to successful decontamination is correct sequencing of operations, and detailed recording of each stage of operations. Each truck decontamination can create between 6,000 - 8,000 liters of wastewater. Wastewater is re-concentrated by passing through a series of activated carbon filters (GAC). It has been possible to strip out the PFAS foam from the waste and achieve sub part-per billion results in the treated wastewater, enabling this to be disposed to trade waste, with the carbon sent for high temperature destruction. Figure 20: The Decontamination Process in pictures (taken from (Fire-Rescue-Victoria 2021)). 55/80 Ramboll - [Title] Costs There is no information available on costs for this technique. Additional information and available case studies Since 2016, over 145 FRV and CFA firefighting appliances and over 150 kms (over 5,500 lengths), of firefighting hoses have gone through this PFAS decontamination process to below the established thresholds and have been successfully cleaned and returned back into commission for operational use. This work has been conducted in a quantitatively measurable manner by independent 3rd parties. Cleaning protocol by FPA Australia Background Fire Protection Association Australia (FPA Australia) is the national peak body for fire safety, providing information, services and education to the fire protection industry and the community. According to an information bulletin provided by FPA Australia, changing from a foam containing PFOS or PFOA to a US EPA PFOA Stewardship compliant C6 foam, a REACH Regulation (EU) 2017/1000 compliant C6 foam or an F3 foam will require thorough washing of the tank and concentrate sections of pipework (including proportioners) until no frothing is visible (FPA-AUS 2020). It also requires collection, remediation and safe disposal of all effluent from this washing process. Cleaning Procedure FPA Australia recommends the following process when cleaning foam tanks or changing out existing C8 foams: 1. Decant existing C8 foam into suitable storage containers, which are also bunded and clearly marked for incineration/destruction. 2. Thoroughly flush system with water and collect effluent in suitable storage containers/tankers, identifying contents. The use of hot water may facilitate cleaning. 3. Using suitable remediation technologies, flushed foam solution and effluent should be treated to concentrate the PFAS into as small a volume as practical and should be held separately and labelled prior to disposal/destruction. 4. Analyse clean water for residual PFAS levels, before any release for re-use to the sewer/environment to ensure local regulatory requirements are met. This is likely to require temporary storage in large clean tanks without any previous PFAS usage or potential pre-existing PFAS contamination. 5. Send concentrated PFAS containing materials for disposal/destruction in accordance with local regulatory requirements. Remaining PFAS concentrations To avoid the possibility of contamination, the tank should not be filled with the replacement foam until the results of this testing are available and confirm sufficiently low levels acceptable to the local environmental regulator. It is recommended a sample of the clean effluent be tested by a NATA accredited laboratory for traces of PFOS/PFHxS/PFOA to determine a baseline level of contamination for future reference and to confirm the storage is essentially PFOS, PFHxS and PFOA free down to the levels specified in the Queensland Policy. Costs There is no information available on costs for this procedure. Additional information and available case studies There is no information available on case studies. 57/80 Ramboll - [Title] Cleaning protocol by the Australian DoD Background The Aircraft Rescue & Firefighting (ARFF) foam transition project will transition of all Army, Air Force and Broad spectrum firefighting vehicles to a suitable Fluorine Free Foam (F3) product (DoD-AUS 2020b). The ARFF Vehicle Foam Transition Sub Working Group will manage this project under delegation from the One Defence Firefighting Foam Management Working Group. As seen in the figure (Figure 22) below, the cleaning procedure relies on the set up of 10 cleaning hubs, where over 100 vehicles will be cleaned. The procedure and the description are very detailed and equipped with further documentation by photos. In the following only a brief overview will be given. Figure 22: Overview on the Aircraft Rescue & Firefighting (ARFF) foam transition project (DoD-AUS 2020a) Cleaning Procedure FPA Australia recommends the following process when cleaning foam tanks or changing out existing C8 foams: 1. Decanting Aqueous Film Forming Foam (AFFF). ARFF vehicles will be decanted of AFFF prior to chain of custody being taken by the Hub Supervisor, and cleaning activities comm Continuous flush. 2. Sample baseline 3. Vehicle CES soaking 4. Outlet and hose flushing 5. Sample for validation 6. Re-fill with F3. ARFF vehicles will be re-filled with F3 upon completion of the required cleaning activities set out in step 4. The Hub Supervisor will apply a colour coded zip tie to cleaned CES items associated with the vehicle to identify them as F3 only. 7. Proportioner Calibration and Return to Service Testing (RTS): The User Units will conduct vehicle foam performance tests (including proportioner calibration) inside, or at, the designated foam test facility or area as per existing testing arrangements. 8. Restart next vehicle 9. Vehicle validation against cleaning criteria There is a checklist, which needs to be checked before the vehicle can leave the hub. 58/80 Ramboll - [Title] Figure 23: Cleaning procedure phases in accordance to the Queensland DoD (DoD-AUS 2020c) Remaining PFAS concentrations There is no information available for the remaining PFAS concentration. Costs There is no information available on costs for this procedure. Additional information and available case studies There is no information available on case studies. Cleaning protocol by Werkfeuerwehrverband Deutschland (WFVD) According to WFVDs homepage20, the plant and company fire departments as well as the company fire protection officers have a special task within the framework of the organization serving fire protection. In addition to the general fire protection tasks, the company fire protection organization must take into account the special company risks. Preventive fire protection, hazard prevention and company rescue services are of particular importance. As a result of the need to adapt to company-specific conditions, the principles and guidelines established for public fire departments cannot be transferred to plant and company fire departments without further ado. The plant and company fire departments as well as the company fire protection officers therefore need their own organization for the purpose of representing their interests and exchanging experience. Now that the relevant organizations have largely been formed at the level of the German states, the Bundesverband Betrieblicher Brandschutz/Werkfeuerwehrverband Deutschland e.V., hereinafter referred to as WFVD, is the appropriate representative body. Background In 2014 it was noticed that PFAS levels in the foam concentrate of two fire apparatus at an industrial facility is higher than expected (for example 30,000g/kg 6:2FTS). The purchased foam concentrate used in this tank was a C6 based AFFF (not based on PFOS, see Figure 3 for a PFAS analysis of the 20 See here, last accessed 24.03.2021 59/80 Ramboll - [Title] new product) and it did not exceed the threshold of 10,000g/kg PFOS. However, the foam concentrates in the tanks of the of two fire apparatus exceeded PFOS levels. This was traced back to a cross contamination from a PFOS-based foam concentrate (3M Lightwater) that was in the same foam concentrate tanks before. It was supposed that during transition from C8 (PFOS based) foam to C6 (PFHxA precursor based) foam, the tanks were not cleaned sufficiently. Residues of 3M Lightwater contained high amounts of PFOS and contaminated the new PFOS-free AFFF. It was decided to develop a foam concentrate tank cleaning procedure, clean the tanks accordingly and transition to fluorine free foam. According to WFVD, from these cases it can be concluded that the described foam concentrate tank cleaning procedure is an effective method to clean tanks for firefighting foam concentrate when transitioning from PFAS-based to fluorine free foam. It is simple enough to be carried out by fire brigades themselves or for example by companies that specialize in industrial cleaning. It sufficiently reduces PFAS levels below applicable standards and is adjustable in case the results do not meet expectations. Cleaning Procedure The foam concentrate tank cleaning procedure is a relatively simple process that in many cases can be carried out by fire services themselves. Basically, it comprises a series of flushing with water, after the tank is emptied. Main challenge in this process is to avoid spills and contamination of equipment outside the foam concentrate tank. During step 2 and 3 the residues of the foam concentrate will cause foaming inside the tank. The overflow of that foam should be avoided to not cause any contamination outside of the tank. Further attention should be paid to a proper disposal of the old foam concentrate and any rinsing water. The standard disposal method would be high temperature incineration in a facility that is able to handle PFAS waste. WFVD recommends the following foam concentrate tank cleaning procedure: 1. Step 1: a. Empty foam concentrate tank, pump and piping b. Dispose foam agent through high temperature incineration 2. Step 2: a. Fill tank with warm water (60-70C) (half full to avoid overflow of foam) b. Drive with apparatus for a 30minutes to allow contact of water with the whole inner tank surface c. Pump water with foam pump in a loop for about 30 minutes d. Empty tank, pump and piping e. Destroy foam inside tank with water and a very fine nozzle and empty tank again f. Dispose water through high temperature incineration 3. Step 3: a. Repeat step 2 one time 4. Step 4: a. Fill tank with water b. Pump water with foam pump in a loop for about 30 minutes c. Take a water sample d. Analyse water sample for PFAS e. Repeat Step 3 if results of PFAS analysis are not sufficient f. Dispose water through high temperature incineration 5. Step 5 a. Drain any rinsing water from tank, pump and any pipes b. Dry tank as good as practically possible c. Fill tank with new foam concentrate 60/80 Ramboll - [Title] Remaining PFAS concentrations According to WFVD, the efficacy of the foam concentrate tank cleaning procedure can be assessed when looking at Figure 24 and Figure 25. The highest remaining PFAS-substances reported in Figure 24 are 6:2 FTS with 0,98 g/L (0.00098 ppm) and PFOS with 0,81 g/L (0.00081 ppm). The highest remaining PFAS-substances reported in Figure 25 are PFOS with 42 g/L (0.042 ppm) and PFOA with 1,2 g/L (0.0012 ppm). If all reported PFAS-substances are added a remaining concentration of 57,5 ppm (0.057 ppm)is measured. These are PFAS analyses of the rinsing water from step 4 of the procedure. As these are analyses for PFAS in water the detection limit for PFAS is lower than in the analyses for PFAS in foam concentrate. The analyses show that cleaning is effective with dilution factors varying between 100 and 100,000. While PFAS can still be detected in the rinsing water in all cases they are lower than current applicable thresholds for PFOS (not further commented by the stakeholder but most likely 10 ppm according to POP-regulation) and PFOA (not further commented by the stakeholder). If the results do not meet expectations step 2/3 can be repeated until levels are sufficiently low. It has to be noted that the water analyzed in step 4 will also be disposed and that PFAS levels can be assumed to be even lower when the new foam concentrate is filled in. Figure 24: PFAS Analysis of rinsing water from apparatus "TMB" from step 4 of tank cleaning procedure (note, that the detection limit is lower as this is an analysis for PFAS in water as opposed to PFAS in foam concentrate in other figures) Figure 25: PFAS Analysis of rinsing water from apparatus "PTLF II" from step 4 of tank cleaning procedure (Note 1: The detection limit is lower as this is an analysis for PFAS in water as opposed to PFAS in foam concentrate in other figures. Note 2: This apparatus is also referred to as "TroTSLF 2" or PTLF 2) 61/80 Ramboll - [Title] Costs Costs for the cleaning of a foam concentrate tank of a fire apparatus highly depend on disposal costs for the foam concentrate and flush water, summing up to 50% of the total costs in this example (4000 ). It is estimated that the volume of the flush water is three times that of the tank volume. Other costs, like work hours are likely to be independent from tank size (unless deviating to a greater extent from this example). In this case study the work was done by the industrial fire brigade itself, so that no external costs arose for work hours. Figure 26: Estimated costs for the cleaning of a 1 m foam concentrate tank with the described cleaning procedure Additional information and available case studies Three years after the cleaning of the tanks, the foam concentrate was analysed for PFAS again. Except for one PFAS in the apparatus all PFAS are below the detection limit and, most important, below the applicable threshold for PFOS and PFOA. The reason for the 56g/kg of 6:2 FTS in apparatus TMB are not known for sure. Possible explanations are: Cross contamination from residues of old foam concentrate, contamination of the sample or measuring error. The procedure is also explained in a video available at Youtube (English and German version). The stakeholder reported there are some mistakes concerning the values in the English version. Final Conclusion on available cleaning procedures for firefighting equipment The following conclusions can be made for available cleaning procedures for firefighting equipment: The procedures are authored by regional (Germany) and national (Australia) authorities, private companies (PerfluorAd & Arcadis), associations and lastly by manufacturers of foams (BioEx). All of them use extensive cleaning steps with (sometimes hot) water, which can also soak in overnight The commercial technique uses also cleaning agents which precipitate the PFAS In some a replacement of highly contaminated material is suggested to avoid high remaining PFAS-concentrations The success (remaining PFAS concentration) is measured using a variety of analytical techniques and respective PFAS-species. Most of the procedures are for fire brigade vehicles and/or tanks. Cleaning costs are reported to be between 4.000 200.000 Euro per vehicle. The highest costs are reported when using the LfU-Guideline. In this case costs of 100.000-200.000 and remaining PFAS levels in the range of 10 ppt are cited. When using the PerfluorAd-cleaning procedure costs between 20,000-25,000 Euro per vehicle and a remaining PFAS level of 0.001 g/l (0,001 ppm) are reported. Around 4,000 are reported by the WFVD (in this case no costs for employees is considered as is foreseen that the firefighters will clean the tanks). The achievable concentration is reported with 57 g/L (0.058 ppm). 62/80 Ramboll - [Title] Two procedures are also claiming to be suitable to installed firefighting systems (sprinklers). However, in this case only very limited data is available. According to a stakeholder from Germany, Mr. Cornelsen, his company is receiving only for 6-12 months requests for cleaning installed systems. He also pointed out that, the PFAS-concentrates normally are contained in the tank, tank to mixer pipes, and finally the mixer (if there has been no incidents/training with PFAS-containing firefighting foam). A large company in the chemical sector indicated that there would be costs of around 1.500.000 per installed system. However, in this case no remaining PFASconcentration is named. According to Eurofeu, the transition from Fluorine containing foam agents to fluorine free ones in fixed installed systems, trucks and storage facilities requires a much more in-depth cleaning compared to a like for like foam agent exchange. This factor particularly heavily depends on the thresholds to achieve. However, the cost for cleaning including disposal cost for foam agents and cleaning residues as well as replacement of systems or parts thereof are considered to be very high and have a high potential to grow exponentially depending on the conditions to reach (Eurofeu 2020). In most cases, incineration of the cleaning water is recommended Only very limited data for long-term success of cleaning procedures 63/80 6. REFERENCES 2010/75/EU. (2010). Directive 2010/75/EU of the European Parliament and of the Council of 24 November 2010 on industrial emissions (integrated pollution prevention and control) Text with EEA relevance. Analytik Berghof, 2019. Modellvorhaben Eignungsprfung und Optimierung von Verfahren zur Reinigung von PFC-Grundwasserkontaminationen. Retrieved from https://www.landkreis- sigmaringen.de/ceasy/resource/?id=4467&download=1 Anderson John, 2021. Biodegradable cleaning agent for PFAS-impacted infrastructure. Paper presented at the Emerging Contaminants in the Environment Conference (ECEC21). AngusFire (2021): Foam storage Guide. Retrieved from https://angusfire.co.uk/wp- content/uploads/6164-Firefighting-Foam-Storage-Guidance.pdf AU-EPA, 2021. Firefighting Foam Policy Waste disposal plan advisory. 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APPENDIX 1 Information submitted by Fire Rescue Victoria - FRV Appliance PFAS Decontamination Project FRV Appliance PFAS Decontamination Project Overview This document outlines some of the work that Fire Rescue Victoria (FRV, formerly the Metropolitan Fire & Emergency Services Board (MFB), has done since 2017, to decontaminate appliances (fire trucks), to agreed poly- and perfluoroalkyl substances, (PFASs) thresholds, from MFBs previous use of PFAS containing Aqueous film forming foams (AFFF). Outcomes The outcomes of this work include; PFAS decontamination of over 145 FRV and CFA (Country Fire Authority) fire fighting appliances and over 150 kms (over 5,500 lengths), of fire fighting hoses to below; o Sum of PFOA either 21,800 or 70 parts per trillion, and o Sum of PFHxS and PFOS either 413,000 or 70 parts per trillion. Background PFAS are a class of man-made substances that are 21extremely persistent environmental contaminants, that are mobile, bioaccumulative and toxic22 in the environment and are described as forever chemicals. There are over 4,600 different types on PFASs. The MFB previously used PFAS containing Aqueous film forming foams (AFFF) as firefighting foam, based on 3Ms earlier recommendation of it being safe. Global use of PFAS containing AFFF fire fighting foam is the source of approximately 30% of the worlds PFAS contamination. In 2007, MFB made a decision to replace existing firefighting foam with fluorine-free firefighting foam. This decision was on the basis of concerns relating to firefighter health and environmental issues. MFB then phased out the use of persistent PFAS-containing firefighting foams across its operations. MFB engaged expert independent environmental consultants to analyse PFAS exposure pathways for MFB firefighters on the job. This report was used to inform and develop MFB PFAS threshold limits and prioritise PFAS mitigation work. 21 https://www internationalairportreview com/article/98795/fire-fighting-foam-chemicals-water/ 22 Ross, I , Hurst, J , Managing Risks and Liabilities associated with Per- and Polyfluoroalkyl Substances (PFASs) CL:AIRE Technical Bulletin TB19 2019; Available from: https://www claire co uk/component/phocadownload/category/17-technical-bulletins?download=668:tb-19-managing-risks-and-liabilitiesassociated-with-per-and-polyfluoroalkyl-substances-pfass-2019 71/82 Appliance Decontamination Record / Release Form Appliance Type: Appliance Number: PFHxS Tas Complet Verificati and ks Description ed Date on Date PFOA PFOS (All (All results results in in ng/litre ng/litre (TEST) (ppt) (ppt) Remove and lay aside 38mm, 50mm & 65mm 1 hoses Remove and lay aside metal hose 2 fittings/connectors Remove and lay aside 3 transfer/pick-up hoses 4 Drain class B foam tank Undertake first flush - 5 class B foam tank Remove & clean class B 6 breathers and probe Confirm removal of class 7 B foam strainer Flush & clean class B tank 8 until no visible foam Drain class A foam tank (if 9 required) Flush class A Foam Inlet 10 back into tank and drain All foam and water tanks were filled with hot water and left to stand 11 overnight (Water tankers and Pumper tankers had two more steps with the flushing of the burn over protection and front 12 sprays ) Flush & clean class A foam 13 tank (TEST) Drain water tank (if 14 required) 76/82 Flush & clean water tank 15 (TEST) Final flush and test Class 16 B foam tank (TEST) Flush and clean injector 17 bypass via calibration line Flush & clean foam 18 Injectors Flush truck pumps with 19 truck tank water Flush & clean hose reel 20 nearside (TEST) Flush & clean hose reel 21 offside (TEST) Flush & clean truck lines 22 and monitor (TEST) Flush & clean truck deluge/halo system(s) (if 23 fitted) Pressure wash 24 transfer/pick-up hoses Pressure-wash hose drum 25 nearside Pressure-wash hose drum 26 offside Pressure-wash pump panels (exterior & 27 interior) Pressure-wash gantries 28 and rear of appliance Pressure-wash hose fittings compartment & 29 drawer(s) Pressure wash hose fittings, and return to 30 drawers Return transfer/pick-up 31 hoses to gantry Pressure wash exterior of 32 nearside hose Pressure wash exterior of 33 offside hose Ensure all tanks and lines 34 are drained 77/82 Email this completed Appliance Decontaminated Record/Release Form to FRV on the completion of 35 each appliance. Carbon Filtering and Sampling process Appliance released to MFB/FRV Released By (Name ) Signature Date This decontamination record is an extract from a full report prepared for FRV. Verification indicates that a test sample was taken by a trained chemist and that laboratory analysis showed compliance with agreed standards. Results for PFOA and for PFHxS and PFOS are as reported by the laboratory engaged to undertake the analysis. 78/82 PFAS residual thresholds 79/82