The European PVC cycle: In-use stock and flows

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The European PVC cycle: In-use stock and flows L. Ciacci a,∗ , F. Passarini a,b , I. Vassura a,b a b

Interdepartmental Center for Industrial Research “Energy & Environment”, University of Bologna, Rimini, Italy Department of Industrial Chemistry “Toso Montanari”, University of Bologna, Bologna, Italy

a r t i c l e

i n f o

Article history: Received 31 March 2016 Received in revised form 3 August 2016 Accepted 8 August 2016 Available online xxx Keywords: Thermoplastic Industrial ecology Polymer recycling Material flow analysis Building and construction Urban mining

a b s t r a c t More than any other material, plastic is likely the commodity that has changed and characterized everyday life in the last 60 years. Although fairly young, the petrochemical industry has grown rapidly and moved to a variety of products and applications that has become one of the biggest industries worldwide. Notwithstanding such a presence in the modern society, plastics have been little analyzed from a material flow analysis perspective; low recycling rates and a strong reliance on primary material inputs give plastic greatest potentials for closing material loops. With this aim, polyvinyl chloride (PVC) stocks and flows in Europe are investigated historically to 2012. By volume, PVC is one the major thermoplastics used today and its employment in applications having relative long lifespans such as building and construction implies accumulation in anthropogenic reservoir as future sources of secondary material. The results show that about two thirds of the cumulative apparent consumption of PVC are still in use, reaching about 270 kg/capita at current levels. The remaining one third that came out of use has been mostly landfilled, with only a minor fraction being recycled. Flow analysis shows that significant margins for improving material and energy recovery at end-of-life do exist for PVC if the recycling challenge is timely and properly addressed in the coming years. Design for recycling, ban on plastic landfilling, and recycling targets with a focus on the recycled content in new products are keys for ensuring resource efficiency and the creation of an adequate recycling infrastructure across Europe. © 2016 Elsevier B.V. All rights reserved.

1. Introduction A growing interest in characterizing the metabolism of modern society has spurred industry and academia to understand how material flows are used within and among economies and dynamics behind the accumulation of product stocks in anthropogenic reservoirs. Ultimately, anthropogenic in-use stock represents a pool of secondary material sources and provides perspectives for investigating long-term demand-supply patterns (Graedel and Lifset, 2016; Liu et al., 2013). Industrialization, urbanization, and needs for improving human wellbeing have determined an on-going development of technology and progress in material manufacturing such that almost the entire periodic table of elements is used in everyday products and goods (Graedel et al., 2015a). The material voracity of modern society is not limited to metal forms, but extends the demand to other commodities, with petrochemicals from crude oil refining and natural gas processing being an example.

∗ Corresponding author. E-mail address: [email protected] (L. Ciacci).

The petrochemical industry is fairly young: it started to grow in the 1940s, but rapidly moved to a variety of forms and uses that became one of the most important industries worldwide. Through cracking and reforming processes, crude oil and natural gas are converted to olefins and aromatics that are key building blocks for commodities as synthetic polymers and rubbers. These major products of petrochemical industry have such an extensive presence in modern society that the XX century was given the name of “plastic age” (Thompson et al., 2009). The plastic industry in Europe counts more than 60,000 companies including raw material producers, plastics converters and manufacturers (PlasticsEurope, 2015), and with about 60 Mt in 2013 follows only China in the global plastics production rank. Five countries (i.e., Germany, Italy, France, United Kingdom, and Spain) concentrate about two thirds of plastics demand in the region. By polymer type, polyethylene, polypropylene, and polyvinyl chloride (PVC) represent about 60% of total plastic volume in Europe for household goods, medical equipment, leisure products, and other major applications (PlasticsEurope, 2015). As known, plastics vary in quality and quantity, in morphology, and end-uses. Two major classes of polymers are thermosets and thermoplastics. Respect to other thermoplastics, PVC has unique properties and great versatility that together with a relative low

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price boosted its use and diffusion. This resin was first polymerized during the second half of the XIX century and since its massproduced manufacturing (circa 1920s) (PlasticsEurope, 2016), PVC has constituted a synthetic substitute for natural rubber. During the World War II, PVC production increased strongly thanks to water resistant features and non-flammable electrical properties. Better quality of PVC compared to caoutchouc was also exploited in the music industry for reducing the thickness of vinyl discs (or simply known as vinyls) and allowed the long-playing recording, which decreased the rotation speed from 78 to 331/3 revolutions per minute. In fact, PVC is still used today for vinyls with no substitute thanks to high quality for music records and relative low cost. More recently, the range of applications has become wider consequently to novel manufacturing routes that have increased its durability and made PVC an essential material for building and construction. In addition, in light of criticality issues due to potential supply risk and restriction, PVC has been identified has a primary substitute with good performance for replacing copper in plumbing (Graedel et al., 2015b). Due to its rigidity at normal temperature, PVC cannot be used alone, but it is always mixed with additives including plasticizers, heat stabilizers, fillers, pigments, lubricants, and other agents to enable PVC manufacturing and to improve its physical and mechanical properties. Rigid, unplasticized PVC has a total additives content less than 10% on weight (Fischer et al., 2014), but much higher concentrations can be found in flexible PVC products (Stringer et al., 2000; Whitfield and Associates, 2008). Intrinsic PVC instability is due to its subjection to heat, which causes selfaccelerating dehydrochlorination reactions. Inorganic and organic salts of metals as calcium, zinc, lead, and tin have been historically used as stabilizers for heat and UV-light degradation or for preventing oxidation at air. Due to harmful effects related with potential release of toxic metals and their accumulation in the human body, the EU has phased out the use of cadmium stabilizers in PVC manufacturing. A voluntary commitment, named “Vynil 2010”, by the European Stabiliser Producers Association and the European Plastics Converters Association aimed at replacing lead stabilizer used in PVC by 2015 (PVCplus, 2012). Bans to toxic metals have increased attention to stabilizers containing calcium and zinc and to novel metal-free systems. Concerns have been raised also on the use of additives to increase plasticity to PVC products. The most common plasticizers are standard phthalates (i.e., esters of phthalic anhydride with C8 –C10 alcohols, representing more than 85% of world plasticizers production), of which 90% is annually used in PVC manufacturing (EVCM, 2016). The greatest concern related to the use of phthalates is due to endocrine modulation and alleged disruption to the human health, particularly to toxic effect to reproduction and fertility. The EU has limited the use of short-chained and low molecular weight phthalates such as bis(2-ethylhexyl) phthalate (DEHP), dibutyl phthalate (DBP), diisobutyl phthalate (DIBP), and benzyl butyl phthalate (BBP), as substance or as constituents of preparations, at concentrations of greater than 0.1% by mass of the plasticized material and banned their use in toys and baby articles (Directive 2005/84/EC); such a restriction has been recently extended to all electrical and electronic equipment (Commission Delegated Directive (EU) 2015/863). The replacement of DEHP, DBP, DIBP, and BBP with other plasticizers will be likely enhanced by the inclusion of the four phthalates within the REACH regulation as “substances of very high concern” (ECHA, 2016). High molecular weight and long-chained phthalates (e.g., diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), and di(n-octyl) phthalate (DNOP)) may be used at limited concentrations in toys and baby articles which children do not place in their mouths (Directive 2005/84/EC). The European Chemicals Agency’s risk assessment indicated that no unacceptable risk has been character-

ized for the use of DINP and DIDP in current consumer applications (ECHA, 2010a,b). Consequently to EU regulations and health concerns, plasticizers derived from adipic acid, therephtalates, and phthalate-free additives have increased their economic importance and their employment in new PVC formulation. Material Flow Analysis (MFA) has been applied extensively to characterize anthropogenic material cycles. Major interest has been oriented to metals due to their wide use in the society and market value. Dynamic and standard MFA studies quantified in-use stock for most base metals, specialty metals, and rare earths with different scope (Chen and Graedel, 2012; Ciacci et al., 2013; Du and Graedel, 2011; Glöser et al., 2013; Izard and Müller, 2010; Kral et al., 2014; Liu et al., 2011; Meylan and Reck, 2016; Pauliuk et al., 2013). Additional studies focused on materials other than metals including construction minerals and biomass (Hashimoto et al., 2007; Krausmann et al., 2009). Notwithstanding their extensive presence in the contemporary society, low recycling rates, and the related environmental implications, plastics, and particularly PVC, have been little investigated from an MFA perspective. Tukker et al. (1996) performed a detailed substance flow analysis for PVC and related emissions in Sweden (Tukker et al., 1996); the results were later employed to estimate outflows of PVC waste as function of delaying mechanism of stock in the same country (Kleijn et al., 2000). Patel et al. (1998) analyzed plastics streams in Germany and estimated resulting long-term production, consumption, and waste generation patterns (Patel et al., 1998); Nakamura et al. (2009) applied input-output tables for characterizing Japanese PVC industry and provided a summary of MFA studies on plastics to 2000 (Nakamura et al., 2009). A dynamic MFA was applied to quantify the U.S. polyethylene terephthalate cycle by (Kuczenski and Geyer, 2010); Zhou et al. (2013) analyzed the Chinese industrial metabolism of PVC and provided insights for future waste generation (Zhou et al., 2013). Bogucka et al. (2008) applied MFA to support multi-resin waste management in Poland and Austria (Bogucka et al., 2008); similarly, Van Eygen et al. (2015) proposed an in-depth analysis of plastics flows and stocks in Austria for 2010 (Van Eygen et al., 2015). Bellstedt (2015) determined PVC stock in civil infrastructure in Amsterdam as case study to support the development of a circular economy (Bellstedt, 2015). In this work, MFA is applied to quantify European flows and stocks of PVC historically to 2012. We expect the results provide significant insights for the European PVC industry, including estimates of potentials for PVC recycling and performance indicators such as recovery rate, end-of-life recycling rate, and annual additions to stock. On a broader perspective, the results will contribute to the international Industrial Ecology community by enlarging the number of material cycles investigated and increasing the knowledge about the metabolism of modern society.

2. Methodology MFA applies the mass conservation to balance for inflows and outflows from each stage of a material’s life cycle. Similarly to metals, the life cycle of PVC can be divided into four main phases, including production, manufacturing and processing into finished goods, use, and waste management. A major distinction with metals (with the exception of those having anthropogenic origin, e.g., technetium) is that plastics are produced artificially. Thus, system boundaries for the anthropogenic PVC cycle are set to include flows and process dealing with a defined and uniform composition of this material. In other words, system boundaries begin with resin PVC production and end with end-of-life treatment of PVC waste. Material flows to incineration, waste to energy plants, or to landifll are not disaggregated further as PVC undergoes processes that change the chemical structure of the material of interest. The scope

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of the study is Europe, according to the EU-27 definition at 2012. As the analysis is carried out backwards fairly before the EU was established, the countries belonging to the EU-27 are consistently investigated back to 1960. All flows are expressed in resin content; additives commonly supplemented to PVC are not included in the analysis. PVC is produced from vinyl chloride monomer (VCM) that is, in turn, industrially prepared by two main reactions: thermal cracking of 1,2-dichloroethane, which is the most important industrial route of VCM production (Fischer et al., 2014; Dreher et al., 2014), and hydrochlorination of acetylene. Building blocks of VCM are chlorine (∼57%), obtained by electrolysis from a solution of brine, and ethylene (∼43%) that is mainly produced from crude oil refining and further cracking steps. The following polymerization of VCM to PVC can follow three different processes: suspension, which provides more than 80% of world PVC, emulsion (12%), and mass (or bulk process, ∼5%). Generally, PVC production plants can vary from stand-alone PVC plants to fully integrated plants, with various intermediate levels of integration. Common reaction yields of VCM polymerization in the suspension process are 97–98%; the unreacted monomer is recovered by stripping and, after a liquefying step, reused in later polymerizations (Fischer et al., 2014). Manufacturing and processing stages focus on the creation of semi-finished (or semis) products and finished products, respectively. Various manufacturing processes are used, e.g. extrusion, calendering, injection molding, and other manufacturing processes. Outflows from these processes have been grouped into five macrocategories including pipes and fittings, tubes and profiles, films and sheets, wires and cables, and other semis goods. Data on PVC resin demand in Western Europe from 1960 to 2012 have been obtained from PlasticsEurope statistics (Sevenster, 2016). Historical first-uses shares have been used to compute annual PVC inflows to manufacturing processes (see Table S1 in Supplementary information). In some cases, semis products can be used standing alone (e.g., pipes and fittings); in some other, they are incorporated into complex products such as cars and electronics (e.g., wires and cables). A clear distinction between either ways of use is not always possible, although each semis category can be linked to major end-use sector. For instance, tubes, profiles, pipes, and fittings are mostly used in building and construction as much as window frames from extrusion, and decorative laminating films and sheets (e.g., flooring, door protection, roofing sheets) from calendering. Other PVC products find application in packaging and containers. Piping and ducts are used for power and telecommunications; insulation cables and sheathing are employed for power supplies, appliances, and automotive. The transportation industry uses PVC also for underbody coating and interior decoration. Blood and urine bags, surgical gloves, and transfusion tubing are examples of PVC uses in the medical sector. Home and leisure products include footwear, tents, garden hoses, inflatables, toys, tablecloths, and similar goods. Market shares distribution is derived from PlasticsEurope (Sevenster, 2016) data and VEC statistics (VEC, 2016), (see Fig. S1 in Supplementary information). The United Nations Commodity Trade Statistics Database (UN COMTRADE, 2016) was used to quantify net-exports of semifinished and finished products containing PVC, according to the 1996 Harmonized System. About seventy commodity codes have been selected and mass-based PVC percent ranges have been applied to compute trade flows in terms of PVC content (see Table S2 in Supplementary information). PVC polymers and co-polymers are produced generally from primary input. PVC from secondary sources is recycled in the processing stage where PVC products are manufactured. Pre-consumer and post-consumer wastes are two main sources of secondary PVC. Pre-consumer waste results from production and processing

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trimmings and off-cuts: thanks to cleanness and quality of PVC, these flows are generally recycled internally at high recycling rates (Sevenster, 2016). Post-consumer waste is the largest source of secondary PVC and it is generated when products are discarded at the end of their life. In these products, PVC is often dispersed in low concentrations and requires large efforts to remove pollutants before further processing. In some cases, PVC products remain uncollected and are never recovered, with water pipes left underground being an example. To estimate the amount of PVC waste and products containing PVC discarded at end-of-life a “top-down” approach is used (Harper et al., 2006). This approach considers the annual flows into use by end-use and applies lifespan distribution models to estimate when a given product in use reaches obsolescence and enters the waste management stage. The annual difference between the amount into use and the amount out of use represents the net-addition (or netsubtraction) to the urban reservoirs or in-use stock. Performing the calculation for each year of investigation provides a measure of the magnitude of PVC accumulated in use and available for future recovery and recycling. Average lifespan and standard deviation assumed in the study are reported in Table S3 in Supplementary information. When discarded, PVC waste and PVC-containing end-of-life products can undergo different fate depending on the waste management system. Generally, separate collection systems do exist for specific type of waste such as packaging waste and waste electrical and electronic equipment (WEEE), but a univocal correspondence between end-use sectors and major waste categories is not always clear to determine. Each waste category is modeled distinguishing between collection for recovery (which may include either material recycling or energy recovery) and collection for disposal through landfilling or incineration (PlasticsEurope, 2013). End-oflife collection rates, recovery rates for each waste category, and information on the European municipal waste management by treatment method were derived from Eurostat statistics (2015a,b,c) and expert elicitation (Sevenster, 2016).

3. Results & discussion 3.1. PVC flow analysis Fig. 1 displays the cumulative European life cycle of PVC from 1960 to 2012. PVC production has increased constantly over time until 2008, when the worldwide financial crisis has likely slowed down the European demand; the production quantity in 2012 was comparable to middle 1980s levels (Fig. 2). Despite a decrease in the domestic production, import and export of PVC polymers and co-polymers keep increasing almost linearly. Flow analysis shows that Europe is historically a net-exporter of unwrought PVC forms (15 Tg), (Fig. 2; for more detail see Fig. S2a in Supplementary information). Total PVC production has input mainly extrusion and calendering manufacturing processes. Injection molding products has slightly increased over time but still remain marginal in terms of magnitude of flows. A feature as a net-exporter characterizes trade flows of European PVC semis too (Fig. 2; for more detail see Fig. S2b in Supplementary information). In first approximation, mass contents of PVC in traded flows are assumed constant over time: despite changes cannot be excluded, this assumption has marginal effects as net-traded flows are not significant compared to domestic production and consumption flows. About two thirds of PVC input has supplied rigid PVC manufacturing. Film and sheets production was the larger first-use sector, before profiles and pipes production increased in recent years. The majority of these semi-finished and finished products

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Fig. 1. Aggregate model for the European PVC cycle (1960–2012); values are in Tg. VCM: vinyl chloride monomer; S-PVC: suspension PVC; E-PVC: emulsion PVC; B-PVC: bulk PVC.

Fig. 2. Annual PVC flow into use and net-import of PVC polymer and co-polymer forms, semi-finished goods, and finished goods. Negative values represent net-export.

find application in the building and construction sector. Building and construction include also a considerable fraction of wires and cables for insulating, of which the remaining part is accounted in electrical and electronic equipment. Packaging is the second largest end-use market of PVC: despite a decrease in PVC bottle production over time, this sector demands annually more than 400 Gg PVC in Europe. The remaining PVC supplies home and leisure products, medical equipment, and the transportation sector. Particularly, the employment of polymers and similar light materials in vehi-

cle manufacturing is expected to increase in the coming years in response to reduce greenhouse gas emissions during vehicles’ use (GHK/BIOIS, 2006; Passarini et al., 2012). As for semis products, net-traded flows of finished products are less relevant in magnitude compared to the domestic production. However, between the end of 1990s and the beginning of 2000s, European import of PVC-containing goods has surpassed exports and the import rate is increasing faster: in 2012, total import of finished goods has

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Fig. 3. Annual per-capita PVC waste generated in Europe, 1960–2012.

almost doubled total exports (Fig. 2; for more detail see Fig. S2c in Supplementary information). The total flow into use amounts at about 200 Tg PVC, of which ∼4 Tg PVC in 2012. Nakamura et al. (2009) reported about 1.5 Gt of PVC flow into use in 2000 in Japan, which leads to 11.7 kg PVC/capita (Nakamura et al., 2009). According to our estimate for PVC flow into use in Europe for the same year, it results about 11.2 kg PVC/capita. As described in the methodology section, the quantity of PVC into use has been disaggregated by major end-use and has input lifetime distribution models to simulate the generation of PVC waste and discarded products at obsolescence. PVC losses during use due to degradation, abrasion or other dissipative phenomena are assumed to be negligible. Fig. 3 displays annual per-capita PVC waste generated at end-oflife disaggregated by major application sector. In 2012, the building and construction sector has generated the largest amount of PVC waste (about 1 Tg/year). More in detail, construction and demolition (C&D) waste is assumed to account for the entire amount of PVC outputs the building and construction sector; the fraction of C&D waste that is not collected for recovery is directly disposed of in landfill. An increase in C&D waste can be expected consequently to the growing demand of PVC products in buildings (e.g., for window frames) and to renovation practices. Packaging waste equals the amount of PVC used annually in containers and packaging as it has been assumed that those products are discarded within the same year of placing on the market. In absolute terms, the packaging sector has generated the greatest quantity of scrap from 1960 to 2012 (24 Tg PVC). Packaging waste increased constantly until middle 2000s; then a decreasing trend has followed. Dedicated collection schemes for packaging waste go back to the beginning of 1990s and nowadays have reached respectable collection rates (about 65% or even higher), (Eurostat, 2015c). The fraction of PVC packaging waste uncollected through separate collection systems is assumed likely to follow the same management route as MSW (Brown et al., 2000). This assumption accounts also for the entire amount of PVC waste from packaging

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that was generated during the years before dedicated collection schemes were adopted. The same assumption was also adopted for WEEE. WEEE is regulated by the EU trough a dedicated collection system; the system was established approximately in 2003 but still struggles to intercept the totality of electrical and electronics at end-of-life. 2012 collection rate is between 50% and 60%, leaving margins for significant improvements. According to EU statistics, in the last decade a still small but increasing fraction of WEEE underwent reusing practices in Europe. 2012 reusing rate was around 2% by volume of total WEEE generated in the same year. A further amount of WEEE was exported, accounting for an additional 2% in 2012 (Eurostat, 2015b). Trade flows of second-hand goods are generally not included in the UN COMTRADE statistics and efforts are ongoing to quantify these hidden flows. Thus, WEEE reuse and export rates may underestimate actual values. Home and leisure products at obsolescence are also accounted as MSW. This end-use market has generated about 0.5 Tg/year PVC waste in the last decade. As for some WEEE, lifetime of home and leisure products may be extended through second-hand markets or simply “hibernated” in houses, for instance for reusing or as collectibles, by owners. Due to lack of data, we were not able to quantify the magnitude of those hidden flows. Medical waste consists mostly of medical tubing, blood and urine bags, which are disposed by incineration as hazardous waste. About 100 Gg of PVC is annually generated from the transportation sector, mostly contained in end-of-life vehicles (ELV). The common management chain for ELV includes shredding for metal (mainly iron/steel and aluminum) recovery. As for materials other than metal, PVC concentrates into the shredder residue (also known as car fluff). The automotive shredder residue is generally disposed of in landfill, with a minor fraction sent to incineration in co-combustion with MSW for energy recovery (Ciacci et al., 2010; Passarini et al., 2012). The amount of waste assumed to follow end-of-life treatments as MSW has been modeled according to the historical evolution of the European MSW management and so separate between material recovery, incineration with energy recovery, incineration with no energy recovery, and landfill disposal (Eurostat, 2015a). The amount of waste collected for recovery, either through dedicated collection systems or as MSW, is then processed for sorting polymers and plastics on a single material basis. Process inefficiencies of material recovery facilities (MRF) reduce the amount available to recycling. In turn, outputs from MRF include material flow to recycling, energy recovery, and flows to final disposal. Post-consumer PVC waste generated in Germany in 2005 and 2007 was quantified at 360 Gg and 430 Gg (PVCplus, 2012); these values result at about 4.3 kg PVC/capita and 5.2 kg PVC/capita, respectively. Our estimates for 2005 and 2007 are 4.6 kg PVC/capita and 4.7 kg/capita; for 2012, about 5 kg PVC/capita is computed. Grand total of PVC to material recovery amounts at about 22 Tg for 1960–2012, of which, however, only 3 Tg were effectively recycled PVC and supplemented more than 220 Tg primary PVC. 1960–2012 end-of-life collection rate, computed as total amount of PVC collected for recovery as fraction of total PVC waste generated at end-of-life, is 34%, while end-of-life recycling rate results at 4%. The overall 1960–2012 recycled content, estimated as fraction of the amount of recycled PVC divided by total PVC production, amounts at about 1%. For the year 2012, end-of-life collection rate, functional recycling rate, and recycled content are estimated at 55%, 17%, and 9% respectively. PVC recycling started to be relevant in the last decade and since then a significant progress in PVC end-of-life collection and recycling rates has resulted. Recycling routes for PVC include mechanical and feedstock recycling. Mechanical recycling consists of material re-melting and re-processing into new products

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through grinding, separating, washing and drying, granulating, and compounding operations (Plastics Recyclers Europe, 2012). Mechanical recycling is generally preferred for flooring, pipes, roof sheets, and window frames (Bellstedt, 2015). Several initiatives have been implemented for the recovery of post-consumer PVC. As mentioned, C&D waste is largest fraction in waste management and tack-back systems for window profiles have been established in some European countries (e.g., Germany, Austria, the Netherlands). The Solvay VINILOOP® process enables the recycling of PVC cables insulation, and recycling options exist for packaging waste. Recycling initiatives are available also for PVC pipes, although the cost of collection is often a barrier and those products remain uncollected. In addition, soft PVC products such as flooring and roof sheets are more difficult to separate and are generally mixed up with waste (PVCplus, 2012). Feedstock recycling implies thermal treatment of PVC waste to produce hydrogen chloride that can be returned back to PVC production. The hydrocarbon fraction of PVC contributes positively to the energy balance of the recovery process by generating heat and electricity, with PVC having low calorific value in the order of about 20 MJ/kg. Recovery processes differentiate on limitations to chlorine content in input flows. Processing of high-content PVC waste and mixed inputs in slag bath gasification, hydrolysis, rotary kilns, and pyrolysis plants has been investigated (Bellstedt, 2015) but is not fully operating on commercial scale yet. Plastic fractions with PVC content up to 10% w/w can be either used to increase volume and calorific value in calcium carbide production, or can be used as carbon-rich input to syngas conversion (PVCplus, 2012). Compared to pyrolysis, incineration has better electrical power output, but also much greater environmental impacts (Wu et al., 2013). During incineration, the chlorine content of PVC is released as HCl that may determine corrosion issues within plant equipment, and contribute to chlorine inflow to waste incinerators. Particular concerns related to the combustion of organic fraction and chlorine presence in flue gas are due to dioxins and furans generation. Dioxins and furans concentration in flues gas is strictly regulated by the EU (Directive 2000/76/EC). Several processes have been developed to neutralize HCl from the flue gas. For instance, limestone scrubbers remove HCl as calcium chloride; the Solvay NEUTREC® process deposits sodium chloride, which is then recovered and purified; chlorine recovery in the form of salt is enabled by the HALOSEP® process. Dioxins and furans formation mechanisms are complex and not fully understand yet (Zhang et al., 2010); consequently, a wide part of the research is aiming at investigating reactions that determine dioxins and furans formation during chlorinated materials combustion. Compared to other plastic waste, PVC contributes significantly to the formation of dioxins and furans (Katami et al., 2002), but process operating conditions seem to be more relevant in determining dioxin formation (Buekens and Cen, 2011; Font et al., 2010). PVC waste input to incineration is distinguished between wasteto-energy plants and incineration plants for disposal only. In 2012, around 35% PVC waste was treated by incineration, of which more than 85% entered waste-to-energy plants for energy recovery. Despite an increase in end-of-life collection and recycling rates show economic interest and technical progress in PVC recycling, the largest fraction of PVC waste has been landfilled. This aspect reflects the evolution of MSW management and end-of-life treatments for waste, determining about half of PVC is disposed of. Environmental behavior of PVC in landfill is widely discussed in literature. Major concerns are related to heavy metal stabilizers, which may leach out to the environment, and to the migration of plasticizers. In general, no severe risk has to be expected from PVC in landfill. The contribution of metals released from PVC is marginal compared to other waste sources, however it should not be neglected. Losses of phthalates from PVC occurs under aerobic conditions at rather low

Fig. 4. Total PVC in-use stock, 1960–2012. Shaded area shows the sensitivity analysis results.

rates but the release may last for long time: considerable amounts of phthalates were found in landfilled PVC waste after more than two decades and is likely that they may last longer than the time required for leachate collection (European Commission DGXI.E.3, 2000). As additives supplemented to PVC are not covered in this study, this aspect is not discussed further. 3.2. PVC stock analysis Fig. 4 displays the evolution of PVC in-use stock over time: at 2012, estimated anthropogenic PVC reservoir amounts at about 137 Tg (or Mt). Shaded area in Fig. 4 shows the results of sensitivity analysis, which has been carried out to evaluate how much robust the model created is. As net-traded flows are relatively marginal compared to domestic production and consumption, and assuming that historical PVC production data are consistently reported, lifetime distribution models applied to PVC end-use markets are likely the most uncertain parameters in the model. Variations related to the shape form of normal distribution (i.e., standard deviation) used for markets resulted negligible compared to the effect of averages. Monte Carlo analysis was applied as a stochastic model to simulate the effect of random changes in lifespan distribution averages on waste generation and annual net-additions to in-use stock. Uncertainty range was set at ±15% for each end-use sector and the model was run 10,000 times. Compared to other methods (e.g., the use of minimum and maximum scenarios) Monte Carlo approach gives the advantage of extracting the probability density of possible results from data simulation, reducing the likelihood of using too low or too high values (Glöser et al., 2013; Laner et al., 2014). The sensitivity analysis individuates as a reasonable range of PVC in-use stock between 130 and 145 Mt. On a per-capita basis (Fig. 5), the size of current PVC in-use stock (270 kg/capita) has an order of magnitude comparable with that of most common metals as aluminum (∼200 kg/capita) (Liu and Müller, 2013) and copper (160 kg/capita) (Ruhrberg, 2006), attesting a significant relevance of PVC in the European society. The largest fraction of PVC stock is embedded in building and construction (126 Tg) consequently to demand-supply dynamics and

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Fig. 5. Per-capita in-use stock of European PVC disaggregated by major application sector.

relative long lifespan distribution, which give this flow the greatest impact under sensitivity analysis. Civil engineering appears hence a major driver for PVC demand and accumulation as much as for several materials in use including construction minerals and metals (Hashimoto et al., 2007; Krausmann et al., 2009). Minor but respectable PVC reservoirs are embedded in home and leisure (5 Tg), transportation (3 Tg), and electrical and electronic goods (2 Tg). Comparing the results of this study with previous in-use stock estimates for various plastics it emerges good consistency and reliability of the model created. Based on estimates in (Tukker et al., 1996), per-capita stock of PVC in Sweden in 1995 amounted at about 230 kg/capita. Previous projections for stocks of plastic in the German economy were between 100 and 150 Tg for 2012 (Patel et al., 1998), which is more than 1500 kg plastic/capita. Germany demands alone about one fourth of EU demand of plastics (PlasticsEurope, 2015): assuming that 1.5 t plastic/capita is representative for Europe, and comparing it to per-capita PVC in-use stock for 2012, it results that PVC constitutes roughly 17% of the total anthropogenic reservoirs of plastics in the region. Bogucka et al. (2008) estimated around 12 Mt of plastic accumulated in inuse stock in Austria to 2004, which is about 1460 kg plastic/capita. Kuczenski and Geyer (2010) applied standard MFA to PET in the US, however, as that material is mostly used in disposable applications, the authors evaluated only marginal addition to anthropogenic reservoirs. With respect to many materials that are used by human society since ages, PVC and other plastics are relatively young; however, the material intensity that characterizes modern society has taken PVC in-use stock to increase remarkably. In the last five years or so, accumulation rate of PVC in stock, either in absolute terms and per-capita values, has slowed down and inflection appears to occur. However, the intensity of PVC stock per economic activity (Fig. 6), similarly to other materials pattern (Ciacci et al., 2014; Liu and Müller, 2013; Müller et al., 2010), shows correlation with the level of development and industrialization of European countries, and saturation of per-capita PVC in-use stock, if any, appears still far to come.

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Fig. 6. Intensity of PVC stock per economic activity (Gross Domestic Product based on Purchasing Power Parity, GDP-PPP) for Europe, 1960–2012.

To put the results of this analysis in perspective, the size of PVC in-use stock is discussed in light of the current European production of the main building blocks for PVC. In 2012, ethylene production was around 19 Mt/year in Europe, of which about 14% was demanded for ethylene dichloride that is the starting material for VCM production (Petrochemicals Europe, 2015). In the same year, the European chlorine production was 12.4 Mt/year, mainly obtained through the membrane process (Eurochlor, 2015). The model estimates about 140 Mt PVC accumulated in anthropogenic reservoirs, which is more than 20 years of domestic ethylene dichloride production and about 6 times the European chlorine production at current levels. This theoretical projection gives the measure of the potential amount of PVC available for recycling. However, as flow analysis has shown, significant margins for improving material and energy recovery at end-of-life do exist for that resin. Thus, the challenge for the future is how to turn that potential into effective recovery and recycling. Collection and separation is a prerequisite for enabling recovery and recycling. Contamination is a great barrier for plastic recycling and the presence of different polymers in the flow to be recycled may limit recovery process efficiency. The development of sorting techniques for separating mixed plastic to single polymer streams is attracting growing interest. Among most suited separation methods are froth flotation, near-infrared spectroscopy, magnetic density separation, optical separation techniques, and Xray detection (Hopewell et al., 2009; Luciani et al., 2015; Wang et al., 2015). Prevention and minimization of waste are priorities for the EU (Directive 2008/98/EC). Polymer labeling can play an important role in public engagement and information, helping consumers to individuate PVC components and discard them through proper collection schemes. However, similar initiatives cannot solve alone barriers that limit PVC recycling. With this regard, a combination of different responsibilities can be summed up. Beside consumer responsibility and education, a strong momentum to recycling may derive from industry through a systematic adoption of Industrial Ecology practices such as Ecodesign, Design for Recycling, and life cycle assessment procedures

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to reduce (primary) material requirements and waste generation (Navajas et al., 2013). Particularly, end-of-life recycling of plastics can be enhanced if design criteria are fundamental part of new monomers manufacturing (Anastas and Beach, 2007; Tabone et al., 2010). Then, constructive actions by governments and policy measures can address the PVC recycling challenge by banning plastic landfilling across Europe, setting appropriate recycling targets, and supporting proper initiatives to drive technological progress (Thompson et al., 2009; Stichnothe and Azapagic, 2013). In particular, notwithstanding the EU has set recovery targets for waste material including plastic (Directive 2008/98/EC), such targets do not focus on the effective recycling at end-of-life but rather claim for “preparing for reuse, recycling, and other material recovery”. According to plastic recyclers’ perspective, more emphasis should be, instead, shifted from collection rates to recycling rates and, at the end, to recycled content targets for new products manufacturing (Plastics Recyclers Europe, 2012). These actions would have the results of extending attention to the entire life cycle of PVC and of stimulating the creation of the required recycling infrastructure in Europe. 4. Conclusions The work provided a first quantification of in-use stock and flows of PVC in Europe. Overall, the PVC cycle has wide margins for improvements on the route towards a sustainable closure of material flows. In this perspective, the results support the discussion about what actions should be undertaken to increase recycling at end-of-life. The flow analysis quantified the magnitude of PVC streams along the resin’s life cycle and showed where dedicated plans may have the best effect in pursuing new recovery opportunities. Building and construction is the largest driver for PVC demand and supply but collection and separation inefficiencies in packaging waste, WEEE, and other major application sectors reduce the amount available to recycling. Lastly, as additives commonly supplemented to PVC were not included in this work, further studies should focus particularly on stabilizers and plasticizers in light of the related environmental implications. With this regard, the analysis performed may constitute a fundamental basis for future characterization and risk evaluation related with anthropogenic PVC stock and flows in Europe. Acknowledgments We wish to thank Dr. Arjen Sevenster from PlasticsEurope for his courtesy and availability to provide historical European PVC statistics. Appendix A. Supplementary data Supplementary data associated with this article can be found, in the online version, at http://dx.doi.org/10.1016/j.resconrec.2016. 08.008. References Anastas, P.T., Beach, E.S., 2007. Green chemistry: the emergence of a transformative framework. Green Chem. Lett. Rev. 1 (1), 9–24. Bellstedt, C.H., 2015. Material Flow Analysis for a Circular Economy Development: a Material Stock Quantification Method of Urban Civil Infrastructures with a Case Study of Pvc in an Amsterdam Neighbourhood. TU Delft. ´ Bogucka, R., Kosinska, I., Brunner, P.H., 2008. Setting priorities in plastic waste management – lessons learned from material flow analysis in Austria and Poland. Polimery-W, T. 53 (1), 55–59. Brown, K.A., Holland, M.R., Boyd, R.A., Thresh, S., Jones, H. and Ogilvie, S.M., 2000. Economic evaluation of PVC waste management. A report produced for

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