Polyvinyl chloride

Degradation

Degradation during service life, or after careless disposal, is a chemical change that drastically reduces the average molecular weight of the polyvinyl chloride polymer. Since the mechanical integrity of a plastic depends on its high average molecular weight, wear and tear inevitably weakens the material. Weathering degradation of plastics results in their surface embrittlement and microcracking, yielding microparticles that continue on in the environment. Also known as microplastics, these particles act like sponges and soak up Persistent Organic Pollutants (POPs) around them. Thus laden with high levels of POPs, the microparticles are often ingested by organisms in the biosphere. Given the ever increasing amount of plastic pollution in our environment, this is an important concept in understanding the health and security of our food web.

However, there is evidence that three of the polymers (HDPE, LDPE, and PP) consistently soaked up POPs at concentrations an order of magnitude higher than did the remaining two (PVC and PET). After 12 months of exposure, for example, there was a 34-fold difference in average total POPs amassed on LDPE compared to PET at one location. At another site, average total POPs adhered to HDPE was nearly 30 times that of PVC. The researchers think that differences in the size and shape of the polymer molecules can explain why some accumulate more pollutants than others. The fungus Aspergillus fumigatus effectively degrades plasticized PVC. Phanerochaete chrysosporium was grown on PVC in a mineral salt agar. Phanerochaete chrysosporium, Lentinus tigrinus, Aspergillus niger, and Aspergillus sydowii can effectively degrade PVC.


Plasticizers

Phthalates, which are incorporated into plastics as plasticizers comprise ∼70% of the U.S. plasticizer market; phthalates are by design not covalently bound to the polymer matrix, which makes them highly susceptible to leaching. Phthalates are contained in plastics at high percentages. For example, they can contribute up to 40% by weight to intravenous medical bags and up to 80% by weight in medical tubing. Vinyl products are pervasive—including toys, car interiors, shower curtains, and flooring—and initially release chemical gases into the air. Some studies indicate that this outgassing of additives may contribute to health complications, and have resulted in a call for banning the use of DEHP on shower curtains, among other uses. The Japanese car companies Toyota, Nissan, and Honda have eliminated PVC in their car interiors starting in 2007.

In 2004 a joint Swedish-Danish research team found a statistical association between allergies in children and indoor air levels of DEHP and BBzP (butyl benzyl phthalate), which is used in vinyl flooring. In December 2006, the European Chemicals Bureau of the European Commission released a final draft risk assessment of BBzP which found "no concern" for consumer exposure including exposure to children.

EU decisions on phthalates

Risk assessments have led to the classification of low molecular weight and labeling as Category 1B Reproductive agents. Three of these phthalates, DBP, BBP and DEHP were included on annex XIV of the REACH regulation in February 2011 and will be phased out by the EU by February 2015 unless an application for authorisation is made before July 2013 and an authorisation granted. DIBP is still on the REACH Candidate List for Authorisation. Environmental Science & Technology, a peer reviewed journal published by the American Chemical Society states DEHP poses a serious risk to human health.

In 2008 the European Union's Scientific Committee on Emerging and Newly Identified Health Risks (SCENIHR) reviewed the safety of DEHP in medical devices. The SCENIHR report states that certain medical procedures used in high risk patients result in a significant exposure to DEHP and concludes there is still a reason for having some concerns about the exposure of prematurely born male babies to medical devices containing DEHP. The Committee said there are some alternative plasticizers available for which there is sufficient toxicological data to indicate a lower hazard compared to DEHP but added that the functionality of these plasticizers should be assessed before they can be used as an alternative for DEHP in PVC medical devices. Risk assessment results have shown positive results regarding the safe use of High Molecular Weight Phthalates. They have all been registered for REACH and do not require any classification for health and environmental effects, nor are they on the Candidate List for Authorisation. High phthalates are not CMR (carcinogenic, mutagenic or toxic for reproduction), neither are they considered endocrine disruptors.

In the EU Risk Assessment the European Commission has confirmed that Di-isononyl phthalate (DINP) and Di-isodecyl phthalate (DIDP) pose no risk to either human health or the environment from any current use. The European Commission's findings (published in the EU Official Journal on April 13, 2006) confirm the outcome of a risk assessment involving more than 10 years of extensive scientific evaluation by EU regulators. Following the recent adoption of EU legislation with the regard to the marketing and use of DINP in toys and childcare articles, the risk assessment conclusions clearly state that there is no need for any further measures to regulate the use of DINP. In Europe and in some other parts of the world, the use of DINP in toys and childcare items has been restricted as a precautionary measure. In Europe, for example, DINP can no longer be used in toys and childcare items that can be put in the mouth even though the EU scientific risk assessment concluded that its use in toys does not pose a risk to human health or the environment. The rigorous EU risk assessments, which include a high degree of conservatism and built-in safety factors, have been carried out under the strict supervision of the European Commission and provide a clear scientific evaluation on which to judge whether or not a particular substance can be safely used.

The FDA Paper titled "Safety Assessment of Di(2-ethylhexyl)phthalate (DEHP)Released from PVC Medical Devices" states that [3.2.1.3] Critically ill or injured patients may be at increased risk of developing adverse health effects from DEHP, not only by virtue of increased exposure relative to the general population, but also because of the physiological and pharmacodynamic changes that occur in these patients compared to healthy individuals.

Lead

The metal lead is frequently added to PVC to improve workability and stability. Lead has been shown to leach into drinking water from PVC pipes.
In Europe (EU 27) the use of Lead stabilizers is being gradually phased out by 2015 under the VinylPlus voluntary commitment with over 80% replaced by 2013.

Vinyl chloride monomer

In the early 1970s, the carcinogenicity of vinyl chloride (usually called vinyl chloride mononomer or VCM) was linked to cancers in workers in the polyvinyl chloride industry. Specifically workers in polymerization section of a B.F. Goodrich plant near Louisville, Kentucky (US) were diagnosed with liver angiosarcoma also known as hemangiosarcoma, a rare disease. Since that time, studies of PVC workers in Australia, Italy, Germany, and the UK have all associated certain types of occupational cancers with exposure to vinyl chloride, and it has become accepted that VCM is a carcinogen. Technology for removal of VCM from products have become stringent commensurate with the associated regulations.

Dioxins

PVC produces HCl upon combustion almost quantitatively related to its chlorine content. Extensive studies in Europe indicate that the chlorine found in emitted dioxins is not derived from HCl in the flue gases. Instead, most dioxins arise in the condensed solid phase by the reaction of inorganic chlorides with graphitic structures in char-containing ash particles. Copper acts as a catalyst for these reactions.

Studies of household waste burning indicate consistent increases in dioxin generation with increasing PVC concentrations. According to the EPA dioxin inventory, landfill fires are likely to represent an even larger source of dioxin to the environment. A survey of international studies consistently identifies high dioxin concentrations in areas affected by open waste burning and a study that looked at the homologue pattern found the sample with the highest dioxin concentration was "typical for the pyrolysis of PVC". Other EU studies indicate that PVC likely "accounts for the overwhelming majority of chlorine that is available for dioxin formation during landfill fires."

The next largest sources of dioxin in the EPA inventory are medical and municipal waste incinerators. Various studies have been conducted that reach contradictory results. For instance a study of commercial-scale incinerators showed no relationship between the PVC content of the waste and dioxin emissions. Other studies have shown a clear correlation between dioxin formation and chloride content and indicate that PVC is a significant contributor to the formation of both dioxin and PCB in incinerators.

The next largest sources of dioxin in the EPA inventory are medical and municipal waste incinerators.[49] Various studies have been conducted that reach contradictory results. For instance a study of commercial-scale incinerators showed no relationship between the PVC content of the waste and dioxin emissions. Other studies have shown a clear correlation between dioxin formation and chloride content and indicate that PVC is a significant contributor to the formation of both dioxin and PCB in incinerators.

In Europe the overwhelming importance of combustion conditions on dioxin formation has been established by numerous researchers. The single most important factor in forming dioxin-like compounds is the temperature of the combustion gases. Oxygen concentration also plays a major role on dioxin formation, but not the chlorine content.

The design of modern incinerators minimises PCDD/F formation by optimising the stability of the thermal process. To comply with the EU emission limit of 0.1 ng I-TEQ/m3 modern incinerators operate in conditions minimising dioxin formation and are equipped with pollution control devices which catch the low amounts produced. Recent information is showing for example that dioxin levels in populations near incinerators in Lisbon and Madeira have not risen since the plants began operating in 1999 and 2002 respectively.

Several studies have also shown that removing PVC from waste would not significantly reduce the quantity of dioxins emitted. The European Union Commission published in July 2000 a Green Paper on the Environmental Issues of PVC. " The Commission states (page 27) that it has been suggested that the reduction of the chlorine content in the waste can contribute to the reduction of dioxin formation, even though the actual mechanism is not fully understood. The influence on the reduction is also expected to be a second or third order relationship. It is most likely that the main incineration parameters, such as the temperature and the oxygen concentration, have a major influence on the dioxin formation". The Green Paper states further that at the current levels of chlorine in municipal waste, there does not seem to be a direct quantitative relationship between chlorine content and dioxin formation.

A study commissioned by the European Commission on "Life Cycle Assessment of PVC and of principal competing materials" states that "Recent studies show that the presence of PVC has no significant effect on the amount of dioxins released through incineration of plastic waste."

End-of-life

The European waste hierarchy refers to the five steps included in the article 4 of the Waste Framework Directive

  • Prevention : preventing and reducing waste generation.
  • Reuse and preparation for reuse : giving the products a second life before they become waste.
  • Recycle : any recovery operation by which waste materials are reprocessed into products, materials or substances whether for the original or other purposes. It includes composting and it does not include incineration
  • Recovery : some waste incineration based on a political non-scientific formula[citation needed] that upgrades the less inefficient incinerators
  • Disposal : processes to dispose of waste be it landfilling, incineration, pyrolysis, gasification and other finalist solutions. Landfill is restricted in some EU-countries through Landfill Directives and there is a debate about Incineration E.g. original plastic which contains a lot of energy is just recovered in energy and not recycled. According to the Waste Framework Directive the European Waste Hierarchy is legally binding except in cases that may require specific waste streams to depart from the hierarchy. This should be justified on the basis of life-cycle thinking.
  • The European Commission has set new rules to promote the recovery of PVC waste for use in a number of construction products. It says: "The use of recovered PVC should be encouraged in the manufacture of certain construction products because it allows the reuse of old PVC This avoids PVC being discarded in landfills or incinerated causing release of carbon dioxide and cadmium in the environment".

    Industry initiatives

    In Europe, developments in PVC waste management have been monitored by Vinyl 2010,[61] established in 2000. Vinyl 2010's objective was to recycle 200,000 tonnes of post-consumer PVC waste per year in Europe by the end of 2010, excluding waste streams already subject to other or more specific legislation (such as the European Directives on End-of-Life Vehicles, Packaging and Waste Electric and Electronic Equipment).

    Since June 2011, it is followed by VinylPlus, a new set of targets for sustainable development.[62] Its main target is to recycle 800,000 tonnes/year of PVC by 2020 including 100,000 tonnes of difficult to recycle waste. One facilitator for collection and recycling of PVC waste is Recovinyl.[63] The recycled PVC tonnage in 2013 was almost 445,000 tonnes.[45]

    One approach to address the problem of waste PVC is also through the process called Vinyloop. It is a mechanical recycling process using a solvent to separate PVC from other materials. This solvent turns in a closed loop process in which the solvent is recycled. Recycled PVC is used in place of virgin PVC in various applications: coatings for swimming pools, shoe soles, hoses, diaphragms tunnel, coated fabrics, PVC sheets.[64] This recycled PVC's primary energy demand is 46 percent lower than conventional produced PVC. So the use of recycled material leads to a significant better ecological footprint. The global warming potential is 39 percent lower.[65]

    Restrictions

    In November, 2005 one of the largest hospital networks in the U.S., Catholic Healthcare West, signed a contract with B. Braun Melsungen for vinyl-free intravenous bags and tubing.
    In January, 2012 a major U.S. West Coast healthcare provider, Kaiser Permanente, announced that it will no longer buy intravenous (IV) medical equipment made with polyvinyl chloride (PVC) and DEHP (di-2-ethyl hexyl phthalate) type plasticizers.

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