Phthalate plasticizers
Many vinyl products contain additional chemicals to change the chemical consistency of the product. Some of these additional chemicals called additives can leach out of vinyl products. Plasticizers that must be added to make PVC flexible have been additives of particular concern.
Because soft PVC toys have been made for babies for years, there are concerns that these additives leach out of soft toys into the mouths of the children chewing on them. Phthalates mimic human hormones and also affect various life forms including fish and invertebrates adversely. Additionally, adult sex toys have been demonstrated to contain high concentrations of the additives. In January 2006, the European Union placed a ban on six types of phthalate softeners, including DEHP (diethylhexyl phthalate), used in toys. In the U.S. most companies have voluntarily stopped manufacturing PVC toys with DEHP[citation needed] and in 2003 the U.S. Consumer Product Safety Commission (CPSC) denied a petition for a ban on PVC toys made with an alternative plasticizer, DINP (diisononyl phthalate).[23] In April 2006, the European Chemicals Bureau of the European Commission published an assessment of DINP which found risk "unlikely" for children and newborns.[24]
Vinyl intravenous (IV) bags used in neo-natal intensive care units have also been shown to leach DEHP. In a draft guidance paper published in September 2002, the US FDA recognizes that many medical devices with PVC containing DEHP are not used in ways that result in significant human exposure to the chemical.[25] The FDA, however, suggests that manufacturers consider eliminating DEHP in certain devices that can result in high aggregate exposures for sensitive patient populations such as neonates.
Due to environmental concernsuse of PVC is discouraged by some local authorities in countries such as UK, Germany and the Netherlands.
Other vinyl products including car interiors, shower curtains, and flooring 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.[28] 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.[29] 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.
In November, 2005 one of the largest hospital networks in the U.S., Catholic Healthcare West, signed a contract with B.Braun for vinyl-free intravenous bags and tubing. According to the Center for Health, Environment & Justice in Falls Church, VA,which helps to coordinate a "precautionary" PVC Campaign,[33] several major corporations including Microsoft, Wal-Mart, and Kaiser Permanente announced efforts to eliminate PVC from products and packaging in 2005.[34] Target is reducing its sale of items with PVC.
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.
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.[37] 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.
Vinyl chloride monomer
In the early 1970s, Dr. John Creech and Dr. Maurice Johnson were the first to clearly link and recognize the carcinogenicity of vinyl chloride monomer to humans when workers in the polyvinyl chloride polymerization section of a B.F. Goodrich plant near Louisville, Kentucky, were diagnosed with liver angiosarcoma also known as hemangiosarcoma, a rare disease.[38] 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. The link between angiosarcoma of the liver and long-term exposure to vinyl chloride is the only one that has been confirmed by the International Agency for Research on Cancer. All the cases of angiosarcoma developed from exposure to vinyl chloride monomer were in workers who were exposed to very high VCM levels, routinely, for many years. These workers cleaned accretions in reactors, a practice that has now been replaced by automated high-pressure water jets.
A 1997 U.S. Centers for Disease Control and Prevention (CDC) report concluded that the development and acceptance by the PVC industry of a closed loop polymerization process in the late 1970s "almost completely eliminated worker exposures" and that "new cases of hepatic angiosarcoma in vinyl chloride polymerization workers have been virtually eliminated."[39]
According to the EPA, "vinyl chloride emissions from polyvinyl chloride (PVC), ethylene dichloride (EDC), and vinyl chloride monomer (VCM) plants cause or contribute to air pollution that may reasonably be anticipated to result in an increase in mortality or an increase in serious irreversible, or incapacitating reversible illness. Vinyl chloride is a known human carcinogen that causes a rare cancer of the liver."EPA's 2001 updated Toxicological Profile and Summary Health Assessment for VCM in its Integrated Risk Information System (IRIS) database lowers EPA's previous risk factor estimate by a factor of 20 and concludes that "because of the consistent evidence for liver cancer in all the studies...and the weaker association for other sites, it is concluded that the liver is the most sensitive site, and protection against liver cancer will protect against possible cancer induction in other tissues."
A 1998 front-page series in the Houston Chronicle claimed the vinyl industry has manipulated vinyl chloride studies to avoid liability for worker exposure and to hide extensive and severe chemical spills into local communities. Retesting of community residents in 2001 by the U.S. Agency for Toxic Substances and Disease Registry (ATSDR) found dioxin levels similar to those in a comparison community in Louisiana and to the U.S. population. Cancer rates in the community were similar to Louisiana and US averages.
Dioxins
Main article: Polychlorinated dibenzodioxins
The environmentalist group Greenpeace has advocated the global phase-out of PVC because they claim dioxin is produced as a byproduct of vinyl chloride manufacture and from incineration of waste PVC in domestic garbage.
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.
According to a 1994 report by the British firm, ICI Chemicals & Polymers Ltd., "It has been known since the publication of a paper in 1989 that these oxychlorination reactions [used to make vinyl chloride and some chlorinated solvents] generate polychlorinated dibenzodioxins (PCDDs) and dibenzofurans (PCDFs). The reactions include all of the ingredients and conditions necessary to form PCDD/PCDFs.... It is difficult to see how any of these conditions could be modified so as to prevent PCDD/PCDF formation without seriously impairing the reaction for which the process is designed." In other words, dioxins are an undesirable byproduct of producing vinyl chloride and eliminating the production of dioxins while maintaining the oxychlorination reaction may be difficult. Dioxins created by vinyl chloride production are released by on-site incinerators, flares, boilers, wastewater treatment systems and even in trace quantities in vinyl resins. The US EPA estimate of dioxin releases from the PVC industry was 13 grams TEQ in 1995, or less than 0.5% of the total dioxin emissions in the US; by 2002, PVC industry dioxin emissions had been further reduced by 23%.
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.[50] 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 February 2007, the Technical and Scientific Advisory Committee of the US Green Building Council (USGBC) released its report on a PVC avoidance related materials credit for the LEED Green Building Rating system. The report concludes that "no single material shows up as the best across all the human health and environmental impact categories, nor as the worst" but that the "risk of dioxin emissions puts PVC consistently among the worst materials for human health impacts."
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.Wikstrom, Evalena; G. Lofvenius,C.Rappe,S. Marklund (1996). "Influence of Level and Form of Chlorine on the Formation of Chlorinated Dioxins, Dibenzofurans, and Benzenes during Combustion of an Artificial Fuel in a Laboratory Reactor". Environmental Science & Technology 30 (5): 1637–1644. </ref>
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. "[57] 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.
Bans
The State of California is currently considering a bill that would ban the use of PVC in consumer packaging[citation needed] due to the threats it poses to human and environmental health and its effect on the recycling stream.[not in citation given] Specifically, the language of the bill analysis stipulates that EPA has listed vinyl chloride, a "constituent element" of PVC, as a carcinogen.[60] It also further cites that there are concerns about the leaching of phthalates and lead from the PVC bag packaging.
Recycling
PVC SPI code, for recycling (Society of the Plastics Industry). The Unicode character for this symbol is U+2675 (HTML character reference ♵).
In Europe, developments in PVC waste management are monitored by Vinyl 2010, a legal entity established in 2000. In the waste management area their commitment is to
1. Support integrated waste management approaches, using raw materials as efficiently as possible
2. Work with the stakeholders to research, develop, and implement recycling of 200,000 tonnes per year of PVC postconsumer waste in 2010 in addition to waste already recycled in 2000, or regulated by the PPW, ELV and E&E Waste Directives
3. Recycle at least 25% of collectable, available PVC postconsumer waste from pipes, window profiles, and roofing membranes by 2003 and increase this to 50% by 2005.
Vinyl 2010 has a Monitoring Committee and publishes annual reviews. In 2011, it reported that 260,842 tonnes of post-consumer PVC waste was recycled in 2010, i.e. an increase of 220,000 tonnes over the 1999 volumes, exceeding the 10-year target of 200,000 tonnes.
Collection and recycling schemes for PVC waste stream are managed through Recovinyl which reported the recycled tonnage as follows: pipe 25 kT, profile 107 kT, rigid film 6 kT, flexible cables 79 kt and mixed flexible 38 kT.
One of the recycling processes is the Vinyloop Texyloop used for solvent-based mechanical recycling. It involves recovering PVC plastic from composite materials through dissolution and precipitation, and is a closed-loop system, recycling the solvent and regenerating PVC.
Many vinyl products contain additional chemicals to change the chemical consistency of the product. Some of these additional chemicals called additives can leach out of vinyl products. Plasticizers that must be added to make PVC flexible have been additives of particular concern.
Because soft PVC toys have been made for babies for years, there are concerns that these additives leach out of soft toys into the mouths of the children chewing on them. Phthalates mimic human hormones and also affect various life forms including fish and invertebrates adversely. Additionally, adult sex toys have been demonstrated to contain high concentrations of the additives. In January 2006, the European Union placed a ban on six types of phthalate softeners, including DEHP (diethylhexyl phthalate), used in toys. In the U.S. most companies have voluntarily stopped manufacturing PVC toys with DEHP[citation needed] and in 2003 the U.S. Consumer Product Safety Commission (CPSC) denied a petition for a ban on PVC toys made with an alternative plasticizer, DINP (diisononyl phthalate).[23] In April 2006, the European Chemicals Bureau of the European Commission published an assessment of DINP which found risk "unlikely" for children and newborns.[24]
Vinyl intravenous (IV) bags used in neo-natal intensive care units have also been shown to leach DEHP. In a draft guidance paper published in September 2002, the US FDA recognizes that many medical devices with PVC containing DEHP are not used in ways that result in significant human exposure to the chemical.[25] The FDA, however, suggests that manufacturers consider eliminating DEHP in certain devices that can result in high aggregate exposures for sensitive patient populations such as neonates.
Due to environmental concernsuse of PVC is discouraged by some local authorities in countries such as UK, Germany and the Netherlands.
Other vinyl products including car interiors, shower curtains, and flooring 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.[28] 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.[29] 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.
In November, 2005 one of the largest hospital networks in the U.S., Catholic Healthcare West, signed a contract with B.Braun for vinyl-free intravenous bags and tubing. According to the Center for Health, Environment & Justice in Falls Church, VA,which helps to coordinate a "precautionary" PVC Campaign,[33] several major corporations including Microsoft, Wal-Mart, and Kaiser Permanente announced efforts to eliminate PVC from products and packaging in 2005.[34] Target is reducing its sale of items with PVC.
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.
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.[37] 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.
Vinyl chloride monomer
In the early 1970s, Dr. John Creech and Dr. Maurice Johnson were the first to clearly link and recognize the carcinogenicity of vinyl chloride monomer to humans when workers in the polyvinyl chloride polymerization section of a B.F. Goodrich plant near Louisville, Kentucky, were diagnosed with liver angiosarcoma also known as hemangiosarcoma, a rare disease.[38] 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. The link between angiosarcoma of the liver and long-term exposure to vinyl chloride is the only one that has been confirmed by the International Agency for Research on Cancer. All the cases of angiosarcoma developed from exposure to vinyl chloride monomer were in workers who were exposed to very high VCM levels, routinely, for many years. These workers cleaned accretions in reactors, a practice that has now been replaced by automated high-pressure water jets.
A 1997 U.S. Centers for Disease Control and Prevention (CDC) report concluded that the development and acceptance by the PVC industry of a closed loop polymerization process in the late 1970s "almost completely eliminated worker exposures" and that "new cases of hepatic angiosarcoma in vinyl chloride polymerization workers have been virtually eliminated."[39]
According to the EPA, "vinyl chloride emissions from polyvinyl chloride (PVC), ethylene dichloride (EDC), and vinyl chloride monomer (VCM) plants cause or contribute to air pollution that may reasonably be anticipated to result in an increase in mortality or an increase in serious irreversible, or incapacitating reversible illness. Vinyl chloride is a known human carcinogen that causes a rare cancer of the liver."EPA's 2001 updated Toxicological Profile and Summary Health Assessment for VCM in its Integrated Risk Information System (IRIS) database lowers EPA's previous risk factor estimate by a factor of 20 and concludes that "because of the consistent evidence for liver cancer in all the studies...and the weaker association for other sites, it is concluded that the liver is the most sensitive site, and protection against liver cancer will protect against possible cancer induction in other tissues."
A 1998 front-page series in the Houston Chronicle claimed the vinyl industry has manipulated vinyl chloride studies to avoid liability for worker exposure and to hide extensive and severe chemical spills into local communities. Retesting of community residents in 2001 by the U.S. Agency for Toxic Substances and Disease Registry (ATSDR) found dioxin levels similar to those in a comparison community in Louisiana and to the U.S. population. Cancer rates in the community were similar to Louisiana and US averages.
Dioxins
Main article: Polychlorinated dibenzodioxins
The environmentalist group Greenpeace has advocated the global phase-out of PVC because they claim dioxin is produced as a byproduct of vinyl chloride manufacture and from incineration of waste PVC in domestic garbage.
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.
According to a 1994 report by the British firm, ICI Chemicals & Polymers Ltd., "It has been known since the publication of a paper in 1989 that these oxychlorination reactions [used to make vinyl chloride and some chlorinated solvents] generate polychlorinated dibenzodioxins (PCDDs) and dibenzofurans (PCDFs). The reactions include all of the ingredients and conditions necessary to form PCDD/PCDFs.... It is difficult to see how any of these conditions could be modified so as to prevent PCDD/PCDF formation without seriously impairing the reaction for which the process is designed." In other words, dioxins are an undesirable byproduct of producing vinyl chloride and eliminating the production of dioxins while maintaining the oxychlorination reaction may be difficult. Dioxins created by vinyl chloride production are released by on-site incinerators, flares, boilers, wastewater treatment systems and even in trace quantities in vinyl resins. The US EPA estimate of dioxin releases from the PVC industry was 13 grams TEQ in 1995, or less than 0.5% of the total dioxin emissions in the US; by 2002, PVC industry dioxin emissions had been further reduced by 23%.
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.[50] 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 February 2007, the Technical and Scientific Advisory Committee of the US Green Building Council (USGBC) released its report on a PVC avoidance related materials credit for the LEED Green Building Rating system. The report concludes that "no single material shows up as the best across all the human health and environmental impact categories, nor as the worst" but that the "risk of dioxin emissions puts PVC consistently among the worst materials for human health impacts."
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.Wikstrom, Evalena; G. Lofvenius,C.Rappe,S. Marklund (1996). "Influence of Level and Form of Chlorine on the Formation of Chlorinated Dioxins, Dibenzofurans, and Benzenes during Combustion of an Artificial Fuel in a Laboratory Reactor". Environmental Science & Technology 30 (5): 1637–1644. </ref>
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. "[57] 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.
Bans
The State of California is currently considering a bill that would ban the use of PVC in consumer packaging[citation needed] due to the threats it poses to human and environmental health and its effect on the recycling stream.[not in citation given] Specifically, the language of the bill analysis stipulates that EPA has listed vinyl chloride, a "constituent element" of PVC, as a carcinogen.[60] It also further cites that there are concerns about the leaching of phthalates and lead from the PVC bag packaging.
Recycling
PVC SPI code, for recycling (Society of the Plastics Industry). The Unicode character for this symbol is U+2675 (HTML character reference ♵).
In Europe, developments in PVC waste management are monitored by Vinyl 2010, a legal entity established in 2000. In the waste management area their commitment is to
1. Support integrated waste management approaches, using raw materials as efficiently as possible
2. Work with the stakeholders to research, develop, and implement recycling of 200,000 tonnes per year of PVC postconsumer waste in 2010 in addition to waste already recycled in 2000, or regulated by the PPW, ELV and E&E Waste Directives
3. Recycle at least 25% of collectable, available PVC postconsumer waste from pipes, window profiles, and roofing membranes by 2003 and increase this to 50% by 2005.
Vinyl 2010 has a Monitoring Committee and publishes annual reviews. In 2011, it reported that 260,842 tonnes of post-consumer PVC waste was recycled in 2010, i.e. an increase of 220,000 tonnes over the 1999 volumes, exceeding the 10-year target of 200,000 tonnes.
Collection and recycling schemes for PVC waste stream are managed through Recovinyl which reported the recycled tonnage as follows: pipe 25 kT, profile 107 kT, rigid film 6 kT, flexible cables 79 kt and mixed flexible 38 kT.
One of the recycling processes is the Vinyloop Texyloop used for solvent-based mechanical recycling. It involves recovering PVC plastic from composite materials through dissolution and precipitation, and is a closed-loop system, recycling the solvent and regenerating PVC.
