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Home , Adipate, Benzyl butyl phthalate, Dibutyl phthalate, Dibutyl sebacate, Diisodecyl phthalate, Diisononyl phthalate

technical briefing

Phthalates and Their Alternatives: Health and Environmental Concerns

january 2011

The Lowell Center for Sustainable Production at the University of Massachusetts Lowell helps to build healthy work environments, thriving communities, and viable businesses that support a more sustainable world. The Lowell Center for Sustainable Production at the University of Massachusetts Lowell developed this technical briefing to provide an overview of alternatives to used as in awide range of (PVC) products, with particular emphasis on children’s products. The document describes uses of and products containing phthalates (Table 1) and outlines some of the health and environmental concerns raised regarding these substances.

Drop-in substitutes are an attractive for manufacturers as they do not require a major production process change, but they may also pose health and environmental concerns, which are summarized in

Table 2. Another solution for manufacturers is to choose a type of plastic that does not require a .

This document identifies petroleum-based and biobased that do not require the use of phthalates and describes the known human health and environmental concerns of these alternative plastics (Tables

3 and 4).

We gratefully acknowledge the support of the New York Community Trust for our continued work on sustainable products.

© 2011 Lowell Center for Sustainable Production Contents

Why There is Concern about Phthalates 4

Sources of Exposure to Phthalates 6

Human Health and Environmental Concerns 7

Chemical Alternatives to Phthalates 8

Alternative Plastics that Do Not Require Phthalates Petroleum-Based 13 Biobased 16

References 21

Phthalates and their Alternatives: Health and Environmental Concerns • 3 Why There Is Concern about Phthalates

hthalates are a class of synthetic chemicals that are widely used in a variety of consumer products including medical devices, food wrap, building materials, packaging, automotive parts, children’s toys, and childcare articles made of polyvinyl chloride (PVC). The annual global production of phthalates is estimated to be 11 billion pounds. The addition of phthalates to PVC makes this brittle plastic Pmore flexible and durable. PVC products may contain up to 50 percent by weight of plasticizers, most com- monly phthalates. Phthalates are also used as in many applications and in cosmetics to hold fragrance, reduce cracking of , reduce stiffness of hair spray, and make products more effectively penetrate and moisturize the skin. Six of the commonly used phthalates in consumer products are di-(2-ethylhexyl) (DEHP), (DINP), (DBP), (DIDP), di-n-octyl phthal- ate (DnOP), and (BBP or BzBP).

Phthalates have been identified as reproductive and developmental toxicants, though their toxicity varies somewhat depending on the specific phthalate structure. In addition, the US EPA classifies DEHP and BBP as probable and possible human respectively. Further, phthalates are not chemically bound to the PVC . Thus, over time they leach out of products and diffuse into the air, water, food, house dust, soil, living organisms, and other media, particularly under conditions involving heat. Because of health concerns, as of February 2009 the Consumer Product Safety Improvement Act restricted DEHP, DBP, and BBP in children’s toys and childcare articles in concentrations exceeding 0.1 percent. DINP, DIDP and DnOP are prohibited pending additional study and review.a

Although six phthalates are now restricted from children’s products in the US and (EU), they are unregulated and continue to be used in toy making in many other parts of the world, such as China and India. In addition, children continue to be exposed to phthalates in cosmetics and personal care products such as nail polish, lotion, , soap, and hair spray. School supplies made of PVC such as notebooks and binders, art supplies, backpacks, lunchboxes, paperclips, and umbrellas may contain phthalates. Raincoats, boots, handbags, and soft plastic shoes such as flip-flops may also contain phthalates.

Other consumer products may also be direct or indirect sources of phthalate exposure. These include medical devices such as plastic tubing and intravenous storage bags, floor tiles, automotive parts, food wrap, , home furnishings, pharmaceutical coatings, and electrical cords. Table 1 identifies six common phthalates, their primary function, and the products in which they are used.

a According to the Consumer Product Safety Commission (CPSC), a children’s toy is a product intended for use by a child 12 years or younger for playing and a childcare article is a product that a child 3 years of age or younger uses for sleeping, feeding, sucking or teething.

4 • Lowell Center for Sustainable Production • University of Massachusetts Lowell Table 1 Six Common Phthalates, Their Primary Functions and Products in Which They Are Used Phthalate Function(s) Product(s) DEHP Primarily used as a plasticizer Dolls, shoes, raincoats, clothing, medical devices (plastic tubing for PVC [1]. and intravenous storage bags), furniture, automobile upholstery, and floor tiles [1,7]. DINP Primarily used as a plasticizer Teethers, rattles, balls, spoons, toys, gloves, drinking straws, rubber, for PVC [1]. , ink, , paints and lacquers, food and food related uses, clothes, shoes, car and public transport interior [1,3,13]. DBP Used as a plasticizer for PVC, Latex adhesives, , car care products, cosmetics, some inks poly vinyl (PVA) and and dyes, insecticides, food wrapping materials, home furnishing, rubber. Also used as , clothing and pharmaceutical coating. (may sometimes be and fixative in paint and present in toys as impurity or by-product in trace amounts) [1,9]. cosmetics [1,9]. DIDP Primarily used as a plasticizer Electrical cords, leather for car interiors and PVC flooring [1]. for PVC [1]. DnOP Primarily used as a plasticizer Floorings, tarps, pool liners, bottle cap liners, conveyor belts and for PVC [1]. garden [1]. BBP Used as a plasticizer for PVC, Vinyl flooring, sealants, adhesives, car care products, automotive , polysulfide and trim, food conveyor belts, food wrapping material, and artificial acrylic-based [12]. leather. (low concentrations have been detected in baby equip- ment and children’s toys as by-products and impurities; not intentionally added to those products) [1,12].

Phthalates and their Alternatives: Health and Environmental Concerns • 5 Sources of Exposure to Phthalates

ince phthalates are not chemically bound to the PVC polymer, they can be released from products or dissolve upon contact with liquids or fats. Phthalates have low volatility and are slowly released from PVC products during use, diffusing into the air. They are also released into the environment during their production, processing and waste disposal. Once in the environment, phthalates bind to particles––primarilyS dust particles in the home––and can be carried in the air over long distances [2]. Human exposure to phthalates occurs through inhalation and ingestion of contaminated air and food as well as from skin contact. Food may become contaminated when it comes in contact with packaging that contains phthalates. For the general population, this may be a major source of expo- sure. Children may be exposed to higher concentrations of phthal- ates from food consumption because they tend to consume more food than adults relative to their body weight [1, 4]. Studies of skin exposure to phthalates are limited, but this route is thought to be insignificant [2].

An additional exposure route for young children is through mouthing toys, childcare articles, and other products containing phthalates. Through mouthing of these products, phthalates can dissolve in saliva and become absorbed into the body [2]. Accord- ing to the CPSC, the duration of mouthing activity for toys and childcare articles varies by age [3]. A study by the US Center for Disease Control and Prevention (CDC) found that younger chil- dren’s higher concentration of phthalates may be partly due to mouthing of toys and childcare articles as well as coming into closer contact with PVC flooring products [4]. The extent of oral absorption through mouthing of phthalate-containing products at amounts to which children are expected to be exposed is not well studied. In addition to the length of time of mouthing activity, oral ab- sorption depends on the migration rate of the phthalate in the product that is being mouthed. Studies suggest 100 % oral absorption of phthalates such as DEHP and DINP at daily exposure levels [3, 8, 13].

Fetal exposure to phthalates has been shown to be correlated with maternal exposure. Neonates and develop- ing fetuses at critical points in their development may be exposed through maternal use of PVC products. For example, major medical uses of PVC are in blood and plasma bags, as well as intravenous bags and tubing which may contain as much as 80 percent DEHP, the most frequently used plasticizer in medical devices. Other uses include intestinal feeding and dialysis equipment, catheters, and gloves. Phthalates may leach when the medical device is heated or when the PVC comes into contact with blood, drugs, or intravenous fluids. Newborns and children in pediatric settings may receive the highest doses from blood transfusions, extra- corporeal oxygenation, and respiratory therapy [4, 11, 40].

6 • Lowell Center for Sustainable Production • University of Massachusetts Lowell Human Health and Environmental Concerns

ost of the early studies on the health effects of phthalates experimented with doses adminis- tered to laboratory animals above human exposure levels. In recent years however, researchers have noted health effects such as reproductive abnormalities and developmental effects in animals given doses of phthalates similar to those to which humans are exposed. Epidemiologic Mstudies have also evaluated the human health impacts of phthalate exposure. These studies have identified a possible association between exposure to phthalates and male reproductive malformation, sperm damage, fer- tility impairment, female reproductive tract diseases, early in girls, , and thyroid effects. Adverse effects on the lungs, and kidneys have been observed in animals and in some limited human studies.

Phthalates may also pose risks for aquatic and terrestrial ecosystems particularly in the vicinity of phthalate processing industries. Some phthalates are bioaccumulative and have been detected in aquatic organisms. For example, BBP has been shown to be toxic to aquatic organisms and may cause long-term adverse effects in aquatic environments. Studies suggest BBP may have endocrine disrupting effects in fish. Birds and mammals may suffer impacts from food chain exposures. However, other phthalates such as DEHP have the potential to biodegrade under aerobic conditions. [See 2, 4, 8, 11, 13, 24, 28, 29, 30, 31, 42, 50.]

Phthalates and their Alternatives: Health and Environmental Concerns • 7 Chemical Alternatives to Phthalates

number of substances have been identified as alternative plasticizers. These alternatives include citrates, sebacates, , and phosphates. They are being substituted in products that traditionally use phthalates, such as toys, childcare articles and medical devices. In addition to their application as alternative PVC plasticizers, these substances are also being used as solvents and fixatives in Acosmetic products, inks, adhesives, and other consumer products.

Most of these alternative plasticizers are not well studied with regard to their potential effects on human health and the environment. Although many of these alternatives show promising application potential, significant exposure may lead to adverse health effects. Like phthalates, these alternative plasticizers are not chemically bound to the polymer and can leach out of products. Some documented effects from exposure to the alterna- tive plasticizers that are currently being used in children’s products and other consumer products include eye, skin, and respiratory irritations. There is also evidence of effects on the kidney, liver, spleen, testes, and uterus. Most evidence on human health effects is derived from laboratory studies as few epidemiologic studies have been conducted on these materials. In addition, some alternative plasticizers may be toxic to aquatic organisms and may not biodegrade in the environment. Table 2 identifies some alternative plasticizers currently used in children’s and other consumer products, and their potential health and environmental effects.

Table 2 Alternative Plasticizers Environmental Alternative Function/Product Human Health Concerns Concerns

ATBC: • Primarily used as a plasti- • Intravenous exposure affects • Can bioaccumulate Acetyl tributyl cizer in cosmetic products, the central nervous system and is inherently citrate toys, vinyl, adhesives, and blood in laboratory biodegradable medical devices, pharma- animals. May have moderate (in an inherent ceutical tablet coatings, irritation effects on eyes and food packaging, flavoring increase liver weights [21]. test, 80 percent substance in foods, print- • Studies show that it inhibits was degraded). ing inks and plastics in the proliferation of Lymph However, in a non- . node T cells [16]. standard test aero- • Also used as a surface • Exhibits fire and bic degradation was in the manufac- hazard in the presence of slow and no data ture of metallic articles strong oxidizers and nitrates is available on an- that contact food [14]. aerobic degrada- [14, 15, 17, 19, 21]. tion [21].

DINCH: • Primarily used as a plasti- • Acute toxicity effect is low. • No data found Di-isononyl- cizer in PVC medical devices However, an increase in regarding effects cyclohexane-1, (blood tubes or packaging testes weight, liver weight, of environmental 2-dicarboxylate for nutrient ), thyroid weight, serum gamma- exposures. toys, food packaging, glutamyl transferase and cosmetics products, shoes, thyroid-stimulating hormone exercise mats and cushions, was observed in laboratory textile coatings, printing animals after repeated expo- inks [17]. sure. Blood and transitional epithelium cells in urine was also observed [22, 40].

8 • Lowell Center for Sustainable Production • University of Massachusetts Lowell Environmental Alternative Function/Product Human Health Concerns Concerns

DOTP: • Primarily used as a plasti- • Slightly irritating to eyes • Potential for biocon- Dioctyl cizer for PVC toys, childcare but will not damage eyes. centration in aquatic terephthalate articles, consumer products, • Prolonged exposure may organisms is low. beverage closures and other cause dermatitis. Studies Likely to be biode- polymer materials including involving rodents showed gradable under aer- -butyrate, inflammatory damage to obic and anaerobic cellulose nitrate, and chlo- the kidneys [23]. conditions [32]. roprene rubbers [32,40].

ESBO: • Primarily used as a plasti- • A worker developed asthma • Toxic to the crusta- Epoxidized cizer in closure gaskets from exposure to vapors from cean Daphnia magna. soybean oil used to seal glass jars, and heated PVC film. Vapor may Estimated to be bio- as a stabilizer to minimize also produce asthmatic symp- accumulative. Two the degradation toms in as little as 5 minutes standard tests ad- of PVC resins baby food jars, [21]. ministered by OECD fillers, paint and lacquers, • Studies involving rats have concluded it is adhesives, printing inks, reported skin and eye irrita- biodegradable in and packaging [18,21]. tions, secondary agent in aerobic environ- bronchospastic reaction. ments [21]. • Suspected to cause some effects on the kidney, liver, testis and uterus by repeated oral administration [18].

Mesamoll II: • Used as a plasticizer in PVC, • Has not been compre- • No data found alkylsulphonic , natural hensively studied for toxic regarding effects phenyl rubber, styrene-butadiene effects. of environmental (ASE) rubber, blends of styrene- exposures. butadiene rubber and bu- tadiene rubber, isobutylene- isoprene rubber, acrylonitrile- butadiene rubber, and chloroprene rubber [24].

TETM: • Primarily used for heat- • May cause irritation, nausea • Very limited data Tri-2-ethylhexyl resistant PVC articles, and vomiting in humans from on environmental trimellitate PVC-products used in the exposure to mists and fumes. effects is available. hospital sector (blood • Toxic to laboratory animals • Potential for envi- platelet bags), packing, through inhalation. ronmental effects is cables, profiles, and floor/ • Shown to irritate the skin associated with the wall coverings [21] of guinea pigs, rabbits and accumulation of the mice and the eyes of rabbits. compound in biota, • Studies in dogs showed in aquatic sediments an increase in weight of liver and in soils treated and spleen. with sewage sludge. • In rats, exposure through diet • Available data indi- resulted in slightly increased cate that it does not liver weights and peroxisome biodegrade readily proliferation [21]. [21].

COMGHA: • Used in PVC-containing • No data found describing • No data found Acetylated films, tubes, bottles, food human exposure. regarding potential monoglycerides packaging materials and • Slightly lower migration rate environmental of fully hydroge- other polymers such as was found when compared effects. nated polyolefin, styrene, and to DEHP [40]. PET [40].

Phthalates and their Alternatives: Health and Environmental Concerns • 9 Environmental Alternative Function/Product Human Health Concerns Concerns

Eastman 168: • Used as a plasticizer in PVC • No data found. • No data found bis(2- toys, bottle caps and clo- regarding potential ethylhjexyl)-1, sures, coatings for cloth, environmental 4-benzenedicar- electric connectors, flexible effects. boxylate film, pavement, striping compounds, walk-off mats, sheet vinyl flooring, other vinyl products, and PVC/VA copolymer resins. [39].

DEHA: • Used as a plasticizer in toys, • Slightly toxic when adminis- • Toxic to algae, Di(2-ethyl hexyl) vinyl flooring, wire and tered intravenously in animal crustaceans and cable, stationery, wood studies. fish. veneer, coated fabrics, • May produce dose-dependent • Chronic data on gloves, tubing, artificial changes in the body. crustaceans show leather, shoes, sealants, • Reported to cause liver tumors, adverse effects on and carpet backing. reduced bodyweight and reproduction of • Also used in films employed increased liver weight (may Daphnia magna. in food packaging materials, be a result of hepatic peroxi- • Not a bioaccumu- fillers, paint and lacquers, some proliferation) in mice lative substance. adhesives, plastic in con- and rats [21, 40]. • Available data indi- crete, and rubber products. cate evidence of • Expected to be widely biodegradability used in the near future in [21]. products for the hospital sector, printing inks and other PVC products [21, 40].

DBA: • Primarily used as a plasti- • Combustible. Mildly irritating • Moderately toxic Di-butyl adipate cizer for resins. Also used to skin and causes coughing to fish, daphnids in floor wax [53]. when inhaled [54]. and algae. • No data found on long-term • Readily exposure effects. biodegradable. • No data found on bioaccumulation [53].

BHT: Butylated • Used in childcare articles • May cause impaired blood • No data found hydroxytoluene intended to be mouthed clotting, hemorrhage, cyto- regarding potential such as teething products toxicity, hepatocellular injury environmental and as an antioxidant in and carcinogenesis [19]. effects. EVA and plastics. Also used as a [19].

HPCL: Hyper- • Intended primary use is in • No data found. • No data found branched poly PVC applications including • According to one study, it regarding potential (Є-caprolactone) coating resins, polymer does not migrate when used environmental additive, agents, in PVC even under harsh con- effects. and processing aids [41]. ditions such as high tempera- ture [41].

10 • Lowell Center for Sustainable Production • University of Massachusetts Lowell Environmental Alternative Function/Product Human Health Concerns Concerns

DEHPA: • Primarily used as a flame • In humans, inhalation • Ecosystem toxicity Di(2-ethylhexyl) retardant in products caused weakness, irritability data indicate it is phosphate with specific fire resistant and headache. harmful to algae, demands. Also used as a • Causes irritation of the eyes, crustaceans and fish. plasticizer in PVC products and first and second degree In a test involving used in the hospital sector, skin burns. Reported to be the microorganism packaging, cables, floor corrosive to the skin and thiobacillus ferrooxi- and wall coverings [21]. eyes in rabbits [21]. dans, respiration was inhibited. • Has low bioaccumu- lation potential and is inherently biode- gradable [21].

TEHPA: • Used in fillers, paint and • May produce moderate • Data show it is toxic Tri(2-ethylhexyl) lacquers, adhesives, plastic erythema and slight irritation to algae. Not readily phosphate in concrete and similar to eyes. biodegradable DEHPA applications [21]. • Observed effects in rats in- according to the clude hematological changes available aerobic and reduced body weight biodegradation data. gain. • Slowly biodegrades • A slight evidence of carcino- under anaerobic genicity has been observed conditions when in female mice [21]. present in weak solutions [21].

OTSA: O-toluene • Information on use is lim- • Reported to be teratogenic • Does not readily sulfonamide ited. Anticipated to be in rats, but only exhibiting biodegrade [21]. used in the future mainly a weak mutagenic effect (this in PVC cables [21]. is however based on studies without detailed descriptions of the study design) [21]. • Sulfonamides may cause hyperbilirubinemia in infants. In addition, sulfonamides may cause hemolytic anemia in glucose-6-phosphate dehydro- genase-deficient neonates [37].

TXIB: • Primarily used as a plasticizer • May be associated with eye ir- • Has some potential 2,2,4-trimethyl in PVC toys, flooring, prod- ritation and nasal allergies [47]. for bioaccumulation 1,3-pentanediol ucts used in the hospital • Has been observed to be [21]. diisobutyrate sector. Also used in fillers, slightly irritating in guinea pigs. wallpaper, paint and lac- • Reversible liver weight quers, printing inks, plastic changes have also been ob- in concrete, , served in rats from chronic packaging, as well as vinyl exposure [21]. and urethanes [21, 47, 48].

DOS: Dioctyl • Primarily used as a plasti- • Exhibits moderate acute tox- • Has a high bioaccu- sebacate cizer for PVC products and icity when administered orally mulation potential . to rats. Oral administration to and has been shown • Compatible with nitrocel- rats also showed increased to degrade slowly lulose and polyvinylidene liver weight, peroxisome pro- [21, 38]. chloride. liferation and increased levels • Anticipated to be used in of peroxisome enzymes [21]. printing ink and adhesives [21, 38].

Phthalates and their Alternatives: Health and Environmental Concerns • 11 Environmental Alternative Function/Product Human Health Concerns Concerns

DBS: Di-butyl • Used as a plasticizer, • Combustible. • biodegradable. sebacate flavoring agent, and • Chronic skin contact may • Low and moderate cosmetic and cause skin sensitization [55]. potential for bio- additive [56]. • Mildly toxic when ingested accumulation and [56]. bioconcentration in aquatic organisms respectively [56].

Grindsted • Primarily used as a • According to the manufacturer • According to the soft-n-safe: plasticizer in food contact (Danisco), it shows no indica- manufacturer, there Made from fully materials (approved for tion of dermal absorption/ is no indication of hydrogenated use in the EU, US, South irritation or eye irritation. aquatic toxicity [27]. castor oil and America and most of Asia), • No hormone-disrupting or • biodegradable [26]. acetic acid medical devices, vinyl mutagenic effects may result flooring, wallpaper, shrink [27]. wrap film, textile dyes, ink applications, adhesives and sealants [26,27].

12 • Lowell Center for Sustainable Production • University of Massachusetts Lowell Alternative Plastics that Do Not Require Phthalates Petroleum-Based Plastics

hoosing a plastic that does not require the addition of phthalates is another substitution approach. Although all plastics require the use of additives in processing to improve material properties, many types of plastic require fewer and less harmful additives than those required by PVC. These plastics have a wide range of applications in toys, children’s products, and other consumer products. Sub- Cstituting alternative plastics for PVC may also alleviate some of the health and environmental concerns that have been identified in the PVC manufacturing and disposal stages of the life cycle.

Petroleum-based plastics are produced from non-renewable fossil fuel resources. The production of these plastics poses a variety of health and environmental concerns. Extraction of raw materials, manufacturing, and disposal of petroleum-derived plastics generate greenhouse gases and pollutants including hydrogen chloride, hydrogen sulfide, , heavy metals, chlorofluorocarbons, polycyclic aromatic compounds, volatile organic compounds, and nitrogen and sulfur dioxides. Table 3 describes nine common petroleum-based plastics that can serve as substitutes for PVC plastic in consumer products and their associated human health and environmental concerns.

Table 3 Petroleum-Based Plasticsb Environmental Plastic Application/Product Human Health Concerns Concerns

PU: • Extensively used for • Combustible. Produces • Methylene diphenyl Polyurethane applications where highly toxic hydrogen cyanide isocyanate and toluene PVC or rubber are in fires. diisocyanate degrade rap- used [6]. Used in foam • Can cause mechanical irritation idly in the environment. toys, fabrics (in furni- to the eyes and lungs in dust • No effects have been ob- ture garments and form. served in disposal upholstery), wheels, • Exposure to high levels of or after incineration [49]. insulators in kitchen methylene diphenyl isocyanate appliances, decoration and toluene diisocyanate (sub- moldings (door frames, stances used to produce PU) windows, columns, causes severe lung and eye medallions), and damage, severe irritation to in construction as mucous membranes, euphoria, sealants. ataxia, mental aberrations, asth- • Also used as adhe- matic attacks, chest tightness, sive for woods and coughing, breathlessness, in- in varnishes [49]. flammation of the bronchi, and noncardiogenic pulmonary edema [49]. • Toluene diisocyanate is classified as a possible human by IARC [52].

b Information in Table 3 is from: Alvarez-Chavez, C. (2009). Sustainability of Bio-Polymers: Comparative Analysis of Corn and Potato Based Bio-Polymers. Doctoral Dissertation. University of Massachusetts, Lowell.

Phthalates and their Alternatives: Health and Environmental Concerns • 13 Environmental Plastic Application/Product Human Health Concerns Concerns

EVA: • Used for toys, teethers, • Produces toxic chemicals in fires. • byproducts of ethylene vinyl acetate doll parts, footwear • Uses carbon monoxide production. Chloride items (shoes insoles in production. catalyst used in some and slippers), exercise • Risk of fire due to pellets or vinyl acetate production. mats, stationery, powder plastic. • Ideal disposal method household, educational • Chloride catalyst is used in some is in landfill. and handcraft items, vinyl acetate production. • Incomplete combustion flexible sheeting, film, • Risk of children choking from produces carbon monox- packaging and coating small parts due to product ide and low molecular applications [6, 49]. breakage [49]. weight [49]. • Ethylene vinyl acetate has been shown to con- tain phthalates, which could be intentionally added to the material or present as a result of contamination dur- ing processing [6].

PET: • Used for fibers, bottles, • Antimony trioxide is a catalyst • Recyclable but Polyethylene electrical components, in production. It remains in the not biodegradable or terephthalate graphics, film base, and material and can leach [49]. compostable [49]. recording tapes [49]. • Workers exposed to antimony trioxide developed gastritis, abdominal pain, diarrhea, neuritis, vomiting, dizziness and headaches. • Exposure to antimony trioxide dust and fumes can irritate the respiratory tract and mucous membranes, and cause antimony pneumoconiosis [51].

HDPE: • Used for toys and • Flammable compounds • Recyclable but High childcare articles, (organometallic compounds not biodegradable or polyethylene water tanks, tubes, and peroxides) are used in compostable [49]. fittings, foil and plastic its production [49]. bags, insulation mate- rial and other soft PVC applications [49].

PP: • Used for tubes, fittings, • Raw materials are flammable • Recyclable but not packing material, and explosive. compostable [49]. hinges, automobile • Formaldehyde and acetaldehyde parts, and other PVC are released during fires [49]. applications; except • International Agency for Re- rotocasting [49]. search on Cancer (IARC) classi- fies formaldehyde as a known human carcinogen) and acetal- dehyde as a possible human carcinogen [52]

14 • Lowell Center for Sustainable Production • University of Massachusetts Lowell Environmental Plastic Application/Product Human Health Concerns Concerns

PS: • Suitable for a wide • Produces toxic chemicals in fire. • Consumes higher range of applications • Styrene can leach from PS and energy during production in children’s products, is toxic to the brain and nervous than PVC. disposable articles, system, red blood cells, liver, • Does not degrade easily signs, cabinets, kidneys and stomach in animals in the environment. machine parts and [49]. Styrene is classified as a • Difficult to recycle and picture frames [49]. possible carcinogen by IARC not compostable. [52]. • Styrene can be found in the air, water and soil after release from manu- facture, use and disposal of products. [49].

ABS: • Used for toys, auto- • Produces toxic chemicals in fire. • Extremely difficult to Acrylonitrile mobile body parts, • Styrene is toxic to the brain and recycle. butadiene suitcases, tubes and nervous system, red blood cells, • Acrylonitrile is volatile styrene bolts. Can be used for liver, kidneys and stomach in and significant quantities polyvinyl chloride, animals [49]. escape into air during use. polypropylene, poly- • IARC classifies acrylonitrile • Styrene can be found in carbonate and poly- and styrene as possible human the air, water and soil styrene applications carcinogens and butadiene is a after release from manu- [49]. known human carcinogen [52]. facture, use and disposal of products [49].

SBS: Styrene • Used for toys and • Styrene produces toxic chemicals • Difficult to recycle. butadiene childcare articles [49]. in fire. • Styrene can be found styrene • Styrene can leach from polysty- in the air, water and soil rene and is toxic to the brain and after release from the nervous system, red blood cells, manufacture, use and liver, kidneys and stomach in disposal of products [49]. animals [49]. • IARC classifies styrene as a possible human carcinogen and butadiene as carcinogenic to humans [52].

ABS/Polyure- • Used for shoe soles, • Polyurethane produces toxic • Extremely difficult to thane Alloy sports boots, automo- chemicals in fires. recycle. Acrylonitrile is tive parts, solid , • Styrene can leach from polysty- volatile and significant industrial rollers and a rene and is toxic to the brain quantities escape into variety of mechanical and nervous system, red blood air during use. goods [49]. cells, liver, kidneys and stomach • Styrene can be found in animals [49]. in the air, water and soil • IARC classifies acrylonitrile after release from the and styrene as possible human manufacture, use and carcinogens and butadiene as disposal of products. carcinogenic to humans [52]. • Methylene diphenyl isocyanate and toluene diisocyanate degrade rap- idly in the environment. • No effects have been ob- served in landfill disposal or after incineration [49].

Phthalates and their Alternatives: Health and Environmental Concerns • 15 Alternative Plastics that Do Not Require Phthalates Bio-Based Plastics

iobased plastics are alternatives to petroleum-based plastics. They may be completely made from plant materials or may be a blend of plant-based and petroleum-based plastics. Plants such as corn, soy, rice, wheat and linseed can be converted to plastics. Many of these plastics are currently under development for a wide range of commercial applications. The production of biobased plastics is not Bwithout hazards. The use of large quantities of in industrial agricultural production and hazardous chemicals/additives such as sodium hydroxide, carbon disulfide, and chlorine in processing are of concern to human health and the environment. Genetically modified organisms (GMOs) used in development of biobased plastics are also a concern because their effects in the environment are not well understood. Furthermore, not all biobased plastics are biodegradable or compostable. The biodegradability or effective composting of bio- based plastics is dependent on the material’s chemical structure and composition. Table 4 lists biobased plastics under commercial development and their potential health and environmental concerns.

Table 4 Biobased Plasticsc Environmental Plastic/Source Application/Product Human Health Concerns Concerns

Polylactic Acid • Used for hard resin for • Purification of lactic acid requires • Concerns about (PLA)/corn, sugar food containers, film sulfuric acid. environmental beets, sugar cane, and fibers (apparel • Uses tin octanoate as a catalyst impacts from use wheat, sweet and carpeting appli- in processing. Tin octanoate can of bioengineered potatoes or rice cations, clothing). cause neurotoxic and cytotoxic microorganisms in May replace thermo- effects in animals. Organic tin crop production. plastics in many appli- compounds can cause irritation • Can be completely cations. Properties of the skin and lungs, and also recycled to lactic are similar to poly- masculinization of female or in- acid (but required ethylene terephthalate, fertility in male aquatic animals. infrastructure for polypropylene and • Emerging health concerns about recycling does polystyrene [57]. tin residues in PLA used in medi- not exist). cal applications. • Will compost at tem- • 1-octanol used as a polymerization peratures above 60 ºC initiator is volatile and combusti- (must hydrolyze first ble and can cause irritation to and needs commercial tissues. composting infrastruc- • E-coprolactone used to improve ture which it is not properties causes skin irritation widely available) and may cause respiratory tract and can be safely irritation [57]. incinerated [57]. • 1-octanol used as a polymerization initiator is toxic to aquatic organisms

c Information in Table 4 is from: Alvarez-Chavez, C. (2009). Sustainability of Bio-Polymers: Comparative Analysis of Corn and Potato Based Bio-Polymers. Doctoral Dissertation. University of Massachusetts, Lowell.

16 • Lowell Center for Sustainable Production • University of Massachusetts Lowell Environmental Plastic/Source Application/Product Human Health Concerns Concerns

Starch derived • Used for packaging, • Finely pulverized starch can • Concerns about plastics toys, films, shopping suspend in the atmosphere ecosystem impacts bags, planters and and cause powerful explosions. from bioengineered starch (TPS)/corn, planting pots, strings, • Titanium dioxide used as addi- microorganisms used potato, rice, straws, tableware, tive is a potential occupational in crops. wheat and tapioca tapes, cups, cutlery, carcinogen. • Can biodegrade edge protectors, golf • Calcium carbonate used as addi- depending on the tees, trays, and man- tive may cause irritation in eyes, type and amount of tling for candles and skin, and respiratory system and additive and copoly- nets. Properties are cough [57]. mer used [57]. similar to polyethylene and polystyrene [57].

PHA: • Used for toys, films, • PHA is non-toxic and non- • Concerns about Polyhydroxyal- fibers, adhesives, allergenic to consumers. impacts on the envi- kanoate/ inks, packaging, • In processing, may use physical, ronment from use Sugar cane, beets, coatings, molded chemical or enzymatic extraction of bioengineered corn steep liquor, goods, and a variety method. Enzymatic method is microorganisms in palm kernel, soy of other applications. safer for workers. crops and during oils, cellulosic Performs better than • Solvents such as chloroform, PHA synthesis. biomass traditional plastics methylene chloride, and 1, 2- • Highly biodegrad- and comparable to dichloroethane used in physical able by numerous acrylic polymers. Can extraction method are consid- aquatic and terrestri- behave both as a ered possible human carcinogens al microorganisms traditional thermo- by IARC. [57]. plastic polymer and • Another solvent, pyridine, is an [57]. flammable and causes irritation in eyes and skin, liver and kidney damage. • Methanol, hexane and diethyl are used in purification. Methanol is flammable and causes irritation in eyes, skin, upper re- spiratory system, visual distur- bance, and optic nerve damage (blindness). Hexane is flammable, causes irritation in eyes, nose and is neurotoxic. is flammable, can produce explosive peroxides in contact with oxygen, causes narcosis, nausea, vomiting, irritation of the eyes, skin, and upper respiratory system. • Sodium hypochlorite used in pro- cessing can burn eyes and skin, and produce toxic chlorine [57].

Phthalates and their Alternatives: Health and Environmental Concerns • 17 Environmental Plastic/Source Application/Product Human Health Concerns Concerns

Urethanes • Used for adhesives, • Combined with isocyanates • No data found Polyol/soy oil/ coatings, flexible (toluene diisocyanate or methy- regarding potential soybean, castor and rigid foams, and lene diphenyl isocyanate) to environmental oil, rapeseed, elastomers [57]. make foam products. effects. sunflower and • Toluene diisocyanate is volatile, linseed and exposure to it can cause severe irritation to mucous mem- branes, euphoria, ataxia, mental aberrations, asthmatic attacks, chest tightness, coughing, breathlessness, inflammation of the bronchitis, and noncardio- genic pulmonary edema [57]. • Toluene diisocyanate is classified by IARC as a possible human carcinogenic [52]. • Methylene diphenyl isocyanate can irritate the skin, eyes and respiratory tract. Chronic expo- sure to methylene diphenyl isocyanate can sensitize the skin or respiratory tract, which may lead to asthma [57].

Cellulose • Used for toys, flexible • Poor fire resistant properties. • Production process Cellulose acetate film substrates for • Corrosive, flammable and toxic has relatively high (CA), cellulose photography, tooth- chemicals including dichlorine, energy and water acetate propio- brush handles, selec- hydrogen peroxide, carbon requirements. nate (CAP) and tive filtration, adhesive disulfide and caustic soda are • The potential for cellulose acetate tapes, cellophane, used in production and can biodegradation of butyrate (CAB)/ semi-permeable and result in worker exposure. cellulose acetate cotton fibers sealable films and • Cellulose acetate is made by may be affected by and wood automotive coatings, reacting cellulose fibers with the number of ether appliance cases, a corrosive mixture of acetic linkages in cellulose steering, pens, con- compounds and sulfuric. backbone. tainers, eyeglass, • N-methylmorpholine n-oxide • One study showed frames and sheeting is used in processing cellulose evidence of com- [57]. and is classified by the Canadian postability of cellu- Workplace Hazardous Materials lose acetate [57]. Information System as a sensitizer, skin and eye irritant, and may cause chronic toxic effects. • N-methylmorpholine n-oxide produces explosive peroxides in contact with oxygen. • , which is used to reduce flammability, is an irritant of the skin and eyes [57].

18 • Lowell Center for Sustainable Production • University of Massachusetts Lowell Environmental Plastic/Source Application/Product Human Health Concerns Concerns

Poly(trimethylene • Used in fibers for • Made by reacting genetically • biodegradable [57]. terephthalate) textiles, carpets and modified sugar from corn with (PTT)/sugar apparel. Can be used or dimethyl from corn with in packaging and as terephtalate derived from terephthalic a substitute product petroleum. acid (PTA) or for [57]. • Methanol, which could be dimethyl tere- used in esterification of dimethyl phthalate (DMT) terephtalate, is flammable, and derived from may cause skin to become dry petroleum and crack. Inhalation and skin absorption of methanol can irritate the mucous membrane and affect the nervous system, particularly the optic nerve. • Terephthalic acid is a suspected neurotoxicant. Accidental dermal contact with dimethyl terephta- late is of concern due to the possibility of burns from molten liquid. • Acrolein and allyl alcohol fumes might be produced in small amounts during processing. • breathing large amounts of acro- lein may damage the lungs and could cause death. Breathing small amounts of acrolein may cause eye watering and burning of the nose and throat and a decreased breathing rate (these acute effects usually disappear after exposure stops) [57].

Lignin/Plants • Used as in ther- • Produced as a byproduct of • Production process and Wood moplastics, thermo- the Kraft process and requires has relatively high sets and rubbers. Can harsh chemical treatment. energy and water be converted into • Workers can be exposed to requirements. carbon fibers [57]. corrosive, flammable and toxic • biodegradation is chemicals including dichlorine, lower than cellulose. hydrogen peroxide, carbon disul- • Compostable [57]. fide and caustic soda that are used in production. • Kraft is non toxic and approved for food and food pack- aging applications according to FDA regulations [57].

Natural fiber- • Can be used for • Potential for toxic exposures • Production has high reinforced reinforcing starch to workers from corrosive and energy and water composites and protein based toxic chemicals including dichlo- requirements. (kenaf, hemp, composites [57]. rine, hydrogen peroxide, carbon • biodegradable and ramie, flax, sisal disulfide and caustic soda used compostable [57]. henequen, jute, in production. pineapple leaf) • Can also be obtained by biologi- cal methods by using enzymes, bacteria and water [57].

Phthalates and their Alternatives: Health and Environmental Concerns • 19 Environmental Plastic/Source Application/Product Human Health Concerns Concerns

Cellulose • Concern about unknown human • Concern about un- nano-composites health impacts of nanoparticles. known environmen- (obtained by • Potential for toxic exposures to tal effects of chemical treat- workers from corrosive, flamma- nanoparticles. ments and steam ble and toxic chemicals including • Production process explosion of dichlorine, hydrogen peroxide, has relatively high cellulose starting carbon disulfide and caustic soda energy and water materials) used in production [57]. requirements [57].

Polysaccharide • Concern about unknown human • Air, water and soil nanocomposites health impacts of nanoparticles emissions need to [57]. be addressed [57].

Soy protein • Can be used to • Production involves the use of • biodegradable and make foams. alcohol or volatile solvent, alka- compostable [57]. • Application limited line and acid substances, and due to low strength formaldehyde or glutaraldehyde and hydrophilicity. [57]. • Soyplus™ has been • Formaldehyde is a known human used for toys, garden carcinogen according to IARC [52]. supplies, food ser- • Chronic exposure to glutaralde- vice items, industrial hyde causes skin sensitivity resulting packaging, mulch, in dermatitis, and irritation of the golf tees and build- eyes and nose and occupational ing materials [57]. asthma [57].

Corn zein • Used for films, • Production involves the use • biodegradable and lacquers, varnishes, of alcohol or volatile solvents, compostable [57]. adhesives, textile alkaline and acid substances, and fibers and molded formaldehyde or glutaraldehyde plastic objects. as crosslinker [57]. • Hot press molding • Formaldehyde is a known human mechanical properties carcinogen [52]. of corn gluten-based • Chronic exposure to glutaralde- materials are similar hyde may cause dermatitis, and to PVC [57]. irritation of the eyes and nose as well as occupational asthma [57].

20 • Lowell Center for Sustainable Production • University of Massachusetts Lowell References

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22 • Lowell Center for Sustainable Production • University of Massachusetts Lowell 45 Barrett, J. R. (2005). Chemical Exposures: The 52 International Agency for Research on Cancer, Ugly Side of Beauty Products. Environmental Health Monographs on the Evaluation of Carcinogenic Risks Perspectives, 13(1): A24. to Humans: Complete List of Agents Evaluated and their Classification. Available at http://monographs.iarc. 46 U.S. Food and Drug Administration (FDA). (2008). fr/ENG/Classification/index.php Phthalates and Cosmetics Products. U.S. Department of Health and Human Services. Available at www.fda.gov/ 53 International Programme on Chemical Safety (IPCS). Cosmetics/ProductandIngredientSafety/SelectedCosmeticIngredients/ (1996). OECD Screening Information DataSet: Dibu- ucm128250.htm tyl Adipate (CAS # 105-99-7). Available at www.inchem. org/documents/sids/sids/105997.pdf 47 Cain, W. S., Wijk, R. A., Jalowayski, A. A., Caminha, G. P., and Schmidt, R. (2005). Odor and Chemesthesis 54 International Programme on Chemical Safety (IPCS). From Brief Exposures to TXIB. Indoor Air, 15: 445–457. (2005). International Chemical Safety Card (ICSC) 1705: Dibutyl Adipate. Available at www.inchem.org/ 48 Eastman, Eastman TXIB Plasticizer in Toys. Available documents/icsc/icsc/eics1705.htm at www.eastman.com/Literature_Center/L/L225.pdf 55 International Programme on Chemical Safety (IPCS). 49 Alvarez, C., Edwards, S. (2008). Draft Report: (2001). International Chemical Safety Card (ICSC) The Potential for Use of Biobased Plastics in Toys 1349: . Available at www.inchem.org/ and Children’s Products. documents/icsc/icsc/eics1349.htm 50 U.S. Environmental Protection Agency, Integrated 56 U.S. National Library of Medicine, Toxicology Risk Information System: Butyl Benzyl Phthalate Data Network (TOXNET), Hazardous Substances (CAS RN 85-68-7). Available at www.epa.gov/IRIS/ Data Bank: Dibutyl Sebacate. Available at subst/0293.htm http://toxnet.nlm.nih.gov/ 51 National Toxicology Program, National Institute of 57 Alvarez-Chavez, C. R. (2009).Sustainability of Environmental Health Sciences, Antimony Trioxide Bio-Polymers: Comparative Analysis of Corn and (CAS # 1309-64-4): Brief Review of Toxicological Potato Based Bio-Polymers (Doctoral Dissertation). Literature, July 2005. Available at http://ntp.niehs. University of Massachusetts, Lowell, MA. nih.gov/ntp/htdocs/Chem_Background/ExSumPdf/ Antimonytrioxide.pdf Lowell Center for Sustainable Production University of Massachusetts Lowell, One University Avenue, Lowell, MA 01854 978-934-2980 • www.sustainableproduction.org