Journal of Cleaner Production 23 (2012) 47e56

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Journal of Cleaner Production

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Sustainability of bio-based plastics: general comparative analysis and recommendations for improvement
Clara Rosala lvarez-Chvez a, *, Sally Edwards b, Rafael Moure-Eraso a, Kenneth Geiser a
a b

Work Environment Department, University of Massachusetts-Lowell, One University Avenue, 83000 Lowell, MA, USA Lowell Center for Sustainable Production, University of Massachusetts-Lowell, One University Avenue, Lowell, MA, USA

a r t i c l e i n f o
Article history: Received 27 February 2011 Received in revised form 28 September 2011 Accepted 4 October 2011 Available online 8 October 2011 Keywords: Bio-based plastic Bioplastic Sustainability Life cycle

a b s t r a c t
This study evaluated the sustainability of bio-based plastics including all the stages of their life cycles (cradle to grave) to assist in decision making about selection of these materials. Plastics are considered essential materials in todays society, but throughout their life cycles they contribute to pollution and depletion of non-renewable natural resources. Bio-based plastics appear to be more environmentally friendly materials than their petroleum-based counterparts when their origin and biodegradability are compared. But which of the bio-based plastics currently on the market or soon to be on the market are preferable from an environmental, health, and safety perspective? Results of this qualitative study were displayed in two Bioplastics Spectrums that provide a visual summary of the data gathered on bio-based plastics according to sustainability criteria. This analysis found that none of bio-based plastics currently in commercial use or under development are fully sustainable. Each of the bio-based plastics reviewed utilizes: genetically modied organisms for feedstock manufacture and/or toxic chemicals in the production process or generates these as byproducts, and/or co-polymers from non-renewable resources. When deciding to substitute conventional petroleum-based plastics with bio-based plastics it is important to understand the ow of these materials and their adverse impacts in all parts of their life cycles in order to select a material that is more sustainable. 2011 Elsevier Ltd. All rights reserved.

1. Introduction Plastic materials are currently considered very important materials due to their exceptional properties and performance over other materials such as metal and wood (Aguado and Serrano, 1999; Azapagic et al., 2003; PlasticsEurope, 2008; Rosato and Rosato, 2003). It is projected that the demand for plastics will continue to rise following a trend that has increased since the 1950s (PlasticsEurope et al., 2008). As plastic materials are of such importance in our society and knowing that materials are a fundamental determinant of sustainability (Geiser, 2001), the substitution of petroleum-based plastics with bio-based plastics is seen as a promising alternative because it will reduce the dependency of plastics on fossil fuels and the pressure on landlls from plastic solid wastes. Development and commercialization of bio-based

plastics for a variety of uses in products and packaging is also of great interest as manufacturers are looking for safer and healthier materials as substitutes for chemicals and materials of concern in consumer products. Bio-based materials are promising as their feedstocks are renewable, theoretically they can be composted or recycled, and their production process may be more energy efcient than petroleum-based plastics processing. This study provides insight into the health and environmental impacts of bio-based plastics. Sustainable materials are those that reduce impacts to occupational and public health as well as to the environment throughout their life cycles (Geiser, 2001). Therefore, the aim of this study was to qualitatively evaluate the general sustainability of different bio-based plastics based on an extensive review of the literature and considering environmental, health and safety impacts throughout their life cycles. A gure called the Bioplastics Spectrum was created to visually summarize the data and to assist in decision making about bio-based plastics selection. 1.1. Dening a sustainable bio-based plastic A consensus denition for a bio-based plastic does not yet exist. The Business-NGO Working Group for Safer Chemicals and

* Corresponding author. Present address: Universidad de Sonora, Departamento de Cs, Qumico-Biolgicas, Rosales y Luis Encinas, Colonia Centro, Hermosillo, C.P. 83100 Sonora, Mexico. Tel.: 52 662 2592163; fax: 52 662 2592164. E-mail addresses: ralvarez@guayacan.uson.mx (C.R. lvarez-Chvez), Sally_ Edwards@uml.edu (S. Edwards), Rafael_Moure@uml.edu (R. Moure-Eraso), Ken_ Geiser@uml.edu (K. Geiser). 0959-6526/$ e see front matter 2011 Elsevier Ltd. All rights reserved. doi:10.1016/j.jclepro.2011.10.003

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Sustainable Materials (a unique collaboration of business and NGO leaders who promote the use of safer chemicals in consumer products) (CPA, 2008) denes bio-based plastics as plastics in which 100% of the carbon is derived from renewable agricultural and forestry resources such as corn starch, soybean protein and cellulose (Business-NGO Working Group for Safer Chemicals & Sustainable Materials, 2007). The US Department of Agriculture denes bio-based plastics as commercial or industrial goods, (other than feed or food), composed in whole or in signicant part of biological products, forestry material, or renewable domestic agricultural materials, including plant, animal or marine materials (USDA, 2005). ASTM denes a bio-based material as an organic material in which carbon is derived from a renewable resource via biological processes (The Biodegradable Products Institute, 2006). Bio-based materials include all plant and animal mass derived from CO2 recently xed via photosynthesis, per denition of a renewable resource. In reality, most bio-based plastics on the market today are blends of bio-based and petroleum-based materials. A bio-based plastic is not necessarily a sustainable plastic; this depends on a variety of issues, including the source material, production process, and how the material is managed at the end of its useful life. Because of the myriad issues to consider, it can be very challenging to determine which plastic materials are safest and healthiest for workers, consumers and the environment. Over the last decade, researchers and citizen advocates have developed several tools to assist in decision making about plastics selection. The plastics pyramid (Fig. 1) developed by Thorpe and Van der Naalde in 1998 was an early attempt to visually display the life cycle hazards of different plastics to assist in materials selection. This ranking focused on the toxicity of the material, considering production hazards, use of harmful additives, hazards in use, and disposal hazards. In this pyramid, bio-based polymers form the bottom of the pyramid, indicating they are most preferable, as they are made from renewable resources, and theoretically are biodegradable and compostable. The Plastics Spectrum, created in 2005 (Rossi et al., 2005), added to the information presented in the Plastics Pyramid by displaying the recyclability of plastics alongside their life cycle hazards (Fig. 2). Since the Plastics Pyramid was developed, bio-based plastics are much further along in their commercial development. These materials need to be evaluated carefully for sustainability. Rossi and Lent (2006) have developed an Environmental Preference Spectrum for the health-care industry (Fig. 3). This spectrum is the rst

Fig. 2. The plastics spectrum. Source: (Rossi et al., 2005).

to take the category of bio-based and begin to provide criteria for what makes these materials preferable. This spectrum prefers biobased plastics that are sustainably grown that can be readily recycled because of existing infrastructure. It suggests avoiding plastics that are manufactured with, contain, or emit highly hazardous chemicals and avoiding those that are not readily recyclable. This report denes sustainably produced bio-based materials as those that are: grown without genetically modied organisms (GMOs), hazardous pesticides, certied as sustainable for the soil and ecosystems, and compostable into healthy and safe nutrients for food crops (Rossi and Lent, 2006). More recently Rossi and Greiner (2009) developed the Plastics Scorecard to rate different types of plastics based on their life cycle impacts and hazards to human health and environment. The three core elements include: sustainable feedstocks, green chemistry and closed loop systems. In this scorecard plastics receive a grade from F (poor life cycle performance) to A (good life cycle performance) (Fig. 4). For example, the maximum attainable grade for PLA is A when corn is grown without GMOs and atrazine pesticide. PLAs grade is C when GMOs and atrazine are used. In contrast, the maximum attainable grade for PVC is F because of its chemical releases and breakdown products (dioxins and furans that are persistent, bioaccumulative, toxic and carcinogenic chemicals). 1.2. Principles for sustainable biomaterials The Sustainable Biomaterials Collaborative (SBC, 2009) is a network of organizations that was formed to spur the development and use of biomaterials that are sustainable throughout their life cycles. Principles for the development of sustainable biomaterials, as developed by this organization, include: 1. Reduce the amount of material, product and packaging used 2. Eliminate single-use products that can be neither recycled nor composted 3. Avoid fossil fuel-based materials in favor of materials and products derived from renewable feedstocks 4. Address sustainability across the life cycle of the material: the growing of the feedstock, manufacturing of the biomaterial and nal product, using the product and reclaiming the material at the end of its original use. 5. Dene sustainability to include issues of environment, health, and social and economic justice 6. Design and use products that is reusable, recyclable or compostable 7. Encourage agricultural systems that are sustainable for farmers, the environment, farm workers and communities. This means to eliminate hazards of concern during feedstock production, conserve, protect and build soil, conserve nutrient cycles, protect air and water access and quality, promote

Fig. 1. The plastics pyramid. Source: (Rossi et al., 2005).

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Fig. 3. . Environmental preference spectrum for the health-care industry. Source: (Rossi and Lent, 2006).

8. 9. 10.

11.

12.

biological diversity, reduce overall energy use and its impacts, reduce transportation impacts, develop and certify a comprehensive sustainable agriculture plan, protect workers health and safety and provide fair compensation. Support small to mid-sized family owned and operated farms Do not use GMOs in agricultural feedstock production Use chemicals that meet the 12 Principles of Green Chemistry. These principles pursue the design and production of chemicals in a way that minimizes the potential for health and environmental hazards (Anastas and Warner, 1998). Avoid engineered nanomaterials and chemicals that have not been tested for environmental and public health effects across the life cycle; and Decentralize production and buy locally to reduce the environmental footprint of production, transportation, and consumption.

2. Methodology Life Cycle Assessment (LCA) is a tool that is used to quantitatively assess the environmental impact of a given product throughout its life cycle; its principles and framework are described in ISO 14040 (ISO, 2011). LCA frameworks have been proposed to assess social and economic impacts (Dreyer et al., 2010a, 2010b; Weidema, 2006) but these are not well developed. LCAs have been conducted for some starch polymers, PLA and PHAs, but these assessments do not consider occupational hazards. For this study, researchers were interested in evaluating the occupational and environmental hazards posed by bio-based plastics and therefore used life cycle thinking to conduct a qualitative evaluation of biobased plastics. An extensive literature review was conducted and manufacturers were contacted for information about bio-based plastics that

are commercially available or soon to be on the market. These include polylactide acid (PLA), starch (pure thermoplastic starch: TPS), polyhydroxyalkanoates (PHAs), poly(trimethylene terephthalate) (PTT), ligno-cellulosics, plastics from corn and soy protein, bio-based urethanes (BURs) and nano-biomaterials. These bio-based plastics were described according to their source, production process, properties, process techniques, uses, environmental, health and safety impacts, costs, and commercial readiness. In order to dene a sustainable bio-based plastic, a review of ranking schemes and criteria that have been developed in the last decade to aid in decision-making was done. The Principles created by the Sustainable Biomaterials Collaborative were used as a framework to develop a denition for a sustainable bio-plastic in this study and to evaluate the sustainability of the bio-based plastics from the information obtained in the literature review. The sustainability criteria included the environmental, health and safety impacts during the life cycle of the plastics, for example, use of GMOs and hazardous pesticides to grow the feedstock to produce the bio-based plastic; use of hazardous chemicals or petroleumbased co-polymers during plastic production and processing; hazardous additives or untested nanomaterials; potential hazards in workplaces, disposal options, potential impacts to the food supply, and efciency in the use of water, energy, and materials, etc. Each bio-based plastic was reviewed according to these criteria. The limitations of this study are related to the commercial environment for the development of bio-based plastics. The industrial production, research and commercialization of these materials are very competitive. Therefore, many developments and innovations in the eld are not made publicly available due to the research and commercial interests. The development of bio-based plastics is still in its infancy and there is little research about environmental, health and safety impacts throughout their life cycles. For this study, the evaluation of sustainability of bio-based

Fig. 4. Plastics scorecard. Source: (Rossi and Greiner, 2009).

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plastics was conducted with information currently available. Further research and improvements in this eld may change the results obtained here. 3. Results The Principles for Sustainable Biomaterials provided a useful framework for evaluating the bio-based plastics currently being commercialized. For bio-plastics to be substituted for petroleumbased plastics, they need to meet performance requirements for a range of products. Currently, bio-based plastics are used in bers, lms, coatings, packaging, apparel, toys, inks, food containers, tableware, and cutlery (Crank et al., 2005; Guilbert and Cuq 2005; Lubick, 2007, Vink et al., 2003). Bio-plastics are not widely used in other product categories either because of cost constraints, performance limitations or lack of knowledge about available substitutes that are commercially available. Although bio-based plastics may be more sustainable than petroleum-based plastics in some aspects (see Table 1), this analysis found that there are environmental and occupational health and safety hazards in their production. Table 2 lists the environmental and occupational health and safety hazards in the production of bio-based plastics. Although advances have been achieved, fully sustainable bio-based plastics with all the highly valued properties of conventional plastics for all types of products are not yet available. The Bioplastics Spectrums for Occupational Health and Environment (Figs. 5 and 6) summarize the data gathered on bio-based plastics according to sustainability criteria and provide a visual comparison of the bio-based plastics. The health and safety impact comparative analysis (Fig. 5), found that PHAs, PLA, and starch (TPS) (shaded as light green in the Spectrum) are preferred to the other bio-based materials. Although there are some occupational hazards in their production, these hazards were considered lower than that of the other bio-based materials. They also are fully bio-based materials as they do not contain a petroleum-based component. The environmental analysis, summarized in the Bioplastics Spectrum in Fig. 6, found that starch, urethanes, PHA, zein, and soy protein (light green) are preferred although GMOs of unknown hazards and persistent bioaccumulative and toxic chemicals (PBTs)

such as pesticides may be used in feedstock production. Bio-based feedstocks are generally grown using methods of industrial agricultural production and therefore signicant amounts of energy, water, land, GMOs, toxic pesticides and fertilizers are used, which deplete natural resources and can pollute water, air and soil. In addition, there is concern about using land for polymer production that could be used to grow crops for human consumption. Advances in biotechnology make it possible to produce plastic directly in microorganisms or in genetically modied crops such as corn. The

Table 2 Environmental and occupational health and safety hazards of bio-based plastics. Bioplastic Environmental hazards Occupational health and safety hazards

Polyhydroxyalkanoates Feedstock is grown using (PHAs) methods of industrial agricultural production, including GMOs. Data on energy requirements are controversial.

Table 1 Sustainability improvements of bio-based plastics relative to petroleum-based plastics (PBP). Bioplastic Sustainability improvement

Polyhydroxyalkanoates Highly biodegradable. (PHAs) Polylactic acid (PLA) Production uses 30e50% less fossil energy and generates 50e70% less CO2 emissions than PBP. Competitive use of water with the best performing PBP, recyclable, compostable at temperatures above 60  C. Thermoplastic Starch Production requires 68% less energy than its PBP (TPS) counterpart. Lower CO2 emissions than PBP. Biodegradable and compostable. Bio-urethanes (BURs) Production requires 23% less energy and 36% less GGH, compared to PBP. Cellulose and Lignin The biological degradation of lignin is lower than cellulose, compostable. Poly(trimethyleneProduction requires 26e50% less energy and 44% lower terephtalate) PTT GHG than its PBP counterpart. No chemicals additives are used. Biodegradable. Potentially recyclable. Corn zein and soy Biodegradable and compostable. protein GMOs: genetically modied organisms, GHG: greenhouse gases.

Exposure to pesticides. Physical extraction of PHAs uses pyridine, methanol, hexane or diethyl ether. Chemical digestion uses sodium hypochlorite, methanol and diethyl ether. Polylactic acid (PLA) Feedstock is grown using Exposure to pesticides, methods of industrial sulfuric acid, tin octoate, agricultural production, 1-otanol and urea. Finely including GMOs. 1-octanol pulverized starch can is ecotoxic and organic tin cause powerful explosions. can build up in living organisms. Thermoplastic Starch Feedstock is grown using Exposure to pesticides, (TPS) methods of industrial glycerol and urea. Finely agricultural production, pulverized starch can including GMOs. cause powerful explosions. Bio-urethanes (BURs) Feedstock is grown using Exposure to pesticides, methods of industrial toluene diisocyanate (TDI), agricultural production, methylene diphenyl including GMOs. isocyanate (MDI), tin derivatives. Cellulose and Lignin The process has relatively Exposure to elevated high energy and water temperature and pressure. requirements. Emissions Exposure to disulde, of pollutants to air and sodium hydroxide, volatile water during kraft process toxic, ammable and need to be addressed. malodorous emissions of sulfur. Exposure to propionic, acetic, sulfuric, nitric acids. Poly(trimethyleneFeedstock is grown using Exposure to pesticides, terephtalate) PTT methods of industrial terephthalic acid, dimethyl agricultural production, terephthalate, and including GMOs. Only 37% methanol. Finely (by weight) from pulverized starch can renewably sourced cause powerful explosions. material GMOs are used in fermentation of glucose to bio-PDO. Feedstock is grown using Exposure to pesticides, Corn zein and soy protein methods of industrial alcohol or volatile agricultural production, solvents, alkaline and acid including GMOs. substances, and formaldehyde as or glutaraldehyde. Nano-biocomposites The process has relatively Exposure to elevated (cellulose and lignin) high energy and water temperature and pressure. requirements. Emissions Exposure to disulde, of pollutants to air and sodium hydroxide, water during kraft process isocyanates, volatile toxic, need to be addressed. ammable and Potential toxicity issues of malodorous emissions of nanoparticles regarding to sulfur, as well as to incineration, composting nanoparticles. or recycling are unknown. GMOs: genetically modied organisms, GHG: greenhouse gases.

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Fig. 5. The Bioplastics Spectrum. Comparative occupational health and safety impacts of bioplastics. BURs: bio-urethanes; PHAs: polyhydroxyalkanoates, isolated and puried by enzymatic methods; PTT: poly(trimethylene terephthalate). GMOs: genetically modied organisms.

use of GMOs in the development of bio-based plastics is a concern, because their effects in the environment are not well understood. Bio-based plastics that are preferred from a sustainability perspective will utilize: a feedstock grown without GMOs and without hazardous pesticides: -will be processed without GMOs, hazardous chemicals or petroleum-based co-polymers, - will avoid hazardous additives or untested nanomaterials, - will address environmental and safety hazards during their production, - will not impact the food supply, - will be exible in disposal options, meaning it could composted or recycled, and in the case of landlling and incineration or (least recommended options), it will not generate toxic emissions, - will be energy and water efcient in production, - will avoid the generation of hazardous byproducts.

4. Discussion 4.1. Comparative analysis of occupational health and safety impacts 4.1.1. PHAs They are aliphatic polyesters produced via fermentation of renewable feedstocks such as sucrose, vegetable oils and fatty acids.

Recently, they have been experimentally produced from waste left over from the production of ethanol from the stalk and leaves of corn plants (Yu and Chen, 2008). PHAs pose safety hazards for workers if physical extraction or chemical digestion methods (Hocking and Marchessault, 1998) are used to isolate and concentrate them. The enzymatic hydrolysis method is the safest method for workers as it does not require the use of toxic chemicals and leaves PHAs intact. In this case, bacterial cells are treated with enzymes (proteases, nucleases and lysozymes) and detergents to remove proteins, nuclei acids, and cell walls (Suriyamongkol et al., 2007). Physical extraction of PHA may expose workers to halogenated solvents including chloroform, methylene chloride, and 1, 2dichloroethane (Hocking and Marchessault, 1998; Lee, 1998). These chemicals are considered occupational carcinogens by NIOSH and IARC has classied them as 2B, possibly carcinogen to humans (DHHS, 2007; Fan, 2005; Parent, 2005). Other chemicals that may be used include pyridine, methanol, hexane or diethyl ether (Hocking and Marchessault, 1998). Pyridine is ammable and causes eye irritation, headache, anxiety, dizziness, insomnia, nausea, anorexia, dermatitis, liver, and kidney damage (DHHS, 2007). Methanol is ammable and causes eye, skin and upper respiratory system irritation, headache, drowsiness, dizziness, nausea, vomiting, visual disturbance, optic nerve damage (blindness), and dermatitis (Shepherd, 2005b). Hexane is ammable and causes eye and nose irritation, nausea, headache, peripheral neuropathy (numb extremities, muscle weakness), dermatitis,

Fig. 6. The Bioplastics Spectrum. Comparative environmental impacts of bioplastics. BURs: bio-urethanes; PHAs: polyhydroxyalkanoates, isolated and puried by enzymatic methods; PTT: poly(trimethylene terephthalate). GMOs: genetically modied organisms; PBT chemicals: persistent bioaccumulative and toxic chemicals.

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dizziness, and chemical pneumonitis (aspiration liquid) (Clough and Mulholland, 2005). Diethyl ether is ammable, can produce explosive peroxides in contact with oxygen under storage conditions and causes irritation in eyes, skin, upper respiratory system, dizziness, drowsiness, headache, narcosis, nausea, and vomiting. Inhalation of high concentrations of diethyl ether may cause unconsciousness and coma (Becaria, 2005). Chemical hazards of the chemical digestion method include sodium hypochlorite, methanol and diethyl ether (Hocking and Marchessault, 1998, Lee and Choi, 1999, 2001). Sodium hypochlorite has a pronounced irritant effect and may cause severe burns to skin and eyes. Poisonous vapor (chlorine gas) is corrosive to respiratory passages and may cause irritation of mouth, nose and throat. If ingested sodium hypochlorite is poisonous, causes burns, abdominal cramps, nausea, vomiting, lowered blood pressure, diarrhea, shock, coma, shock, and death may occur (Weber, 2005). Hazards of methanol and diethyl ether are described above. 4.1.2. PLA and starch PLA is a thermoplastic aliphatic polyester obtained by the polymerization of lactic acid derived from microbial fermentation of corn starch or cane sugar (Vink, 2008). Pure thermoplastic starch (TPS) is obtained without fermentation or chemical treatment of natural corn, potato, rice, tapioca or wheat starch that are extruded or blended to produce TPS (Crank et al., 2005). An unknown health hazard in the production of PLA and starch is the use of GMOs in crops to produce higher yields or to improve starch properties (Ahmann and Dorgan, 2007). Statistics show an increasing trend in the use of GMOs for all biotech corn hybrids planted; in 2008, 85% of acreage in the United States was planted with bioengineered corn (NASS, 2010). Bioengineered microorganisms used in the production of plastics from starch are of concern because impacts from GMOs are not well understood (Graedel and Howard-Grenville, 2005). Human health hazards related to GMOs may include allergic reactions, inherent toxicity of novel gene and its products, and alterations of metabolic pathways (Wolfenbarger and Phifer, 2000; Malarkey, 2003; Pandey et al., 2010). PLA may also use GMOs during fermentation of glucose (Clark and Hardy, 2004). The production of starch poses safety hazards for workers as starch in a nely pulverized form can suspend in the atmosphere and cause powerful explosions (OSHA, 1996). PLA production uses sulfuric acid during the recovery of lactic acid from fermentation broth and organic tin in the polymerization catalytic system (Clark and Hardy, 2004; Crank et al., 2005; Vink et al., 2003). The use of sulfuric acid, a highly corrosive substance (Robles, 2005), and tin based catalysts, is an issue for the health and safety of the workers in the newly emerging PLA industry. During the industrial manufacturing of PLA, an organotin-based catalyst system (tin octanoate) is used in very low concentrations (100e1000 ppm) (Henton et al., 2005). Organotin compounds have showed neurotoxic effects in animals and cytotoxic effects in human and animals and can affect sex differentiation, resulting in masculinization of females or infertility in male aquatic animals (Grun et al., 2006; Shi et al., 2009; Tanzi et al., 1994; Yamada et al., 2008). The toxicological mechanism for organotin compounds is not completely understood and the essential cellular target of organotins has not been identied (Sn(Oct)2). 1-Octanol is also used in the ring opening catalysis step to control molecular weight and accelerate the reaction (Drumright et al., 2000; Sdergrd and Stolt, 2002). 1-octanol is a volatile and combustible liquid that can be absorbed into the body by contact, inhalation, and by ingestion causing irritation to the tissues. 1-octanol is slightly toxic to sh and zooplankton (EPA, 2007a,b).

Glycerol and urea are used in TPS as plasticizers (Crank et al., 2005; Leon and Leszek, 2006). Glycerol is considered a low hazard (Wurzel, 2005). Exposure to urea causes redness and irritation of skin and eyes, headache, nausea, vomiting, disorientation, and transient confusion (Korrapati and Mehendale, 2005). 4.1.3. Bio-urethanes (BURs), cellulose, lignin and PTT BURs are obtained by the reaction of isocyanates with the diol or polyol groups present in vegetables oils such as castor, soy, sunower and linseed. Cellulosic and lignin plastics are produced by chemical modication of natural cellulose and lignin obtained from wood and short cotton bers called linter. Natural bers are typically added as reinforcement to plastics (Mohanty et al., 2000). PTT is a linear aromatic polyester produced by the reaction of 1,3 propanediol (PDO) and a dicarboxylic acid such as terephthalic acid (PTA) or dimethyl terephthalate (DMT). PDO can be obtained by microbial fermentation processes from glucose of corn starch; this microorganism can be a GMO (Rosato and Rosato, 2003; Crank et al., 2005). PTA and DMT are petroleum-based feedstocks (Crank et al., 2005). There are numerous different types of BURs, cellulose and lignin plastics; therefore, it is difcult to address the hazards of their production processes. BURs, cellulose and lignin plastics, and PTT are shown as light yellow in the Bioplastics Spectrum because they may use hazardous chemicals during their manufacturing processes. Producing BURs require the use of hazardous isocyanates (Crank et al., 2005). Toluene diisocyanate (TDI) is a very volatile liquid that is a severe irritant to mucous membranes of the eyes and respiratory tract. Acute exposure to TDI can cause euphoria, ataxia, and mental aberrations. Very low subsequent inhalation exposures to TDI have caused asthma attacks in workers. High dose exposure to TDI by inhalation can lead to chest tightness, coughing, breathlessness, inammation of the bronchi with sputum production and wheezing, and non-cardiogenic pulmonary edema. TDI is classied by the International Agency for Research on Cancer as possibly carcinogenic to humans (IARC, 1986). Because of concerns about the carcinogenic potential of TDI, methylene diphenyl isocyanate (MDI) is often used as an alternative. MDI can irritate the skin, eyes and respiratory tract. Chronic exposure to MDI can sensitize the skin or respiratory tract, which may lead to asthma (EPA, 1998). Reactions with various polyols and isocyanates, are usually catalyzed with tin derivatives like dibutyltin dilaurate (Raquez et al., 2010). Tin hazards were described above in the section on PLA. The conventional production of cellulose by kraft pulping of wood involves the use of elevated temperature, pressure and harsh chemical treatment with sodium sulde and sodium hydroxide (EPA, 2010). Lignin is a byproduct of this process. Sodium hydroxide and sodium sulde are strong corrosives (Chanda and Mehendale, 2005; Lewis, 2004). Hydrogen sulde, methyl mercaptan, dimethyl disulde, and other volatile sulfur compounds are highly ammable, toxic and malodorous air emissions byproducts (Bordado and Gomes, 2003; Locey, 2005). These chemicals pose acute exposure hazards to workers. Cellulose acetate is made by reacting cellulose with acetic acid; cellulose acetate butyrate is made by treating brous cellulose with butyric acid, butyric anhydride, acetic acid and acetic anhydride in the presence of sulfuric acid. Cellulose acetate propionate is made by treating brous cellulose with propionic acid, acetic acid and anhydrides in the presence of sulfuric acid (Crank et al., 2005). Cellulose nitrate is made by treating brous cellulosic materials with a mixture of nitric and sulfuric acids. All of these chemicals have the potential to produce mild to severe irritation of skin, eyes and respiratory tract (Chanda, 2005; Gad and Gad, 2005; Robles, 2005; Shepherd, 2005a). Bioplastics made of natural bers are biodegradable (Mohanty et al., 2000).

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PTA used during the polymerization process of PTT poses a low health risk to humans (OECD. SIDS, 2001b). DMT can also be used for polymerization of PTT as an alternative to PTA. DMT is considered a low hazard in workplaces because of its low volatility; however accidental dermal contact is of concern from possible burns from molten liquid (melting point is 141  C) (OECD. SIDS, 2001a). In case of DMT, methanol is used during polymerization process; hazards of this chemical were described above (Crank et al., 2005). 4.1.4. Proteins from corn and soy Proteins are natural polymers consisting of amino acids; they are present and have important functions in living organisms such as enzymes, and as a component of tissues, bones, etc. Their structure is complex with many sites that can interact with plasticizers and other polymers to be converted into plastics through an extrusion process (Ahmann and Dorgan, 2007). These proteins are shaded as dark yellow in the Bioplastics Spectrum because they may use corrosives and carcinogens in their production processes. Formaldehyde or gluteraldehyde is used as a crosslinking agent to reduce their moisture sensitivity (Guilbert and Cuq, 2005; Ly et al., 1998). Formaldehyde is carcinogenic to humans and chronic exposure to glutaraldehyde can cause skin sensitivity resulting in dermatitis, irritation of the eyes and nose and occupational asthma (Cogliano et al., 2005; Kehoe, 2005; Lewis, 2004). Glycerol, considered a low hazard chemical, can be used as plasticizer in proteins (Liu et al., 2005; Raquez et al., 2010; Wurzel, 2005). 4.1.5. Nano bio-composites These are composite materials that contain bio-based polymers and low additions of nanoparticles of natural bers such as cellulose and lignin for reinforcement purposes (Ahmann and Dorgan, 2007; Lagaron and Lopez-Rubio, in press; Vilaplana et al., 2010). They are shaded orange in the Bioplastics Spectrum because nanoparticles pose unknown hazards and because bers are obtained by the kraft method and can be treated with chemicals (isocyanates, alkalis) to enhance their properties as reinforcements (Vilaplana et al., 2010). Hazards of the kraft method and of these chemicals were described above. The health effects of nanoparticles are of concern because there is a lack of knowledge about their stability during processing and there are potential toxicity concerns related to decomposition and/or migration during service (Lagaron and Lopez-Rubio, in press). Toxicologists hypothesize that nanoparticles may not be detected by the normal defense system of organisms, their small size can modify protein structures, and they can travel from respiratory system to the brain and other organs (Levy et al., 2006). 4.2. Comparative analysis of environmental impacts One common hazard for most bio-based plastics is the use of GMOs in crops; they also can be used during fermentation of substrates to produce building blocks for polymers. Environment concerns of GMOs are increased pest resistance, development of weed tolerance, decreased genetic diversity, and undesirable crop or weed species development (Wolfenbarger and Phifer, 2000; EPA, 2007a; Pandey et al., 2010). PLA manufacture uses organic tin and 1-octanol during lactic acid polymerization (Ahmann and Dorgan, 2007; Drumright et al., 2000; Sdergrd and Stolt, 2002). Small residues of organic tin in PLA products can be a concern during disposal because it has lipophilic properties and can build up on aquatic organisms and plants and it has also been found in human tissues (Shi et al., 2009). According to manufacturers, burning and landlling PLA does not generate toxic emissions and leachates (Vink, 2008). 1-octanol is slightly toxic to aquatic organisms (EPA, 2007b). According to a life

cycle assessment carried out by Vink et al. (2003), PLA used 30e50% less fossil energy and resulted in lower CO2 emissions by 50e70% compared to petroleum-based plastics. More recently, a new ecoprole showed 85% fewer CO2 emissions and 50% less fossil fuel use compared with data of 2003 (Vink et al., 2007). PHA was ranked as light green in the Bioplastics Spectrum, assuming it is isolated and puried using the enzymatic method (other methods require hazardous chemicals) (Crank et al., 2005; Tullo, 2008). Data on energy requirements of PHA production are controversial (Crank et al., 2005), however, PHAs manufacturers reports that the manufacturing of these bio-based plastics uses 3.5% of the energy required to make conventional plastics (Tullo, 2008). PLA, thermoplastic starch, PHA, zein (corn protein), and soy protein are biodegradable and compostable (Ahmann and Dorgan, 2007; Flieger et al., 2003; Vink, 2008). Data about the compostability of BURs were not available. PTT production (light yellow) consumes about 26e50% less energy and 44% lower GHG than its petroleumbased counterpart (nylon 6 and nylon 66), no chemicals additives are used, but requires 37% (by weight) from renewably sourced material, and can be potentially recycled in the polyethylene terephthalate (PETE) waste stream (Dupont, 2007). PTT scrap is usually classied as non-hazardous waste and can usually be landlled or burned, but it uses terephthalic acid (PTA) or dimethyl terephthalate (DMT) as feedstocks, which derive from petroleum. Composites made of natural bers such as cellulose and lignin and biopolymers are ranked as dark yellow in the Bioplastics Spectrum because they are completely biodegradable (John and Thomas, 2008, Mohanty et al., 2000) but the bers are obtained using the traditional method of pulping (kraft process), which requires large amounts of energy and water, uses harsh chemicals such as sodium disulde and sodium hydroxide and generates large amounts of wastewater, greenhouse gases, and malodorous sulfur compounds (dark yellow) (EPA, 2010). Nano biocomposites made of nanoparticles of cellulose or lignin and biopolymers are ranked orange in the Bioplastics Spectrum because nano bers are obtained by the kraft process and hazardous chemicals are used to improve their performance. In addition, there is a lack of knowledge about potential toxicity issues of nanoparticles in regard to incineration, composting or recycling (Lagaron and Lopez-Rubio, in press). 5. Conclusions The general conclusion of the evaluation and comparative analysis of the sustainability of bio-based plastics according sustainability criteria is that none of bio-based plastics currently in commercial use or under development are fully sustainable. Some bio-based plastics are preferable from a health and safety perspective and others are preferable from an environmental perspective. In general, according to the specied criteria, starch, PLA, and PHA polymers are preferred over other bio-based polymers. Because bio-based plastics require land for production, they may compete with land needed to grow food for human consumption. Bio-based feedstocks are generally grown using methods of industrial agricultural production and therefore signicant amounts of toxic pesticides are used, which can pollute water and soil, and impact wildlife habitats. When processing biobased feedstocks to produce plastics, signicant amounts of energy and water are used, as well as hazardous chemicals/additives, genetically modied organisms (GMOs) or engineered nanomaterials. Occupational health and safety hazards are also present during the growing and processing of feedstocks. Biodegradability of bio-based plastics is affected when bio-based polymers are copolymerized with petroleum-based compounds. Infrastructure for composting bio-plastics is not widely available.

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The Bioplastics Spectrums for Health and Environment were developed in this study as a tool to assist in decision making about their selection based on the sustainability criteria. The placement of the bio-based polymers in the Bioplastics Spectrums may change as additional data becomes available. This study is an effort to begin evaluating the potential environmental and occupational and public health impacts of bio-based plastics to contribute to a more comprehensive evaluation of sustainability throughout their life cycles. Biodegradable plastics have the potential to reduce the use of fossil fuels and related environmental and health impacts and to avoid non-degradable and bulky plastic wastes. However, biodegradable plastics also have environmental and occupational health impacts throughout their life cycles. More research is needed to produce novel environmentally friendly and safer plastics, and it is also necessary to create the required infrastructure and new policies to address the range of issues surrounding the sustainability of the bio-based plastics industry. Finally, the current global food crisis has raised serious questions about the use of agricultural land to grow crops for industrial products such as ethanol. Research to develop a second generation of bio-based plastics from sources that do not compete with food production, such as byproducts of agriculture (corn straw, grasses) and wood is imperative. Listed below are recommendations for improving the sustainability of bio-based plastics from a life cycle perspective: 5.1. In feedstock production 5.1.1. Use agricultural or industrial byproducts as feedstocks for bioplastics Possible options include ligno-cellulosics from wood and linter or corn stover, a byproduct of the corn industry; and potato wastes (cull potatoes or potato chips wastes). The use of byproducts from agriculture to produce bio-based plastics would create an opportunity to give economic value to these waste materials, reduce production costs, reduce land used for polymer production instead of food production, and create new jobs. 5.1.2. New technological advances Research and development will bring better and more efcient technologies. However, these advances will have to ensure that hazards are not shifting from the environment to workers or vice versa. For example, in PLA production, calcium hydroxide is used in the initial fermentation stage. This creates calcium sulfate (gypsum), a byproduct that has low value. Ammonium hydroxide has been proposed as alternative neutralizing agent to avoid the large amounts of calcium salt that are difcult to dispose. In this case, the byproduct is ammonium sulfate that can be used for soil fertilization providing economic and environmental benets to the process (Clark and Hardy, 2004). This alternative has some disadvantages. For example, ammonium hydroxide produces a less hazardous waste, but handling this chemical is more hazardous for workers than calcium hydroxide. Currently research is being conducted on the reduction of energy consumption and costs in the purication of lactic acid for the production of PLA. Membrane technology appears to be promising but more research is necessary for this approach to become an efcient and economic process (Datta and Henry, 2006; Muralidhara and Satyavolu, 1999). 5.1.3. Use sustainable agriculture methods in growing crops for bioplastics This means eliminating the use of highly hazardous pesticides and fertilizers, as well as ensuring crop diversity, soil

management to enhance quality, efcient water use and many other factors. Water usage for corn crops and for the production of dextrose and lactic acid should be reduced. Occupational hazards should be reduced in farming practices. In addition, transgenic plants and genetically modied seeds should be avoided until information about health and environmental effects is better understood.

5.2. In consumption of bio-based plastics 5.2.1. Educate consumers to change their attitudes. Promote the reuse of materials and look for alternative materials that are more sustainable Reuse of materials and use of paper, glass, aluminum or other substitute materials in applications when they are more sustainable will reduce the consumption of plastic materials, generation of solid wastes and their potential impacts.

5.3. In production of bio-based plastics 5.3.1. Support production of feedstocks that are sustainable If GMO-free feedstocks are not available, participate in programs to offset GMOs by purchasing offsets equivalent to amount of feedstock used in manufacturing. 5.3.2. Prefer materials that generate useful byproducts In PLA production, calcium hydroxide is used in the initial fermentation stage. This creates calcium sulfate (gypsum), a byproduct that has low value. This salt can be substituted with ammonium salts, which will produce ammonium sulfate. This is a higher value byproduct that can be used as a fertilizer, providing economic and environmental benets to the process (Clark and Hardy, 2004). 5.3.3. Research safer additives, co-polymers, and catalysts Safer additives, co-polymers, and other chemicals that can remain in the bio-based material that can be used to meet required performance are needed. Methods of green chemistry and design for the environment (DfE) will be vital in this arena. 5.3.4. Avoid using engineered nanoparticles until their risks are better understood Instead, blend bio-based plastics such as PLA with other polymers from renewable resources like starch, PHAs, or natural bers. 5.3.5. Reduce hazardous exposures to workers in the bioplastics industry Research alternatives to using sulfuric acid and tin catalysts in PLA production; implement safety measures to minimize risk of re hazard from pulverized starch in manufacturing plants; nd safer alternatives for toxic isocyanates in the production of PURs; replace the kraft process to obtain cellulose with a safer process; eliminate the use of carcinogens in biopolymers obtained from proteins. Avoid the use of carcinogens, mutagens, reproductive toxicants (CMRs) during PHA production by utilizing enzymatic methods. 5.3.6. Avoid mixing starch with petroleum-based plastics This reduces biodegradability, whereas a bio-based mixture will likely be compostable. 5.3.7. Use renewable energy Using renewable energy in production of bio-based plastics can reduce environmental impact and manufacturing costs.

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5.3.8. Recycle water Recycling of water in the production process will reduce environmental impact and manufacturing costs. 5.4. At the end of life 5.4.1. Composting/recycling infrastructure Work with governments and municipalities to put in place infrastructure so that bioplastics can be successfully composted and/or recycled and efciently separated from petroleum-based recycling streams. The role of the funding source LCSP had involvement in the study design, in the collection analysis and interpretation of data, in the writing of the report, and in the decision to submit this paper for publication. Acknowledgment This study was funded by the Lowell Center for Sustainable Production (LCSP). University of Massachusetts-Lowell. References
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