Final Report Summary - NANOSAFEPACK (Development of a best practices guide for the safe handling and use of nanoparticles in packaging industries)
Executive Summary:
The main goal of the project is to provide a better understanding of the environmental, health and safety (EHS) issues related to the use of nanofillers across the packaging life cycle, from production to end-of-life, considering proven best practices and measures to ensure the safety of workers and to reduce potential environmental and human health risks at the consumer stage.
To achieve this aim, the scientific activities conducted were focussed on characterization of the specific physicochemical properties and hazard profile of relevant fillers and polymeric matrices to the packaging sector, including layered nano-clays, silver (Ag), silicon dioxide (SiO2), zinc oxide (ZnO), and calcium carbonate (CaCO3) nanoparticles, the evaluation of the likelihood and extent of human exposure to nanofillers in a lifecycle perspective, and the evaluation of the effectiveness of risk and waste management strategies when dealing with submicron sized particles. The results from the scientific activity were compiled into a best practices guide to the safe handling and use of nanofillers in packaging industries. The recommendations included in the guide were validated in terms of economic viability and effectiveness, providing the industry, specially small and medium-sized enterprises (SMEs) and larger companies involved in the manufacture of polymer-based nanocomposites, with a proven tool to ensure the safety of workers and to reduce potential environmental and human health risks at the consumer stage.
The project revealed that the organic modified layered nanoclays (mechanical and barrier properties), metal nanoparticles (especially silver due to its antimicrobial properties), metal oxides (namely SiO2 and ZnO) and inorganic salts such as CaCO3, are the most widely nanofillers used for developing packaging materials.
The toxicological studies revealed that the severity of the hazard of each nano-filler is dependent on the route of exposure and mode of action of the material, but overall, the materials could be ranked as follows: organomodified clays / silver / zinc oxide / silica / calcium carbonate. In contrast, the nanocomposites under investigation demonstrated little or no toxicity to the cell types tested in vitro, in comparison to the native nanofillers. The migration studies concluded that PLA- and PE-based nanocomposites are more likely to release the tested nanofillers to the foodstuff than PP- and PET-based nanocomposites.
The exposure measurement conducted revealed that the activities involving the handling of powdered materials, i.e. the nanofiller feed hopper loading, calibration and cleaning activities, are the most likely to result in the release of respirable-sized materials into the occupational settings. For its part, the evaluation of common prevention measures revealed that the use of FPP3 filtered half mask respirators, laboratory gloves and non-woven protective suits provide medium to high levels of protection against nanomaterials depending of the specific operative conditions and mode of use.
The results from the life cycle assessment conducted suggest a low impact caused by the release of the nanoparticle itself, which is mainly due to the use of additives in higher quantities. It shall be noticed that the results of the LCA showed that the use of ENM can contribute to the overall saving of environmental impact (around -40% in non-toxicity related impact categories) together with raw material savings (-38.320 wt%)
Concerning the applicability of common end-of-life treatments demonstrated that nanoreinforced materials in study are in general compatible with material recycling, energy recovery and organic recycling. Nevertheless, specific constraints are also identified (e.g. quality of the recycled material)
The best practices guide was finally edited in November 2014, being available upon request in pdf. and/or hard copies. Order details can be consulted directly to CEP, APIP and EuPC.
Project Context and Objectives:
The use of nanoparticles in packaging manufacturing is an area with a broad applicability, providing the opportunity to develop new and innovative packaging materials, principally derived from the manufacture of nanocomposites, polymers reinforced with materials and/or particles that have one or more dimensions of the order of 100 nm or less, commonly called nanofillers or nano-reinforcements.
The development of the polymer nanocomposite industry is rapidly emerging and has recently gained momentum in mainstream commercial packaging, particularly in food packaging where the use of nanocomposites is already a reality. The use of nanofillers - which are typically inorganic and organic materials such as metals (Al, Fe, Au, or Ag), metal oxides (ZnO, Al2O3, TiO2), mixed metal oxides, clays, and carbon nanotubes (CNT) - improves the volume properties, surface properties, dimensional stability, chemical stability and other functional properties of the reinforced polymers, conferring photocatalytic, optical, electrical and thermal stability.
Nanofillers can be introduced into polymers at rates ranging from 1 - 10 % (in mass) depending of the type of polymer matrix, which includes thermoset polymer matrices such as polyesters (UP), polyamide, or polyurethane (PUR), and thermoplastics such as polyethylene (PE), polypropylene (PP) and polystyrene (PS).
Nanofiller-reinforced polymers compare favourably with conventional polymers in terms of gas barrier properties, flexibility, temperature/moisture stability etc. Moreover, nanoparticles may serve as means of interaction between food and the environment and can therefore play a dynamic role in food preservation and protection (active and intelligent packaging)
These new properties, and the further development expected in the near future, results in a continuous growth of nanocomposites in the market. Composite materials are rapidly becoming a mainstream technology and material of choice within many industries, expected to reach 19 % of nanotechnology products and applications in global consumer products by 2015. Moreover, the global use of nanocomposite materials is forecasted to grow from nearly 225,000 metric tons in 2014 to almost 585,000 metric tons in 2019, with a market of greater than €3 billion projected by 2019.
Alongside the benefits of nanofillers in packaging applications, there is an on-going debate about the potential effects of nanomaterials on human health and the environment. The uncertainties are exacerbated by the range of properties and their interaction with biological processes, which are often very different from those demonstrated by the larger-scale form of the same substance. It is these differences in the physico-chemical and biological behaviour which results in differences in the potential hazardous properties.
Regarding the risks from occupational exposure to these materials, workers may be exposed to nanomaterials via three main routes: inhalation, ingestion or through skin penetration. The most common potential risk arises from airborne nanoparticles being released into the workplace, inhaled by workers and potentially depositing in the respiratory tract and lungs. Nanomaterials may also be unintentionally ingested via hand-to-mouth transfer or contaminated food or water, where they may potentially cross the gut wall, enter the bloodstream and subsequently reach other parts of the body.
Lastly, the risks from skin penetration are believed to be lower than that of inhalation; the skin does not allow nanomaterials to easily penetrate, although damaged skin may be less protective. Nevertheless, it is highly recommended that simple yet effective measures are taken to prevent or limit releases which may lead to potential inhalation, ingestion and skin contact through implementing risk management procedures.
In addition to worker exposure, releases can also lead to environmental exposure. The scale and nature of industrial processes can inevitably result in fugitive emissions, which may be monitored and regulated, and inconsequential releases of substances used during the manufacturing of packaging materials which find their way into the environment.
Additionally, once placed on the market, the polymers are susceptible to physicochemical factors such as photodegradation or abrasion, such that, NPs imbedded in the polymer may potentially be released into the environment. Such a release might have an effect to the consumers and the environment and present a barrier on their potential uses.
These aspects have a special relevance for the food packaging industry, where it has raised a number of safety, environmental, and regulatory issues. Therefore, the safety issues related to workers and consumers have to be faced prior to the investment in new resources from the SMEs.
In view of the current situation, the project stemmed from the need to ensure the safety of workers dealing with nanofillers and to guarantee the safety of the nanocomposites placed on the market, avoiding endangering consumers’ health and the environment.
The solution and main goal proposed by the NanoSafePack project is the development of a best practices guide to allow the safe handling and use of nanoparticles in packaging industries. This guide is primarily intended for utilisation by small and medium-sized enterprises (SMEs) and larger companies involved in the manufacture of polymer-based nanocomposites for packaging applications, but will also be of value to trade associations related to the packaging industry, regulatory bodies and relevant international organisations such as the European Food Safety Authority (EFSA), the European Agency for Safety and Health at Work (EU-OSHA) and the Organisation for Economic Co-operation and Development (OECD), as well as international standardisation bodies such as the European Committee for Standardization (CEN).
The mail goal of the guide is to provide a better understanding of the environmental, health and safety (EHS) issues related to the use of nanofillers across the packaging life cycle, from production to end-of-life, considering proven best practices and measures to ensure the safety of workers and to reduce potential environmental and human health risks at the consumer stage.
Besides the best practices guide, the following scientific, technical and integrated objectives were foreseen:
1. To identify the specific nanoclays and metal and metal oxide nanoparticles most employed as nanofiller in the packaging industry.
2. To characterize the endpoints listed by the OCDE in relation to the physical-chemical properties and material characterization of the specific nanofillers: this objective is related to the complete characterization of the most important parameters that may influence the toxicological and airborne behaviour of the target nanofillers.
The characterization techniques and methodologies employed within the project are based on the current recommendations and guidelines of the OECD, and specifically in the list of relevant endpoints included on the guidance manual for the testing of manufactured nanomaterials, which was published by the OECD sponsorship programme for the testing of manufactured nanomaterials in 2010.
3. To characterize the toxicological profile of the target nanofillers: this objective is related to the definition of the adverse effects of the target nanofillers to relevant cell lines that represent significant exposure and target organs in the human body, including lung epithelium, gastrointestinal epithelium, skin keratinocytes and hepatocytes.
4. To characterize the ecotoxicological profile of the target nanofillers: this objective is related to the characterization of the uptake potential and toxicity of the target nanofillers in representative aquatic and terrestrial species, including invertebrates and plants. Moreover, a better understanding of the fate and behaviour of the nanofillers in the environment shall be included to contribute to the implementation of regulatory exposure assessment frameworks.
5. To assess the changes induced by the functionalization of the nanofillers in relation to their toxicological and ecotoxicological profile: this objective is related to the definition of the effects of the use of modifiers in the toxicological and ecotoxicological profile of the target Nanofillers.
6. Hazard characterization of nanoreinforcements including functionalizer agents: this objective considers the characterization of the toxicological and ecotoxicological properties of the modified nanofillers.
7. To characterize the toxicity and ecotoxicity of the nanocomposites us such: this objective refers to the definition of the potential adverse effects of the nanocomposites to the human health and the environment, including the generation of new information on the no observed effect levels (NOEL) and sub-lethal concentrations for relevant cell lines and organism from representative environmental compartments.
8. To characterize the exposure to nanoparticles through the development of specific exposure scenarios: this objective refers to the definition of the levels of exposure in the production sites, including the complete definition of the number of particles, average particle diameter and size distribution at different time periods and different stages of the nanocomposites life cycle.
9. To evaluate the effectiveness of common risk management measures against target nanomaterials: this objective includes the experimental characterization of the performance of respiratory and dermal protection equipment, protective clothes, eye protection and engineering controls.
10. To identify the impacts of the target nanomaterials and nanocomposites in the environment considering a life cycle perspective. The specific objectives included are:
- To validate the viability of common end-of-life treatments, including mechanical recycling, energy recovery and compostability.
- To analyse the applicability of the Life Cycle Analysis (LCA) approach to evaluate the impacts of the nanoreinforcements in the life cycle.
11. To develop best practices and recommendations to support the safe handling and use of nanomaterials in packaging industries.
12. To validate the applicability of the best practices guide developed by SMES, including the evaluation of the viability of the solutions proposed in the industrials settings, the characterization of the effectiveness of the risk management measures proposed, and the evaluation of the improvement of the nanocomposite’s safety once applied the best practices referenced on the guide.
The concept of NanosafePACK stems from the need to ensure the safety of workers dealing with nanoparticles and to guarantee the safety of the nanocomposites placed on the market, complying
with the European regulation and avoiding endangering consumers’ health and the environment.
Moreover, significant regulatory concerns from the European Commission have arisen about unforeseen risks likely to arise from nanocomposites, so that, the project worked to provide legislators and industry with new knowledge for appropriate risk management and decision making, creating the basis to meet the current regulation related to the use of nanometer range additives.
Project Results:
The main expected outcome of the project is the publication of the best practices guide for the safe handling and use of nanofillers in packaging industries, including a compendium of proven and technically feasible handling procedures and protection measures able to guarantee the safety of workers dealing with nanoparticles.In detail, the results expected and outlined in the document of work are the following:
1. Publication of the Best Practices guide by December 2014, including hard and electronic copies.
2. A complete description of the adverse effects posed by the use of nanofillers based on the release and migration potential, and the physicochemical, toxicological and ecotoxicological properties of the most common nanofillers and nanocomposites for packaging applications.
3. A complete description of the current exposure scenarios across the nanocomposites life cycle, including an in depth description of the existing operational conditions, efficient RMMs and measured exposure levels.
4. Reliable data on the levels of submicron sized particles released to the environment on a life cycle basis, including a list of estimated release factors to air, surface fresh and marine water, waste water and soil for each relevant stage on the life cycle.
5. New knowledge on the airborne behaviour of the target NMs, including new data on their aggregation/agglomeration patterns and deposition factors under the specific operative and environmental conditions of use presented in the nanocomposites production facilities.
6. A complete description of the effectiveness of common respiratory protective equipment (RPE), skin protective equipment (SPE), protective clothing, and Engineering Controls (LEV systems and filtration) against common nanofillers applied at industrial scale
7. A list of proven end-of-life treatments, including reliable data to demonstrate the applicability of material recycling, energy recovery and organic recycling.
8. A detailed list of recommendations and best practices applicable at industrial scales, considering both economic viability and effectiveness.
9. Organization of three workshops to support the training of end users and stakeholders in the use and implementation of the Best Practices when working with NMs and packaging nanocomposites.
10. On line access to the results of the project, including workshop presentations, conference talks, publishable deliverables, as well as any other public report containing information of the project.
In order to achieve the objetives listed above, the members of the consortium decided to divide the work plan into eight workpackages, which can be grouped into 4 specific activities, including scientific and technological activities, demonstration, management, and dissemination. These activities were organized in the following workpackages:
WP 1. Characterisation of Nanofillers
WP 2. Hazard Assessment
WP 3. Development of Exposure Scenarios
WP 4. Environmental impact of nanocomposites for packaging
WP 5. Development of the Best Practices Guide
WP 6. Field Testing and Validation
WP 7. Project coordination and management
WP 8. Project dissemination
The project started officially on December 1st 2011 and had its kick-off meeting at the CEP-Centro Español de Plásticos offices in Barcelona on January 12, 2012. The most relevant activities performed are the following:
1. Selection of the specific types of nanofillers employed on the packaging industry on basis of their applications and properties addressed by the use in composite materials
2. Characterization of the chemical and physical properties of the target nanofillers that influence their hazard profile by means of specific techniques and following standards protocols.
3. A complete review of literature evaluating the possible biological effects, environmental fate and behaviour of the nanofillers researched in NanoSafePack
4. Human Toxicology studies based on the characterization of the cell viability and cytotoxicity of several representative cell lines in the human body.
5. Ecotoxicity studies based on the evaluation of the toxicity of the target nanofillers in aquatic and terrestrial species. Several acute toxicity tests have been conducted on the crustacean D.magna the microalga P.subcapitata the rotifer B.plicatilis and the earthworm Eisenia fetida.
6. Evaluation of the fate and behaviour of the target nanofillers in the environment by means of a micro-mesocosm study reproducing the environmental conditions of a fresh water ecosystem.
7. Characterization of the migration potential of the target nanofillers in relevant polymeric matrices for the nanocomposite industry: Polypropylene, Polyethylene, Polyethylene terephthalate and Poly-lactic acid.
8. Quantification of the exposure to NPs during the most relevant exposure scenarios encountered during the production and processing of nanofillers.
9. Study of the effectiveness of personal protective equipment (PPE) and engineering controls (EC) against nanoparticles.
10. Evaluation of the environmental impacts related with the production of nanocomposites, including a complete Life Cycle Assessment (LCA) based on relevant impact categories.
11. Development and edition of the NanoSafePack Best Practices Guide.
12. Organization of dedicated workshops in Italy, Spain and Belgium.
12. Dissemination of the project at internatinal level by means of dedicated materials and representation on relevant conferences.
A more detailed explanation of the activities conducted and the most relevant results encountered is provided in the following paragraphs:
WP1. Characterization of the Nano-fillers
Objectives of the WP: since the aim of the NanoSafePACK project is to develop a best practices guide to guarantee the safe handling and use of nanomaterials in packaging industries, an accurate and complete physicochemical characterization of a selected set of nanometer-sized materials relevant to the packaging sector was required. Thus, WP1 focused on two main points:
• Task 1.1. Identification and selection of the nanoclays, metal and metal oxide nanoparticles most widely employed as nanofillers in the packaging industry. The identification was carried out through the study of the polymer nanocomposites placed on the market nowadays, taking into account the further development of the nanotechnology.
• Task 1.2. Full physicochemical characterization of the endpoints listed by the OCDE in terms of size, shape, mass, surface area, chemical composition, physical and optical properties by means of specific techniques such as transmission electron microscopy (TEM), Scanning Electron Microscopy (SEM), FTIR spectroscopy, and physical gas adsorption, among other properties.
Both tasks have been fully accomplished and the corresponding results are described in greater detail in WP deliverable 1.1 and 1.2 respectively.
Significant results
The activities conducted revealed that the organic modified layered nanoclays (for mechanical and barrier properties), metal nanoparticles (especially silver due to its antimicrobial properties), metal oxide nanomaterials (namely SiO2 and ZnO) and inorganic salts such as CaCO3, are the most widely nanofillers used for developing packaging materials.
On the other hand, according with the market reports and the opinion of the industrial partners involved in the project, the polymeric matrices where the use of the target nano-fillers results in improved and functional materials, considering both economic and technical aspects, are: 1)Polypropylene (PP) and Polyethylene (PE): two of the most versatile polymers available with applications, both as a plastic and as a fibre, in virtually all of the plastics end-use markets 2)Polyethylene terephthalate (PET): is a plastic resin widely used for food packaging materials and thermoforming applications, with relevant properties as strength, thermo-stability and transparency. 3)Poly-lactic acid (PLA): biodegradable and compostable aliphatic polyester derived from renewable resources.
The physicochemical characterization reveled that, in most cases, there is a lack of uniformity in terms of crystal size and shape. In addition tested nanofillers tend to aggregate, thus forming agglomerates, as can be observed from electron micrographs. These aggregation/agglomeration processes make difficult to determine the superficial boundary, due to the coalescence phenomenon happened. However, by SEM analysis is possible to know the basic morphology of the samples, as it is possible to visualize the volumetric form of particles. In the case of CaCO3 and Ag nanoparticles, they show a cubic and spherical shape, respectively, whereas the rest of nanofillers exhibit irregular forms. Finally, organically-modified nanoclays, consist on layer-lattice structures, whose dimensions are difficult to determine by these analysis.
The selected nano-fillers exhibited low surface areas (except SiO2) and poor reactivities (tested through photocatalytic activity essays). With regard to pore structure, we appreciated similar pore sizes (greater than 20Å) and absence of microporosity in most of the NPs. These features will not permit the nanomaterials to act as vectors for other contaminants, such as heavy metals.
The analysis of the results revels an enormous variability on the properties of the NPs. Moreover, small changes in the characterization media such as pH or conductivity are able to generate a different response in the measurement devices, with are sensible enough to detect changes in the catalytical activity, surface area or redox potential, all of them endpoints that may influence the effects on human and environment.
WP2. Hazard Assessment
Objectives of the WP: the activities conducted within WP2 have been focused on the determination of the hazards posed by the use of the target nanofillers to workers, consumer and relevant environmental compartments. To this end, several toxicological and ecotoxicological studies were conducted on the basis of the most relevant routes of exposure.
The toxicological evaluation was mainly focused on respiratory toxicity due to the relevance of the inhalatory route in occupational settings. Additional toxicity studies were conducted to evaluate potential adverse effects on human skin and the gastrointestinal tract considering that a significant exposure can also occur from contact with the skin, or via particle ingestion either directly, or through hand-to-mouth contact. Toxicity was investigated using two in vitro cell models of the alveolar region of the lung (respiratory toxicity), two in vitro models of the skin (dermal toxicity), and a further model of the gastrointestinal tract lining (ingestion toxicity).
The assessment of the potential adverse effect on ecosystems were conducted using selected organisms with ecologically relevant sensitivity to toxicants and ecological importance. The organism selected included the freshwater alga P.subcapitata the water flea Daphnia magna and the rotifer Brachionus plicatilis, covering both freshwater an estuarine/marine environments, and higher plants and the earthworm E.fetida representing soil and sediments respectively.
The evaluation of the fate and behaviour of the nanofillers in the environment was conducted using pocket-sized mesocosms reproducing freshwater ecosystems, where the kinetics of aggregation, deposition rates on sediments and the uptake ratio by microorganism of selected nanofillers was studied.
Finally,a complete analysis of the migration potential of the selected nanofillers was conducted. The objective of this task was to evaluate the migration potential of the nanofillers studied from the target nanocomposites according with the experimental conditions and procedures established by the Commission Regulation (EU) No. 10/2011 on plastic materials and articles intended to come into contact with food.
Significant results
a) Toxic effects of the target nanofillers on cell lines and target organs
The evidence presented in this study confirmed that the nano-fillers under investigation present differential toxicity, and the overall nature of the hazard will be determined by the organ, or cell-type that the particle interacts with. This is largely dependent on the route of exposure, although consideration should be given to the fact that some nanoparticles may translocate throughout the body and cause harm in organs distant from the initial site of exposure regions.
The results showed that the lung is more sensitive to the presence of the nanofillers than the gut. The cytotoxicity of the nanofillers appeared to be driven by inflammatory responses, and only in a few cases appeared to be driven by oxidative stress. Overall, in terms of in vitro toxicity, the native nanofillers could be ranked as follows: Nanoclay > silver = zinc oxide > silica > calcium carbonate.
The studies conducted in the polymers and nanocomposites under investigation presented little or no toxicity to the cell types tested in vitro, in comparison to the native nanofillers. The lack of toxicity appears mainly to be due to the inability of the nanofillers to interact with the cells after they have been embedded in the polymer matrix. In this case, it should be considered that if the particles are able to break-free from the polymer matrix (e.g. through degradation of the polymer matrix) that the potential for toxicity may increase.
Nanoclay was consistently the most cytotoxic of the materials tested. The size of the particles could be driving some aspects of the nano-filler cytotoxicity, however shape can also play an important role in particle toxicity. Nanoclay particles are platelet shaped, and as such have a large surface area which may lead to greater toxicity. This may not be due to the inherent toxicity of the particle, but may at least partially be due to the presence of toxic compounds bound onto the disproportionately large surface of the particle. For example, the potential effects of contaminating components such as transition metals and other contaminants such as polycyclic aromatic hydrocarbons is well established. The pathogenic effects of exposure to various particles have often been linked to the presence of reactive metals, for example in air pollution.
Both silver and zinc oxide nanoparticles have previously been shown in the scientific literature to induce cytotoxicity in a range of mammalian cell types e.g. which is often attributed to the release of soluble ions into the target cells. This study provides further evidence, that despite the tendency for these nano-fillers to form large agglomerates, effectively taking them out of the nano-size range, cytotoxicity resulting from oxidative stress and inflammatory responses still occurs in several in vitro mammalian model systems. However, two recent in vivo studies have shown that silver nanoparticles do not result in cytotoxicity following inhalation. This reinforces the need to apply in vitro data with caution, before drawing sweeping statements about the hazard potential of materials.
The information presented was gathered entirely from in vitro experiments and it is recommended that these findings are considered as indicative of potential health effects rather than definitive statements of the toxicity of nano-fillers in the human body. In vitro studies are an essential aspect of a holistic, tiered approach to hazard screening and are extremely useful for prediction of health effects, however further investigation should be performed prior to drawing any final conclusions about the toxicity of these materials in humans.
In particular the proposed toxicological profiles of the materials should be validated in vivo or in more advanced in vitro models (e.g. multi-cellular, microfluidics), and the target sites within the body following real-life occupational exposure should be confirmed. However, this study does provide detailed predictive information on the toxicity of the nano-fillers and their impact in a range of cell types from the human body which should enable more accurate development of risk assessment strategies during the production and handling of nano-fillers. It is particularly recommended that measures are taken to prevent or limit releases which may lead to potential inhalation or accidental ingestion, by implementing effective risk management procedures.
b) Ecotoxicity profile
The data retrieved from the tests indicate that silver nanofillers display the highest potential toxicity among the NMs tested. It was observed that the toxicity for key species increases in the following order: Silver> Nanoclays > ZnO >SiO2 > CaCO3. When these nanofillers are embedded into the polymer matrix their ecotoxic effect is reduced substantially. Even when weathered, nanocomposite samples show a behaviour comparable to the virgin polymer, with the exception of polypropylene-silver nanocomposite which still present some toxicity in daphnids.
With more detail, the results showed the following ecotoxicological profiles:
Acute toxicity tests with Daphnia magna: the toxicity of studied nanoparticles can be raked as follows: Ag ˃Nanoclay˃ZnO˃SiO2˃CaCO3˃ Montmorillonite. Estimated EC50 values are quite conforming to values obtained in the literature only for nanoparticles of physicochemical characteristics and assay conditions very similar to the ones studied in Nanosafepack project. That confirms the importance of carrying out a completely characterize physico-chemical parameters of nanoparticles as well as having standardized methods in order of being able to compare toxicity results.
Acute Ecotoxicity on estuarine/marine rotifer Brachionus plicatilis: the estimated EC50 values for each nanoparticle can be ranked as follows: Ag, Nanoclay˃CaCO3˃ZnO˃SiO2-Montmorillonite.
Acute Ecotoxicity on the earthworm Eisenia fetida: the results showed the following toxic order of nanoparticles to earthworm Eisenia foetida:Nanoclay˃Ag˃ZnO˃Montmorillonite˃SiO2.
Organomodified nanoclay (Nanoclay) was the most toxic nanoparticle for earthworms, causing 100% mortality after 48 hours, necrosis and edema. However, unmodified nanoclay only showed 10% of mortality after 72 hours. Such results suggest, as in aquatic organisms ecotoxicological assays, that toxicity of the nanoclay is due to ammonium ions released from organoclay, modified with HDTA.
Ecotoxicity on higher plants: Three plant species have been selected, on the basis of the rapid germination of the seeds and the growth of the roots which allows completing the assays after only 3 days of incubation. Seed germination results showed no important toxic effect of studied nanoparticles in higher plants. Only SiO2 showed a significative 20% of seed germination inhibition in lepidium specie, but no effect in the other two studied higher plants, sorghum and sinapis. ZnO also affected germination of lepidium specie, but only in a 10% of the seeds. In the case of modified and unmodified nanoclay, they showed the same effect on seed germination of the studied plants, causing 10% of inhibition in sorghum seeds.
The results showed the following toxic order of nanoparticles to seed germination of higher plants: SiO2˃ZnO, Montmorillonite, Nanoclay. Ag and CaCO3 did not show toxicity at the studied concentration of 1000ppm.
On the other hand, the most affected higher plant by nanoparticle presence, for both roots and stem growth inhibition, was the monocotyledonous specie, sorghum.
Ecotoxicity on freshwater algae: the freshwater alga Pseudokirchneriella subcapitata was exposed to the most toxic nanoparticles for freshwater organisms. The results showed that the freshwater alga Pseudokirchneriella subcapitata, exhibits inhibition in its growth when exposed to Nanoclay, Ag, ZnO and SiO2 nanomaterials. This effect is significantly higher when ZnO and Nanoclay are dispersed in algal medium, since they can release their constituent ions increasing the bioavailability of highly toxic species to algae, such as Zn2+ and hexadecyltrimethylammonium ions respectively.
The toxicity of Ag nanoparticles against freshwater algae seems to be effectively supressed by their polymer coating. From the 72h-EC50 values obtained the toxicity sequence of target nanoparticles against Pseudokirchneriella subcapitata is: ZnO, Nanoclay>Ag>>SiO2
These results point out that the surface properties of nanomaterials are of essential importance for their environmental behaviour and their interactions with algae.
As started previously, meanwhile nanofillers could present an ecotoxic behavior in the most representative environment organisms, when they are incorporated, encapsulated, in a polymeric matrix, its toxic behavior is modified and reduced.
c) Environmental Fate and Behavior
In the Nanosafepack project we investigated the environmental fate of ZnO and Ag nanofillers after 16 days of exposure in a simplified freshwater ecosystem and the results pointed out that these nanoparticles were able to accumulate in all the introduced groups of organisms and compartments: daphnids, ostracods, phytoplancton, algae and water. Moreover, bioaccumulation was dependent on dosing in almost all the organisms since in treatments Ag and Zn, lower concentrations of the nanoparticles were found at lower concentration of nanoparticles compared with the treatments with higher ones. From these studies it was also stated for further works the necessity of introduce another compartment to be analysed, sediments, as a high amount of nanomaterials was not detectable and it was supposed it had precipitated to the bottom of aquaria. And also dead organisms that could accumulate nanomaterials can be found and analysed in such compartment.
Regarding the fate and environmental behavior of nanocomposites could be observed as, at the studied concentrations, in the case of ZnO nanocomposites, sediment was the most affected compartment, followed by periphyton. It showed that this type of pollution would be especially dangerous for the organisms living in the depths.
When we studied ZnO nanofillers, we observed that the higher amount of zinc was detectable in water followed narrowly by periphyton, and more than a 50% supposed to be in the sediments, when studying nanocomposite, such behavior change as is detectable in water in a lower amount and in a quantity similar to the algae compartment. That can be due to the low density of PET which makes it less available in the water column. Moreover, nanocomposite is also detected, although in a low amount compared to other compartments, in ostracods which live in the bottom of the aquaria. In both cases, accumulation in periphyton was dose dependent.
Also when studying silver nanofillers the higher amount was not detected and supposed to be in sediments and from the detected amount, the higher part was detected in water followed by periphyton and daphnidas. But silver nanocomposite was not detectable in water and it was in algae and daphnia so was more easily removed from water column by algae and daphnids, and probably by finally dead and sedimented daphnids.
On the other hand, in the case of silver nanocomposites, all initially introduced ostracods and part of cladocers died at the beginig of the study which can indicates that such nanocomposite was very degraded when aged, release more easily silver than the other nanocomposites. Moreover, different behavior was observed depending on the studied concentration. Meanwhile higher concentration of nanocomposite caused that more silver was detected in sediments and periphyton, as in the case of ZnO nanocomposite, when studding the least silver nanocomposite concentration, it was observed that Ag tended to accumulate mostly in algae, followed by sediment and periphyton. That could suggest a higher tendency of nanomaterial to agglomerate and precipitate at high concentration, whilst at less concentration it can remains in the water column being accessible to algae, which are able to undertake silver from water. Therefore, as periphyton and algae are primary consumers, the whole food chain could be affected by this problem in the long term.
From such results can be predicted that nanocomposites which suffer greater matrix degradation when exposed to the environment suppose a greater threat because a percentage of nanofiller can be released and be biodisponible in the media and thus potentially cause an ecotoxic effect.
Some preliminary results and conclusions have been obtained from these studies, but further work is required in order to enhance the knowledge regarding the environmental effects on freshwater ecosystems of these nanoparticles and nanocomposites since recent trends indicate an increasing use and thus potential release in the environment and unpredictable effects on freshwaters.
To complement the mesoscosm studies, a series of experimental tests were undertaken as part of the NanoSafePack project to assess the potential for release of nanofillers from polymer-based nanocomposites into a freshwater environment (e.g. rivers, streams, etc.). The most sensitive of the environmental models appears to be those localised to the freshwater compartment (in comparison to estuarine/marine and terrestrial/soil which are less sensitive). The tests sought to identify whether metallic nanofillers are released from the polymer matrix into a model OECD medium representing freshwater over a period of four weeks. As a comparator, the release of native nanofillers directly into the freshwater medium was also measured over time.
The zinc oxide (ZnO) and nanoclay native nanofillers released nearly 15% and 20% of their mass, respectively, into the OECD freshwater medium over the four week period. Only the silver (Ag) nanofiller was found to be more highly soluble, releasing over 65% of its mass over the four weeks. A continuous flow experiment determined that the majority of the Ag released from the nanofiller occurred within the first 24 hours, whereas release from ZnO continued beyond three weeks.
In comparison, the silver nanocomposites (PET+Ag and PP+Ag) appeared to be completely stable, showing no evidence of silver release over the four week period. The zinc oxide nanocomposites, on the other hand, released significant levels of zinc over the four week period, with significantly more zinc released from weathered nanocomposites in comparison to unweathered materials.
Careful consideration should therefore be given to the end-of-life processes that may occur for native nanoclay, silver and zinc oxide nanofillers, as well as zinc nanocomposites, with appropriate risk management and controls in place to minimise exposure to environmental freshwater ecosystems.
More information on the toxic and ecotoxic profile of nanofillers, polymers and nanocomposites are included within deliverables D2.1 and D2.2. and D 2.3.
d) Migration potential
We did not observe migration of metal (Ag NPs) and metal oxide nanoparticles (ZnO and SiO2).In the case of CaCO3, it can be easily transferred to aqueous simulants. Regarding to the nanoclay tested, it can release both hydrated alkali and transition metal cations to ethanol and acetic acid solutions. From these results, we can conclude that PLA and PE based nanocomposites are more likely to release their NPs to the media than PP and PET and thus will have more restrictions on use to be bared in mind when selected as nanocomposite food packaging materials.
WP3. Development of Exposure Scenarios
Objectives of the WP: the aim of exposure assessment work package, WP3, is to provide a better understanding of the potential for exposure to engineered nanoparticles in real situations in order to establish the size and impact of the hazard related with the production of nanocomposites, as well as to define effective measures to reduce or prevent a worker's exposure to a health hazard in the workplace, including respirators, protective clothing, face and eye shields, and other engineering controls.
The RTD performers ITENE and IOM conducted the definition of relevant exposure scenarios in the production, processing and use of nanocomposites (Task 3.1) as well as the quantitative characterization of the exposure to nanoparticles for key scenarios (Task 3.2). Moreover, a complete characterization of the release of nanofillers to the environment due to causes such as mechanical forces, weathering, washing and contact was also conducted.
The last task within the WP 3 was focused on the evaluation of the effectiveness of the current risk management measures, hereinafter RMM, implemented at industrial level. To this end, the RTD performers defined the specific properties or “performance factors” to be studied for the list of RMMs selected, including local exhaustive ventilation and containment systems, respiratory protective equipment (RPE), skin protective equipment (SPE), and protective clothing.
Significant results
The main results obtained within WP 3 are described below:
a) Exposure Characterization
The information retrieved from the scoping visits and literature reviews conclude that NPs are released from the production sites. The results show an increase in the number concentration during the synthesis, as well as during the cleaning of the production sites.
We identified a total of 9 key exposure scenarios, including: synthesis of nanofillers, production of polymer nanocomposites by melt-moulding, handling of powders (weighing operation), blending, grinding of nanocomposite materials, dry Cutting of nanocomposites, nanocomposite shredding, cleaning and maintenance operations.
The handling of pure, non-consolidated nanofillers was considered one of the most critical operations because it involves direct manipulation of the nano-fillers (powder) that can potentially disperse as airborne nano-objects in the workplace. Levels up to 1.6 x 106 particles/cm3 were retrieved from the literature.
The publications addressing the grinding process report large amounts of airborne particles, mostly small pieces of polymer containing nano-fillers. The blending process for its hand results in the release of NPs from the place of blending, generating peaks of nanosized particles in the workplace.
b) Exposure Measurement
Analysis of real-time sampling data (FMPS, CPC and APS) identified consistent releases in particle concentrations within 6-120nm range when sampling directly from the extruder exit. The releases were observed while monitoring both the extrusion of pure polymer and the corresponding extrusion of the polymer with the nanofiller.
It is therefore considered that the increases in particle concentrations are associated with particle emissions from either polymeric-based fumes or from the operation of the extruder in general (hot surfaces) and not from the emission of nanofillers.
The analysis of data gathered from the real-time instruments and the contextual observations during hopper loading, calibration and cleaning activities indicates the potential release of Clay1 particles in the 1- 8mm range, during hopper loading activities and potential release of CaCO3 particles in 120nm-10mm range during hopper cleaning activities. In addition, data analysis suggests the potential release of ZnO particles in the 80nm- 3µm range during hopper cleaning activities and potential Ag release between 100nm and 6µm during loading, calibration and cleaning activities. Data analysis is currently being undertaken for the SiO2 nanofiller.
The analysis of samples collected using the Nano-ID provided clear evidence that particles from the lower density nanofillers (clay1, CaCO3 and SiO2) are being emitted into the workplace air environment. The particles are migrating out of the containment envelope afforded by the extruder extraction system with materials being detected in the open laboratory, most noticeably towards the work station next to the extruder.
On the other hand, the analysis of overnight filter samples (adjacent to the work station) provided evidence of the presence of lower density nanofillers (clay1, CaCO3 and SiO2) and ZnO in the workplace environment.
Evidence of all the nanofillers apart from Ag, was found in the background overnight sample prior to any activities taking place. This suggests that there is potential persistence of lower density nanofillers and ZnO in the lab airspace overnight.
Similarly, analysis of background far-field filter samples (far-field location approximately 5 m away from the extruder) confirmed the presence of lower density nanofillers (clay1, CaCO3 and SiO2) in the general laboratory environment. Metal analysis of background gravimetric filters supports the far-field filter sampling SEM –EDXS analysis as Al, Mg, Si and Zn metals were detected in far field samples. This suggests that particles are migrating out of the containment envelope afforded by the extruder extraction system with materials being detected 5 m away from the activity.
Standard filter sampling with a respirable head of each of the hopper loading activities readily identified the presence of clay, SiO2, CaCO3 and ZnO particles in excess of 10-20mm within the respirable (filter head) range (d50<4mm).
Based on the observations made during the exposure measurement visit, it is anticipated that the activities involving the handling of powdered materials, i.e. the nanofiller feed hopper loading, calibration and cleaning activities, are the most likely to result in the release of respirable-sized materials into the laboratory environment.
In summary, from the observations made during the exposure monitoring exercise, it is evident there is a potential for release of nanofiller materials from processes and practical steps are required for controlling exposure to respirable particles such as platelets. Powder handling activities such as nanofiller hopper loading, calibration of the feed rate to the extruder and hopper cleaning activities, were identified as the source of emission where existing control measures and practices were not seen to be sufficient in mitigating a release.
At this time there remains a lack of definitive workplace studies reported in the literature with regards to adverse health effects in workers producing or using these products, and so their occupational health effects is not established clearly. However enough uncertainty remains regarding their hazardous nature, based on toxicology and other general considerations of the mechanisms of inhaled particles, that it is important to limit workers’ exposure, and various guidance documents have been published to help people work safely with these products.
c) Evaluation of the effectiveness of Personal Protective Equipment
The results showed significant differences in the penetration factor for the measures studied. Average penetration levels for respirators were between 15 and 1 %, with a minimum penetration level for the FPP3 Half Mask Respirator of 2 %. The penetration factors for dermal protection equipment and protective clothes were very low, meaning that gloves, suits and coats are effective enough. In the case of laboratory hoods and containment systems, the measurements conducted at the researcher’s breathing zone under different situations and movements (low, middle, high) reported a low quantity of NPs released . The Containment factors (Cf) calculated where very high in all the cases studies.
Established milestones for this period of time in WP 3 have been successfully accomplished.
WP4. Life Cycle Assessment
The work within WP4 has been focused on the set up of the scope of the LCA of nanomaterials and nanoparticles. An exhaustive review on current LCA’s related to nanomaterials has been carried out together with an analysis of the analogies between Risk Assessment (RA) and Life Cycle Assessment (LCA) methodologies.
A special focus has been made in case of Human Toxicity and Ecotoxicity impact assessment categories, since most of the impacts of nanoparticles and nanomaterials are related to toxicity effects. Models for impact assessment of such impact categories in LCA have been analyzed including the models for fate, exposure and severity of the damage.
The impact assessment conducted focussed on the relevant environmental categories, including: climate change, cumulative energy demand, eutrophication, acidification, ozone depletion, photochemical ozone creation potential, and ecotoxicity for freshwater. The methodology applied was based on the use of LCA together with ecotoxicity analysis. The ecotoxicity impacts were based on measured data retrieved from the project (WP 2), as well as on the use of the USEtox™ method (Rosenbaum et al. 2008), a modelling approach accepted to evaluate the severity of the damage posed by nanomaterials in the environment.
To complement the LCA studies, an experimental evaluation of the applicability of common end-of-life treatments to nanocomposite-based packaging waste was completed. The treatments studied included mechanical recycling, incineration and composting.
Significant results
a) Environmental impact assessment:
The analysis of the results retrieved form the LCA studies did not show significant environmental impacts during the production and processing of nanomaterials.
The data suggest a low impact caused by the release of the nanoparticle itself, which is mainly due to the use of additives in higher quantities. It shall be noticed that the results of the LCA showed that the use of ENM can contribute to the overall saving of environmental impact (around -40% in non-toxicity related impact categories) together with raw material savings (-38.320 wt%).
The Life Cycle Assessment of nanomaterials and nanoparticles is still a research question for discussion. The quick development of such materials requires a scientifically sound assessment of their potential environmental impacts vs. the advantages provided.
LCA is a perfect tool to perform such assessment as the life cycle thinking approach will ensure that impacts are not transferred from one life cycle stage to each other. Furthermore, the impacts on Human Toxicity and Ecotoxicity are also a research question still under discussion. With the combined step-wise approach based on scenarios as well as on exposure routes at each life cycle stage we intend to build a link within RA practice and LCA practice which allow a suitable assessment and fair effort on the impact assessment of nanomaterials and nanoparticles.
b) Nanomaterials waste management alternatives
The results on energy recovery shows that the materials studied within NanoSafePack (PET-ZnO, PET-Ag, PET-Nanoclay1, PE-CaCO3, PE-Nanoclay1 and PP-Ag) are aligned with the requirements established in the standard ISO 18605:2013 in terms of organic content, inferior calorific value and compatibility with the process of energy recovery.
In relation to material recycling, the results showed that for PE and PP, in general terms and except for some minor variations in yellowness index, tensile modulus, tensile strength and tear strength (PE with Nanoclay1, PP with Ag), the introduction of NMs in the recycling streams for plastic films does not affect the final recycled plastic material quality.
In the case of PET, results show that the increasing addition of NMs into the recycled PET matrix (especially PET-Ag) could influence important properties of the recycled material, due to a slight degradation of the polymer, such as increasing pinholes and degradation fumes. Colour deviations were visible in most of the samples (PE, PP and PET) in levels higher than 0.3 units (limit perceivable by the human eye
Regarding the energy recovery, an analysis has been performed with the aim of evaluating the extent to which nanocomposites are suitable for energy recovery. As can be seen in Table 23, all the materials studied in the Nanosafepack project meet the requirements.
Finally, in terms of organic recycling, the results demonstrated that the incorporation of NMs in a PLA matrix did not generally affect the compostability of the resulting films. Disintegration was completed in less than 7 weeks in a simulated composting environment. Moreover, no differences were observed in the evolution of the bioresidue with respect to color, aspect, and odor. Only samples incorporating PLA-Nanoclay1 and PLA-CaCO3 reached the 90% required in the standard.
No ecotoxic effects were observed as a result of the incorporation of nanoparticles in the PLA matrix, except for high proportions of compost where sample PLA-Nanoclay1 disintegrated were tested
In relation with the deliverables, the final results of the WP4 have been compiled within Deliverables. Furthermore milestones MS8 and MS9 have also been reached.
WP5. Development of the Best Practices Guide
Objectives of the WP: the purpose of this work package is principally the development of the best practices guide to the safe handling and use of nanomaterials in packaging industries. The preparation of the guide was conducted in three main stages:
• Task 5.1. Design of the best practice structure and contents
• Task 5.2. Integration of the project results into the guide
• Task 5.2. Drawing up of the guide and edition of electronic and hard copies
A first draft of the contents and structure or the best practices guide was agreed among partners during the second general assembly meeting. The development of the guide was conducted after the evaluation of the results encountered in the scientific work packages, being completed by September 2014 (Month 34).
The development of the first version of the guide was conducted by the RTD performers ITENE and IOM, in charge of the experimental activities. The results achieved and activities conducted in each WP were analysed in detail by ITENE and IOM on the basis of the scope of the chapters included into the guide, and taking into account the data of interest for both SMEs and SME Associations.
ITENE and IOM selected those information and results of major interest considering the needs of the industry, and considering mainly the data on the physicochemical, toxicological and ecotoxicological properties of the target nanofillers, data on the exposure, release and migration potential, and data on the environmental impact on a life cycle basis. These activities were all covered under task 5.2.
The drawing up of the guide as such was conducted under task 5.3. The preparation of the best practices requires high expertise in different areas of knowledge, therefore it was decided to split the preparation of the guide among partners considering their area of expertise.
The RTD performers were in charge of the scientific chapters of the guide (chapters 5 to 7), while the SME Associations were in charge of the definition of the packaging life cycle under chapter 4, and chapters 8 to 9, where an in depth analysis of current laws, regulations and standards related with the packaging industry was conducted. CEP, as SME Association, was in charge of the graphic-design and format of the guide.
For its part, the Plasper and SME provided inputs to chapters 1 to 3 related to the application and use of nanofillers in the packaging industry, and chapter 10 to 12, where a compilation of frequently asked questions, cases studies and best practices recommendations was included. Both companies were also involved in the selection of images to support the illustration of the guide.
The drafting of each chapter was scheduled during the general assembly meeting hold in Lisbon in December 2014. A non-academic language was used to support the interpretation of the guide by SMEs. The SME Associations, Tecni-Plasper and Tec Star analysed the contents of the guide carefully to ensure the applicability of the guide by the industry.
The first edition of the guide was finally completed by month 34. Once checked, a second version including new contents and images was developed. This second version was fully analysed by the whole consortium, being finally edited in November 2014.
The guide was edited in two main formats, including a copy-protected copy in USB and a hard copy in paper, available upon request.
Significant Results
The full version of the Best Practices Guide developed contains 12 chapters intended to provide the packaging industry with guidance to support the safe handling and use of nanofillers in the packaging industry. This includes technical information concerning the specific applications and properties of nanofillers, as well as new scientific knowledge on environmental, health, and safety issues.
Provided below is an outline of the structure of the Guide and key contents of each chapter.
1. Introduction and vision
This chapter outlines the purpose and scope of the guide, defines the target audience, and provides an introduction to nanotechnology in the packaging industry.
2. Types and applications of nanomaterials in the packaging industry
2.1. Nanotechnology and packaging: current and future applications
2.2. Types & specific applications of nanomaterials in polymer composites
2.3. Environment, health and safety issues of nanofillers in packaging applications
This chapter details the specific types of nanoparticles currently employed in the packaging industry as nanofillers, provides information on current and future applications and developments, and introduces the potential hazards associated with these nanomaterials.
3. General approach to managing risks from nanoparticles
3.1. Nanomaterial hazard, exposure and risk
3.2. Risk evaluation and management strategy
3.3. Roles and responsibilities of employers and workers
3.4. Good company practice
This chapter provides an overview of the basic principles of risk assessment and risk management for nanoparticles, and outlines a risk evaluation and management strategy for implementation as part of an overall company strategy for the management of health and safety.
4. Overview of the packaging lifecycle
This chapter provides an overview of the lifecycle of packaging materials, detailing the main activities and tasks involved across the various stages of the packaging lifecycle, including nanomaterial synthesis, manufacture of intermediate and final packaging products, use & service life, and end of life processing & disposal.
5. Safety during the manufacture of packaging products
5.1. Nature of the work
5.2. Exposure-prone activities
5.3. Risk management measures
5.4. Potential effects on human & environmental health and safety
5.5. Nature of use in the service life stage
5.6. Health and safety issues during the service life stage.
This chapter provides specific guidance on safe handling and use for those working in the manufacturing stage of the packaging industry. This includes identification of activities with the highest potential for exposure to nanoparticles, recommended risk management measures to minimise worker exposure, and information on potential human and environmental health effects. This chapter also addresses the service life stage, providing information on the types of consumer products produced using polymer-based nanocomposites, and an overview of health and safety issues related to consumer use.
6. Safety during end-of-life processing and disposal
6.1. Nature of processing and disposal
6.2. Exposure-prone activities
6.3. Risk management measures
6.4. Potential effects on human & environmental health and safety
This chapter provides specific guidance on safe handling and use for those working in the end of life processing and disposal stange of the packaging industry. This includes information on the main processing and disposal routes for nano-enabled packaging and identification of the main exposure prone tasks for workers during mechanical recycling processes. Guidance is provided on risk management measures to minimise potential exposure and an overview of potential effects on human and environmental health and sagety provided.
7. Risk communication
7.1. Importance of risk communication
7.2. Informing and protecting workers/emplyees during manufacture of the packaging product
7.3. Informing and protecting professional usersfurther down the supply chain
7.4. Informing and protecting consumers
This chapter highlights the importance of effective risk communication down the pacakgin supply chain and provides guidance in relation to informing and protecting workers, professional users and consumers. This includes guidance on the development and implementation of material safety data sheets, workplace hazard signs, nanomaterial and consumer product labelling
8. Laws, regulation and obligations of European packaging industry
8.1. Overview of key regulatory instruments
8.2. Substances and products
8.3. Product safety and quality
8.4. Worker protection
8.5. End of life and environment
8.6. Reporting schemes
8.7. Goof practice for regulatory compliance and governance
This chapter provides an overview of the key European regulations and legislation of relevance to those working in the packaging industry. This includes the provision of advice for regulatory compliance with the laws concerning substances and products, product sagety and quality, worker and environment protection, end of life waste management as well as nanomaterials reporting schemes.
9. Standards and guidance to support safe development
This chapter provides an overview of key standards and published guidance documents of relevance for nanotechnologies in the packaging industry, including from ISO, CEN, BSI and OECD which can be used in combination with the Best Practice Guide to support the safe development of polymer-based nanocomposites and packaging applications.
10. Best practice recommendations
This chapter provides a summary of best practice recommendations to support the safe handling and use of nanoparticles in packaging industries
11. Case studies
This chapter provides three case studies which demonstrate the application of best practice during the synthesis of nanocomposites for packaging applications at laboratory-scale, pilot-scale and industrial-scale.
12. Frequently asked questions
This chapter provides a selection of FAQs pertinent to the packaging industry in relation to safe handling and use of nanofillers, linking back to further information in the earlier chapters of the guide.
Work package five´s milestone, MS10. Best practices guide developed, was finally achieved last October 2014, month 35.
Task 6.2. Validation of Risk Management Measures
The second action conduced was focused on the selection of adequate risk management measures to control and/or mitigate the exposure to airborne nanoparticles considering the operational conditions and risk management measures that are commonly applied at industrial scale in the packaging industry.
The study conducted was focused on the analysis and evaluation of the applicability of the measures proposed in the best practices guide developed, including including LEV systems, filtration, respiratory protective equipment (RPE), skin protective equipment (SPE), and safety goggles.
The validation study included the experimental evaluation of the concentration of airborne nanoparticles in case studies after the application of selected measures, as well as the compilation of the opinions of a representative number of companies concerning the applicability of the proposed measures. In addition, expertise staff from the research organizations compared the risk characterization ratios (RCR) calculated before the use of the recommended RMM and procedures and after their implementation, comparing the results in terms risk bands or particle concentration.
The list of tasks covered in the validation studies is depicted below:
- Handling of small amounts of nanofillers in research laboratories
- Preparation of mixtures at laboratory scale, including weighting and mixing operations
- Bagging of small amounts of nanofillers / filling small containers (< 500 mg).
- Melt-Compounding at pilot scale, including hopper feeding and extrusion
- Reception of materials in large scale facilities
- Cleaning and maintenance operations
- Mechanical recycling by plastic converters
These tasks were complemented with a complete analysis of the accuracy of the models developed to predict the release of nanofillers from polymers (Task 6.3) and the validation of the quality and applicability of the best practices guide developed within WP 5 (Task 6.4).
The validation of the applicability of the best practices guide as such was conducted before the edition of the final version. The SME Association sent a complete draft of the guide to a sample of representative SMEs, joinly with a specific questioner custom designed to evaluate the applicability of the best practices and procedures described within the guide.
Significant Results
- Viability: the cost- effective analysis (CEA) conducted showed that the higher cost of the nanofillers is counterbalanced as only relatively small amounts (2–5%) of nanofillers are needed. Similarly, the market studied performed showed that polymer nanocomposite packaging materials are relatively inexpensive to manufacture, so numerous companies have already made them available. On the other hand, the implementation of effective risk management measures results in an increase of the indirect cost of the process, especially the use of safety cabinets and local exhaustive ventilation.
As key result, although the manufacturing cost of nanocomposites is currently higher due to still greater price of fillers at nanoscale and the needed extra risk control measures for environmental and worker safety assurance, the analysis shows potential benefits in reducing energy use, required raw materials amount for the same functionalities, and environment discharges by using a nanocomposite design.
- Validation of Risk Management Measures: the analysis showed that workers are most likely to be exposed to nanomaterials during the synthesis and handling of unbound nanomaterials and during the compounding stage. Therefore the analysis on the use of risk management measures was focused on synthesis and compounding.
Based on the findings, the use of LEVs in combination with PPEs and good practices can ensure a high level of protection for both workers and the environment. However risk evaluation performed by expert staff is highly recommended in order to evaluate the risk levels in workplaces. In addition, similarly to chemicals industry, employers should review regularly the effectiveness and adequacy of the risk management measures that are put in place especially in the cases where substances or conditions have changed.
The selection of the risk management measures may vary depending on the type of processes and a series of parameters such as the amount and type of nanomaterials, rate or production, workroom volume, work environment factors (temperature and humidity) etc. Examples of risk management measures and their most appropriate use are provided in deliverable D6.2.
On the basis the outcomes from the project, and information retrieved from published guidelines and scientific articles, the use of good laboratory/good workplace practices, including adequate information and training for workers, and the use of properly designed local exhaust ventilation (LEV) systems will reduce the concentration of airborne NPs to safe levels. It´s also highly recommended the use of FPP3/N100 respirators, non-woven Tyvek/Tychem polyethylene overalls and chemical protective gloves when handling nanofillers.
- Effectiveness of predictions on particle migration and release: currently, there are few available studies about the release of ENMs from nano-based consumer products. According to Froggett S.J. (2014), an examination of the International Council of Nanotechnology (ICON) environmental and health literature database and other search engines indicated that a considerable attention has been directed toward examining intrinsic hazards (83%) of nanomaterials, and less on potential exposure (16%) and least on release of nanomaterials from nanocomposite (0.8%). The authors stated however that based on the results of their literature review, the understanding of release from nanocomposite is gradually receiving more attention.
A literature review was conducted within the context of NanoSafepack which concluded that nanomaterials can be released during the service life of nanocomposite products under certain circumstances. However in the most of the cases the released nanomaterials were mainly matrix particles alone or matrix particles with protruding nanofillers. Very few studies were able to identify dissociated ENMs and therefore based on the current knowledge nanocomposite materials cannot be associated with higher release rates in comparison to conventional materials.
Furthermore it should be added that most of the studies were focused on applications where mechanical forces, weathering or other causes that could lead to release of nanofillers are likely. However all of them are unlikely during the consumer-use of packaging materials and as a matter of fact no studies could be found addressing the release issue during the use of packaging.
Nevertheless, release of nanofillers can be a crucial aspect during the industrial use of nanocomposite materals. The mechanical forces and temperature during the extrusion of compounded pellets can be a source of release.
Regarding migration, based on the analysis performed as part of the NanoSafePack project, factors that may influence the migration potential of nanofillers to the contained product are virtually the same as the ones that influence the release (polymer matrix characteristics, nanofiller characteristics, environmental conditions etc,). Migration can be a result of matrix degradation which in turn can be triggered by mechanical stress, UV light, fire etc.
In relation to the modelling approached, currently available models are based on the physicochemical properties of substances in bulk forms, especially the mass transfer coefficients (Cf) implemented. The results of the comparison between measured and estimates data showed a general overestimation of the migration and release of fillers.
To reduce the uncertainty, the release index applied in NanoSafePAck were calculated using a probabilistic MCMC approach (Monte Carlo – Markov Chain), highly recommended in the literature. This method calculates the probability of the release on the basis of the quantity of materials used and the effectiveness of the RMMs applied, supporting the definition of a reliable release ratio.
- Valuation of the best practices guide: as stated previously, the evaluation and validation of the best practices guide was done by asking potential users to provide feedback through a questionnaire. The questionnaire consisted of 8 questions that aimed to capture the overall impression of the user.
The opinions compiled from surveys demonstrated that the contents of the guide are adequate to support the safe handling and use of nanofillers. most of the respondents stated that the recommendations in the guide are useful and more importantly, applicable.
Work package six´s milestone, MS11. Demonstration activities in industrial facilities completed, was scheduled for being achieved by month 34, being finally completed by month 36, November 2016.
Potential Impact:
Analysis of the Impact of the project
a) Background information
The novel properties offered by the use of nanofillers in packaging materials has resulted in a continuous growth in the market, principally derived from the manufacture of nanocomposites - polymers reinforced with particles that have one or more dimensions of the order of 100 nanometers (nm) or less. The use of nanofillers opens an opportunity for developing innovative and high performance packaging materials. Applications include nano‐filler reinforced packaging (e.g. enhanced barrier properties), active packaging (e.g. antimicrobial), intelligent packaging (e.g. freshness indicators), and biodegradable packaging.
Along with the foreseen benefits and market opportunities , there is an on-going debate about the potential effects of nanomaterials and nano-enabled products on human health and the environment . In this sense, while research on developing new nanocomposite materials has prolific for more than a decade, research aiming to improve the understanding of the health and environmental impacts arising from the manufacture and commercialization of nanocomposites is far less advanced, with a particular concern related with the potential adverse effects of the common nanofillers on workers and consumers.
Given this situation, there is an urgent need to provide the industry with reliable information on the specifications of the nanofillers that can be used as nano-additives in compounding process, as data on the toxicological and ecotoxicological profile of nanofillers and polymer-nanofiller combiantions, and information on the likelihood of human exposure to nanofillers in a lifecycle perspective.
The goal of the project is therefore aligned with the needs of the industry. In these sense, the project have a strong impact in the nanocomposites value chain, providing the producers of nanomaterials and nanocomposites, as well as downstream users of nanomaterials, with a scientific based guide in support of decision making when selecting nanofillers and adequate risk management measures to control and/or mitigate the exposure to nanofillers at all stages of the life cycle.
The development of the Best Practice Guide was informed by research activities undertaken as part ofthe project, which included a complete hazard and exposure assessment to obtain new scientific data about the safety of polymer composites reinforced using nanometer-sized particles, an evaluation of the effectiveness of risk management measures, and a life cycle assessment of nanocomposites to evaluate impacts during manufacture, use and disposal.
In view of the above, the FP 7 project NanoSafePACK have a remarkable impact on the European SME Community and their citizens, clearly identifiable due to the hundreds of applications of the nanocomposite materials every day and the hundreds of people who use them.
It’s expected a direct impact in the packaging and polymer nanocomposite industry, helping the SME to develop new innovative materials, which provide the end users with new products tailored to their needs. On the other hand, as can be derived from the followings paragraphs, the implementation of the project results will enable the packaging and plastic associations , their members and other SMEs across Europe minimise the health impact and environmental risk from the nanofillerts, providing the information to safely design, manufacture and market nanotechnology enable products.
Besides the above, NanoSafePack will also be of value to trade associations related to the packaging industry, regulatory bodies and relevant international organisations such as the European Food Safety Authority (EFSA), the European Agency for Safety and Health at Work (EU-OSHA) and the Organisation for Economic Co-operation and Development (OECD), as well as international standardisation bodies such as the European Committee for Standardization (CEN).
b) Impact on the Industry
Composite materials are rapidly becoming a mainstream technology and material of choice within many industries, expected to reach 19% of nanotechnology products and applications in global consumer products by 2015.
In Europe, packaging applications are the largest application sector for the plastics industry and represent 39.4% of the total plastics demand (45.9 Mtonnes), followed by the building and construction sector. It is also anticipated that the packaging sector will become one of the major end-user industry segments where nanocomposites are used for a variety of applications.Thus a better understanding of the nanofillers’ properties and applications, health, safety and environmental protection and regulatory requirements, are all key aspects to promote the use of nanotechnologies in the European industry
Moreover, the improvement in the safety of the production process and the development of safe and eco-friendly nanocomposites will improve the business opportunities of the European nanocomposites industry, promoting the opening of new business lines based on the use of nanofillers and/or the commercialization of nano-enabled products.
The project promotes the investment in new nanostructured products, being expected to dominate the market and remain widely employed in large-volume markets. In addition, the project provides valuable information to limit the cost related with the use of nanofillers and the production of nanotechnology based products. Furthermore, improved worker and consumer safety have obvious economic benefits for the EU with respect to healthcare provision.
On the other hand, the improvement in the safety of the production process and the fulfilment of a key European regulation such as the regulation on Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH) will improve the business opportunities of those SMEs affected by REACH provisions, with special emphasis in those that handle or manufacture substances at the nanometre scale, as is the case of nanocomposites manufacturers. In fact, The EC recognizes that compliance with Health & Safety directives will play a key role in promoting economic growth and employment in the EU but also realizes that the costs of compliance for SMEs are high, then, the definition of effective protection and prevention measures will minimize the costs to control the risks during the production process, supporting at the same time the economic growth of the SME and their competitiveness.
It shall be noticed that the cost of REACH implementation could reach up to €3.2 billion to the chemicals industry and €2.8–3.6 billion to downstream users. In this sense, NanoSafePack will support the European industry to reduce cost derived from the investment on low-efficiency engineering techniques, and saving money due to the reduction in the insurance premium.
Moreover, improved worker and consumer safety have obvious economic benefits for the EU with
respect to healthcare provision. In this sense, several studies describe business benefits in terms of
savings related to occupational health due to the proven efficiency of the control measures for protecting workers from the risks related to chemical agents.
c) Social impact
Beyond the toxicity risks to human health and the environment which are associated with firstgeneration nanomaterials, nanotechnology has broader societal implications and poses broader
social challenges. In this sense, NanoSafePAck tries to meet social objectives in term of nanotechnology application, principally in terms of safety and health related to the use and commercialization of nanotechnology based products.
The contribution of the project to the safety of the workers and nanocomposites placed on the market will improve the approbation of this kind of products into the society as well as a better image of the new technologies, ensuring the commercialization in the near future. The expected benefits in terms of product quality, safety and environmental respect, will be key issues to accept the changes towards the new nanostructured products, which will be better accepted by the consumers.
Simultaneously, the participation of enterprises in the project implementation and the direct application by the members of the SME associations will help in the dissemination of the project results, providing the industrial stakeholders and the general public with appropriate knowledge to successfully control the risks posed by the use of nanomaterials, as well as with new information to perform a complete risk assessment on the basis of REACH regulation.
c) Impact on EU policies
The project explored legal and policy issues, as well as scientific and technical issues, that might arise in the application of the regulatory process related to the use of NMs at the workplace. At this stage, the project results provide a better understanding of the risk to the human health and the environment of nanofillers and nanocomposites, supporting regulatory bodies with scientific data to establish new legal requirements to the use of NMs in the nanocomposite industry in particular and other nanotechnology fields in general.
The project is aligned with the considerations expressed by the European Parliament resolution of 24 April 2009 on regulatory aspects of NMs, which explains that the use of NMs should respond to the real needs of citizens and that their benefits should be realized in a safe and responsible manner,
considering the potential EHS problems.
Research activities are ongoing under the Research Framework Programmes and the Joint Research
Centre, as well as in EU Member States and internationally within the OECD Working Party on MNMs
and the International Organization for Standardisation. According to the Europe 2020 strategy, one of the strategic goals will be ensuring the safe development and application of nanotechnologies by
advancing scientific knowledge of the potential impact of nanotechnologies on health or on the environment, and providing tools for risk assessment and management along the entire life cycle.
In this sense, the future needs may include identifying and demonstrating the effectiveness of containment technologies for safe handling of NMs through the life cycle, investigating the effectiveness of different work practices for human and environmental exposure mitigation, and strengthening current research on the toxicological and ecotoxicological profile of nanofillers already applied at industrial level.
The project is in line with the research areas underpinning risk assessments and management in which new knowledge is more needed, bringing value to the European development of risk management knowledge by the identification of proven measures and controls to reduce exposure
to NMs during its entire life cycle.
The project have also a strong impact onthe International Standardization since it works on the development of methods for testing RMM against NMs by evaluating the adequacy of the published
harmonized Standards from ISO, CEN, BSI and ASTM, and adapting them to the specific NM properties. In addition, the development of the project has generated new reliable information to be implemented in the current European legislation, considering different stages of the NMs life cycle.
In relation to the nanocomposites safety and consumer health, the project has contributed to the establishment of an overall migration limit (OML) in case of food contact materials, where the nanoparticles are incorporated. In addition, the project has generated new data to support the definition of new provisions and specific restrictions added to the current European and National provisions.
c) Impact on environmental protection
In relation to the environmental impact, the project will promote the development of environmentally benign polymer nanocomposites. The market for worldwide polymer nanocomposites is expected to grow at an average annual rate of 18.4 percent, therefore, NanoSafePAck will allow continued growth in the composite industries without compromising the global environment.
The implementation of efficient procedures to control the exposure and the choice of more efficient techniques will improve the environmental safety, minimizing the release to the environment of nanoparticles with potential ecotoxic effects. In fact, the implementation of new and tested risk management measures improves the effectiveness of the spill control system and the minimization of the release of nanofillers to the environment during the manufacturing process. Simultaneously, the selection of effcientie risk management measures ensure a high level of protection to the environment, and provides new knowledge to the development of new Best Available Techniques (BATs) to prevent pollution, considering both the manufacturing plants of engineered nanoparticles and the industrial settings where the nanoparticles, to be included into the polymeric matrix, are processed.
Beside the above, the outcomes from the release has provided a better understanding of the fate of the nanoparticles in their service life, generating nee reliable data on the potential release of nanoparticles during the their use and disposal.
Finally, the application of a life cycle assessment approach has been essential for the improvement of the current knowledge about resource and energy consumption, emissions and their impact, providing a useful insight about nanocomposites, as well as a proxy for the toxicological and ecotoxicological impact due to the emissions.
In summary, the implementation of the recommendations, procedures and technologies exposed in the best practice guide, the industry will be able to comply with the current regulation in terms of environmental protection, product and worker safety, manufacturing innovative and sustainable composites materials without endanger the human health and the environment and becoming cost competitive with the present and growing threat posed by the Far East.
Dissemiantion activities and foreground generated
a) Dissemination
The dissemination activities were performed through various instruments and media. These have been carefully selected for facilitating collaboration among involved parties. The first activity completed was the design and selection of the project logo. The project web site was published last November 2012, being accessible via the internet site www.nanosafepack.eu.
Regarding the main dissemination materials, classical print media (brochure and poster) have been produced to be freely circulated for project information and promotion at workshops, trade shows, technical fairs, congresses and other events. The electronic version of these materials is downloadable from the website. Several press releases were published by the consortium members with the aim of communicate the goal and scope of the project.
Finally, the project results and contents have been disseminated in several international conferences. In detail, the dissemination activities conducted have been the following:
i) Presence at trade shows and conferences across Europe, including;
- 1srt QNano Integrating Conference. Dublin (Ireland) - 03.2012
- International Packaging Trade Fair “Salón internacional del embalaje” Hispack 2012. Barcelona (Spain) - 05.2012
- Safe Implementation of Nanotechnologies: Common Challenges. Grenoble (France) - 05.2012
- 2nd QNano Integrating Conference.Prague (Czech Republic) - 02.2013
- Los riesgos con los nanomateriales, su relación con el reglamento REACH. Valencia (Spain)- 06.2013
- Euronanoforum 2013. Dublin (Ireland) - 06.2013
- 8th International Conference on the Environmental Effects of NP. Aix-en-Provence, (France)- 07.2013
- NanoSafety Cluster meeting. Birmingham (UK) - 09.2013
- CEP Innova. Barcelona (Spain) - 11.2013
- XXVIII Plastics Seminar. Figueira da Foz (Portugal) - 11.2013
- 1 st National Meeting on Nanotechnology: Regulate to Compete”. Caparica (Portugal) - 04.2011
- International Conference on Aerosol Technology 2014.Karlsruhe (Germany)- 06.2014
- Nanosafe 2014, held from 18-20 November 2014 in Grenoble (France)
ii) Workshops
According with the Document of Work, three specific workshops were organized with the aim of disseminate the best practices guide developed within the project. These workshops were organized by the members of the consortium under the framework of relevant events. In detail, the workshops organized were the following:
- 1st NanoSafePack Workshop during the LET'S 2014 conference (Leading Enabling Technologies for Societal Challenges 2014). Bolognia (Italy) – September 2014
- 2nd NanoSafePack Workshop. Technical Conference of Plastics Additives – Barcelona (Spain) – October 2014
- Final Dissemination Workshop – EuPC facilities. Brussel – November 2014
b) Foreground
The exploitable foreground of the project was anticipated in the DoW, including only the best practices guide for the safe handling and use of nanomaterials. This guide will be owned by the SMEs Associations, which will distribute the guide for their members at a special cost, including either pdf or printed formats.
In addition, the foreground was analysed in depth by the project partners, inditying new relevant results to be consideres as part of the foreground. . The list of exploitable results (foreground) identified are depicted below:
Result 1: Data on the physicochemical and (eco)toxicological properties of the target nanoparticles
Generated by: ITENE / IOM
Use: Free use by consortium members upon request
IPR Strategy: Non-protected
Exploitation potential: To be used by Tec Star as part of the Safety data sheets (SDS)
This result will be exploit by Tec Star and Tecni-Plasper. The data can be requested to the data owners, who will give access to the data without delay. The data owners will use the data to publish scientific papers and prepare conferences after the communication and approval of the whole consortium.
Result 2: Library of exposure scenarios containing information on the operative conditions and risk management measures
Generated by: ITENE / IOM
Use: Free use by consortium members upon request
IPR Strategy: Non-protected
Exploitation potential: To be used by Tec Star as part of the Safety data sheets (SDS)
This result will be exploit by Plasper and Tec Star. The data can be requested to the data owners, who will give access to the data without delay. The data owners will use the data to publish scientific papers and prepare conferences after the communication and approval of the whole consortium.
Result 3. Designs and specifications of new RPE (Respiratory Protection Equipment) and ventilation systems
Generated by: ITENE
Use: Restricted to consortium
IPR Strategy: Trade Secret
Exploitation potential: Potential commercial agreement with RPE manufacturers – License agreement
ITENE, data owner, will negotiate a license agreement with EU manufactures, transferring the specifications to SMEs or Large Companies interested in the commercialization of proven risk management measures against ENMs.
Result 4. Best Practices Guide
Generated by: EuPC / CEP / APIP
Use: SME Associations will be able to establish a market price to the best practices guide in order to commercialize the guide to others stakeholders
IPR Strategy: author rights - ISBN
Exploitation potential: Free commercialization by SME Associations
The best practices guide developed will be exploited directly by the SME Associations CEP, APIP and EuPC. The RTD performers won´t benefint from the guide. The SME Associtions will stablish a market price according with their bussines plans
List of Websites:
NanoSafePack project web site: www.nanosafepack.eu
Relevant Contacts:
Jose Luis Romero, Project Coordinator
Tecni-Plasper S.L. Pol.Ind.Font de la Parera.
C/Bonaventura Aribau s/n. La Roca del Vallés (Spain)
E-mail: JoseLuis.Romero@plasper.com
Angel Lozano, Director
CEP - Centro Español de Plásticos
Enrique Granados, 101. Barcelona
E-mail: alozano@cep-plasticos.es
Website: www.cep-plasticos.com
Isabel Ferreira da Costa, Director
APIP - Associação Portuguesa da Indústria de Plásticos
Edifício Libersil - Torre B. Rua de S. José. 35 - 2º C. Lisboa
E-mail: isabelfcosta@apip.pt
Website: www.apip.pt
Maria Estela Izquierdo
European Plastics Converters
Avenue de Cortenbergh 71. Brussels, Belgium
E-mail: Maria.Estela.Izquierdo@eupc.org
Website: www.plasticsconverters.eu
The main goal of the project is to provide a better understanding of the environmental, health and safety (EHS) issues related to the use of nanofillers across the packaging life cycle, from production to end-of-life, considering proven best practices and measures to ensure the safety of workers and to reduce potential environmental and human health risks at the consumer stage.
To achieve this aim, the scientific activities conducted were focussed on characterization of the specific physicochemical properties and hazard profile of relevant fillers and polymeric matrices to the packaging sector, including layered nano-clays, silver (Ag), silicon dioxide (SiO2), zinc oxide (ZnO), and calcium carbonate (CaCO3) nanoparticles, the evaluation of the likelihood and extent of human exposure to nanofillers in a lifecycle perspective, and the evaluation of the effectiveness of risk and waste management strategies when dealing with submicron sized particles. The results from the scientific activity were compiled into a best practices guide to the safe handling and use of nanofillers in packaging industries. The recommendations included in the guide were validated in terms of economic viability and effectiveness, providing the industry, specially small and medium-sized enterprises (SMEs) and larger companies involved in the manufacture of polymer-based nanocomposites, with a proven tool to ensure the safety of workers and to reduce potential environmental and human health risks at the consumer stage.
The project revealed that the organic modified layered nanoclays (mechanical and barrier properties), metal nanoparticles (especially silver due to its antimicrobial properties), metal oxides (namely SiO2 and ZnO) and inorganic salts such as CaCO3, are the most widely nanofillers used for developing packaging materials.
The toxicological studies revealed that the severity of the hazard of each nano-filler is dependent on the route of exposure and mode of action of the material, but overall, the materials could be ranked as follows: organomodified clays / silver / zinc oxide / silica / calcium carbonate. In contrast, the nanocomposites under investigation demonstrated little or no toxicity to the cell types tested in vitro, in comparison to the native nanofillers. The migration studies concluded that PLA- and PE-based nanocomposites are more likely to release the tested nanofillers to the foodstuff than PP- and PET-based nanocomposites.
The exposure measurement conducted revealed that the activities involving the handling of powdered materials, i.e. the nanofiller feed hopper loading, calibration and cleaning activities, are the most likely to result in the release of respirable-sized materials into the occupational settings. For its part, the evaluation of common prevention measures revealed that the use of FPP3 filtered half mask respirators, laboratory gloves and non-woven protective suits provide medium to high levels of protection against nanomaterials depending of the specific operative conditions and mode of use.
The results from the life cycle assessment conducted suggest a low impact caused by the release of the nanoparticle itself, which is mainly due to the use of additives in higher quantities. It shall be noticed that the results of the LCA showed that the use of ENM can contribute to the overall saving of environmental impact (around -40% in non-toxicity related impact categories) together with raw material savings (-38.320 wt%)
Concerning the applicability of common end-of-life treatments demonstrated that nanoreinforced materials in study are in general compatible with material recycling, energy recovery and organic recycling. Nevertheless, specific constraints are also identified (e.g. quality of the recycled material)
The best practices guide was finally edited in November 2014, being available upon request in pdf. and/or hard copies. Order details can be consulted directly to CEP, APIP and EuPC.
Project Context and Objectives:
The use of nanoparticles in packaging manufacturing is an area with a broad applicability, providing the opportunity to develop new and innovative packaging materials, principally derived from the manufacture of nanocomposites, polymers reinforced with materials and/or particles that have one or more dimensions of the order of 100 nm or less, commonly called nanofillers or nano-reinforcements.
The development of the polymer nanocomposite industry is rapidly emerging and has recently gained momentum in mainstream commercial packaging, particularly in food packaging where the use of nanocomposites is already a reality. The use of nanofillers - which are typically inorganic and organic materials such as metals (Al, Fe, Au, or Ag), metal oxides (ZnO, Al2O3, TiO2), mixed metal oxides, clays, and carbon nanotubes (CNT) - improves the volume properties, surface properties, dimensional stability, chemical stability and other functional properties of the reinforced polymers, conferring photocatalytic, optical, electrical and thermal stability.
Nanofillers can be introduced into polymers at rates ranging from 1 - 10 % (in mass) depending of the type of polymer matrix, which includes thermoset polymer matrices such as polyesters (UP), polyamide, or polyurethane (PUR), and thermoplastics such as polyethylene (PE), polypropylene (PP) and polystyrene (PS).
Nanofiller-reinforced polymers compare favourably with conventional polymers in terms of gas barrier properties, flexibility, temperature/moisture stability etc. Moreover, nanoparticles may serve as means of interaction between food and the environment and can therefore play a dynamic role in food preservation and protection (active and intelligent packaging)
These new properties, and the further development expected in the near future, results in a continuous growth of nanocomposites in the market. Composite materials are rapidly becoming a mainstream technology and material of choice within many industries, expected to reach 19 % of nanotechnology products and applications in global consumer products by 2015. Moreover, the global use of nanocomposite materials is forecasted to grow from nearly 225,000 metric tons in 2014 to almost 585,000 metric tons in 2019, with a market of greater than €3 billion projected by 2019.
Alongside the benefits of nanofillers in packaging applications, there is an on-going debate about the potential effects of nanomaterials on human health and the environment. The uncertainties are exacerbated by the range of properties and their interaction with biological processes, which are often very different from those demonstrated by the larger-scale form of the same substance. It is these differences in the physico-chemical and biological behaviour which results in differences in the potential hazardous properties.
Regarding the risks from occupational exposure to these materials, workers may be exposed to nanomaterials via three main routes: inhalation, ingestion or through skin penetration. The most common potential risk arises from airborne nanoparticles being released into the workplace, inhaled by workers and potentially depositing in the respiratory tract and lungs. Nanomaterials may also be unintentionally ingested via hand-to-mouth transfer or contaminated food or water, where they may potentially cross the gut wall, enter the bloodstream and subsequently reach other parts of the body.
Lastly, the risks from skin penetration are believed to be lower than that of inhalation; the skin does not allow nanomaterials to easily penetrate, although damaged skin may be less protective. Nevertheless, it is highly recommended that simple yet effective measures are taken to prevent or limit releases which may lead to potential inhalation, ingestion and skin contact through implementing risk management procedures.
In addition to worker exposure, releases can also lead to environmental exposure. The scale and nature of industrial processes can inevitably result in fugitive emissions, which may be monitored and regulated, and inconsequential releases of substances used during the manufacturing of packaging materials which find their way into the environment.
Additionally, once placed on the market, the polymers are susceptible to physicochemical factors such as photodegradation or abrasion, such that, NPs imbedded in the polymer may potentially be released into the environment. Such a release might have an effect to the consumers and the environment and present a barrier on their potential uses.
These aspects have a special relevance for the food packaging industry, where it has raised a number of safety, environmental, and regulatory issues. Therefore, the safety issues related to workers and consumers have to be faced prior to the investment in new resources from the SMEs.
In view of the current situation, the project stemmed from the need to ensure the safety of workers dealing with nanofillers and to guarantee the safety of the nanocomposites placed on the market, avoiding endangering consumers’ health and the environment.
The solution and main goal proposed by the NanoSafePack project is the development of a best practices guide to allow the safe handling and use of nanoparticles in packaging industries. This guide is primarily intended for utilisation by small and medium-sized enterprises (SMEs) and larger companies involved in the manufacture of polymer-based nanocomposites for packaging applications, but will also be of value to trade associations related to the packaging industry, regulatory bodies and relevant international organisations such as the European Food Safety Authority (EFSA), the European Agency for Safety and Health at Work (EU-OSHA) and the Organisation for Economic Co-operation and Development (OECD), as well as international standardisation bodies such as the European Committee for Standardization (CEN).
The mail goal of the guide is to provide a better understanding of the environmental, health and safety (EHS) issues related to the use of nanofillers across the packaging life cycle, from production to end-of-life, considering proven best practices and measures to ensure the safety of workers and to reduce potential environmental and human health risks at the consumer stage.
Besides the best practices guide, the following scientific, technical and integrated objectives were foreseen:
1. To identify the specific nanoclays and metal and metal oxide nanoparticles most employed as nanofiller in the packaging industry.
2. To characterize the endpoints listed by the OCDE in relation to the physical-chemical properties and material characterization of the specific nanofillers: this objective is related to the complete characterization of the most important parameters that may influence the toxicological and airborne behaviour of the target nanofillers.
The characterization techniques and methodologies employed within the project are based on the current recommendations and guidelines of the OECD, and specifically in the list of relevant endpoints included on the guidance manual for the testing of manufactured nanomaterials, which was published by the OECD sponsorship programme for the testing of manufactured nanomaterials in 2010.
3. To characterize the toxicological profile of the target nanofillers: this objective is related to the definition of the adverse effects of the target nanofillers to relevant cell lines that represent significant exposure and target organs in the human body, including lung epithelium, gastrointestinal epithelium, skin keratinocytes and hepatocytes.
4. To characterize the ecotoxicological profile of the target nanofillers: this objective is related to the characterization of the uptake potential and toxicity of the target nanofillers in representative aquatic and terrestrial species, including invertebrates and plants. Moreover, a better understanding of the fate and behaviour of the nanofillers in the environment shall be included to contribute to the implementation of regulatory exposure assessment frameworks.
5. To assess the changes induced by the functionalization of the nanofillers in relation to their toxicological and ecotoxicological profile: this objective is related to the definition of the effects of the use of modifiers in the toxicological and ecotoxicological profile of the target Nanofillers.
6. Hazard characterization of nanoreinforcements including functionalizer agents: this objective considers the characterization of the toxicological and ecotoxicological properties of the modified nanofillers.
7. To characterize the toxicity and ecotoxicity of the nanocomposites us such: this objective refers to the definition of the potential adverse effects of the nanocomposites to the human health and the environment, including the generation of new information on the no observed effect levels (NOEL) and sub-lethal concentrations for relevant cell lines and organism from representative environmental compartments.
8. To characterize the exposure to nanoparticles through the development of specific exposure scenarios: this objective refers to the definition of the levels of exposure in the production sites, including the complete definition of the number of particles, average particle diameter and size distribution at different time periods and different stages of the nanocomposites life cycle.
9. To evaluate the effectiveness of common risk management measures against target nanomaterials: this objective includes the experimental characterization of the performance of respiratory and dermal protection equipment, protective clothes, eye protection and engineering controls.
10. To identify the impacts of the target nanomaterials and nanocomposites in the environment considering a life cycle perspective. The specific objectives included are:
- To validate the viability of common end-of-life treatments, including mechanical recycling, energy recovery and compostability.
- To analyse the applicability of the Life Cycle Analysis (LCA) approach to evaluate the impacts of the nanoreinforcements in the life cycle.
11. To develop best practices and recommendations to support the safe handling and use of nanomaterials in packaging industries.
12. To validate the applicability of the best practices guide developed by SMES, including the evaluation of the viability of the solutions proposed in the industrials settings, the characterization of the effectiveness of the risk management measures proposed, and the evaluation of the improvement of the nanocomposite’s safety once applied the best practices referenced on the guide.
The concept of NanosafePACK stems from the need to ensure the safety of workers dealing with nanoparticles and to guarantee the safety of the nanocomposites placed on the market, complying
with the European regulation and avoiding endangering consumers’ health and the environment.
Moreover, significant regulatory concerns from the European Commission have arisen about unforeseen risks likely to arise from nanocomposites, so that, the project worked to provide legislators and industry with new knowledge for appropriate risk management and decision making, creating the basis to meet the current regulation related to the use of nanometer range additives.
Project Results:
The main expected outcome of the project is the publication of the best practices guide for the safe handling and use of nanofillers in packaging industries, including a compendium of proven and technically feasible handling procedures and protection measures able to guarantee the safety of workers dealing with nanoparticles.In detail, the results expected and outlined in the document of work are the following:
1. Publication of the Best Practices guide by December 2014, including hard and electronic copies.
2. A complete description of the adverse effects posed by the use of nanofillers based on the release and migration potential, and the physicochemical, toxicological and ecotoxicological properties of the most common nanofillers and nanocomposites for packaging applications.
3. A complete description of the current exposure scenarios across the nanocomposites life cycle, including an in depth description of the existing operational conditions, efficient RMMs and measured exposure levels.
4. Reliable data on the levels of submicron sized particles released to the environment on a life cycle basis, including a list of estimated release factors to air, surface fresh and marine water, waste water and soil for each relevant stage on the life cycle.
5. New knowledge on the airborne behaviour of the target NMs, including new data on their aggregation/agglomeration patterns and deposition factors under the specific operative and environmental conditions of use presented in the nanocomposites production facilities.
6. A complete description of the effectiveness of common respiratory protective equipment (RPE), skin protective equipment (SPE), protective clothing, and Engineering Controls (LEV systems and filtration) against common nanofillers applied at industrial scale
7. A list of proven end-of-life treatments, including reliable data to demonstrate the applicability of material recycling, energy recovery and organic recycling.
8. A detailed list of recommendations and best practices applicable at industrial scales, considering both economic viability and effectiveness.
9. Organization of three workshops to support the training of end users and stakeholders in the use and implementation of the Best Practices when working with NMs and packaging nanocomposites.
10. On line access to the results of the project, including workshop presentations, conference talks, publishable deliverables, as well as any other public report containing information of the project.
In order to achieve the objetives listed above, the members of the consortium decided to divide the work plan into eight workpackages, which can be grouped into 4 specific activities, including scientific and technological activities, demonstration, management, and dissemination. These activities were organized in the following workpackages:
WP 1. Characterisation of Nanofillers
WP 2. Hazard Assessment
WP 3. Development of Exposure Scenarios
WP 4. Environmental impact of nanocomposites for packaging
WP 5. Development of the Best Practices Guide
WP 6. Field Testing and Validation
WP 7. Project coordination and management
WP 8. Project dissemination
The project started officially on December 1st 2011 and had its kick-off meeting at the CEP-Centro Español de Plásticos offices in Barcelona on January 12, 2012. The most relevant activities performed are the following:
1. Selection of the specific types of nanofillers employed on the packaging industry on basis of their applications and properties addressed by the use in composite materials
2. Characterization of the chemical and physical properties of the target nanofillers that influence their hazard profile by means of specific techniques and following standards protocols.
3. A complete review of literature evaluating the possible biological effects, environmental fate and behaviour of the nanofillers researched in NanoSafePack
4. Human Toxicology studies based on the characterization of the cell viability and cytotoxicity of several representative cell lines in the human body.
5. Ecotoxicity studies based on the evaluation of the toxicity of the target nanofillers in aquatic and terrestrial species. Several acute toxicity tests have been conducted on the crustacean D.magna the microalga P.subcapitata the rotifer B.plicatilis and the earthworm Eisenia fetida.
6. Evaluation of the fate and behaviour of the target nanofillers in the environment by means of a micro-mesocosm study reproducing the environmental conditions of a fresh water ecosystem.
7. Characterization of the migration potential of the target nanofillers in relevant polymeric matrices for the nanocomposite industry: Polypropylene, Polyethylene, Polyethylene terephthalate and Poly-lactic acid.
8. Quantification of the exposure to NPs during the most relevant exposure scenarios encountered during the production and processing of nanofillers.
9. Study of the effectiveness of personal protective equipment (PPE) and engineering controls (EC) against nanoparticles.
10. Evaluation of the environmental impacts related with the production of nanocomposites, including a complete Life Cycle Assessment (LCA) based on relevant impact categories.
11. Development and edition of the NanoSafePack Best Practices Guide.
12. Organization of dedicated workshops in Italy, Spain and Belgium.
12. Dissemination of the project at internatinal level by means of dedicated materials and representation on relevant conferences.
A more detailed explanation of the activities conducted and the most relevant results encountered is provided in the following paragraphs:
WP1. Characterization of the Nano-fillers
Objectives of the WP: since the aim of the NanoSafePACK project is to develop a best practices guide to guarantee the safe handling and use of nanomaterials in packaging industries, an accurate and complete physicochemical characterization of a selected set of nanometer-sized materials relevant to the packaging sector was required. Thus, WP1 focused on two main points:
• Task 1.1. Identification and selection of the nanoclays, metal and metal oxide nanoparticles most widely employed as nanofillers in the packaging industry. The identification was carried out through the study of the polymer nanocomposites placed on the market nowadays, taking into account the further development of the nanotechnology.
• Task 1.2. Full physicochemical characterization of the endpoints listed by the OCDE in terms of size, shape, mass, surface area, chemical composition, physical and optical properties by means of specific techniques such as transmission electron microscopy (TEM), Scanning Electron Microscopy (SEM), FTIR spectroscopy, and physical gas adsorption, among other properties.
Both tasks have been fully accomplished and the corresponding results are described in greater detail in WP deliverable 1.1 and 1.2 respectively.
Significant results
The activities conducted revealed that the organic modified layered nanoclays (for mechanical and barrier properties), metal nanoparticles (especially silver due to its antimicrobial properties), metal oxide nanomaterials (namely SiO2 and ZnO) and inorganic salts such as CaCO3, are the most widely nanofillers used for developing packaging materials.
On the other hand, according with the market reports and the opinion of the industrial partners involved in the project, the polymeric matrices where the use of the target nano-fillers results in improved and functional materials, considering both economic and technical aspects, are: 1)Polypropylene (PP) and Polyethylene (PE): two of the most versatile polymers available with applications, both as a plastic and as a fibre, in virtually all of the plastics end-use markets 2)Polyethylene terephthalate (PET): is a plastic resin widely used for food packaging materials and thermoforming applications, with relevant properties as strength, thermo-stability and transparency. 3)Poly-lactic acid (PLA): biodegradable and compostable aliphatic polyester derived from renewable resources.
The physicochemical characterization reveled that, in most cases, there is a lack of uniformity in terms of crystal size and shape. In addition tested nanofillers tend to aggregate, thus forming agglomerates, as can be observed from electron micrographs. These aggregation/agglomeration processes make difficult to determine the superficial boundary, due to the coalescence phenomenon happened. However, by SEM analysis is possible to know the basic morphology of the samples, as it is possible to visualize the volumetric form of particles. In the case of CaCO3 and Ag nanoparticles, they show a cubic and spherical shape, respectively, whereas the rest of nanofillers exhibit irregular forms. Finally, organically-modified nanoclays, consist on layer-lattice structures, whose dimensions are difficult to determine by these analysis.
The selected nano-fillers exhibited low surface areas (except SiO2) and poor reactivities (tested through photocatalytic activity essays). With regard to pore structure, we appreciated similar pore sizes (greater than 20Å) and absence of microporosity in most of the NPs. These features will not permit the nanomaterials to act as vectors for other contaminants, such as heavy metals.
The analysis of the results revels an enormous variability on the properties of the NPs. Moreover, small changes in the characterization media such as pH or conductivity are able to generate a different response in the measurement devices, with are sensible enough to detect changes in the catalytical activity, surface area or redox potential, all of them endpoints that may influence the effects on human and environment.
WP2. Hazard Assessment
Objectives of the WP: the activities conducted within WP2 have been focused on the determination of the hazards posed by the use of the target nanofillers to workers, consumer and relevant environmental compartments. To this end, several toxicological and ecotoxicological studies were conducted on the basis of the most relevant routes of exposure.
The toxicological evaluation was mainly focused on respiratory toxicity due to the relevance of the inhalatory route in occupational settings. Additional toxicity studies were conducted to evaluate potential adverse effects on human skin and the gastrointestinal tract considering that a significant exposure can also occur from contact with the skin, or via particle ingestion either directly, or through hand-to-mouth contact. Toxicity was investigated using two in vitro cell models of the alveolar region of the lung (respiratory toxicity), two in vitro models of the skin (dermal toxicity), and a further model of the gastrointestinal tract lining (ingestion toxicity).
The assessment of the potential adverse effect on ecosystems were conducted using selected organisms with ecologically relevant sensitivity to toxicants and ecological importance. The organism selected included the freshwater alga P.subcapitata the water flea Daphnia magna and the rotifer Brachionus plicatilis, covering both freshwater an estuarine/marine environments, and higher plants and the earthworm E.fetida representing soil and sediments respectively.
The evaluation of the fate and behaviour of the nanofillers in the environment was conducted using pocket-sized mesocosms reproducing freshwater ecosystems, where the kinetics of aggregation, deposition rates on sediments and the uptake ratio by microorganism of selected nanofillers was studied.
Finally,a complete analysis of the migration potential of the selected nanofillers was conducted. The objective of this task was to evaluate the migration potential of the nanofillers studied from the target nanocomposites according with the experimental conditions and procedures established by the Commission Regulation (EU) No. 10/2011 on plastic materials and articles intended to come into contact with food.
Significant results
a) Toxic effects of the target nanofillers on cell lines and target organs
The evidence presented in this study confirmed that the nano-fillers under investigation present differential toxicity, and the overall nature of the hazard will be determined by the organ, or cell-type that the particle interacts with. This is largely dependent on the route of exposure, although consideration should be given to the fact that some nanoparticles may translocate throughout the body and cause harm in organs distant from the initial site of exposure regions.
The results showed that the lung is more sensitive to the presence of the nanofillers than the gut. The cytotoxicity of the nanofillers appeared to be driven by inflammatory responses, and only in a few cases appeared to be driven by oxidative stress. Overall, in terms of in vitro toxicity, the native nanofillers could be ranked as follows: Nanoclay > silver = zinc oxide > silica > calcium carbonate.
The studies conducted in the polymers and nanocomposites under investigation presented little or no toxicity to the cell types tested in vitro, in comparison to the native nanofillers. The lack of toxicity appears mainly to be due to the inability of the nanofillers to interact with the cells after they have been embedded in the polymer matrix. In this case, it should be considered that if the particles are able to break-free from the polymer matrix (e.g. through degradation of the polymer matrix) that the potential for toxicity may increase.
Nanoclay was consistently the most cytotoxic of the materials tested. The size of the particles could be driving some aspects of the nano-filler cytotoxicity, however shape can also play an important role in particle toxicity. Nanoclay particles are platelet shaped, and as such have a large surface area which may lead to greater toxicity. This may not be due to the inherent toxicity of the particle, but may at least partially be due to the presence of toxic compounds bound onto the disproportionately large surface of the particle. For example, the potential effects of contaminating components such as transition metals and other contaminants such as polycyclic aromatic hydrocarbons is well established. The pathogenic effects of exposure to various particles have often been linked to the presence of reactive metals, for example in air pollution.
Both silver and zinc oxide nanoparticles have previously been shown in the scientific literature to induce cytotoxicity in a range of mammalian cell types e.g. which is often attributed to the release of soluble ions into the target cells. This study provides further evidence, that despite the tendency for these nano-fillers to form large agglomerates, effectively taking them out of the nano-size range, cytotoxicity resulting from oxidative stress and inflammatory responses still occurs in several in vitro mammalian model systems. However, two recent in vivo studies have shown that silver nanoparticles do not result in cytotoxicity following inhalation. This reinforces the need to apply in vitro data with caution, before drawing sweeping statements about the hazard potential of materials.
The information presented was gathered entirely from in vitro experiments and it is recommended that these findings are considered as indicative of potential health effects rather than definitive statements of the toxicity of nano-fillers in the human body. In vitro studies are an essential aspect of a holistic, tiered approach to hazard screening and are extremely useful for prediction of health effects, however further investigation should be performed prior to drawing any final conclusions about the toxicity of these materials in humans.
In particular the proposed toxicological profiles of the materials should be validated in vivo or in more advanced in vitro models (e.g. multi-cellular, microfluidics), and the target sites within the body following real-life occupational exposure should be confirmed. However, this study does provide detailed predictive information on the toxicity of the nano-fillers and their impact in a range of cell types from the human body which should enable more accurate development of risk assessment strategies during the production and handling of nano-fillers. It is particularly recommended that measures are taken to prevent or limit releases which may lead to potential inhalation or accidental ingestion, by implementing effective risk management procedures.
b) Ecotoxicity profile
The data retrieved from the tests indicate that silver nanofillers display the highest potential toxicity among the NMs tested. It was observed that the toxicity for key species increases in the following order: Silver> Nanoclays > ZnO >SiO2 > CaCO3. When these nanofillers are embedded into the polymer matrix their ecotoxic effect is reduced substantially. Even when weathered, nanocomposite samples show a behaviour comparable to the virgin polymer, with the exception of polypropylene-silver nanocomposite which still present some toxicity in daphnids.
With more detail, the results showed the following ecotoxicological profiles:
Acute toxicity tests with Daphnia magna: the toxicity of studied nanoparticles can be raked as follows: Ag ˃Nanoclay˃ZnO˃SiO2˃CaCO3˃ Montmorillonite. Estimated EC50 values are quite conforming to values obtained in the literature only for nanoparticles of physicochemical characteristics and assay conditions very similar to the ones studied in Nanosafepack project. That confirms the importance of carrying out a completely characterize physico-chemical parameters of nanoparticles as well as having standardized methods in order of being able to compare toxicity results.
Acute Ecotoxicity on estuarine/marine rotifer Brachionus plicatilis: the estimated EC50 values for each nanoparticle can be ranked as follows: Ag, Nanoclay˃CaCO3˃ZnO˃SiO2-Montmorillonite.
Acute Ecotoxicity on the earthworm Eisenia fetida: the results showed the following toxic order of nanoparticles to earthworm Eisenia foetida:Nanoclay˃Ag˃ZnO˃Montmorillonite˃SiO2.
Organomodified nanoclay (Nanoclay) was the most toxic nanoparticle for earthworms, causing 100% mortality after 48 hours, necrosis and edema. However, unmodified nanoclay only showed 10% of mortality after 72 hours. Such results suggest, as in aquatic organisms ecotoxicological assays, that toxicity of the nanoclay is due to ammonium ions released from organoclay, modified with HDTA.
Ecotoxicity on higher plants: Three plant species have been selected, on the basis of the rapid germination of the seeds and the growth of the roots which allows completing the assays after only 3 days of incubation. Seed germination results showed no important toxic effect of studied nanoparticles in higher plants. Only SiO2 showed a significative 20% of seed germination inhibition in lepidium specie, but no effect in the other two studied higher plants, sorghum and sinapis. ZnO also affected germination of lepidium specie, but only in a 10% of the seeds. In the case of modified and unmodified nanoclay, they showed the same effect on seed germination of the studied plants, causing 10% of inhibition in sorghum seeds.
The results showed the following toxic order of nanoparticles to seed germination of higher plants: SiO2˃ZnO, Montmorillonite, Nanoclay. Ag and CaCO3 did not show toxicity at the studied concentration of 1000ppm.
On the other hand, the most affected higher plant by nanoparticle presence, for both roots and stem growth inhibition, was the monocotyledonous specie, sorghum.
Ecotoxicity on freshwater algae: the freshwater alga Pseudokirchneriella subcapitata was exposed to the most toxic nanoparticles for freshwater organisms. The results showed that the freshwater alga Pseudokirchneriella subcapitata, exhibits inhibition in its growth when exposed to Nanoclay, Ag, ZnO and SiO2 nanomaterials. This effect is significantly higher when ZnO and Nanoclay are dispersed in algal medium, since they can release their constituent ions increasing the bioavailability of highly toxic species to algae, such as Zn2+ and hexadecyltrimethylammonium ions respectively.
The toxicity of Ag nanoparticles against freshwater algae seems to be effectively supressed by their polymer coating. From the 72h-EC50 values obtained the toxicity sequence of target nanoparticles against Pseudokirchneriella subcapitata is: ZnO, Nanoclay>Ag>>SiO2
These results point out that the surface properties of nanomaterials are of essential importance for their environmental behaviour and their interactions with algae.
As started previously, meanwhile nanofillers could present an ecotoxic behavior in the most representative environment organisms, when they are incorporated, encapsulated, in a polymeric matrix, its toxic behavior is modified and reduced.
c) Environmental Fate and Behavior
In the Nanosafepack project we investigated the environmental fate of ZnO and Ag nanofillers after 16 days of exposure in a simplified freshwater ecosystem and the results pointed out that these nanoparticles were able to accumulate in all the introduced groups of organisms and compartments: daphnids, ostracods, phytoplancton, algae and water. Moreover, bioaccumulation was dependent on dosing in almost all the organisms since in treatments Ag and Zn, lower concentrations of the nanoparticles were found at lower concentration of nanoparticles compared with the treatments with higher ones. From these studies it was also stated for further works the necessity of introduce another compartment to be analysed, sediments, as a high amount of nanomaterials was not detectable and it was supposed it had precipitated to the bottom of aquaria. And also dead organisms that could accumulate nanomaterials can be found and analysed in such compartment.
Regarding the fate and environmental behavior of nanocomposites could be observed as, at the studied concentrations, in the case of ZnO nanocomposites, sediment was the most affected compartment, followed by periphyton. It showed that this type of pollution would be especially dangerous for the organisms living in the depths.
When we studied ZnO nanofillers, we observed that the higher amount of zinc was detectable in water followed narrowly by periphyton, and more than a 50% supposed to be in the sediments, when studying nanocomposite, such behavior change as is detectable in water in a lower amount and in a quantity similar to the algae compartment. That can be due to the low density of PET which makes it less available in the water column. Moreover, nanocomposite is also detected, although in a low amount compared to other compartments, in ostracods which live in the bottom of the aquaria. In both cases, accumulation in periphyton was dose dependent.
Also when studying silver nanofillers the higher amount was not detected and supposed to be in sediments and from the detected amount, the higher part was detected in water followed by periphyton and daphnidas. But silver nanocomposite was not detectable in water and it was in algae and daphnia so was more easily removed from water column by algae and daphnids, and probably by finally dead and sedimented daphnids.
On the other hand, in the case of silver nanocomposites, all initially introduced ostracods and part of cladocers died at the beginig of the study which can indicates that such nanocomposite was very degraded when aged, release more easily silver than the other nanocomposites. Moreover, different behavior was observed depending on the studied concentration. Meanwhile higher concentration of nanocomposite caused that more silver was detected in sediments and periphyton, as in the case of ZnO nanocomposite, when studding the least silver nanocomposite concentration, it was observed that Ag tended to accumulate mostly in algae, followed by sediment and periphyton. That could suggest a higher tendency of nanomaterial to agglomerate and precipitate at high concentration, whilst at less concentration it can remains in the water column being accessible to algae, which are able to undertake silver from water. Therefore, as periphyton and algae are primary consumers, the whole food chain could be affected by this problem in the long term.
From such results can be predicted that nanocomposites which suffer greater matrix degradation when exposed to the environment suppose a greater threat because a percentage of nanofiller can be released and be biodisponible in the media and thus potentially cause an ecotoxic effect.
Some preliminary results and conclusions have been obtained from these studies, but further work is required in order to enhance the knowledge regarding the environmental effects on freshwater ecosystems of these nanoparticles and nanocomposites since recent trends indicate an increasing use and thus potential release in the environment and unpredictable effects on freshwaters.
To complement the mesoscosm studies, a series of experimental tests were undertaken as part of the NanoSafePack project to assess the potential for release of nanofillers from polymer-based nanocomposites into a freshwater environment (e.g. rivers, streams, etc.). The most sensitive of the environmental models appears to be those localised to the freshwater compartment (in comparison to estuarine/marine and terrestrial/soil which are less sensitive). The tests sought to identify whether metallic nanofillers are released from the polymer matrix into a model OECD medium representing freshwater over a period of four weeks. As a comparator, the release of native nanofillers directly into the freshwater medium was also measured over time.
The zinc oxide (ZnO) and nanoclay native nanofillers released nearly 15% and 20% of their mass, respectively, into the OECD freshwater medium over the four week period. Only the silver (Ag) nanofiller was found to be more highly soluble, releasing over 65% of its mass over the four weeks. A continuous flow experiment determined that the majority of the Ag released from the nanofiller occurred within the first 24 hours, whereas release from ZnO continued beyond three weeks.
In comparison, the silver nanocomposites (PET+Ag and PP+Ag) appeared to be completely stable, showing no evidence of silver release over the four week period. The zinc oxide nanocomposites, on the other hand, released significant levels of zinc over the four week period, with significantly more zinc released from weathered nanocomposites in comparison to unweathered materials.
Careful consideration should therefore be given to the end-of-life processes that may occur for native nanoclay, silver and zinc oxide nanofillers, as well as zinc nanocomposites, with appropriate risk management and controls in place to minimise exposure to environmental freshwater ecosystems.
More information on the toxic and ecotoxic profile of nanofillers, polymers and nanocomposites are included within deliverables D2.1 and D2.2. and D 2.3.
d) Migration potential
We did not observe migration of metal (Ag NPs) and metal oxide nanoparticles (ZnO and SiO2).In the case of CaCO3, it can be easily transferred to aqueous simulants. Regarding to the nanoclay tested, it can release both hydrated alkali and transition metal cations to ethanol and acetic acid solutions. From these results, we can conclude that PLA and PE based nanocomposites are more likely to release their NPs to the media than PP and PET and thus will have more restrictions on use to be bared in mind when selected as nanocomposite food packaging materials.
WP3. Development of Exposure Scenarios
Objectives of the WP: the aim of exposure assessment work package, WP3, is to provide a better understanding of the potential for exposure to engineered nanoparticles in real situations in order to establish the size and impact of the hazard related with the production of nanocomposites, as well as to define effective measures to reduce or prevent a worker's exposure to a health hazard in the workplace, including respirators, protective clothing, face and eye shields, and other engineering controls.
The RTD performers ITENE and IOM conducted the definition of relevant exposure scenarios in the production, processing and use of nanocomposites (Task 3.1) as well as the quantitative characterization of the exposure to nanoparticles for key scenarios (Task 3.2). Moreover, a complete characterization of the release of nanofillers to the environment due to causes such as mechanical forces, weathering, washing and contact was also conducted.
The last task within the WP 3 was focused on the evaluation of the effectiveness of the current risk management measures, hereinafter RMM, implemented at industrial level. To this end, the RTD performers defined the specific properties or “performance factors” to be studied for the list of RMMs selected, including local exhaustive ventilation and containment systems, respiratory protective equipment (RPE), skin protective equipment (SPE), and protective clothing.
Significant results
The main results obtained within WP 3 are described below:
a) Exposure Characterization
The information retrieved from the scoping visits and literature reviews conclude that NPs are released from the production sites. The results show an increase in the number concentration during the synthesis, as well as during the cleaning of the production sites.
We identified a total of 9 key exposure scenarios, including: synthesis of nanofillers, production of polymer nanocomposites by melt-moulding, handling of powders (weighing operation), blending, grinding of nanocomposite materials, dry Cutting of nanocomposites, nanocomposite shredding, cleaning and maintenance operations.
The handling of pure, non-consolidated nanofillers was considered one of the most critical operations because it involves direct manipulation of the nano-fillers (powder) that can potentially disperse as airborne nano-objects in the workplace. Levels up to 1.6 x 106 particles/cm3 were retrieved from the literature.
The publications addressing the grinding process report large amounts of airborne particles, mostly small pieces of polymer containing nano-fillers. The blending process for its hand results in the release of NPs from the place of blending, generating peaks of nanosized particles in the workplace.
b) Exposure Measurement
Analysis of real-time sampling data (FMPS, CPC and APS) identified consistent releases in particle concentrations within 6-120nm range when sampling directly from the extruder exit. The releases were observed while monitoring both the extrusion of pure polymer and the corresponding extrusion of the polymer with the nanofiller.
It is therefore considered that the increases in particle concentrations are associated with particle emissions from either polymeric-based fumes or from the operation of the extruder in general (hot surfaces) and not from the emission of nanofillers.
The analysis of data gathered from the real-time instruments and the contextual observations during hopper loading, calibration and cleaning activities indicates the potential release of Clay1 particles in the 1- 8mm range, during hopper loading activities and potential release of CaCO3 particles in 120nm-10mm range during hopper cleaning activities. In addition, data analysis suggests the potential release of ZnO particles in the 80nm- 3µm range during hopper cleaning activities and potential Ag release between 100nm and 6µm during loading, calibration and cleaning activities. Data analysis is currently being undertaken for the SiO2 nanofiller.
The analysis of samples collected using the Nano-ID provided clear evidence that particles from the lower density nanofillers (clay1, CaCO3 and SiO2) are being emitted into the workplace air environment. The particles are migrating out of the containment envelope afforded by the extruder extraction system with materials being detected in the open laboratory, most noticeably towards the work station next to the extruder.
On the other hand, the analysis of overnight filter samples (adjacent to the work station) provided evidence of the presence of lower density nanofillers (clay1, CaCO3 and SiO2) and ZnO in the workplace environment.
Evidence of all the nanofillers apart from Ag, was found in the background overnight sample prior to any activities taking place. This suggests that there is potential persistence of lower density nanofillers and ZnO in the lab airspace overnight.
Similarly, analysis of background far-field filter samples (far-field location approximately 5 m away from the extruder) confirmed the presence of lower density nanofillers (clay1, CaCO3 and SiO2) in the general laboratory environment. Metal analysis of background gravimetric filters supports the far-field filter sampling SEM –EDXS analysis as Al, Mg, Si and Zn metals were detected in far field samples. This suggests that particles are migrating out of the containment envelope afforded by the extruder extraction system with materials being detected 5 m away from the activity.
Standard filter sampling with a respirable head of each of the hopper loading activities readily identified the presence of clay, SiO2, CaCO3 and ZnO particles in excess of 10-20mm within the respirable (filter head) range (d50<4mm).
Based on the observations made during the exposure measurement visit, it is anticipated that the activities involving the handling of powdered materials, i.e. the nanofiller feed hopper loading, calibration and cleaning activities, are the most likely to result in the release of respirable-sized materials into the laboratory environment.
In summary, from the observations made during the exposure monitoring exercise, it is evident there is a potential for release of nanofiller materials from processes and practical steps are required for controlling exposure to respirable particles such as platelets. Powder handling activities such as nanofiller hopper loading, calibration of the feed rate to the extruder and hopper cleaning activities, were identified as the source of emission where existing control measures and practices were not seen to be sufficient in mitigating a release.
At this time there remains a lack of definitive workplace studies reported in the literature with regards to adverse health effects in workers producing or using these products, and so their occupational health effects is not established clearly. However enough uncertainty remains regarding their hazardous nature, based on toxicology and other general considerations of the mechanisms of inhaled particles, that it is important to limit workers’ exposure, and various guidance documents have been published to help people work safely with these products.
c) Evaluation of the effectiveness of Personal Protective Equipment
The results showed significant differences in the penetration factor for the measures studied. Average penetration levels for respirators were between 15 and 1 %, with a minimum penetration level for the FPP3 Half Mask Respirator of 2 %. The penetration factors for dermal protection equipment and protective clothes were very low, meaning that gloves, suits and coats are effective enough. In the case of laboratory hoods and containment systems, the measurements conducted at the researcher’s breathing zone under different situations and movements (low, middle, high) reported a low quantity of NPs released . The Containment factors (Cf) calculated where very high in all the cases studies.
Established milestones for this period of time in WP 3 have been successfully accomplished.
WP4. Life Cycle Assessment
The work within WP4 has been focused on the set up of the scope of the LCA of nanomaterials and nanoparticles. An exhaustive review on current LCA’s related to nanomaterials has been carried out together with an analysis of the analogies between Risk Assessment (RA) and Life Cycle Assessment (LCA) methodologies.
A special focus has been made in case of Human Toxicity and Ecotoxicity impact assessment categories, since most of the impacts of nanoparticles and nanomaterials are related to toxicity effects. Models for impact assessment of such impact categories in LCA have been analyzed including the models for fate, exposure and severity of the damage.
The impact assessment conducted focussed on the relevant environmental categories, including: climate change, cumulative energy demand, eutrophication, acidification, ozone depletion, photochemical ozone creation potential, and ecotoxicity for freshwater. The methodology applied was based on the use of LCA together with ecotoxicity analysis. The ecotoxicity impacts were based on measured data retrieved from the project (WP 2), as well as on the use of the USEtox™ method (Rosenbaum et al. 2008), a modelling approach accepted to evaluate the severity of the damage posed by nanomaterials in the environment.
To complement the LCA studies, an experimental evaluation of the applicability of common end-of-life treatments to nanocomposite-based packaging waste was completed. The treatments studied included mechanical recycling, incineration and composting.
Significant results
a) Environmental impact assessment:
The analysis of the results retrieved form the LCA studies did not show significant environmental impacts during the production and processing of nanomaterials.
The data suggest a low impact caused by the release of the nanoparticle itself, which is mainly due to the use of additives in higher quantities. It shall be noticed that the results of the LCA showed that the use of ENM can contribute to the overall saving of environmental impact (around -40% in non-toxicity related impact categories) together with raw material savings (-38.320 wt%).
The Life Cycle Assessment of nanomaterials and nanoparticles is still a research question for discussion. The quick development of such materials requires a scientifically sound assessment of their potential environmental impacts vs. the advantages provided.
LCA is a perfect tool to perform such assessment as the life cycle thinking approach will ensure that impacts are not transferred from one life cycle stage to each other. Furthermore, the impacts on Human Toxicity and Ecotoxicity are also a research question still under discussion. With the combined step-wise approach based on scenarios as well as on exposure routes at each life cycle stage we intend to build a link within RA practice and LCA practice which allow a suitable assessment and fair effort on the impact assessment of nanomaterials and nanoparticles.
b) Nanomaterials waste management alternatives
The results on energy recovery shows that the materials studied within NanoSafePack (PET-ZnO, PET-Ag, PET-Nanoclay1, PE-CaCO3, PE-Nanoclay1 and PP-Ag) are aligned with the requirements established in the standard ISO 18605:2013 in terms of organic content, inferior calorific value and compatibility with the process of energy recovery.
In relation to material recycling, the results showed that for PE and PP, in general terms and except for some minor variations in yellowness index, tensile modulus, tensile strength and tear strength (PE with Nanoclay1, PP with Ag), the introduction of NMs in the recycling streams for plastic films does not affect the final recycled plastic material quality.
In the case of PET, results show that the increasing addition of NMs into the recycled PET matrix (especially PET-Ag) could influence important properties of the recycled material, due to a slight degradation of the polymer, such as increasing pinholes and degradation fumes. Colour deviations were visible in most of the samples (PE, PP and PET) in levels higher than 0.3 units (limit perceivable by the human eye
Regarding the energy recovery, an analysis has been performed with the aim of evaluating the extent to which nanocomposites are suitable for energy recovery. As can be seen in Table 23, all the materials studied in the Nanosafepack project meet the requirements.
Finally, in terms of organic recycling, the results demonstrated that the incorporation of NMs in a PLA matrix did not generally affect the compostability of the resulting films. Disintegration was completed in less than 7 weeks in a simulated composting environment. Moreover, no differences were observed in the evolution of the bioresidue with respect to color, aspect, and odor. Only samples incorporating PLA-Nanoclay1 and PLA-CaCO3 reached the 90% required in the standard.
No ecotoxic effects were observed as a result of the incorporation of nanoparticles in the PLA matrix, except for high proportions of compost where sample PLA-Nanoclay1 disintegrated were tested
In relation with the deliverables, the final results of the WP4 have been compiled within Deliverables. Furthermore milestones MS8 and MS9 have also been reached.
WP5. Development of the Best Practices Guide
Objectives of the WP: the purpose of this work package is principally the development of the best practices guide to the safe handling and use of nanomaterials in packaging industries. The preparation of the guide was conducted in three main stages:
• Task 5.1. Design of the best practice structure and contents
• Task 5.2. Integration of the project results into the guide
• Task 5.2. Drawing up of the guide and edition of electronic and hard copies
A first draft of the contents and structure or the best practices guide was agreed among partners during the second general assembly meeting. The development of the guide was conducted after the evaluation of the results encountered in the scientific work packages, being completed by September 2014 (Month 34).
The development of the first version of the guide was conducted by the RTD performers ITENE and IOM, in charge of the experimental activities. The results achieved and activities conducted in each WP were analysed in detail by ITENE and IOM on the basis of the scope of the chapters included into the guide, and taking into account the data of interest for both SMEs and SME Associations.
ITENE and IOM selected those information and results of major interest considering the needs of the industry, and considering mainly the data on the physicochemical, toxicological and ecotoxicological properties of the target nanofillers, data on the exposure, release and migration potential, and data on the environmental impact on a life cycle basis. These activities were all covered under task 5.2.
The drawing up of the guide as such was conducted under task 5.3. The preparation of the best practices requires high expertise in different areas of knowledge, therefore it was decided to split the preparation of the guide among partners considering their area of expertise.
The RTD performers were in charge of the scientific chapters of the guide (chapters 5 to 7), while the SME Associations were in charge of the definition of the packaging life cycle under chapter 4, and chapters 8 to 9, where an in depth analysis of current laws, regulations and standards related with the packaging industry was conducted. CEP, as SME Association, was in charge of the graphic-design and format of the guide.
For its part, the Plasper and SME provided inputs to chapters 1 to 3 related to the application and use of nanofillers in the packaging industry, and chapter 10 to 12, where a compilation of frequently asked questions, cases studies and best practices recommendations was included. Both companies were also involved in the selection of images to support the illustration of the guide.
The drafting of each chapter was scheduled during the general assembly meeting hold in Lisbon in December 2014. A non-academic language was used to support the interpretation of the guide by SMEs. The SME Associations, Tecni-Plasper and Tec Star analysed the contents of the guide carefully to ensure the applicability of the guide by the industry.
The first edition of the guide was finally completed by month 34. Once checked, a second version including new contents and images was developed. This second version was fully analysed by the whole consortium, being finally edited in November 2014.
The guide was edited in two main formats, including a copy-protected copy in USB and a hard copy in paper, available upon request.
Significant Results
The full version of the Best Practices Guide developed contains 12 chapters intended to provide the packaging industry with guidance to support the safe handling and use of nanofillers in the packaging industry. This includes technical information concerning the specific applications and properties of nanofillers, as well as new scientific knowledge on environmental, health, and safety issues.
Provided below is an outline of the structure of the Guide and key contents of each chapter.
1. Introduction and vision
This chapter outlines the purpose and scope of the guide, defines the target audience, and provides an introduction to nanotechnology in the packaging industry.
2. Types and applications of nanomaterials in the packaging industry
2.1. Nanotechnology and packaging: current and future applications
2.2. Types & specific applications of nanomaterials in polymer composites
2.3. Environment, health and safety issues of nanofillers in packaging applications
This chapter details the specific types of nanoparticles currently employed in the packaging industry as nanofillers, provides information on current and future applications and developments, and introduces the potential hazards associated with these nanomaterials.
3. General approach to managing risks from nanoparticles
3.1. Nanomaterial hazard, exposure and risk
3.2. Risk evaluation and management strategy
3.3. Roles and responsibilities of employers and workers
3.4. Good company practice
This chapter provides an overview of the basic principles of risk assessment and risk management for nanoparticles, and outlines a risk evaluation and management strategy for implementation as part of an overall company strategy for the management of health and safety.
4. Overview of the packaging lifecycle
This chapter provides an overview of the lifecycle of packaging materials, detailing the main activities and tasks involved across the various stages of the packaging lifecycle, including nanomaterial synthesis, manufacture of intermediate and final packaging products, use & service life, and end of life processing & disposal.
5. Safety during the manufacture of packaging products
5.1. Nature of the work
5.2. Exposure-prone activities
5.3. Risk management measures
5.4. Potential effects on human & environmental health and safety
5.5. Nature of use in the service life stage
5.6. Health and safety issues during the service life stage.
This chapter provides specific guidance on safe handling and use for those working in the manufacturing stage of the packaging industry. This includes identification of activities with the highest potential for exposure to nanoparticles, recommended risk management measures to minimise worker exposure, and information on potential human and environmental health effects. This chapter also addresses the service life stage, providing information on the types of consumer products produced using polymer-based nanocomposites, and an overview of health and safety issues related to consumer use.
6. Safety during end-of-life processing and disposal
6.1. Nature of processing and disposal
6.2. Exposure-prone activities
6.3. Risk management measures
6.4. Potential effects on human & environmental health and safety
This chapter provides specific guidance on safe handling and use for those working in the end of life processing and disposal stange of the packaging industry. This includes information on the main processing and disposal routes for nano-enabled packaging and identification of the main exposure prone tasks for workers during mechanical recycling processes. Guidance is provided on risk management measures to minimise potential exposure and an overview of potential effects on human and environmental health and sagety provided.
7. Risk communication
7.1. Importance of risk communication
7.2. Informing and protecting workers/emplyees during manufacture of the packaging product
7.3. Informing and protecting professional usersfurther down the supply chain
7.4. Informing and protecting consumers
This chapter highlights the importance of effective risk communication down the pacakgin supply chain and provides guidance in relation to informing and protecting workers, professional users and consumers. This includes guidance on the development and implementation of material safety data sheets, workplace hazard signs, nanomaterial and consumer product labelling
8. Laws, regulation and obligations of European packaging industry
8.1. Overview of key regulatory instruments
8.2. Substances and products
8.3. Product safety and quality
8.4. Worker protection
8.5. End of life and environment
8.6. Reporting schemes
8.7. Goof practice for regulatory compliance and governance
This chapter provides an overview of the key European regulations and legislation of relevance to those working in the packaging industry. This includes the provision of advice for regulatory compliance with the laws concerning substances and products, product sagety and quality, worker and environment protection, end of life waste management as well as nanomaterials reporting schemes.
9. Standards and guidance to support safe development
This chapter provides an overview of key standards and published guidance documents of relevance for nanotechnologies in the packaging industry, including from ISO, CEN, BSI and OECD which can be used in combination with the Best Practice Guide to support the safe development of polymer-based nanocomposites and packaging applications.
10. Best practice recommendations
This chapter provides a summary of best practice recommendations to support the safe handling and use of nanoparticles in packaging industries
11. Case studies
This chapter provides three case studies which demonstrate the application of best practice during the synthesis of nanocomposites for packaging applications at laboratory-scale, pilot-scale and industrial-scale.
12. Frequently asked questions
This chapter provides a selection of FAQs pertinent to the packaging industry in relation to safe handling and use of nanofillers, linking back to further information in the earlier chapters of the guide.
Work package five´s milestone, MS10. Best practices guide developed, was finally achieved last October 2014, month 35.
Task 6.2. Validation of Risk Management Measures
The second action conduced was focused on the selection of adequate risk management measures to control and/or mitigate the exposure to airborne nanoparticles considering the operational conditions and risk management measures that are commonly applied at industrial scale in the packaging industry.
The study conducted was focused on the analysis and evaluation of the applicability of the measures proposed in the best practices guide developed, including including LEV systems, filtration, respiratory protective equipment (RPE), skin protective equipment (SPE), and safety goggles.
The validation study included the experimental evaluation of the concentration of airborne nanoparticles in case studies after the application of selected measures, as well as the compilation of the opinions of a representative number of companies concerning the applicability of the proposed measures. In addition, expertise staff from the research organizations compared the risk characterization ratios (RCR) calculated before the use of the recommended RMM and procedures and after their implementation, comparing the results in terms risk bands or particle concentration.
The list of tasks covered in the validation studies is depicted below:
- Handling of small amounts of nanofillers in research laboratories
- Preparation of mixtures at laboratory scale, including weighting and mixing operations
- Bagging of small amounts of nanofillers / filling small containers (< 500 mg).
- Melt-Compounding at pilot scale, including hopper feeding and extrusion
- Reception of materials in large scale facilities
- Cleaning and maintenance operations
- Mechanical recycling by plastic converters
These tasks were complemented with a complete analysis of the accuracy of the models developed to predict the release of nanofillers from polymers (Task 6.3) and the validation of the quality and applicability of the best practices guide developed within WP 5 (Task 6.4).
The validation of the applicability of the best practices guide as such was conducted before the edition of the final version. The SME Association sent a complete draft of the guide to a sample of representative SMEs, joinly with a specific questioner custom designed to evaluate the applicability of the best practices and procedures described within the guide.
Significant Results
- Viability: the cost- effective analysis (CEA) conducted showed that the higher cost of the nanofillers is counterbalanced as only relatively small amounts (2–5%) of nanofillers are needed. Similarly, the market studied performed showed that polymer nanocomposite packaging materials are relatively inexpensive to manufacture, so numerous companies have already made them available. On the other hand, the implementation of effective risk management measures results in an increase of the indirect cost of the process, especially the use of safety cabinets and local exhaustive ventilation.
As key result, although the manufacturing cost of nanocomposites is currently higher due to still greater price of fillers at nanoscale and the needed extra risk control measures for environmental and worker safety assurance, the analysis shows potential benefits in reducing energy use, required raw materials amount for the same functionalities, and environment discharges by using a nanocomposite design.
- Validation of Risk Management Measures: the analysis showed that workers are most likely to be exposed to nanomaterials during the synthesis and handling of unbound nanomaterials and during the compounding stage. Therefore the analysis on the use of risk management measures was focused on synthesis and compounding.
Based on the findings, the use of LEVs in combination with PPEs and good practices can ensure a high level of protection for both workers and the environment. However risk evaluation performed by expert staff is highly recommended in order to evaluate the risk levels in workplaces. In addition, similarly to chemicals industry, employers should review regularly the effectiveness and adequacy of the risk management measures that are put in place especially in the cases where substances or conditions have changed.
The selection of the risk management measures may vary depending on the type of processes and a series of parameters such as the amount and type of nanomaterials, rate or production, workroom volume, work environment factors (temperature and humidity) etc. Examples of risk management measures and their most appropriate use are provided in deliverable D6.2.
On the basis the outcomes from the project, and information retrieved from published guidelines and scientific articles, the use of good laboratory/good workplace practices, including adequate information and training for workers, and the use of properly designed local exhaust ventilation (LEV) systems will reduce the concentration of airborne NPs to safe levels. It´s also highly recommended the use of FPP3/N100 respirators, non-woven Tyvek/Tychem polyethylene overalls and chemical protective gloves when handling nanofillers.
- Effectiveness of predictions on particle migration and release: currently, there are few available studies about the release of ENMs from nano-based consumer products. According to Froggett S.J. (2014), an examination of the International Council of Nanotechnology (ICON) environmental and health literature database and other search engines indicated that a considerable attention has been directed toward examining intrinsic hazards (83%) of nanomaterials, and less on potential exposure (16%) and least on release of nanomaterials from nanocomposite (0.8%). The authors stated however that based on the results of their literature review, the understanding of release from nanocomposite is gradually receiving more attention.
A literature review was conducted within the context of NanoSafepack which concluded that nanomaterials can be released during the service life of nanocomposite products under certain circumstances. However in the most of the cases the released nanomaterials were mainly matrix particles alone or matrix particles with protruding nanofillers. Very few studies were able to identify dissociated ENMs and therefore based on the current knowledge nanocomposite materials cannot be associated with higher release rates in comparison to conventional materials.
Furthermore it should be added that most of the studies were focused on applications where mechanical forces, weathering or other causes that could lead to release of nanofillers are likely. However all of them are unlikely during the consumer-use of packaging materials and as a matter of fact no studies could be found addressing the release issue during the use of packaging.
Nevertheless, release of nanofillers can be a crucial aspect during the industrial use of nanocomposite materals. The mechanical forces and temperature during the extrusion of compounded pellets can be a source of release.
Regarding migration, based on the analysis performed as part of the NanoSafePack project, factors that may influence the migration potential of nanofillers to the contained product are virtually the same as the ones that influence the release (polymer matrix characteristics, nanofiller characteristics, environmental conditions etc,). Migration can be a result of matrix degradation which in turn can be triggered by mechanical stress, UV light, fire etc.
In relation to the modelling approached, currently available models are based on the physicochemical properties of substances in bulk forms, especially the mass transfer coefficients (Cf) implemented. The results of the comparison between measured and estimates data showed a general overestimation of the migration and release of fillers.
To reduce the uncertainty, the release index applied in NanoSafePAck were calculated using a probabilistic MCMC approach (Monte Carlo – Markov Chain), highly recommended in the literature. This method calculates the probability of the release on the basis of the quantity of materials used and the effectiveness of the RMMs applied, supporting the definition of a reliable release ratio.
- Valuation of the best practices guide: as stated previously, the evaluation and validation of the best practices guide was done by asking potential users to provide feedback through a questionnaire. The questionnaire consisted of 8 questions that aimed to capture the overall impression of the user.
The opinions compiled from surveys demonstrated that the contents of the guide are adequate to support the safe handling and use of nanofillers. most of the respondents stated that the recommendations in the guide are useful and more importantly, applicable.
Work package six´s milestone, MS11. Demonstration activities in industrial facilities completed, was scheduled for being achieved by month 34, being finally completed by month 36, November 2016.
Potential Impact:
Analysis of the Impact of the project
a) Background information
The novel properties offered by the use of nanofillers in packaging materials has resulted in a continuous growth in the market, principally derived from the manufacture of nanocomposites - polymers reinforced with particles that have one or more dimensions of the order of 100 nanometers (nm) or less. The use of nanofillers opens an opportunity for developing innovative and high performance packaging materials. Applications include nano‐filler reinforced packaging (e.g. enhanced barrier properties), active packaging (e.g. antimicrobial), intelligent packaging (e.g. freshness indicators), and biodegradable packaging.
Along with the foreseen benefits and market opportunities , there is an on-going debate about the potential effects of nanomaterials and nano-enabled products on human health and the environment . In this sense, while research on developing new nanocomposite materials has prolific for more than a decade, research aiming to improve the understanding of the health and environmental impacts arising from the manufacture and commercialization of nanocomposites is far less advanced, with a particular concern related with the potential adverse effects of the common nanofillers on workers and consumers.
Given this situation, there is an urgent need to provide the industry with reliable information on the specifications of the nanofillers that can be used as nano-additives in compounding process, as data on the toxicological and ecotoxicological profile of nanofillers and polymer-nanofiller combiantions, and information on the likelihood of human exposure to nanofillers in a lifecycle perspective.
The goal of the project is therefore aligned with the needs of the industry. In these sense, the project have a strong impact in the nanocomposites value chain, providing the producers of nanomaterials and nanocomposites, as well as downstream users of nanomaterials, with a scientific based guide in support of decision making when selecting nanofillers and adequate risk management measures to control and/or mitigate the exposure to nanofillers at all stages of the life cycle.
The development of the Best Practice Guide was informed by research activities undertaken as part ofthe project, which included a complete hazard and exposure assessment to obtain new scientific data about the safety of polymer composites reinforced using nanometer-sized particles, an evaluation of the effectiveness of risk management measures, and a life cycle assessment of nanocomposites to evaluate impacts during manufacture, use and disposal.
In view of the above, the FP 7 project NanoSafePACK have a remarkable impact on the European SME Community and their citizens, clearly identifiable due to the hundreds of applications of the nanocomposite materials every day and the hundreds of people who use them.
It’s expected a direct impact in the packaging and polymer nanocomposite industry, helping the SME to develop new innovative materials, which provide the end users with new products tailored to their needs. On the other hand, as can be derived from the followings paragraphs, the implementation of the project results will enable the packaging and plastic associations , their members and other SMEs across Europe minimise the health impact and environmental risk from the nanofillerts, providing the information to safely design, manufacture and market nanotechnology enable products.
Besides the above, NanoSafePack will also be of value to trade associations related to the packaging industry, regulatory bodies and relevant international organisations such as the European Food Safety Authority (EFSA), the European Agency for Safety and Health at Work (EU-OSHA) and the Organisation for Economic Co-operation and Development (OECD), as well as international standardisation bodies such as the European Committee for Standardization (CEN).
b) Impact on the Industry
Composite materials are rapidly becoming a mainstream technology and material of choice within many industries, expected to reach 19% of nanotechnology products and applications in global consumer products by 2015.
In Europe, packaging applications are the largest application sector for the plastics industry and represent 39.4% of the total plastics demand (45.9 Mtonnes), followed by the building and construction sector. It is also anticipated that the packaging sector will become one of the major end-user industry segments where nanocomposites are used for a variety of applications.Thus a better understanding of the nanofillers’ properties and applications, health, safety and environmental protection and regulatory requirements, are all key aspects to promote the use of nanotechnologies in the European industry
Moreover, the improvement in the safety of the production process and the development of safe and eco-friendly nanocomposites will improve the business opportunities of the European nanocomposites industry, promoting the opening of new business lines based on the use of nanofillers and/or the commercialization of nano-enabled products.
The project promotes the investment in new nanostructured products, being expected to dominate the market and remain widely employed in large-volume markets. In addition, the project provides valuable information to limit the cost related with the use of nanofillers and the production of nanotechnology based products. Furthermore, improved worker and consumer safety have obvious economic benefits for the EU with respect to healthcare provision.
On the other hand, the improvement in the safety of the production process and the fulfilment of a key European regulation such as the regulation on Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH) will improve the business opportunities of those SMEs affected by REACH provisions, with special emphasis in those that handle or manufacture substances at the nanometre scale, as is the case of nanocomposites manufacturers. In fact, The EC recognizes that compliance with Health & Safety directives will play a key role in promoting economic growth and employment in the EU but also realizes that the costs of compliance for SMEs are high, then, the definition of effective protection and prevention measures will minimize the costs to control the risks during the production process, supporting at the same time the economic growth of the SME and their competitiveness.
It shall be noticed that the cost of REACH implementation could reach up to €3.2 billion to the chemicals industry and €2.8–3.6 billion to downstream users. In this sense, NanoSafePack will support the European industry to reduce cost derived from the investment on low-efficiency engineering techniques, and saving money due to the reduction in the insurance premium.
Moreover, improved worker and consumer safety have obvious economic benefits for the EU with
respect to healthcare provision. In this sense, several studies describe business benefits in terms of
savings related to occupational health due to the proven efficiency of the control measures for protecting workers from the risks related to chemical agents.
c) Social impact
Beyond the toxicity risks to human health and the environment which are associated with firstgeneration nanomaterials, nanotechnology has broader societal implications and poses broader
social challenges. In this sense, NanoSafePAck tries to meet social objectives in term of nanotechnology application, principally in terms of safety and health related to the use and commercialization of nanotechnology based products.
The contribution of the project to the safety of the workers and nanocomposites placed on the market will improve the approbation of this kind of products into the society as well as a better image of the new technologies, ensuring the commercialization in the near future. The expected benefits in terms of product quality, safety and environmental respect, will be key issues to accept the changes towards the new nanostructured products, which will be better accepted by the consumers.
Simultaneously, the participation of enterprises in the project implementation and the direct application by the members of the SME associations will help in the dissemination of the project results, providing the industrial stakeholders and the general public with appropriate knowledge to successfully control the risks posed by the use of nanomaterials, as well as with new information to perform a complete risk assessment on the basis of REACH regulation.
c) Impact on EU policies
The project explored legal and policy issues, as well as scientific and technical issues, that might arise in the application of the regulatory process related to the use of NMs at the workplace. At this stage, the project results provide a better understanding of the risk to the human health and the environment of nanofillers and nanocomposites, supporting regulatory bodies with scientific data to establish new legal requirements to the use of NMs in the nanocomposite industry in particular and other nanotechnology fields in general.
The project is aligned with the considerations expressed by the European Parliament resolution of 24 April 2009 on regulatory aspects of NMs, which explains that the use of NMs should respond to the real needs of citizens and that their benefits should be realized in a safe and responsible manner,
considering the potential EHS problems.
Research activities are ongoing under the Research Framework Programmes and the Joint Research
Centre, as well as in EU Member States and internationally within the OECD Working Party on MNMs
and the International Organization for Standardisation. According to the Europe 2020 strategy, one of the strategic goals will be ensuring the safe development and application of nanotechnologies by
advancing scientific knowledge of the potential impact of nanotechnologies on health or on the environment, and providing tools for risk assessment and management along the entire life cycle.
In this sense, the future needs may include identifying and demonstrating the effectiveness of containment technologies for safe handling of NMs through the life cycle, investigating the effectiveness of different work practices for human and environmental exposure mitigation, and strengthening current research on the toxicological and ecotoxicological profile of nanofillers already applied at industrial level.
The project is in line with the research areas underpinning risk assessments and management in which new knowledge is more needed, bringing value to the European development of risk management knowledge by the identification of proven measures and controls to reduce exposure
to NMs during its entire life cycle.
The project have also a strong impact onthe International Standardization since it works on the development of methods for testing RMM against NMs by evaluating the adequacy of the published
harmonized Standards from ISO, CEN, BSI and ASTM, and adapting them to the specific NM properties. In addition, the development of the project has generated new reliable information to be implemented in the current European legislation, considering different stages of the NMs life cycle.
In relation to the nanocomposites safety and consumer health, the project has contributed to the establishment of an overall migration limit (OML) in case of food contact materials, where the nanoparticles are incorporated. In addition, the project has generated new data to support the definition of new provisions and specific restrictions added to the current European and National provisions.
c) Impact on environmental protection
In relation to the environmental impact, the project will promote the development of environmentally benign polymer nanocomposites. The market for worldwide polymer nanocomposites is expected to grow at an average annual rate of 18.4 percent, therefore, NanoSafePAck will allow continued growth in the composite industries without compromising the global environment.
The implementation of efficient procedures to control the exposure and the choice of more efficient techniques will improve the environmental safety, minimizing the release to the environment of nanoparticles with potential ecotoxic effects. In fact, the implementation of new and tested risk management measures improves the effectiveness of the spill control system and the minimization of the release of nanofillers to the environment during the manufacturing process. Simultaneously, the selection of effcientie risk management measures ensure a high level of protection to the environment, and provides new knowledge to the development of new Best Available Techniques (BATs) to prevent pollution, considering both the manufacturing plants of engineered nanoparticles and the industrial settings where the nanoparticles, to be included into the polymeric matrix, are processed.
Beside the above, the outcomes from the release has provided a better understanding of the fate of the nanoparticles in their service life, generating nee reliable data on the potential release of nanoparticles during the their use and disposal.
Finally, the application of a life cycle assessment approach has been essential for the improvement of the current knowledge about resource and energy consumption, emissions and their impact, providing a useful insight about nanocomposites, as well as a proxy for the toxicological and ecotoxicological impact due to the emissions.
In summary, the implementation of the recommendations, procedures and technologies exposed in the best practice guide, the industry will be able to comply with the current regulation in terms of environmental protection, product and worker safety, manufacturing innovative and sustainable composites materials without endanger the human health and the environment and becoming cost competitive with the present and growing threat posed by the Far East.
Dissemiantion activities and foreground generated
a) Dissemination
The dissemination activities were performed through various instruments and media. These have been carefully selected for facilitating collaboration among involved parties. The first activity completed was the design and selection of the project logo. The project web site was published last November 2012, being accessible via the internet site www.nanosafepack.eu.
Regarding the main dissemination materials, classical print media (brochure and poster) have been produced to be freely circulated for project information and promotion at workshops, trade shows, technical fairs, congresses and other events. The electronic version of these materials is downloadable from the website. Several press releases were published by the consortium members with the aim of communicate the goal and scope of the project.
Finally, the project results and contents have been disseminated in several international conferences. In detail, the dissemination activities conducted have been the following:
i) Presence at trade shows and conferences across Europe, including;
- 1srt QNano Integrating Conference. Dublin (Ireland) - 03.2012
- International Packaging Trade Fair “Salón internacional del embalaje” Hispack 2012. Barcelona (Spain) - 05.2012
- Safe Implementation of Nanotechnologies: Common Challenges. Grenoble (France) - 05.2012
- 2nd QNano Integrating Conference.Prague (Czech Republic) - 02.2013
- Los riesgos con los nanomateriales, su relación con el reglamento REACH. Valencia (Spain)- 06.2013
- Euronanoforum 2013. Dublin (Ireland) - 06.2013
- 8th International Conference on the Environmental Effects of NP. Aix-en-Provence, (France)- 07.2013
- NanoSafety Cluster meeting. Birmingham (UK) - 09.2013
- CEP Innova. Barcelona (Spain) - 11.2013
- XXVIII Plastics Seminar. Figueira da Foz (Portugal) - 11.2013
- 1 st National Meeting on Nanotechnology: Regulate to Compete”. Caparica (Portugal) - 04.2011
- International Conference on Aerosol Technology 2014.Karlsruhe (Germany)- 06.2014
- Nanosafe 2014, held from 18-20 November 2014 in Grenoble (France)
ii) Workshops
According with the Document of Work, three specific workshops were organized with the aim of disseminate the best practices guide developed within the project. These workshops were organized by the members of the consortium under the framework of relevant events. In detail, the workshops organized were the following:
- 1st NanoSafePack Workshop during the LET'S 2014 conference (Leading Enabling Technologies for Societal Challenges 2014). Bolognia (Italy) – September 2014
- 2nd NanoSafePack Workshop. Technical Conference of Plastics Additives – Barcelona (Spain) – October 2014
- Final Dissemination Workshop – EuPC facilities. Brussel – November 2014
b) Foreground
The exploitable foreground of the project was anticipated in the DoW, including only the best practices guide for the safe handling and use of nanomaterials. This guide will be owned by the SMEs Associations, which will distribute the guide for their members at a special cost, including either pdf or printed formats.
In addition, the foreground was analysed in depth by the project partners, inditying new relevant results to be consideres as part of the foreground. . The list of exploitable results (foreground) identified are depicted below:
Result 1: Data on the physicochemical and (eco)toxicological properties of the target nanoparticles
Generated by: ITENE / IOM
Use: Free use by consortium members upon request
IPR Strategy: Non-protected
Exploitation potential: To be used by Tec Star as part of the Safety data sheets (SDS)
This result will be exploit by Tec Star and Tecni-Plasper. The data can be requested to the data owners, who will give access to the data without delay. The data owners will use the data to publish scientific papers and prepare conferences after the communication and approval of the whole consortium.
Result 2: Library of exposure scenarios containing information on the operative conditions and risk management measures
Generated by: ITENE / IOM
Use: Free use by consortium members upon request
IPR Strategy: Non-protected
Exploitation potential: To be used by Tec Star as part of the Safety data sheets (SDS)
This result will be exploit by Plasper and Tec Star. The data can be requested to the data owners, who will give access to the data without delay. The data owners will use the data to publish scientific papers and prepare conferences after the communication and approval of the whole consortium.
Result 3. Designs and specifications of new RPE (Respiratory Protection Equipment) and ventilation systems
Generated by: ITENE
Use: Restricted to consortium
IPR Strategy: Trade Secret
Exploitation potential: Potential commercial agreement with RPE manufacturers – License agreement
ITENE, data owner, will negotiate a license agreement with EU manufactures, transferring the specifications to SMEs or Large Companies interested in the commercialization of proven risk management measures against ENMs.
Result 4. Best Practices Guide
Generated by: EuPC / CEP / APIP
Use: SME Associations will be able to establish a market price to the best practices guide in order to commercialize the guide to others stakeholders
IPR Strategy: author rights - ISBN
Exploitation potential: Free commercialization by SME Associations
The best practices guide developed will be exploited directly by the SME Associations CEP, APIP and EuPC. The RTD performers won´t benefint from the guide. The SME Associtions will stablish a market price according with their bussines plans
List of Websites:
NanoSafePack project web site: www.nanosafepack.eu
Relevant Contacts:
Jose Luis Romero, Project Coordinator
Tecni-Plasper S.L. Pol.Ind.Font de la Parera.
C/Bonaventura Aribau s/n. La Roca del Vallés (Spain)
E-mail: JoseLuis.Romero@plasper.com
Angel Lozano, Director
CEP - Centro Español de Plásticos
Enrique Granados, 101. Barcelona
E-mail: alozano@cep-plasticos.es
Website: www.cep-plasticos.com
Isabel Ferreira da Costa, Director
APIP - Associação Portuguesa da Indústria de Plásticos
Edifício Libersil - Torre B. Rua de S. José. 35 - 2º C. Lisboa
E-mail: isabelfcosta@apip.pt
Website: www.apip.pt
Maria Estela Izquierdo
European Plastics Converters
Avenue de Cortenbergh 71. Brussels, Belgium
E-mail: Maria.Estela.Izquierdo@eupc.org
Website: www.plasticsconverters.eu
