Life Cycle Assessment of nanotio 2 and its applications
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1 Life Cycle Assessment of nanotio 2 and its applications Martina Pini LCA Working Group DISMI Università di Modena e Reggio Emilia
2 This presentation concerns the research activities of Martina Pini s PhD Doctorate School in Industrial Innovation Engineering
3 Summary 1. Overview of research activities 2. Determination of potential damage of nanotio 2 3. Determination of indoor and outdoor benefits of nanotio 2 4. LCA case studies 5. Conclusions
4 Overview of research activities ARACNEItalian project 3 companies of Emilia-Romagna region University of Modena and Reggio Emilia University of Bologna Aim: study new and eco-friendly building materials with higher technological properties obtained by the addition of specific nanomaterials.
5 Nanoparticles and ENPs nanoparticles : materials with all three dimension between 1 and 200 nm in size. Commonly nanomaterials are based on engineered nanoparticles (ENPs). ENPs is referred to manufactured materials: 1. Metal oxides (TiO 2, ZnO ect.) 2. Carbon based products (carbon nanotubes) 3. Metals (gold and silver NPs) 4. Quantum dots (semiconductor nanocrystal) 5. Dendrimes (multifunctional polymers)
6 Properties & Applications of nanotio 2 Self-cleaning -Building and Road materials -Electrical & Electronic Equipment Air cleaning - Indoor air cleaners - Outdoor air purifiers nanotio 2 +Light Photocatalysis Superhydrophilicity Anti-fogging -Building and Road materials -Vehicles -Electrical & Electronic Equipment -Paint Water purification - Drinking water Self-sterilizing -Hospital - Clean rooms Cosmetic and skin care products
7 Determination of potential damage of nanotio 2
8 Nanotoxicity assessment Uncertainties and knowledge gaps on behavior and toxicity of nanoparticles. We cannot remain silent!! The LCA methodology can help to determine the potential impacts of nanoproducts and nanomaterials on human health and enviroment.
9 Nanotoxicity assessment Damage caused by nanotio 2 emissions: Human Health (HH) Aquatic Organism (AO) 1. released in air (outdoor) 2. inhaled by workers (indoor) 3. released in freshwater ecosystem 4. released in freshwater ecosystem
10 Damage to HH caused by nanotio 2 emissions 1. released in air (outdoor) 2. inhaled by workers (indoor) References NIOSH National Institute for Occupational Safety and Health Occupational exposure limits for ultrafine TiO 2 (primary particles diameter < 100 nm) 0.3 mg/m 3 Reducing the risk of developing lung cancer with concentration level of 0.3 mg/m 3 < 1/1000 IARC International Agency for Research on Cancer TiO 2 reviewsufficient evidence of carcinogenicity in experimental animals and inadequate evidence of carcinogenicity in humans Group 2B possibly carcinogenic to humans
11 Assumptions for the production step Emissions released into the production room during the production step: 1% 99% of emissions are captured by the vacuum system 1% of emissions are released directly into the production room 99.97%is captured by HEPA filter. 0.03% is directly released in air A fraction of emissions is inhaled by the worker, the rest is released outdoor by opening windows.
12 1. Damage to HH caused by nanotio 2 emissions released in air Calculation of the damage caused by carcinogenic substance by Eco-indicator 99 method: 1- Fate analysis ASSUMPTION: nanotio 2 fate factor= PM 2.5 µm Fate Factor (F)= 1.70E-5 m 2 yr/m 3 2- Effect analysis Unit risk factor (UR): 9.44E-5 persons/m 2 Effect factor (E): UR*PD= 4.49E-13 cases/µg/m 3 /yr*persons/m 2 Incidence factor(i): E*F= E-9 cases/kg nanotio2 3- Damage analysis YLL (years of life lost)= 40 years Damage assessment factor of Carcinogenscategory of IMPACT method: 2.8E-6DALY/kg C2H3Cl Characterization factor: 3.052E-7DALY/kg/2.8E-6DALY/kg=0.109kg C2H3Cl /kg nanotio2
13 1. Damage to HH caused by nanotio 2 emissions released in air Modification of IMPACT method In Carcinogensimpact category: New substance: Particulates, <100 nm, in air Characterization factor: kg C2H3Cl /kg nanotio2 Data input Quantity of nanotio 2 emissions release in air.
14 2. Damage to HH caused by nanotio 2 emissions inhaled by workers Concentration limit of indoor emissions in the production room: g/h/1200m 3 = 0.227mg/m 3 /h Probability to contract the lung cancer: 1/1000*0.227mg/m 3 /0.3mg/m 3 = 7.56E-4 Damage assessment factor: 5workers*40YLL/workers*7.56E-4/ kg/h= 5.56 DALY/kg/h
15 2. Damage to HH caused by nanotio 2 emissions inhaled by workers Modification of IMPACT method New substance: Particulates, <100 nm indoor New impact category: Carcinogens indoor [kg] Characterization factor: 1kg/kg New damage category: Carcinogens indoor [DALY] Damage assessment factor: 5.56 DALY/kg Data input Quantity of nanotio 2 emissionsinhaled by workers
![indoor [kg] Characterization factor: 1kg/kg New damage category: Carcinogens indoor [DALY]](/docs-images/45/7044913/images/page_15.jpg "Damage assessment factor: 5.")
16 3. Damage to HH caused by nanotio 2 emissions released in freshwater ecosystem ASSUMPTIONS Emissions released during the purification of nanocontaminated water: 1kg/yr Water bodies volume of Reggio Emilia province: 9E6m 3 Nanoparticles Concentration (C): 1.111E-7 kg/m 3 Emissions per m 2 (E): 1E-4 kg/(m2*yr) The limit concentration it has been assumed of 8.33µg/L Kumar A., et al., Exposures to TiO 2 and Ag Nanoparticles: What are Human Health Risks?, Science and Society, 9(2), 2011.
17 3. Damage to HH caused by nanotio 2 emissions released in freshwater ecosystem Calculation of the damage caused by carcinogenic substance by Eco-indicator 99 method: 1- Fate analysis: Fate Factor (F):C/E= 1.111E-3 m 2 *yr/m 3 2- Effect analysis: Unit risk factor (UR): 2.34E-4 persons/m 2 Effect factor (E): UR*PD= 4.02E-13 cases/µg/m 3 /(m 2 *yr)*pers Incidence factor(i): E*F= 4.464E-7cases/kg nanotio2 3- Damage analysis: YLL (years of life lost)= 30 years, YLD (years lived disability)= 2 years. Probability to cure cancer: 50% Damage Factor=16 DALY/case Damage assessment factor: I*D=4.46E-7cases/kg*16DALY/case= 7.14E-6DALY/kg
18 3. Damage to HH caused by nanotio 2 emissions released in freshwater ecosystem Modification of IMPACT method New substance: NanoTiO 2 Human toxicity, in water New impact category: NanoTiO 2 carcinogens in water [kg] Characterization factor: 1kg/kg New damage category: NanoTiO 2 carcinogens in water [DALY] Damage assessment factor: 7.14E-6 DALY/kg Data input Quantity of nanotio 2 emissionswhich are not captured by filter.
![water [kg] Characterization factor: 1kg/kg New damage category: NanoTiO 2 carcinogens in water [DALY]](/docs-images/45/7044913/images/page_18.jpg "Damage assessment factor: 7.")
19 4. Damage to AO caused by nanotio 2 emissions released in freshwater ecosystem Reference Salieri B., Olsen S.I., Righi S., How to calculate the characterisation factor for nanoparticle? A case study on n TiO 2, Rete Italiana LCA, Milano 2013.
20 4. Damage to AO caused by nanotio 2 emissions released in freshwater ecosystem Modification of IMPACT method New substance: Particulates,<100nm, in water New impact category: Nano ecotoxicity in freshwater [kg] Characterization factor: 1kg C2H3Cl /kg New damage category: Nano ecotoxicity in freshwater [PAF*day*m 3 /kg] Damage assessment factor: 0.28 PAF*day*m 3 /kg Data input Quantity of nanotio 2 emissionsrelease in water (not captured by filter).
![Characterization factor: 1kg C2H3Cl /kg New damage category: Nano ecotoxicity in freshwater [PAF*day*m 3 /kg]](/docs-images/45/7044913/images/page_20.jpg "Damage assessment factor: 0.")
21 Determination of indoor and outdoor benefits of nanotio 2
22 Benefits indoor of nanotio 2 Reduction of NO 2 emissions in air Reference: Italian environmental protection agency study (ARPA Lombardia, 2004). Results: reduction of 37% NO 2 indoor emissions. Evaluating of the survival ratio of Escherichia Coli exposed to a nanotio 2 It has been assessed in agreement with the results of Caballero et al., The survival ratio of E. Coli is 16.83%.
23 Benefits outdoor of nanotio 2 Reduction of NO emissions in air: 4.01 mg h -1 m -2 of NO removal Poon CS et al., Construction and Building Materials 2006;21(8): Reduction of VOC (Toluene) emissions in air: 100 mg h -1 m -2 of Toluene removal Demeestere et al., Building and Environment 2008;43(4):406 14
24 LCA case studies 1. nanotio 2 suspension obtained by a liquid-phaseprocess Collaboration: Colorobbia Italia S.p.A. Life Cycle Assessment of nanotio 2 coatings 1. nanotio 2 -polyurea resin applied on an aluminium panel Collaborations: Industrial Mechanical Plant research group and SRS S.p.A. company. 2. nanotio 2 coated self-cleaning float glass. Collaboration: Department of Engineering Enzo Ferrari, Modena. 3. nanotio 2 -glaze applied on an steel panel. Collaborations: Industrial and Mechanical Plant research group (DISMI) and Smaltiflex S.p.A. company.
25 1. LCA of nanotio 2 suspension
26 1. LCA of nanotio 2 suspension Composition of nanotio 2 suspension Titanium isopropoxide (TIP) 23.22% Water (H 2 O) 73.40% Nitric Acid (HNO 3 ) 63% 2.38% Polyethylene glycol (PEG) 1% Total 100% Recycled Isopropanol Coproduct 12% Yield 88% Products nanotio 2 + H 2 O + HNO 3 + PEG 85.71% H 2 O deionized Coproduct 14.29% Physical and Chemical properties +/- TiO 2 concentration (%w/w) Density (g/ml) Viscosity 20 C (mpas/sec) Nanoparticle size (nm) - 30 Polydispersity index (pdi) ph Supplier: Colorobbia Italia spa US 2008/ A1, Dec. 25, Method for preparation of aqueous dispersion of TiO 2 in the form nanoparticles, and dispersions obtainable with this method. Inventors: Baldi G. et al.
27 1. LCA of nanotio 2 suspension Goal definition: assess the environmental impacts of the nanotio 2 suspension obtained by a liquid-phase process. Functional unit: multi output process Products UF Unit Mass allocation Nano TiO 2 suspension =1kg*88%*85.71% kg % Coproduct Isopropanol 0.12=1kg*12% kg 12% H 2 O deionized =1kg*88%*14.29% kg % Function of the system: functionalize building materials. System boundaries: from cradle to gate. Data quality: primary data and secondary data (literature and DB data). Calculation software: SimaPro Impact method: modified IMPACT 2002+
28 1. LCIA of 1kg of nanotio 2 suspension 58.13% Electricity 13.66% Titanium isopropoxide Heat 10.34% Impact category Amount Non-renewable energy 36.6% Global warming 29.2% Respiratory inorganics 21.3% Total damage: mpt Nano ecotoxicity in fresh water NanoTiO2 carcinogens in water 3.4E-6% 6.75E-7%
29 Life Cycle Assessment of nanotio 2 coatings «from cradle to grave» SimaPro Modified IMPACT 2002+
30 Life Cycle Assessment of nanotio 2 coatings Studied System System Function Funtional unit Life time Damage Benefits nanotio 2 - polyurea resin applied on an aluminium panel INDOOR coating surface with selfcleaning and selfsterilized functions 3 m 2 20 years OUTDOOR and INDOOR Emissions Application step Use phase End of life INDOOR NO 2 reduction E. Coli reduction Use phase nanotio 2 coating applied on a float glass OUTDOOR coating surface with selfcleaning and solar factor reduction functions h * l m 2 20 years OUTDOOR and INDOOR Emissions Application step Use phase End of life OUTDOOR NO reduction VOC reduction Use phase nanotio 2 -glaze applied on an steel panel OUTDOOR coating surface with selfcleaning and antismog functions h * l m 2 20 years OUTDOOR and INDOOR Emissions Application step Use phase End of life OUTDOOR NO reduction VOC reduction Use phase
31 Ecodesign approach Installation of HEPA (High Efficiency Particulate Air filter 99.97%) air filter where there is the risk to have a release of nanoparticle emissions. Closed manufacturing system Use of specific packaging to limit the release of nanoparticle emissions during the transports. PPE (Personal Protective Equipment): face mask with 95% of efficiency. Waste treatment: nanotio 2 -polyurea applied on an Al panel Heat treatment, T=660 C: Recycling of aluminum panel (melting point: 660 C) Evaporating of the residual-nanotio 2 -polyurea resin (melting point: 350 C) nanotio 2 -coating applied on a float glass Making inert the float glass with nanotio 2 coating nanotio 2 -glaze applied on an steel panel Making inert the steel panelwith nanotio 2 coating
32 2. LCIA of 1 m 2 of nanotio 2 -polyurea resin applied on an aluminium panel 40.12% 38.47% 6.97% Impact category Amount Non-renewable energy 32% Global warming 25.86% Respiratory inorganics 23.98% Carcinogens indoor 1.60% Non-carcinogens indoor -0.36% Respiratory inorganics indoor -4.06% Total damage: mpt
33 3. LCIA of 1 m 2 nanotio 2 coating applied on a float glass % Production Installation 1.38% Use phase % End of life 12.78% Impact category Amount Global warming 31.87% Non-renewable energy 29.87% (46.7%-16.84%) Respiratory inorganics 19.84% (39.84%-20%) Carcinogens indoor 4.76% Respiratory organics -4.52% Total damage: mpt
34 4. LCIA of 1 m 2 of nanotio 2 -glaze applied on an steel panel 49.64% Production of steel panel Use phase -4.64% End of life 18.97% Impact category Amount Global warming 39.5% Non-renewable energy 22.3% Carcinogens 10.87% Carcinogens indoor 7.04% Respiratory inorganics 6.88% (30%-23.12%) Respiratory organics -9.47% Total damage: mpt
35 Conclusions and remarks Damage of nanotio 2 : the Use Phase and End of life are the more affected life cycle steps. Parametric analysis varying % of nanoparticle emissions, TiO 2 concentration and filter efficiency. Nanotoxicological indicators: this is a preliminary research to evaluate the risks and the safe use of nanoparticles. The LCA case studies follow the Ecodesign approach giving a guidance on how it should be the production, the handling, the transport, the end of life of nanoparticles/nanomaterials. Assessment of the actual environmental performance of functionalized building materials once embedded in entire building. Case study: Municipio di Fiorano Modenese.
36 Thank you for your attention
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