# Presentation: 327596

## Implications of Nanomaterials Manufacture & Use

- Earl R. Beaver
- USEPA Nanotechnology STAR Review
- August 19, 2004

## Outline

- Introduction
- Project background & approach
- Progress review
- Next steps
- Personnel

## Introduction

*“**Implications of Nanomaterials Manufacture and Use:  Development of a Methodology for Screening Sustainability”** *
- BRIDGES to Sustainability and Rice University
- Period: July 1st 2003 – June 30th 2005

**Notes:**
I changed the project period.  These are the official dates in the contract.

## Underlying Question

*How can we incorporate sustainability considerations early in the development of an emerging technology?*

## Underlying Question

*How can we incorporate sustainability considerations early in the development of an emerging technology?*

- _Focus on near-term nanotechnology_

## Eco-Efficiency vs. Sustainability

- Eco-Efficiency

- Effectiveness

- Social & Cultural Factors

- Pollution
- Prevention

- Social Welfare

- Service Value

- Environmental
-  Impact

- Toxics
- Reduction

- Business
- Efficiency

- New Markets
- New Technology

- New Business
- Models

- Freedom to
- Operate

- Sustainability

- Profitability

- License to
- Operate

## Eco-Efficiency at BASFSaling, Wall, et al., 2002

**Environmental Impact **(normalized)

**Total costs**** **(normalized)

**1.0**

**1.0**

- Single-score
- aggregate, includes
- Energy
- Raw materials
- Land area
- Emissions & waste
- Toxicity potentials
- Process risk

- High Eco-Efficiency

- Low Eco-Efficiency

## Decision-Support Tools

- Sustainability metrics
- Lifecycle assessment
- Total benefit & cost assessment
- Thermodynamic analysis (exergy, etc.)
- Sustainability screen (list- and question-driven)

**Notes:**
These are some of the sustainability decision-support tools available to assess new/emerging technologies.  
Thermodynamic analysis such as exergy, emergy, being developed, mostly at the conceptual level --- largely untested in industry
Sustainability screen --- mostly qualitative, commonly used (under various names) by companies for the assessment of new technologies in the R&D stage-gate.  Some more sustainability oriented than others.

## Screening Framework

## Example Data Available

- 	**Geographical Reference****	****Effects/Pathways****	****      Costs Estimates, 2001$/ton ****	**
- 					_Low__	__High__	__Best_
- 	U.S. overall	Mortality & morbidity – 2nd nitrate PM10	 1,326 	 21,533
- 		Mortality & morbidity - NO2	 	    195 	      949
- 		Mortality & morbidity - ozone (50%)	       7 	        72
- 		Visibility - NOx		   247 	   1,443
- 		Total	 		1,775 	 23,997 	 6,526
- 	U.S. urban       Mortality & morbidity – 2nd nitrate PM10	 1,807 	 29,101
- 		Mortality & morbidity - NO2	                            247 	   1,248
- 		Mortality & morbidity - ozone (50%)	      13 	        91
- 		Visibility - NOx 	   	    247 	   1,443
- 		Total			 2,315 	 31,883 	 8,590
- 	Los Angeles	Mortality & morbidity – 2nd nitrate PM10	 7,867 	 98,601
- 		Mortality & morbidity - NO2	 	    676 	   3,433
- 		Mortality & morbidity - ozone (50%)	    332 	   2,822
- 		Visibility - NOx **)	 	    247 	   1,443
- 		Total	 		 9,122             106,299 	 31,139

- "McCubbin & Delucchi, 1999; Delucchi et al, 2001"

## Linking Metrics to TBCAMaleic Anhydride Production

- Source: BRIDGES to Sustaianbility; SOx & NOx valuations based on So. California; GHG from IPCC

**$0**

**$200**

**$400**

**$600**

**$800**

**$1,000**

- Fixed Bed

- Fluid Bed

- SOx Emission

- NOx Emission

- GHG Emission

- Water

- Energy & Material

- Operations & Facility

- Per ton Maleic Anhydride

## What is important?

**Dimensions of Sustainability**
**What is important?**

**Notes:**
Examples of considerations in a sustainability screen --- considered at each stage of product lifecycle, from extraction to end-of-life

## Project Issues

- Integrate both quantitative and qualitative aspects of sustainability assessment for emerging technology.
- The most important sustainability cost and benefit drivers for near-term nanomaterials.
- How to communicate with stakeholders.

**Notes:**
These are research questions we will address, at least partially, in this project

## Near-Term Nano

- Very broad, hard to generalize
- Continuous improvements (c.f. disruptive technologies)
- Many unknowns/uncertainties
- Nano-particle vs. bulk properties
- Exposure in use
- Fate at end-of-life (PBT concerns)

**Notes:**
Characteristics of near-term nano applications (focus of this study)
Nanotechnology and nanomaterials are of course very broad terms and therefore difficult to generalize
However, these near term applications generally represent continuous improvements, not the disruptive technologies that underlie most of popular concerns regarding nano (I.e. not the gray goo and the like)
Yet, even with these near-term applications, there remains many unknowns and uncertainties, especially when it comes to safety and environmental impacts
Current industrial practice is to use the same MSDS for bulk materials, but there are indications (e.g. Colvin 2003) that nanoparticles have different toxicity.  This is a concern primarily for manufacturing (workplace safety)
Exposure --- especially for consumer products.  Most, to be sure, are safe.  Nanoparticles used in cosmetics and sunscreens, for example, exist in suspension, no absorption to skin.  However, even in this case, consumers are concerned.
The greatest concern may be end-of-life.  In small quantities, not much concern.  But as nanomaterials become more pervasive, greater concerns.  What’s gonna happen?  Low solubility favors persistence.  Experiments shown biological uptake and undesirable effects.  E.g. Oberdoerster (the father) showed ultrafine particles may cross blood-brain barrier.  More recent SMU study (by Oberdoerster the daughter) showed buckyballs may induce oxidative damages in neurons and are possible bactericides.  There remain many questions regarding these studies, none of these conclusive, but nevertheless raise concerns about safety and environmental impacts.

## Project Approach

- Identify sustainability aspects/impacts along the lifecycle of nanomaterials
- Literature review
- Focus on drivers of costs and opportunities
- Construct inventory of resource use, waste, and emissions in manufacturing
- Focus on three case studies
- Identify “preferred recipe” for each nanomaterial
- Literature + expert “interviews”
- Expand analysis to upstream and downstream
- Quantitative and qualitative
- Generalize approach

**Notes:**
First is largely completed, now being summarized
Second is on-going, making use of expertise available at Rice University and the Houston area in constructing the “method inventory” for some key nanomaterials examined in the case studies.  (Without the “interviews”, this info difficult to get.)

## Nanomaterials – GeneralManufacturing

- Eco-efficiency
- Resource use intensity & impacts
- Pollutant intensity & impacts
- Land use
- Economic value generation
- Workplace health and safety

## Nanomaterials – GeneralUse

- Product performance/service value
- Eco-efficiency in use
- Consumer health & safety

## Nanomaterials – GeneralEnd-of-Life

- Recyclability
- Release to the environment
- PBT concerns
- Low solubility favors persistence
- Biological intake and possible bioaccumulation
- Toxicity of nanoparticles (as opposed to their bulk counterparts) largely unknown

## Nanotechnology & Sustainability:Promises

- Better and more cost-effective technologies
- Separation
- Process sensors and control
- Emission/effluent/waste treatment and remediation
- Greater material & energy efficiency
- Renewable energy (solar)
- ...

**Notes:**
See cautions on next slide.

## Health & Safety Concerns

- Ultra-fine particles (< 100 nm)
- More reactive
- More potent in inducing respiratory inflammation
- May cross blood-brain barrier
- Properties of nanoparticles (as opposed to bulk) largely unknown
- Workspace intake (inhalation, oral, ...)
- Consumer intake/chemical trespass (inhalation, skin absorption, ...)

## Nanotechnology & Sustainability:Threats

- “Nano-pollutants” and new exposure routes
- Changes faster than human ability to ponder and make necessary corrections
- Affordability leading to increased worldwide consumption
- Widening gap between rich and poor, North and South
- Pseudo-Science

**Notes:**
This slide and the one before are product of Matt and I from way back then.  Use at your own risk.
Third and fourth point are contradictory, either (c) or (d) kind of thing
Of course, these threats aren’t unique to the imaginations of Matt and I.  Other people (including group from Royal Society) talked about these as well.  

## Cost Types

- More Difficult to Measure

- Future		Current

*Cost Type*

*Description*

*Examples*

**Notes:**
TCA is a life cycle approach for internal decision making that seeks to ensure that all EH&S costs are fully considered when choosing between alternate products or process designs.  This methodology involves developing LCA data for the options under consideration and evaluating those alternates by estimating the true economic cost of each: whether tangible or intangible, direct or indirect, internal or external, presently captured or future.

## Sustainability Model

- Invest when

**Business revenues > Business costs**

- and

**Total **

**benefits > **

**Total**

**costs**

**Societal **

**Benefits**

**+**

**Business**

**Revenues**

**Societal **

**Costs**

**+**

**Business **

**Costs**

## General Nanotechnology

|  | Supplier | Production | Use | End-of-life |
| --- | --- | --- | --- | --- |
| Benefits | Higher price
Less mass | Higher heat transfer
More uniformity
Less land
Less waste | Time to market
New products | Recyclability?
 |
| Costs | Higher costs
 | Workplace safety issues | Consumer safety issues | Disposal issues |

*Public Concern about Nanotechnology*

**Notes:**
The use of ultrasmall metal oxide particles in sunscreens
Primary benefit is protection against broader UV spectrum
The risk is that they may be absorbed by skin.  The nano sunscreens have essentially the same compositions as the conventional ones, and technically same toxicity.  However, they are of ~100nm and can be absorbed by skin, and may result in greater allergic reaction and possible DNA damage.  FDA approval based on studies on larger size particles, not nanoparticles.

Production should be about the same as conventional.

## Selected Cases

- Inorganic sunscreens – *bulk- vs. nano-sized titania*
- Ceramic membrane – *sol-gel vs. alumoxane nanoparticles*
- Fullerenes (buckyballs)

## Nano-tech vs Conventional Inorganic Sunscreens

|  | Extraction | Production | Use | End-of-life |
| --- | --- | --- | --- | --- |
| Benefits | ? | ? | Aesthetic
Broader protection spectrum | ? |
| Costs | ? | Workplace inhalation? | Skin absorption? | Aquatic releases |

*Public Concern about Nanotechnology*

**Notes:**
The use of ultrasmall metal oxide particles in sunscreens
Primary benefit is clarity (improve aesthetic, that may lead to greater use) and potentially better protection against broader UV spectrum
The risk is that they may be absorbed by skin.  The nano sunscreens have essentially the same compositions as the conventional ones, and technically same toxicity.  However, they are of ~100nm and can be absorbed by skin, and may result in greater allergic reaction and possible DNA damage.  FDA approval based on studies on larger size particles, not nanoparticles.  Nevertheless, the nanoparticles exist as suspension, so this concern may not be realistic.
The greater concern is environmental release, especially to the aquatic environment. We don’t know what the impacts will be, but we know there will be releases.

Will know more about production and extraction by end of project.

## Alumoxane vs. Sol-gel Membranes

|  | Extraction | Production | Use | End-of-life |
| --- | --- | --- | --- | --- |
| Benefits | ? | Less energy
No hazardous substances | ? | ? |
| Costs | ? | Worker exposure to nanoparticle? | ? | ? |

*Public Concern about Nanotechnology*

**Notes:**
Production of ceramic membranes using metal oxide nanoparticles is generally more environmentally friendly than the sol-gel process.  It uses less energy, due to lower baking temperature, and eliminate the need for various hazardous solvents.  Worker exposure to the nanoparticles is a potential risk (the next asbestos?)

Use and end-of-life issues about the same.  Extraction will know after “method inventory”

## Story: C&ENews December 22, 2003

## Sustainability Model

- Invest when

**Business revenues > Business costs**

- and

**Total **

**benefits > **

**Total**

**costs**

**Societal **

**Benefits**

**+**

**Business**

**Revenues**

**Societal **

**Costs**

**+**

**Business **

**Costs**

**Societal**
**Concerns**

## Evolution of Costs: “Harmless” Odors

**Reduced Enjoyment of Property**
**Psychological Impacts**
**Physical Health Impacts**

**Join Citizen Groups**
**Take Legal Action**
**Contact Regulatory Agency**
**Relocate**

**Property Devalues**
**Tourism Declines **
**Development Hindered**
**Employment Declines**

- Capital for equipment

- Internal legal costs
- Punitive Damages
- Public Relations Staff

- Fines & penalties

- Lost good will
- Job productivity

-   Society
- "The Commons"

- Company

**Individual Choice**

- System Imposed

- Societal
- Costs

- Direct

- Indirect

- Fines &
- Penalties

- Internal
- Intangible

## Next Steps

- Continue manufacturing inventory
- Collect safety and LCA data on materials used in manufacturing
- Expand analysis of cost/benefit drivers to extraction and end-of-life
- Solicit comments

## Implications of Nanomaterials Manufacture and Use: Project Plan  

## Implications of Nanomaterials Manufacture and Use: Project Plan  

- Research
- production
- methods &
- required
- materials

- Preferred “recipe(s)” for each nanomaterial
- Process used with each recipe

## Implications of Nanomaterials Manufacture and Use: Project Plan  

- Implications of Nanomaterials Manufacture and Use: Project Plan

- Research
- production
- methods &
- required
- materials

- Preferred “recipe(s)” for each nanomaterial
- Process used with each recipe

**Deliverables  for Existing Project**

## Implications of Nanomaterials Manufacture and Use: Future 

- Identify
- key nano-
- materials

- Research
- production
- methods &
- required
- materials

- Project
- production
-  volumes
- based on
- expected
- applications

- Collect
- material
-  characteristics
- of inputs,
- additives,
- and outputs

- Model
-  relative
-      manufacturing
-  risk of nano-
- materials

- Projected market uses
- Projected production volumes
- Variety of opinions
- Variety of time horizons

## Implications of Nanomaterials Manufacture and Use: Future 

- key nano-
- materials

- Research
- production
- methods &
- required
- materials

- Project
- production
-  volumes
- based on
- expected
- applications

- Collect
- material
-  characteristics
- of inputs,
- additives,
- and outputs

- Model
-  relative
-      manufacturing
-  risk of nano-
- materials

- Implications of Nanomaterials Manufacture and Use: Future

## Implications of Nanomaterials Manufacture and Use: Future 

- key nano-
- materials

- Research
- production
- methods &
- required
- materials

- Project
- production
-  volumes
- based on
- expected
- applications

- Collect
- material
-  characteristics
- of inputs,
- additives,
- and outputs

- Model
-  relative
-      manufacturing
-  risk of nano-
- materials

- Based on:
-  Material properties
-  Process characteristics
-  Projected volumes

- Implications of Nanomaterials Manufacture and Use: Future

## Project Personnel

- PI: Earl Beaver
- BRIDGES to Sustainability
- Beth Beloff (co-PI)
- Dicksen Tanzil (co-PI)
- Balu Sitharaman (intern, Rice Dept. of Chemistry)
- Rice University
- Mark Wiesner (co-PI)
- Christine Robichaud
- Maria Cortalezzi

## Acknowledgement

- USEPA Nanotechnology STAR
- Funding