Nanomaterials Introduction And Background: Applications .
Nanomaterials Introduction and Background:Applications, Life-cycle, Toxicity, andHazardous Waste Management Implications2014 California CUPAConferenceBurlingame, CA2/5/14
Background of Nanotechnology Types of Nanomaterials Unique Properties Applications Potential Hazards for CNTs and TiO2 Environmental Fate and Transport Managing Occupational Exposures Life Cycle Environmental Management Regulatory Outlook End of Life For Nanomaterials Conclusions and Future Research Needs
Background of Nanotechnology What is “nanotechnology”? Engineering and manipulationof matter on atomic and molecular scalePhysical substances with structural dimensions between 1and 100 nanometers (nm) 1 nm 1 billionth of a meterNatural vs. engineered nano-sized particles (NSPs)
Engineered NP’s vs Naturally Occurring NP’s
Name “Nanotechnology” popularizedEric Drexler popularized the term in mid-1980’s— In 1986 he wrote the book“Engines of Creation” and subtitled "The ComingEra of Nanotechnology.”— Predicted “Grey Goo” from uncheckedreproduction of nanobots-Michael Chrichton 2008- “Prey”Story about nano robots on the loose
New Imaging Technology DrivesNanotechnology TEM resolution improves 20x Scanning tunneling microscope1981 Atomic force microscope-1986STM ImageAFM ImageTEM image
Nanotechnology Overlaps many Fields
Acheivements for Nanotechnology:Bible on Head of a Pin, 2007Iconic IBM Advertisement from 1989With 35 Xenon atoms using TEM2 Nobel Prizes for Nanocarbon Buckyball: Discovered in 1985 by RobertF. Curl, Harold W. Kroto and Richard E.Smalley.”—1996 Nobel Prize in ChemistryAwarded for this discovery Followed by Nobels for graphene (2010)
Types of nanomaterials: Structure Composition Functionality Carbon-based materials:Composed of carbon, taking shape as spheres, cylinders,or tubes: Carbon nanotubes also known as CNTsLarge aspect ratio- (1: 132,000)Uses: sports gear, electronics, solar cells, vehicles,medicine, Lightweight batteries, constructionSpace Elevator:SWCNT100,000 km longsci-fi or reality?
Metal-based Nanomaterials:Quantum dots, nano-gold, nano silver,metal oxides: Titanium Dioxide TiO2, BNPs Found in cosmetics, sunscreen,coatings, toothpaste, food additivesAlso utilized in remediation technologiesWater quality:- Contaminant Removal- Drinking Water Treatment
Unique Properties of engineeredNSPs lEngineered NSPs exhibit uniqueproperties as result of larger surface area,increased reactivity, and quantum effectsat molecular level based on morphologyand composition
Applications for NanomaterialsWhat’s in it for me?Materials Science Battery technology, solar cells, Sporting goods Cosmetics, paints, coatings Semiconductors, renewableenergy technology Military apps, transportation
Consumer Products Inventory- IndustryOverview 1600 manufacturer-identifiednanotechnology-based consumer productsintroduced to market to date:http://www.nanotechproject.org/cpi/As of March 2011 nano-enabled productsincreased 521% since 2006 (212 products)NSF Estimated 1 trillion industry by 2015with 2 million workers.Silver, carbon, TiO2 most common738 products in health & fitness sector
Newest Nano-products on Market Nanoflex Cotton Suit:Anti-microbial and hydrophobic NanoChar Increased fire protection, hardness Uvex Variomatic Sunglasses No fog technology and scratch protection MesoSilver Antifungal Spray Silver spray kills bacteria and fungal pathogens
Medical Applications: Advanced bio-sensorsTargeted drug delivery systemsBone-grafting and tissue repair
Nanomedicine Goals: 1) Understand how the biologicalmachinery inside living cells is built andoperates at the nanoscale and,2) use this information to re-engineerthese structures, develop newtechnologies that could be applied totreating diseases, and/or leverage thenew knowledge to focus work directly ontranslational studies to treat a disease orrepair damaged tissue.
Recent Nanomedical Discoveries: Early lung cancer screening: Detects early stagevia micro RNA samplingGold nanoparticle flu test: test from 2 weeks toinstantaneous (gold scatters light)Sandia Cancer hunters: Protocells seek anddestroy cancer cells, no more chemo!Cell feedback: makes drugs more effective andspeeds up drug trialsSpinal cord repair: Rebuilding spinal cords withCNTs and proteins, success observed in rats, akthroughs-in-nanomedicine/
Environmental ApplicationsEnvironmental remediation: Toxic spill clean up Heavy metals / pesticides Soil and groundwater treatment Drinking Water treatment using Ti02
In-Situ Nanoremediation Potential to reduce costs of clean-up large-scalecontaminated sitesReduce cleanup time, eliminate the need for treatmentand disposal of contaminated soil, and reduce somecontaminant concentrations to near zero—all in situ.More research needed to address adverse environmentaleffects such as fate and transport and biological uptake.
Nanomaterials Desired Properties for InSitu Remediation Nano-size increased surface area andreactivity more pervasive 20 m in GWInnovative surface coatings for desiredcontaminants, effects.CNTs, metal oxides, zeolites, TiO2, BNP (bimetallic nanoscale particulate)nZVI (nanoscale zerovalent iron) mostcommon: (10-100 nm diameter)Organic solvents, pesticides, PCB’s, metalsOne case study showed 99% reduction ofTCE within days of injection (Zhang 2003)Thorough site characterization required:
Hazardous Waste Clean-up sites: EPA estimated haz waste sites in US and cost
Nanoremediation Applications:
EPA study 2009 “Drinking watertreatment and sunscreen case study forTitanium Dioxide (TiO2) NSPsEPA case study: 2 applications: Arsenic removal TiO2 in sunscreen ComprehensiveEnvironmentalAssessment andimplications 2007 NanotechnologyWhite Paper:
What are the hazards of NSPs?New field of nanotoxicology: Human toxicity and exposure routes- Inhalation isprimary occupational exposure route. Secondaryexposures: IngestionPhysico-chemical properties and interactions withecosystems unknownEnvironmental Fate and Transport Uncertain ifmaterials enter environment at the end of their life.(some intentionally released) e.g. TiO2 in Watertreatment or remediation technologies
Common Drivers of “Nanotoxicity” Intrinsic elemental toxicityIndividual atoms or ions interfere withbiological systems(Lead, cadmium, fluoride, etc)Usual dose metric is mass Surface area/reactivity driven toxicitySurface catalyzes damaging reactionsSurface area is likely the most relevant dosemetric Morphology-driven toxicityFiber toxicity(Asbestos, fibrous zeolites, MMMF)Usual dose metric is particle count
History tends to repeat itself: Miracle materials— Asbestos— Lead— PCBs— MTBE— Nano?
Primary EH&S Issue: UnboundEngineered NanoparticlesNot firmly attached to a surface Not part of a bigger item or (embedded instructure or liquid solution) Can result in exposurevia inhalation, skin absorption or ingestion (orother nanospecific routes of exposure!) NSPs crossing blood/brain barrier?(Oberdorster 2004)—New properties of NSPsEnhanced toxicity of materials— New toxicologicalproperties not seenin bulk material
Respiratory Hazards of NSPsSize Does Matter!
Carbon Nanotubes already here! Sporting goods,aerospace/defense,wind turbinesautomobile industry,batteries, electronics,filtration 500 consumerproducts thatcontainnanomaterials atlast count
Some People Are Showing TheirConcern!
Toxicity assessment and exposureroutes for CNTs: Inhalation- (Primary route)Effects: Carcinogenic- Pulmonary fibrosis,granulomas, mesothelioma, genotoxicity DNAdamage (observed in mouse pathology)CNTs compared to asbestos exposures by NIOSH:Detection methods inadequateHigh tendency to stick together
Titanium dioxide (TiO2) exposureroutes and toxicityTiO2 dust or powder- exposures can occur during researchand development, manufacture, product use Inhalation (Primary route)- Carcinogen (IARC) tumors- Inflammation Ingestion- secondary routeDNA damage observed in miceTranslocation to Central NervousSystem (CNS)ENPs can potentially cross the bloodbrain barrier to CNS as observed inrodent studies and pathology.(Oberdorster 2004) http://www.ncbi.nlm.nih.gov/pubmed/15204759
Potency of nanoparticles vs. largerrespirable particles
Managing Occupational Exposuresto NSPs Administrative Controls Mechanical Controls Personal Protective Equipment Monitoring Equipment Medical Monitoring
Best Management Practices,Administrative, Engineering Controlsand Exposure Limits Preliminary Hazard AssessmentChemicals/materials being used in theprocessProduction methods used during eachstage of productionProcess equipment and engineeringcontrols employedWorker’s approach to performing jobduties4 Current Strategies for EngineeringControls in Nanomaterial Production andDownstream Handling ProcessesExposure potential to the nanomaterialsfrom the task/operationsThe facility that houses the operation
Nanomaterial Risk Management Plan Automated product transfer between operations—aprocess that allows for continuous process flow toavoid exposures caused by workers handlingpowdered or vaporous materials.Closed-system handling of powdered or vaporousmaterials, such as screw feeding or pneumaticconveying.Local exhaust ventilation. Steps should be taken toavoid having positive pressure ducts in work spacesbecause leakage from ducts can cause exposures.Ducts or pipes should be connected using flangeswith gaskets that prevent leakage.Continuous bagging for the intermediate outputfrom various processes and for final products. Aprocess discharges material into a continuous bagthat is sealed to eliminate dust exposures caused bypowder handling. Bags are heat sealed after loading.
Nanomaterial Risk Management Plan Minimizing the container size for manual materialhandling. Minimizing the size of the container orusing a long-handled tool is recommended so thatthe worker does not place his breathing zoneinside the container.NIOSH recommends a maximum container depthof 25 inches [NIOSH 1997]. If large containersare required, engineering controls to provide abarrier between the container and the breathingzone of the worker are recommendedCurrent Strategies for Engineering Controls inNanomaterial Production and DownstreamHandling Processes
Nano Tool-Kit .pdf Working Safely with EngineeredNanomaterials in Academic ResearchSettingsDeveloped by University of CaliforniaCenter for Environmental Implications ofNanotechnology UCEIN, and DTSC, as wellas other academic institutions: Stanford,UCLA, UCSB, UCI, USCEasy to use tool kit to minimize oreliminate exposures and develop SOP’s forspecific nanomaterials, and operations.
Occupational Health and SafetyConcerns (nano toolkit) Routes of Exposure: inhalation, dermalcontact, ingestionLack of Information on Full Health Effects:lack of data, apply precautionary principleToxicity: Respiratory tract, cross cellmembranes, penetrate skinOther: Catalytic effects: Fire or Explosion;can be caused by processes
Occupational Exposure Limits (OEL)Although there are currently no(legally enforceable) exposure limitsin US or Int’l, NIOSH has developedRecommended Exposure Limits(RELS) for CNTS (TWA 7 ug/m3)and nano TiO2 (TWA .3 mg/m3)Some private companies have theirown exposure limits.
Risk Level And Controls: Category 1: Low exposure potentialbound in substrate, water basedsuspension. No airborne release potential.Category 2: Moderate exposure potentialpowders, pellets, or solvent based liquidsuspensions. Airborne release potentialwhen handlingCategory 3: High exposure potential:Powders or pellets with extreme potentialfor release into air, or suspended in gaswith high release potential.
Heirarchy of Controls in laboratory:Nano toolkit ilationWork PracticesPersonal Protection
Engineering Controls: Minimizeairborne releases with equipment Fume hood or Bio-safety cabinet: (must beducted if using volatile compounds)Glove box or fully enclosed system: Useful forgrinding operations or gas phaseLocal capture Exhaust hoodsUse High-Efficiency Particulate Air (HEPA)system:Ensure performance and maintenance: Wetwipes and HEPA vacuums for any maintenanceto be performed: complete monitoring,maintenance checks
Acceptable Practice?Raw single walled carbon nanotube material (HiPCO Process)
BMPs for ENPs in laboratory Use solutions or substrates: Prevents airbornereleases: liquid solution/ solid matrixKeep safety equipment and spill kitUse signs and labels: Indicate “ENM work”warning, caution, specific hazard warningClean and maintain: sticky floor mats,absorbent pads, wet wipe and/ or HEPAvacuum work surfaces and equipment afteroperationsPersonal Hygiene: No eating or drinkingStore and label properly “indicate nano” hazardTransport in Secondary containment to avoidrelease:
PPE Selection and Usage:Nanomaterial / State Glove Type (Recommendation) Carbon Nanotubes (CNTs)Nitrile overLatex*, ** TiO2 Latex**, Nitrile, Neoprene*** Graphite Latex**, Nitrile, Neoprene, Vinyl Consult MSDS, and PPE quick-guide on nanotool kit for specifics.PPE is always last line of defense:Respiratory protection will require full RPPprogram:Research has shown current PPE does haveefficacy:
Proper Disposal: Waste Management General Rule: Until more informationavailable, assume ENM containingwastes to be hazardous unless theyare known to be non-hazardous:Label all nanowaste and specific hazardcharacteristics include “nano” in name.Keep containers closed at all times!Maintain containers in good condition andfree of exterior contamination.
Hazardous Waste Management ofNanomaterials: Waste streams and management methodsSolid Dry ENM product Filter media containing ENMs Debris / dust from ENMs bound in matrix 1. Follow General Nanomaterial Waste Management Practices2. Collect waste in rigid container with tight fitting lid.Liquid Suspensions containing ENMs 1. Follow General Nanomaterial Waste Management Practices.2. Indicate both the chemical constituents of the solution andtheir hazard characteristics, and the identity and approximatepercentage of ENMs on container labels.3. Use leak proof containers that are compatible with allcontents.4. Place liquid waste containers in secondary containment andsegregate from incompatible chemicals during storage.
Hazardous Waste Management:Laboratory ENP waste (continued)Laboratory trash with trace nanomaterials PPE Tacki mats Spill clean-up materials1. Follow General Nanomaterial Waste ManagementPractices.2. Dispose of in double clear plastic bags, folded overand taped atthe neck.3. Avoid rupturing the bags during storage andtransport.Solid Matrix embedded with nanomaterials (intact and in good condition) 1. Consult with your EH&S department, as thesematerials may be non-hazardous
Develop Specific Nanomaterial EHSProgram and SOPs for ENPs
Nanomaterials and the Environment:Lifecycle Assessments:
Environmental Fate and Transport:Defining Exposure Pathways Management and detection of materialsfrom cradle to grave.May enter water and food cycles aslandfill waste, incineration intentionalrelease as remediation.Unknown dangers- Most nanomaterialshave not been mass produced until now.(grey goo ?)Responsible development is key
Exposure Pathways
LIFECYCLE EXPOSURE ROUTESAND ASSESSMENTS
Nano Products end of life
Regulatory OutlookFeatureExampleEPA VerdictAggregates or particles ofknown substancesSAMENanoscale versions ofknown substancesSAMEWhile Nano particles differ in particle size and may exhibit differentphysical and/or chemical properties, EPA considers the two forms tobe the “same” chemical substance because they have the samemolecular identity.
Berkeley Nano Ordinance Berkeley Manufactured Nanoscale MaterialsHealth and Safety Disclosure Ordinance,December 2006 An “add on” to the HMBP process Only local nano ordinance, focused ondisclosure Compels facilities that produce or handlemanufactured engineered nanoscalematerials to report what they are workingwith, describe known toxic effects andprovide a plan on how the materials arehandled safely.
Berkeley Nano Ordinance: Criticism No de minimis quantitiesspecified “Open” reporting format Limited amount of informationcaptured Burdensome and may drive outstartups
State of California Call-InsCalifornia Health and SafetyCode 699: Basis for requiring producers ofspecified nanomaterials to report onnanoparticles--quantity, detection methods,risks, protective steps etc Do you consider your waste or material to behazardous waste? Two stages complete— Call 1: Carbon nanotubes— Call 2: Assortment of metal and metaloxide nanoparticles
California/Federal OSHA No specific regulations for newengineered nanomaterials
EPA: TSCAProhibit/Regulate introduction ofnanoparticles into commerce underTSCA:— Underway for CNTs and othernanoparticles since 2008 Regulate as a pesticide (FIFRA):— Already underway for nano-silver Prohibit releases to air (Clean Air Act)or Water (Clean Water Act, SafeDrinking Water Act) Classify as hazardous Waste (RCRA)
EPA: TSCAGenerally, you can only market and usechemicals that are on the EPA ToxicSubstances Control Act(TSCA) inventory Carbon nanotubes are fundamentallynew and are not among the 84,000chemicals on that inventory Most other “nano materials” arechemically identical to largermaterials and thus not subject toregulation as new chemicals, yet
Evolving EPA Rules for CNTsEPA receives at least 100 PMNs to import or manufacturenanomaterials, many for CNTs. Eventually the EPA entersinto “5(E)” consent decrees with many of these companies,with the following typical requirements:— Use the material only for the listed (semi-secret!)purposes Examples: polymer composite materials, electronics,catalyst support— Conduct a 90-day rat inhalation toxicity study on theirmaterial— Require employees who may be exposed to use specifiedtypes of personal protective equipment at facilities underits control (fullface respirator/protective coveralls andgloves)— Only distribute the material to persons who agree tocomply with all of the restrictions of the 5(e) order(except the tox study).
EPA Issues Significant New UseRules (SNURs)for Multi-Walled Carbon NanotubesAfter signing a Section 5(e) Consent Order, EPA generallypromulgates a Significant New Use Rule (SNUR) that mimics theConsent Order to bind all other manufacturers and processors tothe terms and conditions contained in the Consent Order for thatexact, specific PMN material. The SNUR requires that manufacturers, importers and processorsof PMN substances notify EPA via a SNUN at least 90 days beforebeginning any activity that EPA has designated as a "significantnew use”. These new use designations are typically thoseactivities prohibited by the Section 5(e) Consent Order.”— Significant new uses of multi-walled carbon nanotubes aredeemed to occur when employees do not “use gloves imperviousto nanoscale particles and chemical protective clothing;” and/orfail to “use a NIOSH approved full-face respirator with an N-100cartridge while exposed by inhalation in the work area.”— “Significant new use” applies to the use of a substance outside ofthe list of approved uses in the PMN (e.g. catalyst support, filler,polymer).
Conclusions and Further ResearchNeedsToxicology Regulatory Instrumentation Lifecycle Management Approach Recyclability International Collaboration
Nano Resources: Nano kit.pdfNIOSH Guide: Current Intelligence BulletinsEPA White Paper on NanotechnologyASTM E 2535-07 (10/07) guide for Handling ENPS inoccupational settingISO Technical Report 12885 (10/2008)NNI National Nanotechnology Initiative: http://www.nano.gov/UC CEIN: University of California Center for EnvironmentalImplications of Nanotechnologyhttp://www.cein.ucla.edu/new/PEN; Project on Emerging nanotechnologiesUSEPA: Nanomaterial Remediation StrategyNanosafety at the OECD:http://www.oecd.org/env/ehs/nanosafety/CDC/ NIOSH- Nanomaterial Production and Downstreamhandling Processes: 2.pdf
Questions?Dan Rompf, M.S.Hazardous Materials Specialist(650)372-6201 Office(650)627-8244 Faxdrompf@smcgov.orgOffice Hours: 0700-1800 Tues-Fri2000 Alameda de Las PulgasSan Mateo, CA
Jan 07, 2014 · Nanomaterials in Academic Research Settings Developed by University of California Center for Environmental Implications of Nanotechnology UCEIN, and DTSC, as well as other academic institutions: Stanford, UCLA, UCSB, UCI, USC Easy to use tool kit to minimize or eliminate exposures and develop SOP’s for
Production and Applications of Cellulose Nanomaterials iii Production and Applications of Cellulose Nanomaterials Michael T. Postek National Institute of Standards and Technology Robert J. Moon USDA Forest Service, Forest Products Laboratory, School of Materials Engineering, and the Bir
particles in size between 1 to 100nm is known as nano science and nano technology. b) Classification of nanomaterials on the basis of dimensions On the basis of reduction in size of materials in different dimensions, nanomaterials are classified into three groups. S. No. Reduction in size in different coordinates Size Examples 1.
nanomaterials and applications of nanomaterials in terms of market volumes and societal benefits; A list of indicators on fitness-for-purpose. The reason why manufactured nanomaterials are of such interest and offer such potentially significant benefits to society is that they of
STUDY Nanomaterials in Food Prof. Jorge Gardea-Torresdey with some of his research group members. 2 Characterization of Nanomaterials Even though the properties of these manufactured nanomaterials are ideally-suited for the applications they are
particles in size between 1 to 100nm is known as nano science and nano technology. b) Classification of nanomaterials on the basis of dimensions On the basis of reduction in size of materials in different dimensions, nanomaterials are classified into three groups. S. No. Reduction in size i
A nanometer is one millionth of a millimeter - approximately 100,000 times smaller than the diameter of a human hair. Nanomaterials . The history of nanomaterials began immediately after the big bang when Nanostructures were formed in the early meteorites. Nature later evolved many other Nanostructures like
nanomaterials differ remarkably from bulk materials. This difference can be mainly attributed to the quantum confinement effects, unique surface phenomena, and efficient energy and charge transfer over nanoscale distances within nanomaterials. The origin of the color difference in the cup is attributed to the
environmental fate and behaviour of engineered nanomaterials (ENMs) is the first report from the project “Nanomaterials – Occurrence and effects in the Danish Environment” (“NanoDEN”). NanoDEN was commissioned by the D
