Sediment and Terrestrial Toxicity and Bioaccumulation of Nano Aluminum Oxide. Click to edit Master subtitle style

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1 Sediment and Terrestrial Toxicity and Bioaccumulation of Nano Aluminum Oxide Jessica G Coleman ERDC, Environmental Laboratory Vicksburg, MS

2 Research Team Dr. Jacob K. Stanley, Research Biologist Dr. David R. Johnson, Research Biologist Dr. Anthony J. Bednar, Research Chemist Dr. Charles A. Weiss, Jr., Material Scientist Dr. Jeffery A. Steevens, Research Toxicologist Research Team

3 Risk Assessment of Nanomaterials Problem Formulation Analysis and Risk Characterization Risk Management Exposure Effects Identify and quantify environmental attributes of nanomaterials Sources? Fate and transport mechanisms? Likely exposure scenarios? Biological effects? Characterize physical / chemical interactions between engineered nanomaterials and environmental media GOAL Establish approaches for predicting relevant characteristics associated with toxicity and environmental impacts(persistence, fate, toxicology)

4 ERDC Nanomaterials Risk Research Cluster Material characterization Fate and transport Ecotoxicology Computational chemistry Risk and decision analysis Interdisciplinary team of experts in fields of materiel science, geology, soil science, toxicology, and computational chemistry

5 Conceptual Model: Environmental Impact of Nanomaterials Conceptual Model: Environmental Impact

6 Current Research Materials Silver Fullerene Aluminum Oxide (Al ) MWCNT

2008) in rocket propulsion Increase burning rate, heat, and energy density - lower ignition time -reduces ignition time and

7 Potential military uses: Nano Aluminum Oxidizer in energetics / propellants - High energy release during oxidation to Al 2 O 3 -Diesel fuel additive (Tyagi et al. 2008) in rocket propulsion Increase burning rate, heat, and energy density - lower ignition time -reduces ignition time and temperature by two-fold (Armstrong et al. 2003; Meda et al. 2007). Industrial uses: Coatings Abrasives Nano Al 2 O 3 TEM image Polishing of optics and jewelry All create potential sources of release for nano Al 2 O 3 to environment

8 Assessing Impact of Nano Al 2 O 3 Need to assess both human and environmental impact Arising regulatory requirements could limit military use if not extensively characterized; i.e. European Union on the Registration, evaluation, Authorization and Restriction of Chemical substances (REACH) Aim to follow a comprehensive environmental assessment (CEA); provides holistic outlook on material life cycle and environmental risk New DoD technologies undergo an technology development and acquisitions process; track R&D, production, deployment, use and disposal

9 Stages of Acquisition Process Benefiting from Environmental Hazard Assessment Milestones Analyze Concept Begin Development Commitment to Rapid Acquisition A B System Integration C System Demonstration Full-Rate Production & Deployment Sustainment Disposal Concept Decision Design Readiness Review FRP Decision Review CONCEPT REFINEMENT TECHNOLOGY DEVELOPMENT SYSTEM DEVELOPMENT & DEMONSTRATION PRODUCTION & DEPLOYMENT OPERATIONS & SUPPORT Pre-Systems Acquisition Systems Acquisition Sustainment & Maintenance Technology development and acquisitions process. Adapted from Mike McDevitt, Installations Management Command 9

Due to use of material over land ranges and potential for water runoff and soil mobility, how do factors

10 Environmental Risk of Nano Al 2 O 3 What are the potential environmental risk of nano Al 2 O 3 particle release? Due to use of material over land ranges and potential for water runoff and soil mobility, how do factors such as fate, transport in terrestrial and aquatic environments affect organisms? Use in additives/explosives/ propellants Nano Al 2 O 3 particles dispersed Potential impact on terrestrial/aquatic organisms

11 1. Sources 2. Media and Transport Processes Engineered Nanostructure Case Study: Nano Al 2 O 3 in Terrestrial Systems Air Aggregation/ UV Degradation Settling / suspension Soil Terrestrial Invertebrates 3. Exposure Pathways and Receptors Terrestrial Vertebrates Engineered Nanodevices Degradation Contact, Ingestion Reaction Intermediates Production Waste Sorption / desorption Water Aquatic Invertebrates Contact Click Aggregation/ to edit Master subtitle Ingestion style Ingestion Degradation Fish Ingestion Fish Product Degradation Deposition, Spills Intentional application Settling / suspension Sediment Degradation Contact Ingestion Benthic Invertebrates Ingestion

12 Model Species: Eisenia fetida Habitat: upper layers of soil Ecological impact: nutrient cycling and food source for larger predators Dermal Exposure Ingestion Rationale for exposure of Eisenia fetida to nano Al 2 O 3 : Earthworms imbed in soils potential for whole body exposure Earthworms exhibit toxicity response to certain metals Potential for bioaccumulation through ingestion and dermal uptake

Experimental Approach 28-Day Sub-Chronic

soil avoidance study exposing earthworms to nano

13 Experimental Approach 28-Day Sub-Chronic Bioaccumulation/ Toxicity Study: E. fetida exposed to a nano and micronsized Al 2 O 3 treated soil Soil Avoidance Bioassay: 48-hour soil avoidance study exposing earthworms to nano and micron-sized Al 2 O 3 amended soils utilizing a soil avoidance wheel.

Nano Al 2 O 3 Characterization Nano Al 2 O 3 TEM

11nm Spherical particles and rods present DLS-

water Micron-sized Al 2 O 3 SEM Image Consistent

14 Nano Al 2 O 3 Characterization Nano Al 2 O 3 TEM Image Particles 1->100nm present, manufacturer size 11nm Spherical particles and rods present DLS- bimodal populations Zeta potential- not stable in water Micron-sized Al 2 O 3 SEM Image Consistent with manufacturer statement, Al 2 O 3 particles between µm

Sub-Chronic Bioaccumulation Toxicity Study: Earthworms depurated 24-hours Adults 0.3-0.

15 Sub-Chronic Bioaccumulation Toxicity Study: Earthworms depurated 24-hours Adults g Soil Exposures 10 added per treatment Test conducted 28-days at 22 C, 80% humidity, continuous light Endpoints assessed: bioaccumulation, toxicity, growth, reproduction Treatments 0-10,000 mg/kg

Aluminum in Tissue (mg/kg) 300 250 200 150 100 50 0 Bioaccumulation 0 100 300 1000 3000 10000 Results Click to edit Master 20 subtitle style Aluminum Oxide Soil Concentrations (mg/kg) * *

16 Aluminum in Tissue (mg/kg) Bioaccumulation Results Click to edit Master 20 subtitle style Aluminum Oxide Soil Concentrations (mg/kg) * * Micron-sized Nano # cocoons Reproduction 100% survival, but reproductive toxicity observed Micron-sized Nano Aluminum Oxide Soil Concentrations (mg/kg) *

earthworms recovered in control soil * Nano * Micron-sized

17 Soil Avoidance Results: 48-h Al 2 O 3 Control Control Al 2 O 3 Control Al 2 O Ratio of 10 =100% of earthworms recovered in control soil * Nano * Micron-sized Nominal Al Soil Concentrations mg/kg *

18 Discussion: Terrestrial Impact of Nano Al 2 O 3 Nano Al 2 O 3 may cause negative impacts in terrestrial invertebrate populations such as reduced reproduction and habitat Negative impacts only observed at > 3,000 mg/kg nano Al 2 O 3 Concentrations Click to edit where Master effect subtitle is observed style is unlikely to be found in the environment except under extreme circumstances Coleman et al Assessing the fate and effects of nano aluminum oxide in terrestrial earthworm, Eisenia fetida. Environ. Toxicol. Chem.

19 Case Study: Nano Al 2 O 3 in Aquatic systems 1. Sources 2. Media and Transport Processes 3. Exposure Pathways and Receptors Air Aggregation/ UV Degradation Terrestrial Vertebrates Engineered Nanostructure Settling / suspension Soil Terrestrial Invertebrates Engineered Nanodevices Degradation Contact, Ingestion Reaction Intermediates Production Waste Sorption / desorption Water Aquatic Invertebrates Contact Click Aggregation/ to edit Master subtitle Ingestion style Ingestion Degradation Fish Ingestion Fish Product Degradation Deposition, Spills Intentional application Settling / suspension Sediment Degradation Contact Ingestion Benthic Invertebrates Ingestion

20 Organisms Tested Tubifex tubifex Hyalella azteca Lumbriculus variegatus Click to edit Master Corbicula subtitle fluminea style

21 Nano Al 2 O 3 Sediment Tests - Survival Tubifex tubifex Survival up to 100,000 mg/kg Proportion Survival Control 10,000 25,000 50, ,000 mg/kg Al 2 O 3 Hyalella azteca Significant mortality at 2500 mg/kg in sediment 0.8 Mean proportion survival Nano Al 2 O 3 Micron-sized Al 2 O 3 * 0.0 Control 625 mg Bulk 625 mg Nano 2500 mg Bulk 2500 mg Nano Al 2 O 3 treatment

22 28-d Nano Al 2 O 3 Sediment Bioaccumulation BAF ([tissue Al]/[sedment Al]) Lumbriculus variegatus Bioaccumulation factor (BAF)- ratio of the contaminant in an organism to concentration in environment at steady state Control Bulk Nano Treatment 25g/kg Al 2 O BAF ([tissue Al]/[sediment Al]) Corbicula fluminea 0 Control Bulk Nano

23 Hyalella azteca 10-d - Bioaccumulation Bioaccumulation Factor (BAF) ([tissue]/[sediment]) Control Al 2 O 3 Treatment Level Bulk Al2O3 Nano Al2O3 Hyalella azteca Confocal Image

24 Discussion Aquatic Exposures No toxicity observed to Tubifex Nano more toxic than bulk to Hyalella BSAFs similar for nano and bulk in Hyalella and Corbicula bioaccumulation studies BSAF for bulk higher than nano in Lumbriculus However, significant effects observed only at high, environmentally unrealistic concentrations Therefore, Click our results to edit support Master a finding subtitle of low style environmental risk of nano Al 2 O 3 to benthic and terrestrial invertebrates Stanley et al Sediment toxicity and bioaccumulation of nano and micron-sized aluminum oxide

25 Steps Forward: Incorporate into Comprehensive Environmental Assessment (CEA) Adapted from Davis,

26 To learn more about the nano CEA: # A Comprehensive Environmental Assessment Approach to Making Informed Decisions about Engineered Nano Particles Dr. David Johnson Click to edit Thursday, Master 2:30 subtitle style Room 278

27 US Army Engineer Environmental Laboratory, Vicksburg, MS, USA Contact Information:

Sediment and Terrestrial Toxicity and Bioaccumulation of Nano Aluminum Oxide. Click to edit Master subtitle style

Sediment and Terrestrial Toxicity and Bioaccumulation of Nano Aluminum Oxide Jessica G Coleman ERDC, Environmental Laboratory Vicksburg, MS Report Documentation Page Form Approved OMB No. 0704-0188 Public