Nanotechnology in Consumer Products

Transcription

1 Nanotechnology in Consumer Products Occurrence, Removal and Regulation of Nanomaterials at Publicly Owned Sewage Treatment Works Thursday, October May 26, 31, The webinar will begin at 1pm Eastern Time CLICK HERE FOR THE WEBINAR RECORDING

2 Occurrence, Removal and Regulation of Nanomaterials at Publicly Owned Sewage Treatment Works Begin Recording Paul Westerhoff, PhD, PE, BCEE School of Sustainable Engineering and The Build Environment Ira A. Fulton Schools of Engineering Arizona State University (Tempe, AZ)

3 Benefits & Risks of Nanotechnology GOOD nano Quantum size effects result in unique mechanical, electronic, photonic, and magnetic properties BAD nano Stone & Donaldson, 2006 Nanoparticles operationally defined as < 100 nm in at least one-dimension

4 Presentation Outline NM Sources & Uses in Society Wastewater Treatment Plants Liquid Effluent to Surface Waters Biosolids to Land Application, etc

5 Society is a source of incidental & engineered Nanomaterials Air Land Application of Biosolids ~60% of biosolids land applied in the USA Society Wastewater Treatment plant Drinking Water Treatment Plant Wastewater Treatment plant Incineration Society Landfill

6 Projections indicate high NM loadings to Sewers & WWTPs Nanomaterials most likely to occur: TiO 2 > ZnO > Ag > CNT > fullerene

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8 Product Line A Polishing Agents Industrial processes for electronics, optics etc use polishing agents in fluids >>$1B industry SiO 2, Al 2 O 3, CeO 2 are common polishing agents Polishing agents end up in sewers not consumer products No direct regulation exists for their discharge to sewers

9 Common Direct NM Detection Method NM Type Generalized Detection Limit Comments Light scattering (UV/VIS) any > 1 mg/l in water 0.05 mg/l with HPLC of NM extract ICP-MS (better than ICP-AES) TOF-MS (emerging) metals LC-MS C60 ~ 1 ppt > 10 ppt in water (total metal conc) Ability to get size, # and concentration dosimetry (sp-, FFF-, centrifugal ICP-MS) Thermal combustion or Microwave thermal analysis MWCNT SWCNT ~ 1 ppb Isotopes 14 C Metal isotopes < 1 ppb by Scintillation counting Isotopic ratios

10 Environ. Sci.: Nano, 2015, 2,

11 On-site Chemical Lime Softening Treatment of CMP wastestreams

12 Total Si removal, NS colloidal silica Total Si removal, NS fumed silica Total Ce removal, NS ceria Total Al removal, NS alumina Removal Effeciency (%) Removal efficiencies of Si, Ce and Al for 4 CMP slurries under different ph conditions. Ca dosage was 2mM in all cases. Started concentrations: C 0Si,slurry 1=24 mg/l, C 0Si,slurry 2 =20mg/L, C 0Ce,slurry 3 =19.5mg/L, C 0Al,slurry 4 =31mg/L. ph values are obtained after jar test when reactions are considered in equilibrium. ph 12

13 J. of Hazardous Materials , (2012)

14 Product Line B Nanomaterials in foods Nanomaterials added to food for a variety of reasons: Texture Anti-caking Color Oxygen barrier Abrasives Antimicrobial Little to no regulation exist Difficult to monitor

15 Nanomaterials Dispersed in Products Nano-Ag in Toothpaste Silver in Shampoo Titanium Conc (mg Ti/g food) Benn et al., J. Environmental Quality, 39:1-8 (2010) Weir et al., ES&T (2012)

16 Test thousands of products? Go to suppliers instead of food grade products Can assess fundamental properties of NPs Example: food grade TiO 2 contains P-surface groups & is primarily anatase Yang, et al., ES&T, 48:11: (2014)

17 Beverages contain all types of nanoparticles ACS Sustainable Chem. Eng. 2014, 2,

18 Silica, Anti-caking agent in food In the United States, the Food and Drug Administration allows up to 2% by weight of silica to foods as an anti-caking agent. Nature Nanotechnology 9, (2014) doi: /nnano e_monsters_eating_disorder_and_failed/

19 Foods Claim Containing Silica

20 Transmission Electron Microscopy (TEM) on Separated Silica from Foods Nano silica present in foods

21 Ag + -doped polymers Product Line C Example: nano-ag in plastics Ag + monomer Ag + in situ NP formation compatibilizers/ additives curing agents Ag NP e.g., 1% MWCNT 5% TiO 2 Ag-NPdoped polymers Ag N P monomer compatibilizers/ additives curing agents Ag-impregnated Tupperware Sharper Image

22 Product Line D Nano-enabled fabrics Why? Anti-microbial (no stink) Flame Retardant Self cleaning Common nanomaterials: Silver Silica CNT What happens during use (wearing & washing)?

23 Environ. Sci. Technol. 2016, 50,

24 Part I - Summary NMs are released from commercial products into sewage wastewater The functionality of the product influences how NMs are used in different product lines NM Sources & Uses in Society Wastewater Treatment Plants Liquid Effluent to Surface Waters Biosolids to Land Application, etc

25 Nanomaterial removal in Wastewater Treatment Processes 1 o settling Biological 2 o settling process Optional Filter or membrane River / Lake Red Arrows represent flux of nanomaterials

26 Primary Settling 1 o settling Biological 2 o settling process Optional Filter or membrane River / Lake Removal of nanomaterials that are aggregated to clays, bacteria or other solids > 20 um in size

27 Biological Treatment 1 o settling Biological 2 o settling process Optional Filter or membrane River / Lake Removal of nanomaterials occurs when they interact with biofilms or biosolids

28 Batch Sorption Experiments Fresh wastewater biomass Mixing and settling times mimic hydraulic residence times at plant Analyze settled supernatant Can readily screen many properties Quick test Standard EPA method exists for organic pollutants using freeze-dried biomass too Nanoparticle Control (No Biomass Sorbent) NP mg TSS/L Biomass Sorbent NP mgtss/l Biomass Sorbent

29 Standard Batch Methods OPPTS Activated Sludge Sorption Isotherm Uses freeze-dried biomass Validated for organics, and has been used for metals Data here shows fresh and freeze-dried biomass provide comparable removals when applied at similar mgtss/l biomass Percentage Removal Fresh Freeze-dried after 105C heating EE2 Methylene Blue AgNO3

30 Does OPTT Test work for NPs? NO! X-axis is different types of nanoparticles Fresh and rinsed biomass shows much more capacity for NMs than freeze-dried biomass Percentage Removed % Removal Fresh Freeze Dried - 105C heating for 14 d 0% Removal 0% Removal 0% Removal 0 CIT- Ag PVP- Ag PVP-Vive- Au Ag GA- Ag TA- Au Car- PS Sulf- PS aqnc60

31 Freeze-drying and heating denatured proteins & released bacterial surfactants Fresh Freeze Dried Freeze Dried after 105C drying Percentage Removed h 12h 24h 3d 7d 14d 3h 12h 24h 3d 7d 14d 3h 12h 24h 3d 7d 14d 3h 12h 24h 3d 7d 14d Sulf-PS Car-PS Vive-Ag AgNO3

32 Removal by biomass of different Nanoparticles (1 gtss/l)

33 Biological Treatment 1 o settling Biological 2 o settling process Optional Filter or membrane River / Lake Removal of nanomaterials occurs when they interact with biofilms or biosolids 2.5 L SRT = 6 to 10 days Influent COD: ~750 mg/l Influent NP: 0.07 to 2 mg/l

34 Results of SBR tests with continuous, daily addition of Nanoparticles

35 Results of SBR tests with continuous, daily addition of Nanoparticles TSS (mg/l) 2.0 Concentration Days of Continuous Operation

36 Results of SBR tests with continuous, daily addition of Nanoparticles TSS (mg/l) nc60 (Influent) 2.0 Concentration Days of Continuous Operation

37 Results of SBR tests with continuous, daily addition of Nanoparticles TSS (mg/l) nc60 (Influent) nc60 (effluent) 2.0 Concentration Days of Continuous Operation

38 Results of SBR tests with continuous, daily addition of Nanoparticles 3.0 TSS (mg/l) nc60 (Influent) nc60 (effluent) fn-ag (influent) Concentration Days of Continuous Operation

39 Results of SBR tests with continuous, daily addition of Nanoparticles TSS (mg/l) nc60 (Influent) nc60 (effluent) fn-ag (influent) fn-ag (effluent) Concentration Days of Continuous Operation

40 Modeling NP Removal Kiser et al., Sep. Sci Tech Hypothesis: Batch NP sorption experiments linked with dynamic bacterial growth models and reactor models can predict nanomaterial removal Example: Isotherm in batch reactor Fresh biomass 10 nm diameter citrate functionalized nano Silver Linear Partition Coefficient for : K = L/g

41 Substrate (mg COD/L) Model Predictions Isotherms with NPs predict removal in Sequencing Batch Reactors Degradation of Substrate (Influent COD) Model SBR Data time (h) Ce (mg Ag/L) Reduction of Vive-Ag from Liquid Phase Model SBR Data Time (h) Conclusion: Preliminary confirmation exists that we can go from batch experiments to simulations of continuous flow performance. Difference in NP effluent concentration probably related to NP association with non-settlable colloids

42 Part I - Summary Products potential to release NMs into the environment can be grouped into 4 product lines NMs are released from commercial products into sewage wastewater NM Sources & Uses in Society Wastewater Treatment Plants Liquid Effluent to Surface Waters Biosolids to Land Application, etc

43 Titanium at Full Scale WWTPs Titanium is removed from liquid & accumulates in biomass Kiser et al.,est 2010; Westerhoff et al., JEM 2011

44 Titanium at Full Scale WWTPs Titanium Content of water (ugti/l) Different Facilities Headworks Effluent Activated sludge Act. Sludge + filter Activated sludge Activated sludge Activated sludge Activated sludge 8 Activated sludge Trickling filter Membrane bioreactor (MBR) MBR Average 377 6

45 NM Sources & Uses in Society Wastewater Treatment Plants Liquid Effluent to Surface Waters Biosolids to Land Application, etc

46 Under typical TSS levels ( mg/l) greater than 90% of even highly negatively charged NMs will distribute into biomass 1 o settling Biological 2 o settling process Optional Filter or membrane River / Lake Let s go Nanoprospecting What type of NMs do we find in real biosolids?

47 TiO 2 in commercial products are similar to TiO 2 extracted from biosolids TiO 2 in Toothpaste TiO 2 in Biosolids

48 Barium Sulfate & Calcium Phosphates

49 Zinc & Iron Oxides

50 Sodium Tantalate Catalysts

51 Iron & Silver Sulfides

52 Solder & Facet released material

53 Fun Complex Stuff

54 Where do Biosolids Go? Air Land Application of Biosolids Society Wastewater Treatment plant Drinking Water Treatment Plant Wastewater Treatment plant Society Incineration ~60% of biosolids land applied in the USA Landfill

55 USDA Field Site Near Austin, TX Long-term Biosolid Applications

56 Each element has different soil profile after applying biosolids Ag concentration (mg/kg) Ti concentration (mg/kg) Depth (cm) SR-10 t/ac/y 30 t/ac/y Depth (cm) t/ac/y 10 t/ac/y Control

57 TiO 2 Nanomaterials are present in Biosolid Ammended Fields cm 20 t/ac/yr ENM 1500 Ti Counts 1000 Ti Ti O Cu Cu C Ti N Cu Fe Fe Cu Cu Cu Fe Cu Mg Mg Al Al Si Si 2.0 Ti Ca S S K K Ca Fe Fe Energy (kev) 8.0

58 SIR (µg C-CO2/ g soil h-1) Do NMs in Biosolids Amended Soils Impact Biological Activity? Substrate Induced Respiration (28 day) Control 1 mg/kg AgNPs BDL 1000 mg/kg AgNPs 1 mg/kg TiO mg/kg TiO2 1 mg/kg ZnO BDL 1000 mg/kg ZnO 1 mg/kg CeO mg/kg CeO2

59 Carbon dioxide content ( µg C-CO2/ g soil) Basal Respiration Tests CeO 2 increases CO 2 production Control 1 mg AgNPs/kg 1000 mg AgNPs/kg 1 mg TiO2/kg 1000 mg TiO2/kg 1 mg ZnO/kg 1000 mg ZnO/kg 1 mg CeO2/kg 1000 mg CeO2/kg Incubation time (day)

60 Summary Nanomaterials will be emitted from various industrial, commercial and residential products into sewers On-site treatment systems (lime, membranes) can be effective Uniqueness of Nanomaterials: They accumulate at interfaces At current levels, engineered NMs are UNLIKELY to impact WWTP operations NM Sources & Uses in Society Wastewater Treatment Plants Liquid Effluent to Surface Waters Biosolids to Land Application, etc

61 Acknowledgements Water Environment Research Foundation (WERF) Paul L. Busch Award 2006 Project U1R10 NIH/NIEHS - NIH/NIEHS Nano-Go Funding: RES018801Z NSF (CBET ) EPA (RD83322 & RD835580) SRC & Contact: p.westerhoff@asu.edu DOE BER Grant number: DE-FG02-08ER64613 RD833322

62 Upcoming Webinars Monday, June 13, pm Eastern Time Self-Powered Wearable Devices for Monitoring Personal Health Presenter: Veena Misra, Ph.D. Director, NSF ASSIST Nanosystems Center Professor, Department of Electrical Engineering

63 The effects of slurries on the proliferation, viability, or membrane integrity of model organisms.

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66 Lifecycle Perspective of NMs Societal Use of Products Measuring Releases of NPs in various media NPs in biosolids that are land applied Removal of NPs at WWTPs

67 Lifecycle Perspective of NMs Societal Use of Products Measuring Releases of NPs in various media NPs in biosolids that are land applied Removal of NPs at WWTPs

68 Lifecycle Perspective of NMs Societal Use of Products Measuring Releases of NPs in various media CPS Time(sec) NPs in biosolids that are land applied Removal of NPs at WWTPs

69 Lifecycle Perspective of NMs Societal Use of Products Measuring Releases of NPs in various media CPS Time(sec) NPs in biosolids that are land applied Removal of NPs at WWTPs

70 Lifecycle Perspective of NMs Societal Use of Products Measuring Releases of NPs in various media CPS Time(sec) NPs in biosolids that are land applied Removal of NPs at WWTPs

71 Big Picture EPA Composite Biosolids Enrichment Factor 10, , Biosolid concentrations, normalized to Upper Continental Crust Group 1 Group 2 Group 3 Group 4 Group 5 Mesa WTP Na Mg Al P K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga As Rb Sr Y Nb Mo Ru Pd Ag Cd Sn Sb Cs Ba La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Hf W Re Ir Pt Au Tl Pb Th U

72 Webinar Recordings & Slides To access this recording and slides nano4me.org/webinars.php Or

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