Nanotech in Water Science & Engineering Sustainably harnessing the power

of nanotechnology Greg Lowry

Walter J. Blenko, Sr. Professor of Civil & Environmental Engineering

Deputy Director-CEINT

Carnegie Mellon University

NDSU-February 19, 2015 (-15 ºC)

Students and Post Docs Brian Reinsch

Megan Leitch Rui Ma

Amy Dale

Clement Levard John Stegemeier

Fabienne Schwab

Ben Colman

Jason Unrine

Nanotechnology

Control of matter at dimensions of roughly 1 to

100 nanometers,

where unique phenomena arising from its size

enable novel applications.

Energy

Lighter and stronger

materials

Water Treatment Drug Delivery

The Evolution of Engineered

Nanomaterials

Lim et al., Nature

Materials 2010

Schumacher et al.

NanoLett. 2013 (ASAP)

1997 2005

Ren et al. ACS Nano 2014 (ASAP)

Origin of Nanoscale Phenomena

Nanotechnology for Water Treatment

Perreault et al., 2014 ES&T Lett. 1, 71−76

Lin et al., 2014 ES&T Lett. 1, 449-447

Biofouling resistant

membranes

Better MD performance

Bacterial Nanocellulose Aerogel

Membranes for Membrane Distillation

[ML1]Fix caption

Nano alumina Promotes Horizontal Gene

Transfer & Antibiotic Resistance in

Microorganisms

Qiu et al. 2012 PNAS 109 (13) 4944-4949

Reactive Fe0 Nanoparticles (NZVI)

Fe0

Fe3O4

Fe0

Fe3O4

TCE

Acetylene

Nano Fe0 is

oxidized

Contaminants

are reduced

H+ H2

H+ is reduced

Fe0

Fe3O4

Liu et al, (2005) ES&T 39, 1338

Liu and Lowry, (2006) ES&T, 40 (19) 6085

Lifetime depends on oxidant loading, pH,

and potentially on microbial activity

Liu, et al., (2007) ES&T 41 7881

Hybridized Nanomaterials

Reddy et al., 2015 Applied Catalysis A: General 489 1-16

Do Nanohybrids Pose New Risks?

Saleh et al., 2015 ES Nano 2 11-18

Need for Screening Rules to

Decrease Parameter Space

Saleh et al., 2015 ES Nano 2 11-18

Assessing the Risks of Engineered

Nanomaterials

Risk

Characterization Factors

Influencing

Exposure

Factors

Influencing

Effects?

Distribution

Lifetime

Biouptake

Bioaccumulation

Reactivity

Stability

Size

Charge

Goal: Determine Spatial and Temporal Uniqueness

Center for the Environment

Implications of Nanotechnology

Core Institutions: Duke, CMU, Stanford, Howard, Kentucky, Va Tech

$30M from NSF + EPA

10-years (currently in yr 7)

43 faculty, >130 Students/P-docs

Interdisciplinary Env. Eng., Geochemistry, Public Policy, Chem E., Mat Sci.,

Chemistry, Ecology, Toxicology

17 International partners on 3 continents

Collaborators from 5 US government entities

CEINT Goal: Predict Behaviors from

ENM Properties

Increasing Complexity

Nanomaterial

Properties

System

Properties

Nanomaterial

Descriptors What is it?

What can happen

because of it?

Nanoparticle

Impacts

In the Beginning……

Ma

teri

al &

Sys

tem

Pro

pe

rtie

s

Ma

teri

al a

nd

Sys

tem

Inte

rac

tio

ns

Ma

teri

al Im

pa

cts

hazard

Nanoparticle

Properties

System

Properties

Cellular and

Organismal

Hazard

Bio-Geo-Chemical

Transformations in

the System

Distribution in

the System

Ecosystem

Hazard

exposure

risk

Biouptake /

System Transfer

Exposure Potential

Bio-Distribution Bio-Transformation

What is it?

Where does it go

and

what does it do?

What can happen

because of it?

LE

VE

L 2

Pro

cesses P

reced

ing

Bio

up

take

LE

VE

L 4

Ou

tco

mes

LE

VE

L 1

Mate

rial an

d S

yste

m P

rop

ert

ies

LE

VE

L 3

Pro

cesses F

oll

ow

ing

Bio

up

take

Ecosystem

Hazard

Cellular and

Organismal

Hazards

Biodegradation

ROS

Aggregation

Nanoparticle

Properties System

Properties

NOM/

Macromol

Ionic

Composition

pH

Surfaces

(bacteria,

clay…)

Size

Composition

Coating

Fluid

Flow

Shape

Light

Environmental

Stressors

Collision

Rate

Deposition

Distribution

in the

System

Settling

Transport

Nutrient Cycling

Community

Composition

Attachment

Product

Properties

Release

Fraction

Milieu

(solid matrix,

suspension…)

Amount

Dissolution

Bio-Geo-Chemical

Transformations

Geochemical

Transformations

Biodistribution

Maternal Transfer Trophic Transfer

LE

GE

ND

Parameter

or Process

Mechanism

Example of

Mechanism

Discovered Via

Integrated

Research

Biouptake /

System Transfer

Speciation/

Exposure Potential

Availability

Biotransformation

Redox

Environmental Transformations of

Nanomaterials

ENM Inputs

Distribution & Form

Effects

NP Attachment to

Environmental

Surfaces

Physical and Chemical

Transformations

Interactions with

Macromolecules

July 1, 2012

Lowry et al, Environ. Sci. Technol, 2012, 46, 6893−6899

Dissolution

Sulfidation

Ag NPs Readily Sulfidize

Levard et al., ES&T 2011 45 (12), 5260.

Ag2S(s) Ag+ + S2- K=6x10-51 M2

Ag(0)

Ag2S (am)

Ag2S (crys)

Greater S/Ag

O2/HS-

Ag

+

Time

Sulfidation greatly

decreases Ag+ release

Sulfidation Decreases Toxicity?

Levard, Hotze, et al., ES&T (in press)

Zebrafish Killifish C. Elegans Duckweed

CuO NP Sulfidation

Ma et al., ES Nano (in prep)

CuS Dissolution

0 50 100 150 200 250 300 350

0.0

0.4

0.8

1.2

1.6

2.0

2.4

2.8

3.2

CuO

S/Cu 0.22

S/Cu 0.43

S/Cu 0.62

S/Cu 2.16

Dis

so

lve

d C

u (

mg

/L)

Time (hrs)

With DO

0 50 100 150 200 250 300

0.0

0.4

0.8

1.2

1.6

S/Cu 0.22

S/Cu 0.43

S/Cu 0.62

S/Cu 2.16

Dis

so

lve

d C

u (

mg

/L)

Time (hrs)

No DO

Cu2S+ 2.5O2 + 2H+ = 2Cu2+ + SO42- + H2O

CuS+ 2O2 = Cu2+ + SO42-

pH 7 pH 7

Ma, R., et al. 2014 ES Nano 1 p347.

Sulfidation of CuO NPs Increases

Toxicity To Zebrafish

CuS NPs in Filtrate

Li et al 2015 ES&T 49, 2486−2495

AgNPs Sulfidize Naturally in Sediment

Lowry et al., ES&T 46 2012 (13), pp 7027–7036

Ag Bioavailability in Mesocosms

A

[Ag

] (

g/g

wet w

eig

ht)

A

[Ag

] (

g/g

wet w

eig

ht)

Roots (20 mg/kg)

Lowry et al., ES&T 46 2012 (13), pp 7027–7036; Colman et al., (in prep)

How do Plants uptake of Ag0 and Ag2S NPs?

Ag NPs

Ag2S NPs

Synthesized:

PVP-coated

~15 nm diameter

Exposed

Alfalfa

Medicago sativa

Duckweed

Lemnoideae

Ag+ ions

Resin Embedded

EtOH/OsO4 fixed

“Fresh” sample

EtOH fixed

Fresh sample

Kapton sealed

Water filled pouch

Root Association of Ag was independent

of Ag added, but uptake was different

Stegemeier et al., ES&T (in prep)

TEM Reveals Uptake NP NPs into

Plant Cell Walls

Control AgNO3 Ag(0)-NP Ag2S NP

Stegemeier et al., ES&T (in prep)

Speciation of Ag Affects Routes of

Uptake of Silver into Plants

Stegemeier et al., ES&T (in prep)

Unique Ecosystem Responses to Ag NPs?

Colman et al., 2013 PLoS One 8(2), 1-10

0.14 mg/kg Ag

NP in biosolids

Ag metal

Ag2S

75/25

Ag/Ag2S

EXAFS

Above ground Plant Biomass

Effect of Low Doses on Ag on

Microorganisms and Nutrient Cycling

Day 50

Day 0 and 1

Day 50-

control

These shifts increase N2O

flux from soils

Ag result in shifts in the

microbial communities

Colman et al., 2013 PLoS One 8(2), 1-10

ZnO Fate in the Wastewater System?

Primary

clarifier

(180 L)

Anaerobic

digester

(150 L)

\Secondar

y clarifier

(150 L)

Zn2+

Control

ZnO

NP

Little Difference in Zn Speciation between

Zn2+, ZnO, and Control

Control NP Ion

Anaerobic

1wk 37◦C

Aerobic,50◦C

30%

80%

50%

ZnS

Zn3(PO4)2

Zn-FeOOH

Increasing

loss of ZnS

Ma et al., ES&T 48 (1) 104–112

• No ZnO in biosolids!

• NP addition and

control look identical

ZnO NPs Behave Differently than

Bulk ZnO or ZnCl2

Effect on Medicago sativa

Nodulation

Zn associated with plants

Judy et al. ES&T (in prep)

Modeling Nanomaterial Fate and Effects

Dale et al., 2015 ES&T (in press)

Westerhoff and Nowack, 2013 Accounts in

Chemical Research 46: 844-853

Particle Based vs. Mass Based Models

Haven and Cohen, ES&T 2014

Praetorius et al., Environ. Sci. Technol. 2012, 46, 6705−6713

Putting “Nano-chemistry” into the Models

DiToro et al., Environ. Toxicol. Chem. 1996, 15, 2168.

Dale et al., 2013 Environ Sci Technol. 47, 12920−12928

Ag+ flux

Ag2S

shell

Agd+

Ag2S

S2-

Ag0

O2

O2

AgΞPOC

AgΞFeOOH

solid phase

partitioning

Effe

ct o

f Su

lfid

ati

on

on

Sp

ecia

tio

n

No sulfidation

Ag0 allowed to sulfidize

50, 85, 100% sulfidized at t=0

Dale et al., 2013 Environ Sci Technol. 47,

12920−12928

Effect of Organic Carbon on Efflux and Persistence

JPOC,max = 75 mg/m2-d,

foc = 0.1%

JPOC,max = 150 mg/m2-d,

foc = 10%

JPOC,max = 300 mg/m2-d,

foc = 35%

Eutrophic systems have lower Ag+ formation

Ag NP half-life ranges from years to centuries depending on

redox conditions

Dale et al., 2013 Environ Sci Technol. 47, 12920−12928

“Functional Assay” Approach to

Capture Relevant Behaviors

RISK

Hazard

Nanoparticle

Properties

System Properties

Social & Engineered Properties

Exposure

• Product life cycles

• Product use behaviors

• ENM production

magnitudes

• Environmental

(natural, simulated,

engineered)

• Biological (natural,

simulated)

• Analytical method

preparations

• Size

• Core composition

• Band gap

RISK

Hazard

Nanoparticle

Properties

System Properties

Social & Engineered Properties

Functional

Assays

Exposure

• Aggregation rate

• Attachment efficiency

• Distribution coefficient

• Dissolution rate

Figure3a.Nanoparticleproperty-rootedapproach

Figure3b.FunctionalAssay-RootedApproach

Models

Risk

Safer Design:

Balancing Risks and Benefits

LC Nano-New EPA Center February 1, 2014

Mechanism

Phenomena/

Behavior

Upstream vs. Downstream Effects

Concluding Thoughts

• Environmental Implications • Must identify global descriptors of ENM behaviors

• Transformations

• System feedback loops

• Develop functional assays to quantify descriptors

• Develop models based on these descriptors

• Harness the Power of Nanotechnology

• Nanomaterials are not terribly toxic

• Possible to replace materials known to be more toxic? Or create new antibiotics?

Nanotechnology Applications

• Energy

• Carbon sequestration

• Managing the nitrogen cycle

• Clean water

• Restore/improve urban infrastructure

• Better medicines

Thank You for your attention!

Acknowledgements