NanoSorb Sorption to engineered nanomaterials and its impact on the - - PowerPoint PPT Presentation

▶
nanosorb
SMART_READER_LITE
LIVE PREVIEW

NanoSorb Sorption to engineered nanomaterials and its impact on the - - PowerPoint PPT Presentation

Jan 24, 2024 186 likes •372 views

NanoSorb Sorption to engineered nanomaterials and its impact on the bioavailability/toxicity of fossil fuel-derived hydrocarbons to aquatic organisms Andy Booth , Berit Glomstad , Jingfu Liu, Mohai Shen, Dag Altin, Bjrn Munro Jenssen, Florian

slide-1
SLIDE 1

Materials and Chemistry 1

NanoSorb

Sorption to engineered nanomaterials and its impact

  • n the bioavailability/toxicity of fossil fuel-derived

hydrocarbons to aquatic organisms RCEES

Research Center for Eco- Environmental Sciences

Andy Booth, Berit Glomstad, Jingfu Liu, Mohai Shen, Dag Altin, Bjørn Munro Jenssen, Florian Zindler

slide-2
SLIDE 2

Materials and Chemistry

Goals

2

Phenanthrene

 Study how CNT properties affect the adsorption of organic pollutants  Investigate how the bioavailability and toxicity of organic pollutants are affected by the presence of CNTs  Understand how carbon nanomaterial physicochemical properties influence fate in aqueous environments  Determine the influence of environmental parameters on carbon nanomaterials behaviour

slide-3
SLIDE 3

Materials and Chemistry 3

Carbon nanomatrials (CNTs)

SWCNT MWCNT C60 Fullerene

 Fullerenes 'Buckyball clusters' are spherical carbon molecules  Can vary from C20 to C100 with C60 fullerene the most common  Nanotubes (CNTs) consist

  • f rolled up graphite sheets

 Different diameters and surface area, number of walls  Different surface chemistry

slide-4
SLIDE 4

Effects of molecular weight-dependent physicochemical heterogeneity of natural organic matter on the aggregation of fullerene nanoparticles in mono- and di-valent electrolyte solutions

C60 aggregation studies

nC60

Na+

Enhanced attachment

Ca2+

Mg2+

MW-dependent stabilization

20 1000 3 10 30 100 Mf-SRNOM 100 2

nC60

30 100 10 100 MW (kD) C (mmol L-1) C (mmol L-1) MW (kD) Mf-SRNOM

slide-5
SLIDE 5

Molecular weight fractions

  • f SRNOM (Mf-SRNOM)

Suwannee River NOM (pristine-SRNOM)

S R N O M > 1 S R N O M 3

  • 1

S R N O M 1

  • 3

S R N O M 3

  • 1

S R N O M < 3 20 40 60 Total Mass Recovery 97.0%

wt% carbon SRNOM type

7.2% 6.6% 13.0% 15.5% 57.6%

Stepwise separation of SRNOM by Ultrafiltration

Molecular Weight Fractions of SRNOM

slide-6
SLIDE 6

Preparation and Characterization of nC60 Dispersion

10 20 30 40 50 60 70 20 40 60 80

Particle number

Size (nm)

Particle number Gauss Fit of Particle number

(b)

Z-average radius Zeta-potential Electrophoretic mobility 58.2±0.7 nm 41.2±1.3 mV

  • 3.6±0.1 μmcm/Vs

TEM DLS

slide-7
SLIDE 7

1 10 100 1000 1E-3 0.01 0.1 1 NaCl CaCl2 MgCl2

Attachment efficiency

Electrolyte concentration (mmol L

  • 1)

6.2 mmol L

  • 1

8.0 mmol L

  • 1

143 mmol L

  • 1

Attachment efficiency (a) and Critical Coagulation Concentration (CCC) 1

      

t h

t t R N k d ) ( d

     

fast , fast fast

d d d d 1 α 1 1

 

              

t h t h

t t R N t t R N k k W

In the absence of SRNOMs

Aggregation of nC60 determined by Time- Resolved DLS Method

slide-8
SLIDE 8

100 1000 1E-3 0.01 0.1 1

no SRNOM pristine-SRNOM SRNOM>100 SRNOM30-100

Attachment efficiency

NaCl concentration (mmol L

  • 1)

CCC=234 mmol L

  • 1; =0.084

CCC=522 mmol L

  • 1; =0.017

CCC=167 mmol L

  • 1;

=0.41

(a)

100 1000 1E-3 0.01 0.1 1

CCC=152 mmol L

  • 1;

 =0.57 CCC=163 mmol L

  • 1;

 =0.60 CCC=205 mmol L

  • 1;

 =0.49 no SRNOM SRNOM10-30 SRNOM3-10 SRNOM<3

Attachment efficiency

NaCl concentration (mmol L

  • 1)

(b)

  • 1. In mono-valent electrolyte (NaCl)

Effect of Mf-SRNOM on nC60 Aggregation

MW of Mf-SRNOM , the stabilization of nC60

slide-9
SLIDE 9

10 100 0.01 0.1 1

CCC=25.3 mmol L

  • 1;

 =0.31 CCC=16.3 mmol L

  • 1;  =0.35

CCC=9.0 mmol L

  • 1;

 =0.50 no SRNOM pristine-SRNOM SRNOM>100 SRNOM30-100

Attachment efficiency

(a)

10 100 0.01 0.1 1

CCC=7.3 mmol L

  • 1;

 =0.80 CCC=9.1 mmol L

  • 1;

 =0.82 CCC=10.1 mmol L

  • 1;

 =0.78 no SRNOM SRNOM10-30 SRNOM3-10 SRNOM<3

Attachment efficiency MgCl2 concentration (mmol L

  • 1)

(b)

10 100 0.01 0.1 1

CCC=11.2 mmol L

  • 1;

 =0.78 no SRNOM pristine-SRNOM SRNOM>100 SRNOM30-100

Attachment efficiency

(a)

CCC=7.6 mmol L

  • 1;

 =0.71 CCC=9.4 mmol L

  • 1;

 =0.57

10 100 0.01 0.1 1

CCC=6.3 mmol L

  • 1;

 =0.79 CCC=7.5 mmol L

  • 1;

 =0.64 CCC=8.2 mmol L

  • 1;

 =0.71 no SRNOM SRNOM10-30 SRNOM3-10 SRNOM<3

Attachment efficiency CaCl2 concentration (mmol L

  • 1)

(b)

CaCl2 MgCl2

Effect of Mf-SRNOM on nC60 Aggregation

  • 2. In di-valent electrolytes

HIGH electrolyte concentration & HIGH MW Mf-SRNOMs: Enhanced Attachment of nC60 (through Cation-bridges between NOM molecule and nC60 )

LOW electrolyte concentration: MW of Mf-SRNOMs , Stabilization of nC60 . TEM evidence

slide-10
SLIDE 10

Materials and Chemistry 10

CNT characterization

 Characterization of CNTs is important to understand the influence of chemical and physical parameters on CNT fate and adsorption behaviour

a Measured from TEM images b Given by manufacturer c Calculated by the BET method d Obtained from XPS e Measured on CNTs

dispersed in NOM solution

slide-11
SLIDE 11

Materials and Chemistry 11

CNT fate in the environment

 CNT dispersion and stability in aqueous phase depend

  • n their chemical and physical properties

 And on environmental factors – natural organic matter (NOM)

CNT dispersion concentration in algal media (TG201) containing NOM after sonication and 24 h settling Stability of CNT dispersions over time

S W C N T M W C N T -2 M W C N T -3 M W C N T -O H M W C N T -C O O H 2 4 6 8

C o n c e n tra tio n (m g /L )

0 d a y s 3 d a y s 5 d a y s 7 d a y s 1 0 d a y s 1 4 d a y s 5 0 1 0 0

% C N T s re m a in in g in d is p e rs io n

S W C N T M W C N T -2 M W C N T -3 M W C N T -O H M W C N T -C O O H

slide-12
SLIDE 12

Materials and Chemistry

Phenanthrene adsorption by CNTs

 Adsorption capacity

 Increasing with

increased surface area

 Decreasing with

increased surface

  • xygen content

12

1 1 0 1 0 0 1 0 0 0 1 0 6 1 0 7 1 0 8 1 0 9

C w [µ g /L ] C C N T (µ g /k g ) S W C N T M W C N T -1 5 M W C N T -3 0 M W C N T -O H M W C N T -C O O H

Adsorption isotherms of phenanthrene by

  • CNTs. Dotted lines represent fitting of the

Dubinin-Astakhov adsorption model to the experimental data.

slide-13
SLIDE 13

Materials and Chemistry

CNT effect on phenanthrene toxicity to algae

13

P h e n a n t h r e n e

  • n

l y S W C N T M W C N T

  • 1

5 M W C N T

  • 3

M W C N T

  • O

H M W C N T

  • C

O O H 3 0 0 3 5 0 4 0 0 4 5 0 5 0 0 5 5 0 6 0 0 E C 5 0 ,to ta l (µg /L ) P h e n a n t h r e n e

  • n

l y S W C N T M W C N T

  • 1

5 M W C N T

  • 3

M W C N T

  • O

H M W C N T

  • C

O O H 2 5 0 3 0 0 3 5 0 4 0 0 4 5 0 5 0 0 E C 5 0 ,m e a s u re d (µg /L ) P henanthrene only S W C N T M W C N T -1 5 M W C N T -3 0 M W C N T -O H M W C N T -C O O H

 Significant reduction in phenanthrene toxicity only seen in the presence of SWCNT  Based on measured concentrations of freely dissolved phenanthrene an increase in toxicity observed for all CNTs Phenanthrene adsorbed to CNTs contribute to toxicity – still partly bioavailable

Pseudokirchneriella subcapitata

slide-14
SLIDE 14

Materials and Chemistry

CNT interaction with algae

 Contribution to toxicity by adsorbed phenanthrene might be due to the direct contact between CNTs and algae attached to CNT aggregates  A slight reduction in algal growth rate was seen in the presence

  • f MWCNT-COOH, probably due to shading by the dark

coloured dispersion

14

100 µm

S W C N T M W C N T

  • 2

M W C N T

  • 3

M W C N T

  • O

H M W C N T

  • C

O O H 1 .4 1 .5 1 .6

A v e ra g e g ro w th ra te

Average growth rate in CNT dispersions compared to control (TG201-NOM; dotted line). Error bars and shaded area represent standard deviations Microscopy image of P. subcapitata attached to MWCNT-15 (Photo: Dag Altin, Biotrix).

slide-15
SLIDE 15

Materials and Chemistry

CNT uptake by Daphnia magna

 Microscopic imaging showed ingestion of all CNT types by D. magna

15

Light microscopy images of 5-6 d old daphnids (x40 magnification). exposed to the 5 CNT types. No feeding 48 h exposure Fed algae

  • nly

48 h exposure SWCNT 48 h exposure MWCNT-2 48 h exposure MWCNT-3 48 h exposure MWCNT-OH 48 h exposure MWCNT- COOH 48 h exposure

slide-16
SLIDE 16

Materials and Chemistry

CNT effect on phenanthrene toxicity to Daphnia magna

 CNT SSA and surface chemistry appear important for their effect on Phen toxicity to D. magna.  Free phenanthrene does not account for the observed toxicity Indicates a large proportion of Phen adsorbed to CNTs is bioavailable to D. magna through ingestion

16

C f r e e [µ g un bou nd p henan threne L - 1] Im m obilised D aphnids [% ]

50 100 100 300 700

S W C N T (E C 50 = 2 5 7 .5 µ g/L ) M W C N T -O H (E C 50 = 2 5 0 .0 µ g/L ) M W C N T -C O O H (E C 50 = 2 5 1 .3 µ g/L ) M W C N T -2 (E C 50 = 2 2 2 .1 µ g/L ) M W C N T -3 (E C 50 = 2 2 7 .9 µ g/L ) P h e n a n th re n e O n ly (E C 50 = 3 2 4 .9 µ g/L )

50

C n o m in a l [µ g phenanthrene L - 1] Im m obilised D aphnids [% ]

50 100 100 300 700 S W C N T (E C 5 0 = 423.2 µ g/L ) M W C N T -O H (E C 5 0 = 347.2 µ g/L ) M W C N T -C O O H (E C 5 0 = 369.0 µ g/L ) M W C N T -2 (E C 5 0 = 347.8 µ g/L ) M W C N T -3 (E C 5 0 = 417.9 µ g/L ) P henanthrene O nly (E C 5 0 = 335.4 µ g/L ) 50

slide-17
SLIDE 17

Materials and Chemistry 17

Conclusions

 C60 aggregation influenced by electrolyte type and conc  C60 aggregation influenced by NOM composition  CNTs readily adsorb phenanthrene but influenced by SSA and surface chemistry  CNTs not acutely toxic but directly interact with algae and D. magna  Adsorbed phenanthrene is bioavailable to both algae and D. magna