Particles

Introduction and Overview

William P. Johnson
Professor
Geology & Geophysics
Civil & Environmental Engineering (adjunct)
University of Utah
Complexity of particle filtration in porous media requires many
kinetic parameters, mechanistic basis needed for robust prediction
THE
UNIVERSITY
Particle filtration in porous media involves limited diffusion, and so OF UTAH
is partly deterministic, allowing prediction of attachment rates

Previous approaches failed, assumed surfaces to be homogenous

(mean field approach), need to recognize nano-scale heterogeneity

Developing representative nanoscale heterogeneity greatly

improves predictive capabilities for complex behaviors
Bruce Whitteberry Hydrogeologist
Greater Cincinnati Water Works
 A rivers liver the hyporheic zone

From:
Susa Stonedahl
St. Ambrose U.
http://susa.stonedahl.com/research.html
 Washington County Fair,
New York, September 1999

2800 5000 ill, 127 cases of E. coli O157:H7, 45 Campylobacter,

14 HUS, 71 hospitalized, 2 died (3-year old, 79-year old)
7 m shallow well responsible was located ~11m from septic
tank seepage field
Quarterly microbiological monitoring at this site since 1995 had
only ever shown E. coli for one other well, but there was no
monitoring evidence of contamination reported for the well
which caused the outbreak
Dye testing showed toilet flush appearing in well in less than
10h
Inadequate frequency of monitoring to catch an intermittent
contamination event. Practical frequency of monitoring will
never be enough to compensate for an inherently flawed
system
From Steve Hrudey
University of Alberta
 Subsurface
transport
is influenced at
multiple scales We need to to
do more than
All scales are observe.
mediated by
nanoscale We need to
physicochemical predict transport
interactions
 Scales, diffusion, and predictable behaviors

Diameter (m)
10-10 10-9 10-8 10-7 10-6 10-5 10-4 10-3 10-2

1A 1 um 1 mm
molecules
colloids

suspended particles

viruses bacteria protozoa

reduced diffusion allows defined trajectories

 C Tracer C Partitioning
1.0 = =
t t
0.9 C 2C C
C 2C
v +D 2 v +D K b
0.8 x x x x 2 d
t
0.7 b
1 + Kd = R
0.6
C/C0

0.5
0.4 Filtration

0.3 C C 2C
= v +D kfC
0.2 t x x 2
C kf
= exp( L)
0.1 Co v
0.0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0
Pore Volumes
 DLVO theory: Unfavorable conditions (repulsion)

Born repulsion
Sep. dist. = 200 nm
Increased ioniclayer
strength

Repulsive
Electric double repulsion

+ + Repulsive
+ Barrier Secondary

Force
Sep. dist. minimum
+ +
+ = 50 nm 1 50 200
+

Attractive
+ Separation distance (nm)

Primary
minimum
Van der waals attraction
Sep. dist.
< 0.2 nm
Column experiments breakthrough-elution behavior
and distribution of retained colloids
 Breakthrough-elution behavior

= + +

+

C=C0

Unfavorable
C
(at L)
Favorable

Step injection Elution

C=0
Time

= +

Advection Dispersion Attachment
 Profiles of Retained Colloids

= +

Ln Csed

More
Unfavorable
sticky
Less sticky = big challenge for
design and protection
Favorable

Distance from source

=

 They do become less sticky!
Colum ns in series
Heterogeneity in a seemingly homogenous population

1.1 m microspheres

1.0E+09

# of Retained Microspheres
1.0E+08

1.0E+07
0.00 0.10 0.20
Up-gradient Down-gradient Low Co
Same as Meters
Down-
gradient
Simulation

translationz = u zt t

Newtons
Place the 2nd
Numerical
Change + law
particle
approximationold = new

[ [F + +FF ] t]=+=(umu )=uudtzt

dut 1z
F zz z
Drag+
FDrag
z
z z
FBrownian
Brownian +F
++FGravity + +F+Colloidal
FGravity FFColloidal t
zp
Drag Brownian Gravity Colloidal t 1

mmp p
z
t z
Favorable conditions, 10 m colloids
The key is the forward flow stagnation zone

Strategy:
Force/torque balance
Which particles intercept surface?

Variables:
Many starting locations upstream
Different colloid sizes
Different fluid velocities

Result:
Key = forward flow stagnation zone
Diffusion and settling help
Collector efficiency () =
stream lines # intercept / # introduced
 Upscaling porous media as a series of collectors

C0
1
1 1 =
0
C1
2
2 1 = = 1
1 0
C2
3 1 2 3
3 1 = = = 1
2 0 0 0 1 2 1

C3

= From ADE
0
Cn-1

Nc 1 = = 1
1
Cn
Gives kf as a function of velocity
( and kf remain constant across distance)
Agreement between theory (blue) and experiment (black)

High
diffusion

High
settling
 Repulsive

Decreased ionic strength

Force

1 10 20
Attractive

Separation distance (nm)

Change of attachment mode with colloid size
 Profound influence of repulsion:
Force/torque simulations predict no retention
(meters)

1.00E-04

1.00E-05
separation

1.00E-06 For repulsive barriers of any significance

(M)

CFT predicts no deposition Secondary

Cells (colloids) glance off of repulsive barrier
Colloid-surface H

minimum
1.00E-07
Repulsive

1.00E-08 = Barrier
Primary
sticks/strikes = chemistry
minimum
= near surface transport
intercept/introduced = physics = bulk transport
1.00E-09
Force
0.00E+00 1.00E-04 2.00E-04 3.00E-04 4.00E-04
Attractive Repulsive 5.00E-04
r(m) (meters) Semi-empirical only!
Transport distance
No detachment either!
 But the surface isnt all repulsive!
There are nanoscale zones of attraction

1 10 20
Separation dist (nm)

heterodomains = nanoscale zones of attraction

 Simulating nano-scale surface heterogeneity X
Y

P
Z
dA

nA
D
h
e1

nS

dS

e0
Unfavorable: 33% coverage; 350 nm heterodomains; 10 m colloids
Quantifying Heterodomains impinging jet
Radial Higher ionic
stagnation strength =
point flow deeper
(impinging jet) secondary
energy
TIRF minimum
Total internal
reflection Low ionic
fluorescence strength =
shallow
Particles secondary
(2-m) energy
fluoresce minimum
when within
~150 nm of
surface
Johnson and Tong,
2006, ES&T 40(16),
5015-5021
 1.2e-5

Different sizes
different diffusion 8.0e-6
behavior

Y (m)
4.0e-6

Plan view (looking

down on surface) 0.0
green =
heterodomains
-4.0e-6

0.25 m -4.0e-6 0.0 4.0e-6 8.0e-6 1.2e-5

X (m)
1.0e-5

1.95 m
1.0e-6

Cross-sectional view
H (m)

surface at H = 0
1.0e-7

1.0e-8
-4.0e-6 0.0 4.0e-6 8.0e-6 1.2e-5
X (m)
 1.5E-09 Net interaction depends on heterodomain size
versus zone of interaction (ZOI)

1.0E-09

F (N) 5.0E-10

ZOI decreases with decreasing colloid size & increasing IS

(ionic strength)
0.0E+00
0.0E+00 1.0E-08 2.0E-08 3.0E-08 4.0E-08
Greater repulsion when ZOI >> heterodomain size
A heterodomain has a maximum particle size that it can attract
There is a minimum IS required for net attraction to occur
-5.0E-10
H (m)
-1x10-6 m Discrete heterogeneity on surfaces colloid art & science

-1x10-7 m

-1x10-8 m

-1x10-9 m
-1x10-6 m Mechanistic simulations in impinging jet geometry - movie

-1x10-7 m

-1x10-8 m

-1x10-9 m
Hetero-domains:
120 nm radius

% coverage
changes with:
a) Mineral
b) pH

Pazmino et
al, 2014,
Langmuir,
30(19),
54125421

Trauscht et
al, 2015,
Langmuir,
31 (34),
93669378
 1.0E+00 a MSRlog= 0.98 1.0E+00
Silica b

Muscovite
1.0E-01 Albite 1.0E-01
Elimelech

Maxwell
1.0E-02 1.0E-02

MSRlog= 0.80
1.0E-03 1.0E-03
1.0E-03
1.0E+00 1.0E-02 1.0E-01 1.0E+00 1.0E-03
1.0E+00 1.0E-02 1.0E-01 1.0E+00
c Experimental d Experimental

Discrete Hetergneity
modified Ncol

1.0E-01 1.0E-01

1.0E-02 1.0E-02

MSRlog= 0.15 MSRlog= 0.17

1.0E-03 1.0E-03
1.0E-03 1.0E-02 1.0E-01 1.0E+00 1.0E-03 1.0E-02 1.0E-01 1.0E+00
Experimental Experimental
 1.00
Muscovite
= 0.52(% )0.56 p
Coeficient of Ncol optimized eq.

Trauscht et
al, 2015,
0.10 Langmuir,
31 (34),
Silica 93669378
Albite

132
=
0 1
0.01
0.001 0.01 0.1 1
Surface Coverage (%)
Pazmino et
al, 2014,
Environ. Sci.
Technol.,
48(16),
92279235
Experiment IS at 0 seconds Simulation IS at 15 seconds
 1.00E-03
1.00E-03 v = 2 m/day
v = 2 m/day

1.00E-04
1.00E-04

1.00E-05 1.00E-05

Fav Sim
1.00E-06 Fav 0.2 nm RMS Fav Sim
1.00E-06
Fav 38 nm RMS Fav 38 nm RMS
Unf 0.2 nm RMS Unfav 38 nm RMS
Unfav 38 nm RMS Fav 546 nm RMS
1.00E-07 1.00E-07
Unfav 546 nm RMS

1.00E-08 1.00E-08
1.00E-03
v = 8 m/day v = 8 m/day

1.00E-04

1.00E-05

1.00E-06 Fav Sim Fav Sim

Fav 0.2 nm RMS
Fav 38 nm RMS Fav 38 nm RMS
1.00E-07 Unf 0.2 nm RMS
Unfav 38 nm RMS
Unfav 38 nm RMS

1.00E-08
0.01 0.1 1 10 0.01 0.1 1 10
Colloid Diameter (m) Colloid Diameter (m)
Blocking emerges organically from limited parking spots?

= + +

C=C0

C
(at L)

C=0
Time
 1.5E-09 Slight differences in colloids emerge as
large differences in stickiness?

1.0E-09
Less
sticky More
sticky

More
F (N) 5.0E-10
sticky
Ln Csed

ZOI decreases with decreasing colloid size & increasing IS

Less sticky (ionic strength)
0.0E+00
0.0E+00 1.0E-08 2.0E-08 3.0E-08 4.0E-08

Distance from source

-5.0E-10
H (m)
Complexity of particle filtration in porous media requires many
kinetic parameters, mechanistic basis needed for robust prediction
THE
UNIVERSITY
Particle filtration in porous media involves limited diffusion, and so OF UTAH
is partly deterministic, allowing prediction of attachment rates

Previous approaches failed, assumed surfaces to be homogenous

(mean field approach), need to recognize nano-scale heterogeneity

Developing representative nanoscale heterogeneity greatly

improves predictive capabilities for complex behaviors