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NAPL transport and dissolution

Mette M. Broholm

DTU Environment
B115 room 160
mmb@env.dtu.dk
45251475
NAPL transport and dissolution
Lecture B1
NAPL transport
Conceptual models with field experiment examples
Parameters and estimation
Part of assignment B1

Lecture B2
NAPL dissolution and site investigations
Conceptual models and parameters
Site Investigations, cases and summary
Second part of assignment B1
NAPL transport and dissolution

Readings
B1. Bedient, Rifai & Newell. Chapter 11. Nonaqueous
phase liquids.
B2. Corrections and comments to Bedient et al. Chapter
11.
B3. Stroo & Ward. Chapter 8. Mercer, Cohen & Noel.
DNAPL site characterization issues at chlorinated
solvent sites. Readings: Chapter 8.1-8.2 p. 218-224.
Optional: Remaining Chapter 8.

Alternative – if you like mathematical explanations:


Mayer & Hassanizadeh. Soil and Groundwater
Contamination: Nonaqueous Phase Liquids. (Not uploaded)
Goal

After the lectures the students should:


Have a conceptual understanding of transport and
dissolution of NAPLs
Know the most important parameters related to transport
and dissolution of NAPLs
Be able to estimate selected parameters important for
NAPL site diagnosis
NAPL transport (B1)

Definitions (8.30-8.45) Parameters (9.50 – 10.35)


Compounds Exercise B1 (10.35-12.00)
Use Question 1-6
Contamination problem
Conceptual models (8.45-9.30)
Discuss exercise B1 q2-3
LNAPL
DNAPL
Field examples included

Break (9.35-9.50)
Definitions

NAPL LNAPL
Non Aqueous Phase Liquid Light NAPL
(Water) Immiscible Phase Lighter than water
Liquid Floater
Oily Liquid
Ikke vandblandbar væske DNAPL
Dense NAPL
Denser (heavier) than
water
Sinker

Show examples
Typical NAPLs

LNAPLs DNAPLs
Gasoline Chlorinated solvents
Diesel (PCE, TCE, TCA, …)

Oils PCB-oils

Aromatic hydrocarbons Other halogenated


(BTEX) compounds (freons,
bromated flame retardents,
…)
Coal-tar, creosote
Selected NAPL parameters

Density Dynamic viscosity


(g/ml) (m Pa s)

Water 1.00 1

TCE 1.46 0.57

Creosote 1.05 1080

Gasoline 0.75 0.45


trans-1,2-DCE
Chlorinated solvents Cl H
C C

PCE = perchloroethylene = tetrachloroethylene H Cl

PCE TCE cis-1,2-DCE


H2 HCl H2 HCl
Cl Cl Cl Cl H H
C C C C
trans-1,2-DCE C C
Cl Cl ClH HCl Cl Cl
C C
H Cl 1,1-DCE
TCE = trichloroethylene Cl H
C C
PCE TCE cis-1,2-DCE H2 HCl VC
H2 HCl H2 HCl Cl H H
Cl Cl Cl Cl H H Cl H
C C C C C C C C
Cl Cl H Cl Cl Cl H H

1,1-DCE
1,1,1-TCA = 1,1,1-Trichloroethane Cl H
C C
1,1,1-TCA Cl 1,1-DCA H CA

Cl H H2 HCl Cl H H2 HCl Cl H

Cl C C H Cl C C H H C C H
Biotisk Biotisk

Cl H H H H H
Use of chlorinated solvents

Degreasing Amount
Metals DK 1987: 6500 tons
Galvanising industry
Metal foundries
Auto paintshops
Electronics industry
Film Consumption of tetrachloroethylene in Denmark from 1959 to 2000.

Textiles
Drycleaning

Johansen K et al. Occup Environ Med 2005;62:434-441


DK Sites
contaminated with
chlorinated solvents
Monitoring

Remediation

V2 registered sites w.
chlorinated solvents

oil and BTEX


Contamination with chlorinated solvents

Oil and gasoline Chlorinated solvents


(LNAPLs) (DNAPLs)
Chlorinated solvents Constitute the majority of
(DNAPLs) the sites with long term
The 2 largest sources of remediation (continuous)
groundwater contami- 22% of the drinking water
nation in DK aquifer wells in greater
Chlorinated 70% Copenhagen area were
contaminated in 1997
A large % of the sites
requiring remediation US TCE, PCE and/or TCA in
Chlorinated 80% ~10% of waterworks
>10000 prs.

DNAPLs
2/3 of the megasites are
DNAPL sites in DK
2D-box
experiment
PCE release in
2D-box with
water saturated
sand

4 different grain-
size filter sands

Very large effect


of small
difference in
grainsize
Exercise B1 Questions 2-3

Discuss question 2 and 3 in assignment B1 with the person


sitting next to you
You have 10 minutes
Conceptual model 1: NAPL

In solution Flow direction Water table


PCE NAPL vadose zone experiment
PCE release to unsaturated sand deposit
6 L infiltrated in 1½ minute

Horisontal

6 L constant drip-release over 1½ hour

Vertical

PCE distribution in unsat. sand


High sensitivity to small
variations in poresize
Residual saturation 1-18% of
porosity
Conceptual model 2: LNAPL
Conceptual model 2: LNAPL

Can LNAPL occur under the WT?


If so why/how?
What control the flow direction of LNAPL?
2 min discussion
Conceptual model 2b:
LNAPL on fluctuating watertable
Conceptual model 2b:
LNAPL on fluctuating watertable
Conceptual model 2b:
LNAPL on fluctuating watertable
Conceptual model. LNAPL transport

LNAPL flow
direction –
controlled by:
Water table
LNAPL gradient
and
Bouyancy
effect (upward)

CL:AIRE, 2014
Conceptual model 3: DNAPL
Conceptual model 4: DNAPL with pool
Conceptual model 4: DNAPL with pool

What controls the flow direction for mobile


DNAPL?
1 min discussion
Conceptual model 4: DNAPL with
upgradient pool
PCE releases in sand aquifer, field exp.
Fractured clay till

Tar in
fracture

Foto: Knud Erik


Klint, GEUS
Conceptual
model 4:
DNAPL,
fractured
aquitard
Accidental release from field experiment
Retention capacity
Residual saturation Examples

Retention capacity Residual saturation


(L/m3 soil) (% of porespace)

Unsaturated sand 3-30 2-18

3-15
Saturated sand 5-50
(Pool 15-25)
Fractured low-
permeability media 0,15
(e.g. clay)
Fractured porous
media (e.g. 0,5-5
sandstone)
NAPL transport (B1)

Definitions (8.30-8.45) Parameters (9.50 – 10.35)


Compounds Exercise B1 (10.35-12.00)
Use Question 1-6
Contamination problem
Conceptual models (8.45-9.30)
Discuss exercise B1 q2-3
LNAPL
DNAPL
Field examples included

Break (9.35-9.50)
NAPL transport and dissolution

Parameters

Residual saturation
Relative permeability
NAPL flow
Interfacial tension
Wetting and non-wetting phases
Capillary pressure
Entry/displacement pressure
Pool heights
Porous media
Fractured media
NAPL in saturated porous media
NAPL in saturated porous media – silica
and quartz sand

Al-Raoush 2014 JCH


NAPL in aquifers

Blobs and ganglia

SEM
photomicrographs of
blob casts from sand
columns

From Conrad et al.


1992 WRR
Saturation

Residual saturation
NAPL saturation (residual or mobile)
(Residual concentration)

Defined as the fraction of one phase relative to the total


pore space (porosity)

In two phase system


Swater + SNAPL = 1

In three phase system


Swater + SNAPL + Sair = 1
Relative permeability
Water saturation
decreases
Less pores are filled
Small area for flow

Increase in NAPL
saturation
More pores are
isolated from flow

Drainage of water
Large pores are
emptied first
Resistance to flow
increase, as
resistance is
greater in smaller
pores
Relative
permeability

Residual
DNAPL source
in aquifer

Relative
permeability
change

Effect on flow
field

Effect on
plume from
source?
Emplaced DNAPL source experiment

A: 1m ∙ 0.5m, H: 0.5 m
Mixed source
Afstand (m)
40% TCE
Eq. conc. 560 mg/L

Very narrow highly


Kote (m)

concentrated plume

Why is vertical effect <


horisontal effect
Afstand (m)
NAPL flow

Darcy’s law:
v = Q/A = - K∙dh/dx
Hydraulic conductivity:
K = k∙g∙ρ/μ
Water:
K = k∙kr,w∙g∙ρw/μw

NAPL:
K = k∙kr,NAPL∙g∙ρNAPL/μNAPL

Where
k: permeability (m2), kr: relative permeability
g: force of gravity (ms-2)
ρ: density (kgm-3), μ: dynamic viscosity (kgm-1s-1)
Interfacial tension, wettability

NAPL in water
Air Air LNAPL Water Water
Air

Water

Water in NAPL

Water NAPL Water DNAPL


DNAPL

System Air-water Air-NAPL Water-NAPL Air-water-NAPL


Wetting Water NAPL Water Water > NAPL
Non-wetting Air Air NAPL > air
Capillary pressure
Water
Definition
Pc = Pnw – Pw Wetting
phase

Capillary tube / straw


Pc = 2∙σ/r Pw

Pnw
Pore throats
Pc = 2∙σ ∙ cosφ/r
DNAPL
If perfectly water wetting
Non-
cosφ = 1 wetting
phase
r: pore radius, σ: interacial
tension (surface tension), φ:
contact angle
Capillary pressure - saturation curves

Pd
Capillary pressure - saturation curves

Coarse sand (r1)

Fine sand (r2)


Fine sand

r1 > r2
Pd = Pc = 2∙σ/r
Pd1 < Pd2
Coarse sand
2D-box
experiment
PCE release in
2D-box with
water saturated
sand

4 different grain-
size filter sands

Very large effect


of small
difference in
grainsize
Pool height

Zn = HD = Pd/(Δρ∙g)

Zn: Pool height (m), g: force of gravity (ms-2)


Pd: Displacement (entry) pressure
Δρ: Density difference between DNAPL and water (kgm-3)
Fractures
Iregular fracture
and idealizations

Parallel plate:
Pd = 2∙σ/e

Series of tubes:
Pd = 4∙σ/e

e
e

Parallel plate Series of tubes


Pool height

Zn = HD = Pd/(Δρ∙g) = 2∙σ/(e∙Δρ∙g)
to Zn = HD = Pd/(Δρ∙g) = 4∙σ/(e∙Δρ∙g)

Zn: Pool height (m), g: force of gravity (ms-2)


Pd: Displacement (entry) pressure (kgm-1s-2 = Nm-2)
Δρ: Density difference between DNAPL and water (kgm-3)
σ: interfacial tension (Nm-1), e: fracture apperture (m)
Pool heights on fractured media

Clayey till
Sandstone
Stop vertical NAPL migration

NAPL can move against an upward vertical hydraulic


gradient untill:

Δh/Zn = (ρn – ρw)/ρw

Δh∙ρw = Zn∙(ρn – ρw)

Where:
Δh: hydraulic gradient (m)
Zn: pool height of NAPL (m)
ρn, ρw : density of NAPL and of water (kg/L)
NAPL transport (B1)

Definitions (8.30-8.45) Parameters (9.50 – 10.35)


Compounds Exercise B1 (10.35-12.00)
Use Question 1-6
Contamination problem
Conceptual models (8.45-9.30)
Discuss exercise B1 q2-3
LNAPL
DNAPL
Field examples included

Break (9.35-9.50)