Partitioning and Migration of NAPLs and VOCs in Subsurface Environments

NAPLs, VOCs, Two classes of NAPLs
Partitioning of contaminant •LNAPLs (Lighter (than water) NAPLs) < w at 20- 25 ℃

- immiscible petroleum hydrocarbon liquids typical soil temp.
NAPLs: Non-Aqueous Phase Liquids - gasoline, fuel oils
NAPLs: -organic liquids that do not mix freely with water - Benzene, Toluene, Ethyl Benzene, Xylene (BTEX) detection limits
(sparingly soluble：難溶性). 2g/L, 5g/kg
-the most common contaminants:
•DNAPLs (Denser (than water) NAPLs) > w at 20- 25 ℃
-traveling large distances in subsurface
- chlorinated solvents, trichloroethene (TCE),tetrachloroethane (PCE),
-difficulty in the ground water clean-up
(有機塩素系溶剤) etc. for high-tech industry, cleaning
carcinogen (発癌物質)
- wood preserving process wastes (creosote)
intensive researches in the last two decades - coal tars
regulations with respect to site remediation
- pesticides
July 5, 2019 EnvGeo_Eng Dr. Jiro Takemura 1 July 5, 2019 2
EnvGeo_Eng Dr. Jiro Takemura
Properties of NAPLs
Properties
The distribution of NAPLs in the subsurface is the net
results of coupled chemical and physical interaction between -specific gravity (TCE:1.47)
the NAPL, pore water, pore gases and porous medium. -aqueous solubility (TCE:0.1%)
(水溶性) immiscible, sparingly soluble
The chemical properties of NAPL, pore phase and porous -viscosity (TCE:0.566cP)
medium, together with chemical equilibria determine the more permeable than water
partitioning of the compounds between the various phase. -vapor pressure *(63kPa at 25oC) cf. water 3.2kPa
(分配) （蒸気圧) highly volatile same as Benzene
The physical properties of the pore fluid and porous media VOCs (Volatile Organic Compounds)
determine the mobility of each phase.
（揮発性有機化合物）
SVOCs(Semi-volatile Organic Compound)
p1-2
July 5, 2019 EnvGeo_Eng Dr. Jiro Takemura 3 July 5, 2019 EnvGeo_Eng Dr. Jiro Takemura 4
vapor pressure Four distinct phases
The pressure exerted by vapor=the pressure of the gas in equilibrium
(saturated condition) with respective to the liquid or solid at a given •gas phase in vadose zone
gas
temperature. It represents a compound’s tendency to evaporate and solid
is essentially the solubility of the gas. •solid phase:
Raoult’s law(ラウールの法則) giving the equilibrium partial pressure of soil grains and organic matter water
a component of a NAPL mixture in the atmosphere above the mixture.
•aqueous phase: polar
Pa = xa Pna (1)
NAPL
Pa:the partial vapor of the NAPL component in the gas phase •NAPL phase: nonpolar
xa: the mole fraction of the NAPL component in the mixture
Pna:the vapor pressure of the NAPL component in pure-phase form
Mass transport process involved in partitioning of

Existence in subsurface NAPLs into solid, water, and gas phases
•dissolution into aqueous phase molar concentration (mol/L)

of dissolved gas pressure in atm
(溶解）
C  kP
•volatilization into gas phase Volatilization
constant (mol/L)
（Raoult’s law) Volatilization
（揮発、気体） Sorption depending only
（Henry‘s law)
on temperature
•NAPL phase as entrapped residual
Sorption Dissolution
（液体)
•partition (sorption) onto solid phase Sorption
（吸着)
Mechanism of migration by DNAPLs Conceptual model of point source contamination
In vadose zone - DNAPL case -
- NAPL plume move downward by gravity force. by gravity
- volatilized DNAPLs move more laterally.
volatilization
In saturated zone GAS
- moving rate slows due to the resistance of water (displacing GWF
water) and buoyancy force
- some chemical will dissolve in the flowing ground water,
forming contaminant plume
- remainder will move downward and create residual NAPL zone
- Mobil DNAPL will reach to impervious layer, spreading (Cherry et al.,1996)
laterally as liquid pool. sorption
dissolution
Mechanism of migration by LNAPLs

Conceptual model of point source contamination
- Non-NAPL case - In vadose zone
Similar to DNAPLs
In saturated zone
- spreads out laterally by gravity, forming a “pancake” or lens” on
the top of water table.
GWF - after formation, the lens will migrates primarily in the direction of
natural ground flow.
dissolution sorption - Change of ground water table due to seasonal fluctuations or

pumping may enhance the spread vertically and area of contamination.
(Cherry et al.,1996)
Conceptual model of point source contamination 3 important migration pathway of NAPLs
- LNAPL case -
by gravity •Vapor-phase transport
wide spreading and diluting
volatilization
GAS
or lens •Aqueous-phase transport as solute with in
contaminant plume
GWF
faster and spreading
•NAPL phase transport
slower but high concentration, source of CM
(Cherry et al.,1996)
Vapor phase transport Henry’s law

The vapor transport depends on vapor pressure of chemical. Volatilization of dissolved organic solutes from water depends:
n: mole number Henry’s law, relating the aqueous-phase concentration of a chemical
n p
gas law  (2) V: volume to its partial pressure in the gas phase.
V RT p: pressure
R: universal gas constant Px = HL Cx (3)
T: absolute temperature Px: partial pressure of gas (atms at a given temperature)
Volatilization: Cx: equilibrium concentration of the gas in solution (mol/m3,mol/L )
volatile: vapor pressure more than 1.3 x 10-3 atm *Note: HL: Henry’s law constant in atm/(mol/m3 , mol/L)
semi volatile: 1.3 x 10-3 – 1.3x10-13 atm accuracy in the
concentration The larger Henry’s law constant is, the greater volatilization from
Volatilization can be related to Henry’s constant. measurement in
the soil or water.
dissolved phase HL less than about 3x10-7 atm/(mol/m3 water): non-volatile
Migration of gas: advection and dispersion in vadose zone, larger than For HL > 10-7 atm/(mol/m3 water), volatilization might be a
saturated zone. significant in mass-transfer mechanism.
vapor extraction method
NAPL Phase transport
Aqueous phase transport
NAPL in water flow
When a wetting fluid (such as water) displaces a nonwetting fluid (such as oil)
The propensity of aqueous phase transport depends on in a porous medium, a proportion of the nonwetting fluid will remain entrapped
aqueous (water) solubility and ground water flow. in the medium pores once the wetting front has passed. In general, the
nonwetting fluid is trapped in the form of disconnected blobs or ganglia whose
Magnitude of aqueous solubility of NAPLs is a few order complicated morphology and distribution are dependent upon (i) the geometry
difference, depending on p1-2 of the pore space; (ii) fluid-fluid properties such as interfacial tension, density
contrast, and viscosity ratio; (iii) the fluid-solid interfacial properties
polarity, temperature, salinity, dissolved organic matter. affecting wetting behavior; (iv) the applied pressure gradient; and (v) gravity.
(極性） (塩分濃度) （溶解有機分)
During stable fluid displacement, nonwetting phase (NAPL) entrapment is
Movement is caused by advection and dispersion.
caused by capillary forces and overcome by viscous pressure forces and/or
buoyancy forces (Mayer and Miller, 1992). The ratios of viscous pressure to
dilution in case of enough travel distance capillary forces and gravity to capillary forces are usually expressed as
（希釈） dimensionless groups, known as the capillary number (Ca) and the Bond
number (Bo), respectively
nonwetting fluid Saturation (Snw)

Snw
Capillary number: Ca and Bond number: Bo Capillary –
v v: displacing (Darcy) fluid velocity, pressure-wetting
Ca  : displacing fluid viscosity, fluid saturation
 : interfacial tension,
Residual saturation of fluid

curves for two
Irreducible wetting fluid

gD 2 : fluid density contrast,
nonwetting fluid (Snwr)

Capillary pressure (cm of water)
Bo  g: gravitational acceleration, phase flow
 D: average particle radius of the porous medium
Saturation (Swi)
“Contaminant Hydrology”
Fetter (1999)
Above a certain upper, critical Capillary or Bond number, no capillary trapping occurs, and the
residual nonwetting phase saturation is close to zero. Conversely, below a certain lower, critical Drainage/
capillary or Bond number, the trapping is dominated by capillary forces, and the residual Drying curve
nonwetting phase saturation reaches a constant maximum value.
Between these two extremes, the residual nonwetting phase saturation depends upon the
combined effects of capillary, viscous pressure, and gravity forces.
The mapping of these three domains in the plane Ca - Bo, constitutes the "phase-diagram" for a
Imbibition/ Pd: Displacement/
given system. The aim of this work was to establish experimental phase-diagrams for several imbibition
uniform porous media systems, under vertical displacement conditions Wettnig curve pressure/
Swi or Air entry value
wetting fluid Saturation (Sw)
Experimentally derived capillary –pressure-wetting fluid saturation curves Changes in the vertical distribution of oil（LNAPL) with time
after a slug of oil is added to the top of a column of sand
Contaminant Hydrology Fetter (1999)
Air and water Air and trichloroethylene
in medium sand in medium sand
Capillary fringe
Air and water

Trichloroethylene and air
in fine sand
in fine sand
Relative permeability of two phase system

Sorption of contaminant
Darcy’s law for the steady state flow of
saturated water in the presence of NAPL
krwki  w dhw Sorption causes contaminants to move slower than the
Qw   A
NW W w dl flowing ground water (interstitial velocity), resulting
:Relative permeability krw
Qw: volume of water flowing retardation.

krw: relative permeability of water in the
presence of the nonwetting fluid Effects of sorption should be considered both in
ki: intrinsic permeability
w: density of the water - evaluating the potential for movement of the
w: dynamic viscosity of the water
A: cross-sectional area of the flow contaminants in soils (aquifer, clay liner).
dhw/dl: gradient of the head of the water
- designing remediation activities at hazardous-waste site.
For nonwetting fluid
krnwki  nw dhnw
Qw  A
 nw dl
Concept of sorption Concept of sorption, cont.
Sorption can be defined as the interaction of contaminant with a solid.
Sorption is determined experimentally by measuring the
The process of sorption can be divided in adsorption and absorption.
partitioning of a contaminant onto a particular sediment, soil or
Adsorption: an excess contaminant concentration at the surface of a rock.
（吸着） solid. In batch tests, a number of solutions with various concentration
Absorption: penetration into the solid by a contaminant are well mixed with the solid, and then the mount of contaminant
（吸収) removed (sorbed) is determined by measuring the concentration of
the solution after mixing.
Sorbate and sorbent are the terms used in sorption behavior. Sorbate
is the contaminant that adheres to the sorbent, that is, sorbing material. The results of batch tests are plotted on a graph, known as an
isotherm, which shows the relationship between the concentration
sorbate: organic molecules; ions, sorbent: soils; aquifer matrix of contaminant of the solution and the amount sorbed on the solid.
Partitioning（分配）refers to the process by which a contaminant,
originally in solution, distributes itself between the solution and the
solid phase.
Concept of sorption, cont. Batch test and isotherm
If the sorption process is rapid compared with the flow velocity, Liner equilibrium isotherm
the dissolved contaminant will reach an equilibrium condition with (1  n)  s K d
the sorbed phase and process can be described using equilibrium
・sorbent Cs  K d C (4) Rd  1 
n
・sorbate
isotherm. Cs = mass of contaminant / unit mass of soil grain
unit: g/kg
If the sorption process is slow compared with the rate of fluid flow C= mass of contaminant / unit volume of pore fluid
in the porous media, a kinetic model is needed. Cs unit:mg/l, g/m3
Distribution coefficient
or
Kd Linear equilibrium
mixing 1 or 2 days 1 adsorption coefficient
measuring equilibrium （分配係数)
concentration in the solution
C
Freundlich sorption isotherm
Limitation of liner equilibrium isotherm - nonlinear -
Cs
overestimation Cs  KC N
(5)
Liner
- upper limit of Cs K,N: constants
Cs - nonlinear relation in wide
range of C. (5) => (14) and neglecting reactions
C
C C 2
C (1  n)  s  ( KC ) (6) N
 Dhl 2  vint 
t x x n t
C  1  n   2C C logCs
1   s KNC N 1   Dhl 2  vint
t  n   x x
C (7) log Cs  log K  N log C
1 n
R df  1   s KNC N 1 (8)
n
logC
Langmuir sorption isotherm Effect of sorption

- nonliner - - results of numerical calculation on column test-
C Cs
Cs  (9)
1  C
vint=0.1cm/s
: adsorption constant related to the binding energy (L/mg) 8cm Dhl=0.1cm2/s
: the maximum amount of solute adsorbed by solid (mg/kg) no retardation 16cm
n=0.37
(9) => (5.14) and neglecting reactions Ci=0.0mg/L
C C s  K d C ( 4)
C retardation
( )
C  2C C (1  n)  s 1  C with Kd=0.476g/g C=0.05mg/L is injected into
 Dhl 2  vint  (10) the top of the column for
t x x n t lower peak value
C/Cs 2mins as pulse injection.
C  1  n      2C C After 2 min injection, C is
1      Dhl 2  vint (11) C

1 C
 set back to 0.0mg/L.
 
 1  C   
s
t  n 2
x x C s  
1  n   
R dl  1   s  
2  (12)
n  1  C   C “Contaminant Hydrology” Fetter, 1999
Effect of sorption Isotherm for Contamination: Batch tests
- results of numerical calculation on column test-
Clay sand mixtures
5.0 Volume of solution V (L) Soil
Freundlich sorption isotherm Langmuir sorption isotherm 4.5
CC=100% Initial concentration Ci (mg/L) ms (ｇ)
4.0
CC= 70%
Csolid increase with CC

3.5
Csolid (mg/g)
3.0 CC= 50%
Langmuir isotherm with
Cs  KC (5)N
=0.345L/mg, =0.476g/g, 2.5
CC= 30%
N=0.7 C 2.0
Cs 
1  C (9) 1.5
1.0
liner isotherm CC= 10% CC= 0%
N=1.3
with Kd=0.476g/g
0.5 Mixing
0.0
0 100 200 300 400 500 600 700 800 900 1000
C eql (mg/L)
Concentration in liquid phase Contaminant
Ceql (mg/L) sorbed on soil
Csolid (mg/g)
Isotherms are showing the non linear relationship
“Contaminant Hydrology” Fetter, 1999
July 5, 2019 EnvGeo_Eng Dr. Jiro Takemura 33
CC and Csolid are affected by Ceql 34
July 5, 2019 EnvGeo_Eng Dr. Jiro Takemura
Koide’s experimental results

Column test Vertical stress
CC= 10%
C0=500mg/L
Clay –sand mixture CC=100%
CC= 70% C0=50mg/L
CC= 30%
60mm CC= 50%
C/C0
CC= 30%
20mm
Hydraulic gradient C0 Nearly 6 times difference

i~ 100
specimen
C
5 20 30
One PV~0.3day
120 Pore Volume (PV) tvint/H
July 5, 2019 EnvGeo_Eng Dr. Jiro Takemura 36
35 July 5, 2019 EnvGeo_Eng Dr. Jiro Takemura
Examples of nonequilibrium (Kinetic) sorption model Factors influencing sorption
Irreversible first order kinetic sorption model: rate of the sorption - contaminant characteristics -
is a function of the solute remaining in solution and once it sorbed (1)water solubility
onto the solid, the solute cannot be desorbed. The higher the solubility of chemical is, the easier or faster
C s
 k1C (13) the chemical distributes by the hydraulic cycle, showing lower
t
adsorption coefficient.
C  2C C (1  n)  s Cs
 Dhl 2  vint  (14) (2)polar-ionic character: three classes
t x x n t
k1: a first order decay rate constant 1) ionic or charged species: ex) pesticide and phenol
2) uncharged polar species: benzene, toluene, xylene
Reversible liner kinetic sorption model: rate of the sorption is
related to the amount that has already been sorbed and the reaction is 3) uncharged and nonpolar species: TCE,PCE, chlorinated benzene
reversible. C The higher polarity, the lower adsorption.
s
 k 2C  k3C s (15)
t (3) octanol-water partition coefficient
k2: forward rate constant, k3: backward rate constant （オクタノール/水分配係数）
Octanol-water partition coefficient: Kow Factors influencing sorption

オクタノール／水分配係数 - soil characteristics -
The octanol-water partition coefficient represents the distribution
•Mineralogy
of a chemical between octanol(C8H17OH) and water in contact with
each other at equilibrium conditions. Key parameter in the studies •Permeability – porosity
of the environmental fate of organic chemicals •Texture
concentration in octanol phase •Homogeneity
K ow 
concentration in aqueous phase
•Organic carbon content:
Range of Kow : 10-3 – 107 => it is often given by log Kow particularly important NAPLs （活性炭吸着）
-smaller molecular, higher polarity => lower Kow •Surface charge（表面電荷） ex: activate carbon sorption
to exclude NAPLs
•Surface area(粒子表面積）:
-larger molecular, lower polarity => more hydrophobic (low solubility)
（疎水性） clay and silt having higher specific surface associate with natural
=> higher Kow => larger partition on solid phase organic matter, creating a rich sorptive environment.
Sorption of hydrophobic compounds (NAPLs) Sorption of hydrophobic compounds (NAPLs)
(Karichhoff et al. 1979) (Karichhoff et al. 1979)
The partitioning of a solute onto strong correlation between Koc
Kd
mineral surface or organic carbon and Kow,
contents of soil is almost
exclusively on to the organic K d  0.6 K ow (17)
carbon fraction, foc if it constitutes Koc
at least 1% and strong correlation 1
between Kd and organic carbon especially for log Koc and log Kow
content of the sediment.
sorption constant log K d  log K ow  0.21
Kd
K oc  (16)
f oc foc
“Ground water contamination” by Bedient, Rifai & Newell “Ground water contamination” by Bedient, Rifai & Newell
Natural gradient field test at the Borden landfill site

Field retardation data from the Borden landfill site
conservative tracer: Cl-
ave.vint= 0.091m/d
two conservative tracers
Relative concentration (C/C0)
Relative concentration (C/C0)

(Chloride, Bromide)
five VOCs (Bromoform
CTET, PCE, DCB, HCE)
were injected for one day PCE
and intensive monitoring PCE
was conducted for two
years. 0 200 400 0 200 400
Time (days) Time (days)
at location (b) at location (c)

“Ground water contamination” by Bedient, Rifai & Newell
Determination of retardation factor from the Determination of retardation factor from the field data
field data
distance from source of nonreactive plume (xn) Kow=3.98x103
Rd 
Distance traveled (m)

distance from source of reactive plume (xr) Chloride:
Nonreactive
Retardation factor
xn plume Kow=3.98x102
time for reactive chemical to reach a given point (tr)

Rd 
time for nonreactive chemical to reach a given point(tn)
tn
xr Kow=4.37x102
tr
Time (days) Time (days)

Example of exposure pathway

home work 5
GAS due July 12
Investigate the environmental standards of
HMs, VOCs , DIOXINs and others
(Ground W, Surface W, soils, water supply, effluent)
in your country
liquid Compare the standards and discuss the similarity and
differences
Solute
Working Groups
Contaminant transport equation cont. Group
1
1
student ID
15_02927
17M58316
last name
Omura
FENG
Naoya
Yi
first name
Japan
China
Country Field of research
Geotech
Structure
1 17M58322 GUO Yuliang China Geotech
total mass(adsorbed + fluid phase) 1
1
18M51116
18M51180
Isozumi
Ogawa
Shouta
Kouhei
Japan
Japan
Steel Structure
Planning
   1 18M51205 Kawakami Jyun Japan Geotech
x y z 1 18M51429 GUNAWAN DEVIN Indonesia Concrete Structure
m 1 Tommaso Italy Hydrology

18R51503 DURATORRE
general mass
 J  R  m
1 18R57014 IDHAR Ridha Amalia Indonesia Planning
balance eq. (13) 2 15_08663 Takayama Shinichiro Japan Geotech
t
2 18M51168 Otani Yuto Japan Geotech
2 18M51257 Koizumi Daiya Japan Planning
2 18M51369 Hashimoto Kana Japan Hydrology
a general rate constant in 2 18M51435 JIA Pengfei China Concrete Structure
2 18R57011 AZIS Faisal Brahmanstya Indonesia Planning
chemical reaction radio active and/or biological 2 18R57015 MUHAMMAD Fadel Indonesia Planning
3 15_12682 Fujimoto Shouta Japan Geotech
decay 3 17M58374 LYU Hang China Geotech
For 1-D flow 3 18M51197 Kawai Tomohiro Japan Planning
3 18M51263 Kobayashi Kenta Japan Concrete Structure
 (nC )  ((1  n)  s Cs )   C 
  R   nC  (1  n)  s Cs 
3 18M53032 HONG-IN Phadungsak Thailand Geotech
    nvint C  Dhl n 3 18R51007 SAMIE Sierra Jalet U.S.A. Hydrology
t t x  x  3 18R57012 MIRHANTY Nandita Indonesia Planning
3 18R57016 Suranto Anindya Hiswara Indonesia Planning
(14) 4 17M58405 PRASOMSRI Jitrakon Thailand Geotech
Adsorption（on solid phase） 4
4
18M51286
18M51300
Sato
Shiroma
Michitaka
Hiroya
Japan
Japan
Water Env
Planning
4 18M51352 Noda Shouta Japan Geotech
In fluid phase 4
4
18M51398
18M51458
Muro
XIAO
Shoutaro
TENGXIANG
Japan
China
Planning
Geotech
July 5, 2019 EnvGeo_Eng Dr. Jiro Takemura 49 4 18R51005 Esponazs Jasson Mexico
4 18R57013
July 5, 2019 NURSHAFIYANAEnvGeo_Eng
Safyra Indonesia
Dr. Jiro Takemura Planning 50

Partitioning and Migration of NAPLs and VOCs in Subsurface Environments

Uploaded by

Document Information

Original Description:

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Partitioning and Migration of NAPLs and VOCs in Subsurface Environments

Uploaded by

Copyright:

Available Formats

NAPLs, VOCs, Two classes of NAPLs

Partitioning of contaminant •LNAPLs (Lighter (than water) NAPLs) < w at 20- 25 ℃

Mass transport process involved in partitioning of

•dissolution into aqueous phase molar concentration (mol/L)

Mechanism of migration by LNAPLs

dissolution sorption - Change of ground water table due to seasonal fluctuations or

Vapor phase transport Henry’s law

nonwetting fluid Saturation (Snw)

Residual saturation of fluid

Irreducible wetting fluid

nonwetting fluid (Snwr)

Air and water

Relative permeability of two phase system

Qw: volume of water flowing retardation.

Concept of sorption, cont. Batch test and isotherm

Langmuir sorption isotherm Effect of sorption

Csolid increase with CC

Koide’s experimental results

Hydraulic gradient C0 Nearly 6 times difference

Octanol-water partition coefficient: Kow Factors influencing sorption

Natural gradient field test at the Borden landfill site

Relative concentration (C/C0)

Relative concentration (C/C0)

at location (b) at location (c)

Distance traveled (m)

time for reactive chemical to reach a given point (tr)

Time (days) Time (days)

Example of exposure pathway

m 1 Tommaso Italy Hydrology

balance eq. (13) 2 15_08663 Takayama Shinichiro Japan Geotech

You might also like