Clase 3-Distribucion Fases

Clase 3 Distribucin de
contaminantes entre fases

1
Destino y Transporte de Contaminantes II-2012
Prof. Jorge E. Pachon, Ph.D.
Properties of Chemicals: Aqueous
Solubility
When a chemical is contacted with water for an extended
period of time, the chemical will enter the aqueous phase until
the water is fully saturated with that chemical.
= Maximum saturation concentration of A in water (mol/L
or g/L)
For solid chemicals:
For gaseous chemicals:
Larger nonpolar organic contaminants have lower aqueous
solubility.
Inclusion of polar groups (OH
-
, NH
2
-
)on the benzene ring results
in higher solubility in water.
A
sat , w
C
| => | C T
A
sat , w env
+ => | C T
A
sat , w env
2
Properties of Chemicals: Vapor Pressure
Vapor pressure is the analog of aqueous solubility for the air
system
Smaller nonpolar compounds are lighter and more readily
escape to the vapor phase
env
A
A
sat air
RT
MW
C
A
v
,
P
(g/L) air in the A of conc. saturation = =
| => | P T
A
v env
Antoine Equation
a
T
b
env
+
=
303 .. 2
P log
A
v
3
Henrys Law
4
( )
( ) L mol
atm
s Henry
A
/ C
P
Constant Law ' K
A
eq w,
eq air,
A
H
= =
Para gases inorgnicos
(O
2
, CO
2
)
Impacts of Environmental Factors on C
w,sat
, P
v
and K
H
Environmental Factors Impacts on C
w, sat
Impacts on P
v
and K
H
T
env
increase
C
w, sat
of solid increase
P
v
and K
H
increase
C
w
of gas decrease
Aqueous salt conc.
increase
C
w, sat
decrease P
v
and K
H
increase
Presence of co-dissolved
chemicals in water
Solubility increase
Varies, depending on
volatility of the co-solvent
pH increase
When pH> pKa, aqueous
solubility increase
When pH> pKa, P
v
and K
H
decrease
5
Intermedia Equalibrium
5 L Air
5 L Water
5 L Benzene
Container:
5L air
5L water
5L benzene
Calculate
benzene
air
benzene
eq , air
benzene
water
benzene
eq , w
M , C
M , C
6
Partition Coefficient
At equilibrium, the balance in contaminant
concentration C between two media i and j is
described by a partition coefficient:
Air-water exchange
Soil-water exchange
Octanol-water exchange
j
i
ij
C
C
K =
Medium 1
Medium 2
i
C
j
C
7
Environmental Partitioning
water) A/L of (mass water in A of ion concentrat m Equilibriu
soil) A/kg of (mass soil in A of ion concentrat m Equilibriu
C
C
K
octonal) A/L of (mass octonal in A of ion concentrat m Equilibriu
C
C
K
air) A/L of (mass air in A of ion concentrat m Equilibriu
C
C
K
A
eq w,
A
eq soil, A
d
A
eq w,
A
eq o, A
ow
A
eq w,
A
eq air, A
aw
= =
= =
= =
The concept of environmental partitioning was
developed to describe the distribution of a
contaminant between pairs of media.
We define three equilibrium partition coefficients:
8
Air-Water Partitioning
Contaminant concentrations in air are represented in
terms of partial pressure (atmospheres)
Aqueous concentrations of contaminants are in
mass/volume (M L
-3
) units.
( )
( ) L / mol C
atm P
Constant Law s ' Henry K where

RT
K
K
A
eq w,
A
eq air, A
H
env
A
H
A
aw
= =
=
9
Henry's law constants ( K
H
)
In general, lighter (smaller)
and more nonpolar organic molecules will
prefer air to water.
Figure 3.3
10
11
12
Water Equilibrium
10L Water
0.1 g
benzene
Container:
10L water
0.1g benzene
Calculate
Solution: saturated or insaturated?
benzene
sat w
benzene
eq w
C C
, ,
>
13
Air-Water Partitioning Example
10 L Air
10L Water
0.1 g
benzene
Container:
10L air
10L water
0.1g benzene
Calculate
Solution: using 1. Mass balance
2. air-water partitioning coefficient
benzene
eq , w
benzene
eq , air
C and C
14
Container:
5L air
5mL water
5L benzene
Calculate
Intermedia Equalibrium
5 L Air
5 L Water
5 mL Benzene
benzene
air
benzene
eq , air
benzene
water
benzene
eq , w
M , C
M , C
15
Air-Water Partitioning Excercise
Un tanque de 0.21 m
3
de capacidad contiene
100 L de una mezcla de solventes
desengrasantes en agua. La presin parcial del
tricloroetileno (TCE) en la fase gaseosa arriba
del agua es de 0.00301 atm. Cul es la
concentracin del TCE en el agua? Cul es la
masa de TCE en las dos fases (aire y agua)?
R/ C
w,TCE
=0.037 g/L; M
w,TCE
=3.70g.; M
a,TCE
=1.76g.
16
Octonal-Water Partitioning
Large organic and highly
nonpolar compounds
(hydrophobic) prefer to
partition to octanol relative to
water and hence have a
correspondingly large value of
K
ow.
The less soluble a chemical is
in water, the more likely is to
sorb to the surfaces of
sediments (organic material).
Figure 3.4
17
Octonal-Water Partitioning
Laboratory procedure for measuring K
ow
:
1. Chemical is added to a mixture of pura octanol
(non-polar solvent) and pure water (polar
solvent).
2. Mixture is agitated until equilibriumis reached.
3. Mixture is centrifugated to separate the two
phases.
4. K
ow
is the ratio of the chemical concentration in
the octanol phase to chemical concentration in
the water phase.
18
Soil Organic Matter/Carbon -Water Partitioning
Soil = mineral + organics from plants and animals
The mass fraction of organic material in soil
- f
OM
: mass fraction of organic matter (OM) in soil
- f
OC
: mass fraction of organic carbon (OC) in soil
water) A/L of (mass in water A of ion concentrat m Equilibriu
OC) A/kg of (mass OC soil in A of ion concentrat m Equilibriu
C
C
K
water) A/L of (mass in water A of ion concentrat m Equilibriu
OM) A/kg of (mass OM soil in A of ion concentrat m Equilibriu
C
C
K
A
eq w,
A
eq OC, A
OC
A
eq w,
A
eq OM, A
OM
= =
= =
19
Emipirial determination of KOM and KOC
Karickhoff log K
OC
=1.00 log K
OW
0.21
Schwarzenbach log K
OC
=0.72 log K
OW
+ 0.49
20
Compounds with larger K
OW
have larger values of K
OM
and K
OC
.
Soil OM-Water Partitioning Example
5 L Air
5 L Water
5 L Benzene
100g
OM
Container:
5L air
5L water
5L benzene
Add 100 g OM
Calculate
Solution:
eq w OM
benzene
eq OM
xC K C
, ,
=
21
(
=
(
=
(
soil kg
OC of
water L per A of mass
OC kg per A of
K
soil kg per A of
K
soil kg
OM of
OM kg per A of
K
soil kg per A of
K
A
OC
A
d
A
OM
A
d
mass
f
mass mass
mass
f
mass mass
OC
OM
Soil -Water Partitioning
22
Soil -Water Partitioning Example
Container:
10L air
10L water
0.1g benzene
Add 10 kg soil (with 1% OM)
Calculate
Solution: 1. Mass balance for benzene
2. using
10 L Air
10 L Water
benzene
eq , soil
benzene
eq , air
benzene
eq , w
C and C , C
benzene
d
benzene
aw
K and K
10 kg soil
23
NAPL -Water Partitioning
A
sat , w
A
eq , w
C C =
NAPLs can serve as long-term sources of
contamination to the surrounding environment.
Hence, equilibrium transfers of contaminants from
NAPL to water and from NAPL to air are of interest.
Pure NAPL
24
Multi-component NAPL for Ideal NAPL Mixture
A
v
A
NAPL
A
eq , air
A
sat , w
A
NAPL
A
eq , w
P X P
C X C
=
=
Raoults Law (for ideal NAPL mixture)
NAPL in A compound of fraction mole X
A
NAPL
=
Raoults Law: Discovered by Franois-Marie Raoult in 1880s.
25
NAPL-Water and NAPL-Air Partitioning
5 L Air
5 L Water
5 L NAPL
Container:
5L air
5L water
5L NAPL with 10% Naphthalene
Calculate
e naphthalen
eq , w
e naphthalen
v
C and P
26
Environmental Intermedia Problems
- great abundance of pure chemicals
A
eq , w
A
d
A
eq soil,
A
w
A
eq air, A
eq w,
A
v
A
eq air,
A
sat w,
A
eq w,
C K C
RT
M P
C
P P
C C
=
=
=
=
weight molecular W
pressure vapor P
y solubilit aqueous C
: properties compound Pure
A
w
A
v
A
sat w,
=
=
=
t coefficien ng partitioni water - soil K
: t coefficien ng Partitioni
d
=
27
- great abundance of chemicals with a
multicomponent NAPL mixture
A
eq , w
A
d
A
eq soil,
A
w
A
eq air, A
eq w,
A
v
A
NAPL
A
NAPL
A
eq air,
A
sat w,
A
NAPL
A
NAPL
A
eq w,
C K C
RT
M P
C
P X P
C X C
=
=
=
=
NAPL in A of fraction Mole

1 NAPL in A of Activity
: properties NAPL
A
NAPL
A
NAPL
=
~ =
X

d
=
28
- limited mass of chemicals
A
eq , w
A
d
A
eq soil,
A
eq w,
A
aw
A
eq air,
A
eq w,
A
H
A
eq air,
soil
A
d air aw w
A
total
A
eq w,
C K C
C K C
C K P
M K V K V
M
C
=
=
=
+ +
=
pressure vapor V
air of Volume V
: size t compartmen Media
air
=
=
t coefficien ng partitioni water - ir a K
Constant law s Henry' K
d
aw
H
=
=
=
29
Pregunta del primer examen I-2012
Se disuelven 0.5 gramos de naftaleno en un
recipiente hermtico que contiene 40L de
agua, 60L de aire y 500g de sedimentos (con
1.5% de carbono orgnico). Estimar las
concentraciones de naftaleno en los tres
medios (agua, aire, suelo) en equilibrio.
Asumir K
OC
=0.41*K
OW
. Qu porcentaje de la
masa total se distribuye en cada medio?
30
Bioconcentration and Bioaccumulation
Bioconcentration: the uptake of toxic organics
through the gill membrane and epithelial tissue
fromthe dissolved phase.
Bioaccumulation: the total biouptake of toxic
organics by the organismfromfood items (fish
prey, sediment ingestion, etc.)
Biomagnification: circumstance where
bioaccumulation causes an increase in total body
burden as one proceeds up the trophic ladder
fromprimary producers to top carnivore.
31
Pollutant Interactions with Fish
Bioconcentration Factor (BCF)
Physical exchange between the fish tissue and water.
Bioaccumulation factor (BAF)
ingestion, respiration, and physical exchange.
water) of A/kg of (g water in A of ion concentrat state Steady
tissue) fish A/kg of (g fish in A of ion concentrat state Steady
C
C
BCF
A
ss w,
A
ss f, A
=
=
Physical
exchange
ingestion,
respiration
32
Relationships between BCF in Fish and
Chemical K
ow
Table 3.3
33
BCF Example
Ideal NAPL with 10% mole
fraction benzene
Estimate the equilibrium benzene
concentration in the fish:
34
Pollutant Interactions with Plants
Plants can serve as important living links between air,
water, and soil, and transfer pollutants between the
different media.
Interaction between air pollutants and vegetation occurs
on a regional scale, with pollutant concentrations in leaves
often being monitored to determine the level of air
pollution.
Plant uptake of pollutants from soil and water occurs on a
more local scale and has been studied for application in
phytoremediation, that is, plant-assisted remediation at
contaminated land sites.
35
Interaction between Atmospheric PAHs
and Plants
Polycyclic aromatic hydrocarbons (PAHs) reach pine
needles via atmospheric transport and deposition
processes.
Atmospheric PAH concentrations are calculated through
BCF based on octanol-air partition coefficients (K
oa
).
Tremolada, ES&T, 1996
36
Phytoremediation of Organic
and Nutrient Contaminants
Schnoor, ES&T, 1995
37
Root Concentration Factor (RCF)
root
BCF
C
C
RCF
=
=
water) of A/kg of (g water - soil in A of on oncentrati
tissue) A/kg of (g roots plant in wet A of on oncentrati
The RCF addresses sorption of organic pollutants
from soil to plant root tissues, as well as pollutant
uptake by the root xylem-water that flows through
the plant during transpiration.
38
Transfer of pollutant from soil-water to the transpiration
Stream within the plant (TSCF)
(mg/L) water - soil in A of on oncentrati C
(g/L) stream ion transpirat plant in A of on oncentrati C
TSCF =
RUBIN & RAMASWAMI, Water Research, 2001
|
.
|
\
|
=
100
V
dV
% dM
TSCF
initial
transp
Slope
39
RCF
TSCF
K
leaf-air
BCF
plant-soil
BCF
plant-water
Table3.4
40
Impacts of K
ow
on TSCF
Kow =100 Kow =10
Largest
TSCF
How to find the K
ow
for the
largest TSCF if only the
equation is known?
41

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