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CEE 697K ENVIRONMENTAL REACTION KINETICS
Introduction
CEE697K Lecture #21 1 Updated: 1 December 2013
Print version
Lecture #21 Case Study: NOM-oxidant kinetics Primary Literature as noted
http://www.ecs.umass.edu/cee/reckhow/courses/ERK/slides/ERKl21p.pdf
Kinetic Spectrum Analysis
CEE697K Lecture #21
2
For mixtures of many closely related compounds A new continuum of rate constants E.g., NOM
Kinetic: Shuman model Equilibria: Perdue model
Very general, but highly subject to errors
∑=
−=n
i
tkit
ieCC1
0][][
3
Factors affecting DBP levels
Raw water NOM levels (e.g., TOC) Specific precursor content of the RW NOM NOM removal Disinfection regime
type & dose location in plant contact time & temp pH
Degradation in DS (affects some) CEE697K Lecture #21
NOM Origins
Aquifer
Lake
Upper Soil Horizon
Lower Soil Horizon
Sediment & Gravel in Lake Bed
Litter Layer
Algae
CEE697K Lecture #21
4
Practical Management Question: Which is the more important source?
allochthonous autochthonous
or
CEE697K Lecture #21
5
An Aquatic Humic “Structure”
COOH
O
COOH
COOH
COOH
HOOC
HOOC
HO
OH
COOH
H3CO
OHHydroxy Acid
AromaticDicarboxylicAcid
AromaticAcid
Aliphatic Acid
AliphaticDicarboxylicAcid
Phenolic-OH
HO
From Thurman, 1985
CEE697K Lecture #21
6
7
Chlorination of Resorcinol From Boyce & Hornig, 1983
All structures identified by GC/MS except those in brackets
Chorine + Aromatics
CEE697K Lecture #21
8
Aliphatics: Haloform Reaction
RLS is deprotonation (k1) under many conditions
Many LFERs exist for estimating Kas E.g., Perrin et al., 1982
Then relate k1 to Ka
CH 3 C
O
CH 3
H+
CH 3 C
O
CH 2
-
CH 3 C
O
CH 2
-
[ ]
CH 3 C
O
CH 2Cl
HOCl
CH 3 C
O
CHCl 2
HOCl
CH 3 C
O
CCl 3
CH 3 C
O
CCl 3
OH
CH 3 C
O
OH CH 3 C
O
CHCl 3
-
OH
-
CCl 3-
O -
OH -
H2O
HOCl
H2O
CEE697K Lecture #21
An Aquatic Humic “Structure”
COOH
O
COOH
COOH
COOH
HOOC
HOOC
HO
OH
COOH
H3CO
OHHydroxy Acid
AromaticDicarboxylicAcid
AromaticAcid
Aliphatic Acid
AliphaticDicarboxylicAcid
Phenolic-OH
HO
From Thurman, 1985
CEE697K Lecture #21
9
NOM Fractions: Mass Balance
HA8%HPL-N
25%
HPO-B2%
W-HPO-A4%
HPO-N7%
FA42%HPL-A
9%
HPL-B3%
10
HA0%
FA29%
W-HPO-16%
HPO-B0%
uHPL-A22%
HPL-B5%
HPL-N11%
HPL-A15%
HPO-N2%
Forge Pond Granby, MA
Northeast MA Tap Water
HPL=Hydrophilic HPO=Hydrophobic
A=Acids B=Bases N=Neutrals
W=Weak u=ultra
10 CEE697K Lecture #21
Absorbance of Acid Fractions
11
Wavelength (nm)
200 250 300 350 400 450 500 550 600 650
Sp.
Abs
. (L/
m/m
g-C
)
0.1
1
10
Weak Hydrophobic Acids
Hydrophilic Acids
Humic Acid
Fulvic Acid
Same DOC
254 nm
CEE697K Lecture #21
Formation Potentials of NOM Fractions 12
FP High dose Forces
reaction to endpoint
Neu
trals
TTH
MFP
(µg/
mg-
C)
0
10
20
30
40
50
60
70
Hydrophobic
Base
s
Acid
s
Neu
trals
Base
s
Wea
k Ac
ids
Hum
ic A
cid
Fulv
ic A
cid
Hydrophilic12 CEE697K Lecture #21
Leaching Experiments
White Pine
Red Maple
White Oak
Aged leaves from 3 locations in Wachusett watershed
CEE697K Lecture #21
13
14
Level 2 ecoregions
CEE697K Lecture #21
Leaching Time (days)
0 2 4 6 8
UV 2
54 A
bsor
banc
e (c
m-1
)
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
SU
VA
(L/m
g-C
/m)
0
1
2
3
4
5
6
7
8
9
Maple UV Oak UV Pine UV Maple SUVA Oak SUVA Pine SUVA
Leaching of leaves Dark
Non-sterile conditions
Substantial slow leaching of organics
100254 xDOCUVSUVA
≡
CEE697K Lecture #21
15
Leaching: Sp-THAAFP
Filtered leachate Chlorinated &
analyzed for THAAs Mostly
trichloroacetic acid
THAA yield divided by DOC Specific THAA
(precursors)
Specific THAA Formation for Leaching Study
Dar
k M
aple
#1
Dar
k M
aple
#2
Dar
k O
ak #
1
Dar
k O
ak #
2
Dar
k P
ine
#1
Dar
k P
ine
#2
Ligh
t Map
le
Ligh
t Oak
Ligh
t Pin
e
D.B
ioci
de M
aple
D.B
ioci
de O
ak
Spec
ific
THAA
For
mat
ion
(µg/
mg-
TOC
)
0
20
40
60
80
100
120
140
160
180
CEE697K Lecture #21
16
Lignin Monomers
Aromatic structures from CuO
degradation
Syringyl Vanillyl Cinnamyl
COOH
OH
4-Hydroxy-benzoic acid
COOH
OH
Vanillic acid
CHO
OH
4-Hydroxy-benzaldehyde
COOH
OH
CH3O OCH3
Syringic acid
CHO
OH
Vanillin
CO
OH
CH3
4-Hydroxy-acetophenone
CHO
OH
CH3O OCH3
Syringaldehyde
CO
OH
CH3
OCH3
COOH
OH
COOH
OHOH
CH3O OCH3
Acetovanilione
4-Hydroxy-cinnamic acid
CO
CH3
Acetosyringone
OCH3
Ferulic acid
OCH3
OCH3
CEE697K Lecture #21
17
18
Lignin
From: Perdue & Ritchie, 2004
CEE697K Lecture #21
Other plant products
Pyruvate
Acetate
Water Soluble Acids
Porphyrins
Amino Acids
Nucleic Acids
Misc. N & S compounds
Proteins Shikimic Acid
Carbohydrates Saponifiable
Liquids
Unsaponifiable Liquids
Mevalonic acid
Terpenoids
Steroids
Flavonoids
Aromatic Compounds
From: Robinson, 1991 Activated non-N precursors
Nitrogenous precursors
CEE697K Lecture #21
19
Aromatic Amines
Proposed degradation pathway for 3-amino benzoic acid.
C
NH2
O
OH 1, 2, or 3 chlorinations initially
NH2
Cl
Cl Cl
COOH
NCl2
Cl
NH2
Cl
Cl
COOH
Cl
Cl
OHAnd or chlorination of the amine
OH
NH2
Cl
Cl
COOH
Cl
ClCl2
COOH
Cl
Cl
O
Cl
Cl
COOH
Cl
Cl
Cl
Cl
O
OHOH
OH
Cl
Cl
Cl
Cl
Cl
COOHOHl
Cl
O
COOH
Cl
Cl
O
Cl
Cl
COOH
Cl
Cl
O
Cl
Cl
- NCl2H
Cl
Cl
O
Cl
Cl
OH
O
OH
Cl
Cl
O
Cl
Cl
O
OH
HO
COOH
Cl
Cl
O
Cl
Cl
COOH
Cl
Cl
Cl
Cl
Cl
Cl
COOH
Cl
Cl
O
Cl
Cl
COOH
Cl
Cl
O
Cl
Cl
Cl
Cl
O
Cl
Cl
Cl
HO
HO
HO
Cl
-CO2
O
OH
O
Cl
OH
O
Cl
Cl
ClHOOC
Cl
ClInitial decarboxylation that we would predict for thepara substituted compound is less likly here because the intermediateis not resonance stabilized
CEE697K Lecture #21
20
Aromatic Amines
0.000.010.020.030.040.050.060.070.08
Anthranilic acid 3 Aminobenzoicacid
4 Aminobenzoicacid
M/M
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
M-C
l/M
THMs HAAs HANs TOX Unknown TOX
THMs38%
Unknow nTOX16%
HAA645%
HANs1%
Anthranilic Acid
THMs25%
Unknow nTOX58%
HAA615%HANs
2%3-Aminobenzoic Acid
THMs31%
HAA615%HANs
3%
Unknow nTOX51%
4-Aminobenzoic Acid
6.0 7.7 7.8 Cl2 Demand (M/M)
CEE697K Lecture #21
21
22
THM Precursors (µg/mg-C)
0.01 0.1 1 10 100 1000 10000
TriH
AA
Pre
curs
ors
(µg/
mg-
C)
0.01
0.1
1
10
100
1000AromaticsNucleic BasesSimple AliphaticsAmino AcidsAmino Sugars
Wide range for models
Narrow range for NOM
10-90%ile range for NOM
Compare with Model Compounds
CEE697K Lecture #21
23
Elemental Ratios
From: Perdue & Ritchie, 2004
Van Krevelen Plot
CEE697K Lecture #21
24
Molecular Weight
100 1000 10000 100000
Cha
rge
Den
sity
@ p
H 7
(meq
/g-C
)
-25
-20
-15
-10
-5
0
5
10
Hydrophilic BasesHydrophobic Bases
Neutrals
Hydrophilic Acids
Weak Hydrophobic Acids
Humic AcidFulvic Acid
from: Bezbarua and Reckhow, 1995
Size and Charge Relationships for NOM Fractions
CEE697K Lecture #21
Van Krevelen diagram for the Dismal Swamp DOM, compound classes are represented by the circles overlain on the plot. The distinctive lines in the plot denote the following chemical reactions: (A) methylation/demethylation, or alkyl chain elongation; (B) hydrogenation/dehydrogenation; (C) hydration/condensation; and (D) oxidation/reduction.
25
Sleighter & Hatcher, 2007 [J. Mass Spec. 42:559] CEE697K Lecture #21
Fate & Transport:
Watershed Natural system
Physical processes
Chemical processes
Biological processes
Water Treatment Plant Engineered System
Physical processes
Chemical processes
Biological processes
“Full-scale monitoring
“Lab-scale simulation
Fundamental Testing CEE697K Lecture #21
26
Time (Days)
0 20 40 60 80 100
DO
C F
ti R
o)
0.0
0.2
0.4
0.6
0.8
1.0
1.2
Phase 1 (Co=6.7 mg/L)Phase 2 (Co=5.4 mg/L)Phase 3 (Co=7.9 mg/L)
Biodegradation of leaf leachate ~ 50% biodegradable
Bacteria grow preferentially on NOM
Leaching & Biodegradation
Cumulative Frequency
0.0 0.2 0.4 0.6 0.8 1.0
Spe
cific
TH
MFP
(µg/
mg-
C)
0
20
40
60
80
100
120
Spe
cific
TH
M-S
DS
(µg/
mg-
C)
0
10
20
30
40
50
60
Pre
-exp
onen
tial T
erm
(a)
0.0
0.1
0.2
0.3
0.4
0.5
0.6
Surface WatersGroundwaters
Maple
Oak Pine
CEE697K Lecture #21
28
29
Transport & Soil Properties
Case study: TOC & soil properties Parallel watersheds in Australia (Cotsaris et al., 1994) Clearwater Creek, high clay content: 2.5 mg/L TOC Redwater Creek, sandy soil: 31.7 mg/L TOC
Presumed Attenuated of TOC by adsorption to clay soils
Impacts on specific NOM components & precursors ??
CEE697K Lecture #21
Effect of Bank Filtration on Precursors
DOC (mg/L)
0 1 2 3 4 5
THM
FP/D
OC
(µg/
mg)
0
20
40
60
80
100
Ohio RiverWabash RiverMissouri River
Subsurface processes
River Bank Filtration Weiss et al., 2001 AWWA ACE
Groundwater recharge Aiken & others
Ratio climbs over very short distances and then declines
CEE697K Lecture #21
30
The Future: Higher MW DBPs
NOM research ESI with Ultra High-
Resolution Fourier Transform Ion Cyclotron Resonance Mass Spectrometry
Benefits Unambiguous molecular
formulae
CEE697K Lecture #21
31
32 m/z
900800700600500400300
Abu
ndan
ce
121110
987654321
Raw Water - Winnipeg
0.00E+00
5.00E+01
1.00E+02
1.50E+02
2.00E+02
2.50E+02
3.00E+02
3.50E+02
4.00E+02
150 250 350 450 550 650
m/z
Inte
nsity
-ve ion + ve ion
ESI-TOF MS
ESI-FTICR MS
Same: comparison side-by-side CEE697K Lecture #21
33
m/z425420415410405400395390
Abu
ndan
ce
7
6
5
4
3
2
1
Chlorinated Water + Br Winnipeg
m/z409.436409.354409.272409.19409.108409.027408.945408.863
Abu
ndan
ce
7
6
5
4
3
2
1
CEE697K Lecture #21
Ultra-high resolution MS 34
Area of predicted fulvic acid molecules in a C- vs molecular mass diagram for the mass range m/z 310-370 (marked by the lines) and fulvic acid molecules detected by SEC-FTICR-MS in the river isolate (dots (island no. 24) and triangles (island no. 25)).
Reemtsma et al., 2006 [ES&T: 40:19:5839]
Zone of low solubility
CEE697K Lecture #21
The dilemma of NOM
CEE697K Lecture #21
35
How to model reaction kinetics in such a complex mixture? Kinetic spectrum? Fictive components? Fully empirical?
Lee & Von Gunten, 2010
CEE697K Lecture #21
36
Comparative study of 5 oxidants
Looked at rates of removal for micropollutants for each
Compared to bulk oxidant demand
Lee, Y. and U. von Gunten (2010). "Oxidative transformation of micropollutants during municipal wastewater treatment: Comparison of kinetic aspects of selective (chlorine, chlorine dioxide, ferrate(VI), and ozone) and non-selective oxidants (hydroxyl radical)." Water Research 44(2): 555-566.
http://www.ecs.umass.edu/eve/secure/ferrate/Lee von Gunten 2010 micropollutants.pdfhttp://www.ecs.umass.edu/eve/secure/ferrate/Lee von Gunten 2010 micropollutants.pdfhttp://www.ecs.umass.edu/eve/secure/ferrate/Lee von Gunten 2010 micropollutants.pdf
Rate
con
stan
ts v
s pH
CEE697K Lecture #21
37
ss
Fig. 1. pH dependent second-order rate constants (k) for the reaction of the oxidants, chlorine (HOCl), chlorine dioxide (ClO2), ferrateVI (HFeO4−), hydroxyl radicals (HO), and ozone (O3)
Lee, Y. and U. von Gunten (2010). Water Research 44(2): 555-566.
http://www.ecs.umass.edu/eve/secure/ferrate/Lee von Gunten 2010 micropollutants.pdf
CEE697K Lecture #21
38
Fours species
Fig. 2. Consumption kinetics of the selective oxidants, (a) ozone, (b) ferrateVI, (c) chlorine, and (d) chlorine dioxide, in a secondary wastewater effluent (RDWW) at pH 8. Symbols represent measured data and lines connect each data point to show the trend.
Oxi
dant
Res
idua
ls
Lee, Y. and U. von Gunten (2010). Water Research 44(2): 555-566.
http://www.ecs.umass.edu/eve/secure/ferrate/Lee von Gunten 2010 micropollutants.pdfhttp://www.ecs.umass.edu/eve/secure/ferrate/Lee von Gunten 2010 micropollutants.pdfhttp://www.ecs.umass.edu/eve/secure/ferrate/Lee von Gunten 2010 micropollutants.pdfhttp://www.ecs.umass.edu/eve/secure/ferrate/Lee von Gunten 2010 micropollutants.pdf
CEE697K Lecture #21
39
gd
Fig. 3. Logarithm of the residual concentrations (log(c/c0)) of selected micropollutants as a function of oxidant doses in a secondary wastewater effluent (RDWW) at pH 8: (a) EE2, (b) SMX, (c) CBZ, (d) ATL, and (e) IBP. Symbols represent measured data and lines connect each data point to show the trend. The lines for hydroxyl radicals represent the linear regression of data. For the selective oxidants, the reaction time of 1 h was given to simulate realistic treatment conditions.
Micropollutant Destruction Lee, Y. and U. von Gunten (2010). Water Research 44(2): 555-566.
http://www.ecs.umass.edu/eve/secure/ferrate/Lee von Gunten 2010 micropollutants.pdf
CEE697K Lecture #21
40
cs
Fig. 4. Effect of (a) ammonia (NH4+) and (b) nitrite (NO2−) on the transformations of EE2 during treatment of a secondary wastewater effluent (RDWW) by different oxidants at pH 8. Preliminary experiments were conducted to determine the oxidant dose for each oxidant to achieve a 80% transformation of EE2 in RDWW without additionally spiked ammonia and nitrite. They were 20 μM for chlorine, 3 μM for chlorine dioxide, 8 μM for ozone, 8 μM for ferrateVI, and 37 μM for hydroxyl radicals. Symbols represent measured data and lines connect each data point to show the trend. Lee, Y. and U. von Gunten (2010). Water Research 44(2): 555-566.
http://www.ecs.umass.edu/eve/secure/ferrate/Lee von Gunten 2010 micropollutants.pdfhttp://www.ecs.umass.edu/eve/secure/ferrate/Lee von Gunten 2010 micropollutants.pdfhttp://www.ecs.umass.edu/eve/secure/ferrate/Lee von Gunten 2010 micropollutants.pdfhttp://www.ecs.umass.edu/eve/secure/ferrate/Lee von Gunten 2010 micropollutants.pdf
Ferrate reaction with surface waters
25 µM ferrate dose, pH 6.2
Time (min)
0 5 10 15 20 25 30
Ferra
te C
once
ntra
tion
( M
)
0
5
10
15
20
25
30
Ferra
te C
once
ntra
tion
(mg/
L as
Fe)
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6pH 6.2 Buffered BlankHouston TX pH 6.2Palmer MA pH 6.2Readsboro VT pH 6.2
From: Jiang et al., 2013
CEE697K Lecture #21
41
Low Dose, High pH
Time (min)
0 5 10 15 20 25 30
Ferra
te C
once
ntra
tion
(M
)
0
10
20
30
40
Ferra
te C
once
ntra
tion
(mg/
L as
Fe)
0.0
0.5
1.0
1.5
2.0pH 7.5 Buffered BlankAmherst MA pH ~7.5Houston TX pH 7.5Palmer MA pH 7.5Readsboro MA pH 7.5
25 µM, pH 7.5
From: Jiang et al., 2013
CEE697K Lecture #21
42
High Dose, Low pH
Time (min)
0 5 10 15 20 25 30
Ferra
te C
once
ntra
tion
(M
)
0
10
20
30
40
50
60
Ferra
te C
once
ntra
tion
(mg/
L as
Fe)
0
1
2
3pH 6.2 Buffered BlankHouston TX pH 6.2Palmer MA pH 6.2Readsboro VT pH 6.2
50 µM, pH 6.2
From: Jiang et al., 2013
CEE697K Lecture #21
43
High Dose, High pH
Time (min)
0 5 10 15 20 25 30
Ferra
te C
once
ntra
tion
(M
)
0
10
20
30
40
50
60
Ferra
te C
once
ntra
tion
(mg/
L as
Fe)
0
1
2
3pH 7.5 Buffered BlankAmherst MA pH ~7.5Houston TX pH 7.5Palmer MA pH 7.5Readsboro MA pH 7.5
50 µM, pH 7.5
From: Jiang et al., 2013
CEE697K Lecture #21
44
Houston Data Isolated
CEE697K Lecture #21
45
More data improves accuracy
Time (min)
0 5 10 15 20 25 30
Ferr
ate
Con
cent
ratio
n (
M)
0
10
20
30
40
50
60
Ferr
ate
Con
cent
ratio
n (m
g/L
as F
e)
0
1
2
3Houston TX pH 7.5
Integrate curve to get CT vs time
CEE697K Lecture #21
46
Simple “rectangle” method
Time (min)
0 5 10 15 20 25 30
Ferr
ate
Con
cent
ratio
n (
M)
0
10
20
30
40
50
60
Ferr
ate
Con
cent
ratio
n (m
g/L
as F
e)
0
1
2
3Houston TX pH 7.5
Light scattering background (not ferrate)
Model for pollutant oxidation
CEE697K Lecture #21
47
Simple 2nd order kinetics Pollutant (P) reacts with an oxidant (O)
Integrate but keep [O] time variable
And you end up with an expression in terms of CT
𝑑𝑑𝑑𝑑
= −𝑘 𝑑 𝑂 𝑑𝑑𝑑
= −𝑘 𝑂 dt
𝑙𝑙 𝑑𝑡 − 𝑙𝑙 𝑑0 = −𝑘� 𝑂 𝑑𝑑𝑡
0
𝑑𝑡 = 𝑑0𝑒−𝑘 ∫ 𝑂 𝑑𝑡𝑡0 𝑑𝑡 = 𝑑0𝑒−𝑘 𝐶𝐶
𝑙𝑙 𝑑 = −𝑘� 𝑂 𝑑𝑑𝑡
0
Po
Pt
pH
6.0 6.5 7.0 7.5 8.0 8.5
Frac
tion
Rem
aini
ng
0.0
0.2
0.4
0.6
0.8
1.0
ethynlestradiol sulfamethoxazole bromide Sulfide Nitrite Phenol Analine
Kinetic Analysis, high dose
50 µM dose, Houston Water
Alkyl alcohols
Alkyl amines
sulfides CEE697K Lecture #21
48
Kinetic Analysis, low dose
pH
6.0 6.5 7.0 7.5 8.0 8.5
Frac
tion
Rem
aini
ng
0.0
0.2
0.4
0.6
0.8
1.0
ethynlestradiol sulfamethoxazole bromide Sulfide Nitrite Phenol Analine
25 µM dose, Houston Water
Alkyl alcohols
Alkyl amines
sulfides CEE697K Lecture #21
49
The “problems” with ozone
CEE697K Lecture #21
50
Many important secondary oxidants, especially OH radical
Ozone decomposition in real waters does not match predictions
Mechanistic model is “off”
CEE697K Lecture #21
51
Initiation reaction rate constant must be “adjusted” to match actual data
Elovitz, M. S. and U. Von Gunten (1999). "Hydroxyl Radical Ozone Ratios During Ozonation Processes. I-the R-Ct Concept." Ozone-Science & Engineering 21(3): 239-260.
A simpler view: Direct & Indirect Pathways
52
O3
·OH
High pH UV light H2O2
H2O, O2
H2O, O2
Direct Reaction
Indirect Reaction
NOM VOCs Fe/Mn
Oxidized Products
Oxidized Products
Use of peroxide with ozone is an “advanced oxidation process” (AOP)
Bicarbonate
Classic “ozone demand” D
ecom
posi
tion
Natural waters cause ozone decomposition to varying degrees without any added initiators
CEE697K Lecture #21
Ozone Loss: focus on NOM
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
0.45
0 1 2 3 4 5
Specific UV Absorbance
5-m
in o
zone
con
sum
ptio
n (m
g/m
g-C
)
53
» Ozone loss in first 5
minutes
fulvic acids data from Legube
et al., 1989
Organic Demand in colored waters – Empirical stoichiometric approach
Direct reaction with NOM, Doesn’t really account for “decomposition”
CEE697K Lecture #21
Ozone loss: focus on decomposition
Incorporating Inorganic Reactions: Semi-empirical kinetic approach First-order decay in solution
Specific ozone loss rate (w) in s -1 Yurteri & Gurol (1988)
Orta de Velasquez et al. (1994)
tinitialOO eCC
ω−= ,33
54
Log pH TOC Alkω = − + + −356 0 66 0 61 0 42. . . log . log
Log pH Abs TOC Alkω = − + + + −393 0 24 0 75 108 019254. . . log . log . log
Takes inorganic matrix into account, and allows for variable contact times, but treats all DOC as the same
][][ 33 OdtOd ω−=
CEE697K Lecture #21
Ozonation of trace organics: Direct Rcn
CEE697K Lecture #21
55
Shut down OH radical formation to isolate molecular ozone (O3) rate.
Oxidation of nitroimidazoles during ozonation. [Nitroimidazole]0 = 10 mg/L., T = 298 K.
pH = 2; [t-BuOH] = 0.1 M
(♢), MNZ; (□), DMZ; (▵), TNZ; (○), RNZ.
Sanchez-Polo, M., J. Rivera-Utrilla, et al. (2008). "Removal of pharmaceutical compounds, nitroimidazoles, from waters by using the ozone/carbon system." Water Research 42(15): 4163-4171.
Indirect Rcn: But we can’t measure OH•
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If you can’t measure them directly maybe you can do it indirectly Use small amounts of a “probe compound” Sacrificial reactant that is easy to measure and selective
Benzene (Hoigne & Bader, 1979) by GC p-chlorobenzoic acid is now more common Easy to measure by HPLC 5x10-9 M-1s-1 with OH radical, but ≤0.15 M-1s-1 with O3
Hoigne, J. and H. Bader (1979). "Ozonation of Water - Oxidation-Competition Values of Different Types of Waters Used in Switzerland." Ozone-Science & Engineering 1(4): 357-372.
Competitive kinetics with probe
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Pollutant (P) and probe compound (pCBA)
𝑑𝑡 = 𝑑0𝑒−𝑘𝑃 𝐶𝐶 𝑝𝑝𝑝𝑝𝑡 = 𝑝𝑝𝑝𝑝0𝑒−𝑘𝑝𝑝𝑝𝑝 𝐶𝐶
𝑙𝑙𝑑𝑡𝑑0
= −𝑘𝑑 𝑝𝐶 𝑙𝑙
𝑝𝑝𝑝𝑝𝑡𝑝𝑝𝑝𝑝0
= −𝑘𝑝𝐶𝑝𝑝 𝑝𝐶
𝑝𝐶 = −1
𝑘𝑝𝐶𝑝𝑝𝑙𝑙
𝑝𝑝𝑝𝑝𝑡𝑝𝑝𝑝𝑝0
𝑙𝑙𝑑𝑡𝑑0
=𝑘𝑑
𝑘𝑝𝐶𝑝𝑝𝑙𝑙
𝑝𝑝𝑝𝑝𝑡𝑝𝑝𝑝𝑝0
If you know kp and want to estimate oxidation of P:
If you want to determine kp from measurements of P:
𝑘𝑑 = 𝑘𝑝𝐶𝑝𝑝𝑙𝑙 𝑑𝑡𝑑0
𝑙𝑙 𝑝𝑝𝑝𝑝𝑡𝑝𝑝𝑝𝑝0
�
Determining OH• rate constants
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Fig. 3. Determination of OH radical reaction constant. pH = 9; T = 298 K; [nitroimidazole]0 = 7 × 10−5 M;
[pCBA]0 = 7.25 × 10−5 M. (♢), MNZ; (□), DMZ; (▵), TNZ; (○), RNZ.
Sanchez-Polo, M., J. Rivera-Utrilla, et al. (2008). "Removal of pharmaceutical compounds, nitroimidazoles, from waters by using the ozone/carbon system." Water Research 42(15): 4163-4171.
𝑘𝑑 = 𝑘𝑝𝐶𝑝𝑝𝑙𝑙 𝑑𝑡𝑑0
𝑙𝑙 𝑝𝑝𝑝𝑝𝑡𝑝𝑝𝑝𝑝0
�
Can we simplify a bit?
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Oxidation competition values Based on relatively linear pseudo-1st order loss rate for
micropollutants (i.e., ln(P/Po) vs t gives a straight line) Expected if aggregate OH• reacting substances do not
undergo appreciable depletion during ozonation
Ozone decomposition produces a uniform yield of OH• over time and ozone dose (typically ~0.5M/M)
Hoigne, J. and H. Bader (1979). "Ozonation of Water - Oxidation-Competition Values of Different Types of Waters Used in Switzerland." Ozone-Science & Engineering 1(4): 357-372.
Oxidation-competition method
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First assume a near constant OH• yield from ozone decomposition so that monitoring loss of ozone provides an estimate of the OH reactions taking place
Then all OH• produced either reacts with the target pollutant (M) or the background matrix (Si) and the two are in direct competition
And the fraction reacting with M is: 𝑓 = 𝑘𝑀 𝑀∑𝑘𝑖 𝑆𝑖
From: Hoigne & Bader, 1979
Using M as a probe
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Now:
Where the oxidation-competition value is defined as:
And as we’ve shown previously
We can now use Ω to estimate loss of “P” by simply measuring ∆O3
−𝑑 𝑀𝑑𝑑
= 𝜂𝑑 Δ𝑂3𝑑𝑑
𝑘𝑀 𝑀∑𝑘𝑖 𝑆𝑖
=𝑑 Δ𝑂3𝑑𝑑 Ω𝑀
𝑓 =𝑘𝑀 𝑀∑𝑘𝑖 𝑆𝑖
Ω𝑀 =∑𝑘𝑖 𝑆𝑖𝜂𝑘𝑀
=Δ𝑂3
𝑙𝑙 𝑀𝑡 𝑀0�
𝑙𝑙𝑑𝑡𝑑0
=𝑘𝑑
𝑘𝑝𝐶𝑝𝑝𝑙𝑙
𝑝𝑝𝑝𝑝𝑡𝑝𝑝𝑝𝑝0
𝑙𝑙𝑑𝑡𝑑0
=𝑘𝑑𝑘𝑀
𝑙𝑙𝑀𝑡𝑀0
𝑙𝑙 𝑀𝑡 𝑀0� =Δ𝑂3Ω𝑀
𝑙𝑙𝑑𝑡𝑑0
=𝑘𝑑𝑘𝑀
Δ𝑂3Ω𝑀
Production rate of OH radicals
Fraction of OH that reacts with M
And rearranging:
This is what we can actually measure
or
Field Values
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Values of Ω have been measured on many natural waters
Hoigne, J. and H. Bader (1979). "Ozonation of Water - Oxidation-Competition Values of Different Types of Waters Used in Switzerland." Ozone-Science & Engineering 1(4): 357-372.
Some complications
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63
Yet they noted an initial reaction that did not conform to their simple model
RCT concept
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Recall from the discussion on simple consecutive reactions:
The ratio of the concentrations of intermediate to the
reactant approaches a constant, when kii>>ki
Now consider A to be ozone and B to be OH radical, and
we get:
ii
i
iii
i
kk
kkk
AB
≈−
→][][
CBA iii kk →→
𝑅𝐶𝐶 ≝𝑂𝑂𝑂3
= 𝑐𝑐𝑙𝑐𝑑𝑐𝑙𝑑
RCT concept
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Elovitz & Von Gunten, 1999 Use the same competitive OH reaction approach with a
probe compound as Hoigne & Bader
Elovitz, M. S. and U. Von Gunten (1999). "Hydroxyl Radical Ozone Ratios During Ozonation Processes. I-the R-Ct Concept." Ozone-Science & Engineering 21(3): 239-260.
However, instead of measuring ∆O3, they chose to record the full ozone CT
RCT concept II
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The simple 2nd order model is:
Rearranging and integrating we get:
Which gives the final form used in experimental evaluation:
𝑑 𝑝𝑝𝑝𝑝𝑑𝑑
= −𝑘𝑝𝐶𝑝𝑝 𝑝𝑝𝑝𝑝 𝑂𝑂
𝑅𝐶𝐶 ≝𝑂𝑂𝑂3
= 𝑐𝑐𝑙𝑐𝑑𝑐𝑙𝑑
𝑑 𝑝𝑝𝑝𝑝𝑑𝑑
= −𝑘𝑝𝐶𝑝𝑝 𝑝𝑝𝑝𝑝 𝑅𝐶𝐶 𝑂3
𝑑 𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝
= −𝑘𝑝𝐶𝑝𝑝𝑅𝐶𝐶 𝑂3 𝑑𝑑 𝑙𝑙𝑝𝑝𝑝𝑝𝑡𝑝𝑝𝑝𝑝0
= −𝑘𝑝𝐶𝑝𝑝𝑅𝐶𝐶 � 𝑂3 𝑑𝑑𝑡
0
𝑅𝐶𝐶 =𝑙𝑙 𝑝𝑝𝑝𝑝𝑡𝑝𝑝𝑝𝑝0
−𝑘𝑝𝐶𝑝𝑝 ∫ 𝑂3 𝑑𝑑𝑡0
�
RCT concept III
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Simple model system
Elovitz, M. S. and U. Von Gunten (1999). "Hydroxyl Radical Ozone Ratios During Ozonation Processes. I-the R-Ct Concept." Ozone-Science & Engineering 21(3): 239-260.
𝑅𝐶𝐶 =𝑙𝑙 𝑝𝑝𝑝𝑝𝑡𝑝𝑝𝑝𝑝0
−𝑘𝑝𝐶𝑝𝑝 ∫ 𝑂3 𝑑𝑑𝑡0
�
RCT concept IV
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Lake Zurich water Apparent 2-stage
kinetics 1st stage may or may not
be linear
Elovitz, M. S. and U. Von Gunten (1999). "Hydroxyl Radical Ozone Ratios During Ozonation Processes. I-the R-Ct Concept." Ozone-Science & Engineering 21(3): 239-260.
𝑅𝐶𝐶 =𝑙𝑙 𝑝𝑝𝑝𝑝𝑡𝑝𝑝𝑝𝑝0
−𝑘𝑝𝐶𝑝𝑝 ∫ 𝑂3 𝑑𝑑𝑡0
�
Incorporating both pathways
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The expanded 2nd order model is:
Rearranging and integrating we get:
or:
𝑑 𝑑𝑑𝑑
= −𝑘𝑂𝑂 𝑑 𝑂𝑂 + 𝑘𝑂3 𝑑 𝑂3
𝑅𝐶𝐶 ≝𝑂𝑂𝑂3
= 𝑐𝑐𝑙𝑐𝑑𝑐𝑙𝑑
𝑑 𝑑𝑑𝑑
= −𝑘𝑂𝑂 𝑑 𝑅𝐶𝐶 𝑂3 + 𝑘𝑂3 𝑑 𝑂3
𝑑 𝑑𝑑
= − 𝑘𝑂𝑂𝑅𝐶𝐶 + 𝑘𝑂3 𝑂3 𝑑𝑑 𝑙𝑙𝑑𝑡𝑑0
= − 𝑘𝑂𝑂𝑅𝐶𝐶 + 𝑘𝑂3 � 𝑂3 𝑑𝑑𝑡
0
𝑑𝑡 = 𝑑0 𝑒− 𝑘𝑂𝑂𝑅𝑝𝐶+𝑘𝑂𝑂 ∫ 𝑂𝑂 𝑑𝑡𝑡0
both pathways II
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Porrentruy Water
Elovitz, M. S. and U. Von Gunten (1999). "Hydroxyl Radical Ozone Ratios During Ozonation Processes. I-the R-Ct Concept." Ozone-Science & Engineering 21(3): 239-260.
CEE697K Lecture #21
71
both pathways III
Elovitz, M. S. and U. Von Gunten (1999).
Natural waters
𝑓𝑂𝑂 =𝑘𝑂𝑂𝑅𝐶𝐶
𝑘𝑂𝑂𝑅𝐶𝐶 + 𝑘𝑂3
Role of Temperature
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Increase in RCT
Elovitz, M. S., U. Von Gunten, et al. (2000). "Hydroxyl Radical/Ozone Ratios During Ozonation Processes. II. The Effect of Temperature, pH, Alkalinity, and DOM Properties." Ozone-Science & Engineering 22(2): 123-150.
Role of pH
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Elovitz, M. S., U. Von Gunten, et al. (2000). "Hydroxyl Radical/Ozone Ratios During Ozonation Processes. II. The Effect of Temperature, pH, Alkalinity, and DOM Properties." Ozone-Science & Engineering 22(2): 123-150.
Increase in RCT
Role of Bicarbonate
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Elovitz, M. S., U. Von Gunten, et al. (2000). "Hydroxyl Radical/Ozone Ratios During Ozonation Processes. II. The Effect of Temperature, pH, Alkalinity, and DOM Properties." Ozone-Science & Engineering 22(2): 123-150.
Decrease in RCT
Similar approach used for AOPs
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Advanced oxidation processes UV with H2O2
Rosenfeldt, E. J. and K. G. Linden (2007). "The R-OH,R-UV concept to characterize and the model UV/H2O2 process in natural waters." Environmental Science & Technology 41(7): 2548-2553.
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76
To next lecture
http://www.ecs.umass.edu/cee/reckhow/courses/ERK/slides/ERKl22.pdf
CEE 697K�Environmental Reaction KineticsKinetic Spectrum AnalysisFactors affecting DBP levelsNOM OriginsPractical Management Question:�Which is the more important source?An Aquatic Humic “Structure”Chorine + AromaticsAliphatics: Haloform ReactionAn Aquatic Humic “Structure”NOM Fractions:� Mass BalanceAbsorbance�of Acid�FractionsFormation Potentials of NOM FractionsLeaching ExperimentsSlide Number 14Leaching of leavesLeaching: Sp-THAAFPLignin MonomersLigninOther plant productsAromatic AminesAromatic AminesCompare with Model CompoundsElemental RatiosSlide Number 24Slide Number 25Fate & Transport:Biodegradation of leaf leachateLeaching & BiodegradationTransport & Soil PropertiesSubsurface processesThe Future: Higher MW DBPsSlide Number 32Slide Number 33Ultra-high resolution MSThe dilemma of NOMLee & Von Gunten, 2010Rate constants vs pHOxidant ResidualsMicropollutant DestructionSlide Number 40Ferrate reaction with surface watersLow Dose, High pHHigh Dose, Low pHHigh Dose, High pHHouston Data IsolatedIntegrate curve to get CT vs timeModel for pollutant oxidationKinetic Analysis, high doseKinetic Analysis, low doseThe “problems” with ozoneMechanistic model is “off”A simpler view: Direct & Indirect PathwaysOzone Loss: focus on NOMOzone loss: focus on decompositionOzonation of trace organics: Direct RcnIndirect Rcn: But we can’t measure OHCompetitive kinetics with probeDetermining OH rate constantsCan we simplify a bit?Oxidation-competition methodUsing M as a probeField ValuesSome complicationsRCT conceptRCT conceptRCT concept IIRCT concept IIIRCT concept IVIncorporating both pathwaysboth pathways IIboth pathways IIIRole of TemperatureRole of pHRole of BicarbonateSimilar approach used for AOPsSlide Number 76