SCRUBBERS:

A
NOVEL
SYNERGY
OF
TWO
TECHNIQUES
IN
THE
REMOVAL
OF
CHLORINATED
AROMATIC
COMPOUNDS

and

A
RECENTLY
RECOGNISED
ISSUE:
ULTRA­FINE
PARTICLES

BY

NAUMAN
MITHANI
(#301016320)

CHEM
372

2008‐3‐7
SECTION
1: SYNERGY
OF
COMBINING
SONOLYSIS
AND
PHOTOLYSIS


IN
THE
DEGRADATION
AND
MINERALISATION
OF
CHLO­

RINATED
AROMATIC
COMPOUNDS [ref.
1]

PRELUDE:

__________________________________________________________________________________________

During
the
past
few
years
,
advanced
oxidation
processes
(AOP's)
have
received


much
attention
in
the
relatively
nascent
quest
of
environmental
remediation
[ref.
1.1
‐
.4].
In

such
processes,
which
may
feature
other
processes
and
mechanisms,
the
strong
hydroxyl


radical
is
the
prime,
common
oxidant.
An
AOP,
with
certain
compounds,
may
however
bring

about
the
formation
of
toxic
or
overall
undesirable
chemical
intermediates;
such
a
process


could
also
fail
to
fully
mineralise
the
organic
compounds.
INTRODUCING
THE
SOLUTION:

__________________________________________________________________________________________

Background:
It
has
been
known
that
the
AOP
of
high‐frequency
ultrasound
is
efai‐

cient
at
breaking
down
non‐polar
substances
such
as
hydrocarbons
and
aromatic
organic


compounds
[ref.
1.5
‐
.7].
The
sonolysis
processes
include
oxidation
via
•OH
radical,
pyrolitic

degradation
and
in
some
cases,
H2O2
and
HO2•―‐mediated
oxidation.
However,
the
effective‐

ness
of
the
ultrasonic
environment
is
reduced
as
the
compounds
become
more
polar
by
the


oxidation
processes;
and
so,
complete
mineralisation
is
not
achieved
[ref.
1.5,
.8
‐
.11].

The
other
AOP
is
TiO2
assisted
photocatalysis/photolysis,
also
the
subject
of
extensive

research.
In
addition
of
its
ability
to
effectively
remediate
organic
compounds,
it
succeeds


where
sonolysis
fails,
degradation
during
the
latter
stages
when
the
compounds
have
been


rendered
more
polar
(rapid
breakdown
to
CO2
and
H2O).
The
•OH
radical
bears
a
role
in
this,

but
direct
hole
induced
oxidation
on
the
surface
of
the
catalyst
opens
up
a
new
avenue
for


the
degradation
mechanism
[ref.
1.13
‐
.16].
However,
neither
is
this
process
all‐successful


in
the
break
down
all
organic
compound
contaminants.

The
bright
idea:
The
effects
of
the
two
aforementioned
AOP's
on
organic
com‐

pounds
are
not
at
odds
with
each
other,
and
so
a
technique
combining
both
would
seem


worthwhile.
A
combination
and
sequential
test
were
run
simultaneously
on
the
naphthol

blue
dye
as
the
model
compound
[ref.
1.9].
Not
only
was
the
rate
of
degradation
enhanced


but
degradation
reached
(near)
completion
in
the
sonolysis‐photolysis
combination
test.


Similar
combinations
of
photolysis
+
ozonolysis
[ref.
1.18]
and
+
hydrogen
peroxide
[ref.
1.19,

.20]
have
also
been
investigated.

Apart
from
the
rate
and
degree
of
completion,
the
combinative
approaches
also
re‐

solve
the
matter
of
accumulation
of
toxic
intermediates
during
the
degradation
process(es).
EXPERIMENTAL
OVERVIEW:

__________________________________________________________________________________________

Four
chlorinated
aromatic
compounds
were
selected
for
the
experiment(s)
as
the


model
compounds:
O

O
2,4‐dichlorophenoxyacetic 2,4‐D
OH
acid

Cl Cl
(common
herbicide)

O
2‐(2,4‐dichlorophe‐ 2,4‐DP
OH
noxy)propionic
acid

Cl Cl
(common
herbicide)

2,4‐dichlorophenol OH

(oxidation
product
of
the
two 2,4‐DCP

above) Cl Cl

Cl

OH
2,4,6‐trichlorophenol 2,4,6‐TCP

(drinking
water
contaminant)
Cl Cl
 Many
experiments
have
seen
the
formation
of
the
long‐lasting
2,4‐DCP
from
2,4‐D


under
advanced
oxidation
systems
[ref.
1],
which
is
more
toxic
than
the
starting
material


[ref.
1.5,
.27
‐
.32].
The
sonolysis
+
photolysis
technique
resolves
such
an
issue
of
stable,


prevalent
intermediates
of
greater
toxicity
in
addition
to
higher
rates
and
degree
of
comple‐

tion
of
the
overall
degradation
process.
EXPERIMENTAL
MAIN:

__________________________________________________________________________________________

FIGURE 2. Structure
experiment. 2,4-D and
is also classified as a
in the breakdown of

acid was utilized. Th

92% water, and 2%
FIGURE 1. Experimental setup employed for sonolysis, photolysis, mixture was 70% m
photocatalysis, and combination experiments. The transducer and solution, and it retu
lamp were turned on as needed to conduct the individual experiment. the 30 min mark. A
the 200-400 nm r
mounted about 4 cm above the transducer (Figure 1). This comparison to the
configuration allows for the separation of the transducer from samples.
the reaction mixture. The power output as determined by TOC. Mineralize
Setup:
Sonolysis
experiments
employed
an
ultrasound
of
frequency
of
660
kHz.
The

the calorimetric method is approximately 50 W. The cell was Total Organic Carb
set horizontally on a fitted plastic base, which held it in a with an ASI-500A au
sonication
cell's
volume
was
700
mL, actual sample volumes were 475 to 500 mL. The pow‐
consistent position. Throughout the experiments, the trans- out at least in dupli
ducer and the lower portion of the cell remained submerged
o experimental error
er
output
was
50
W,
the
temperature
was
maintained
at
308
K
(35
 C)
by
the
ice‐water
bath
in an ice-water bath, to maintain the temperature inside
the glass vessel around 308 K. The solutions were sparged Results and Discus
and
oxygen
was
used
to
sparge
the
the
solutions.
The
transducer
was
used
in
sonolysis.
with oxygen gas throughout the experiments.
Sonolytic Degrada
Photocatalysis and Photolysis. Photocatalysis and pho-
pounds. The herbic
tolysis experiments were performed in the same vessel as
when subjected to
described in the sonolysis experiments. A Hanovia (medium
Hydroxyl radicals g
pressure) quartz, mercury-vapor immersion lamp distributed
are the primary oxi
by Ace Glass, Inc. was placed next to the reaction vessel. The
reactions 1 and 2.
lamp was set inside a jacketed glass cylinder. This allowed
obtained from selec
for the circulation of water-cooled copper sulfate solution,
to demonstrate the
 Photolysis
and
photocatalysis
were
performed
in
the
same
vessel
and
conditions,
ex‐

cept
that
a
Hanovia
quartz,
mercury‐vapour
immersion
lamp,
jacketed
in
a
glass
cylinder


was
set
beside
the
reaction
vessel.
This
allowed
for
the
water‐cooled
copper
(II)
sulphate
to

circulate
uniformly
and
remove
(by
absorption)
all
light
of
wavelength
less
than
315
nm.


Also,
the
ice‐water
bath
was
covered
with
foil
so
as
to
maximise
light
exposure.

Combination
setup:
the
only
change
was
the
inclusion
of
ultrasonic
waves;
the
lamp

and
the
transducer
were
both
turned
on.

Reagents
and
data:
100
mL
solutions
of
2,4‐D
and
2,4‐DCP
of
concentrations
rang‐

ing
from
1×10‐4
to
7×10‐4
mol/L,
along
with
0.2
g
of
TiO2.
The
TiO2
was
removed
by
centrifu‐

gation,
the
concentrations
were
determined
by
HPLC.
The
equilibrium
concentrations
were


measured
and
plotted
vs.
no.
of
moles
of
compound
adsorbed
per
gram
of
TiO2;
the
equilib‐

rium
adsorption
coefaicient
was
determined
from
the
gradients
of
the
graphs.

Detection:
compounds
and
intermediates
present
(thereby
the
extent
of
degrada‐

tion)
were
detected
by
HPLC.
Samples
were
drawn
at
different
intervals
during
the
oxida‐

tion
processes
(the
TiO2
was
removed
by
centrifugation
if
it
was
present).

TOC:
total
organic
carbon.
Mineralised
carbon
was
detected
with
an
error
margin
of


±
5%.
 92% water, and 2% of the acetic acid solution. By 18 min, the
or sonolysis, photolysis, mixture was 70% methanol, 27% water, and 3% acetic acid
nts. The transducer and solution, and it returned back to the original composition at
he individual experiment. the 30 min mark. A Photodiode Array detector monitored
the 200-400 nm range. Intermediates were identified by
ducer (Figure 1). This comparison to the retention times and spectra of authentic
of the transducer from samples.
put as determined by TOC. Mineralized carbon was measured using a Shimadzu
ely 50 W. The cell was
RESULTS
AND
PERFORMANCE
se, which held it in a
Total Organic Carbon: Analyzer, model TOC-5050 equipped
with an ASI-500A autosampler. All experiments were carried
xperiments, the trans- out at least in duplicate. The reported values are within the
remained submerged experimental error of (5%.
__________________________________________________________________________________________
e temperature inside
lutions were sparged Results and Discussion
riments.
Sonolytic Degradation of 2,4-D and Other Model Com-
otocatalysis and pho-
pounds. The herbicide 2,4-D undergoes quick degradation
n the same vessel as
when subjected to sonolysis in Ar or O2 saturated solutions.
s. A Hanovia (medium
SONOLYTIC
Hydroxyl
rsion lamp distributed
: generated during the cavitation process
radicals
DEGRADATION
are the primary oxidants responsible for 2,4-D degradation,
e reaction vessel. The
reactions 1 and 2. By comparing the products with those
ylinder. This allowed The
herbicide,
2,4‐D
readily
degraded
under
sonolysis
(in
argon
or
oxygen
saturated

obtained from selective radiolytic degradation we were able
pper sulfate solution,
to demonstrate the role of •OH radicals in sonolytic degrada-
ngths lower than 315
tion of aromatic •compounds
solutions,
oxidised
by
the
 (5).
OH
radical
as
illustrated
below:
the one described in
ed in Figure 1. During
ysis experiments, the H2O ⊃⊃⊃f •OH + H• (1)
to maximize the light
•
iments, the solutions OH + 2,4-D f products (2)
hout the experiments.
lysis. The setup for the In addition to 2,4-D, three other model compounds were
as that used in the The
three
other
model
compounds
were
also
tested,
with
similar
results.
Since
2,4‐
also tested in the present study (2,4-DP, 2,4-DCP, and 2,4,6-
addition of ultrasonic TCP) to compare the effectiveness of sonolysis and photo-
DCP
is
a
main
intermediate
of
the
degradation
of
2,4‐D
and
2,4‐DP,
its
breakdown
is
crucial

were turned on during catalysis in overall degradation. The structures of these
compounds are shown in Figure 2. 2,4-DCP is the major
of 2,4-D and 2,4-DCP chemical intermediate formed during the initial oxidation of
in
the
evaluation
of
the
performance
of
the
techniques.
The
break‐down
of
the
herbicides

M of 100.0 mL volumes 2,4-D and one of the major intermediates in the breakdown
olutions were covered of 2,4-DP. Hence, the accumulation/degradation of 2,4-DCP
followed
a
quasi‐airst
order
decay
with
lifetimes
of
12
an
11
min.
for
2,4‐D
and
2,4‐DP

xposure and were set during the breakdown of 2,4-D/2,4-DP is crucial in deci-
TiO2 was removed by phering the overall rate of degradation and mineralization.
ntrations were respectively.
deter- In the sonolysis of O2-saturated 2,4-D and 2,4-DP solu-
concentrations were tions, we observed quick degradation of the herbicides. The
f compound adsorbed decay of the herbicides follows a pseudo-first-order decay
used to calculate the with degradation lifetimes of 12 and 11 min for 2,4-D and
2,4-DP, respectively. Figure 3 shows the decrease of 2,4-D
taken out at different upon exposure to high frequency ultrasound, and the small
experiments. For the amount of 2,4-DCP that is detected and subsequently
s were removed by degraded. A key observation in the degradation of 2,4-D is
und degradation and that no real build-up of the main intermediate, 2,4-DCP,
d using a Waters HPLC occurs, revealing the main strength of the sonolytic degrada-
7 plus Autosampler, tion process. The sonolytic degradation of 2,4-DCP in solution
with an Alltech Econo- indicated a degradation rate that is similar (lifetime ) 11
m). A solvent gradient min) to 2,4-D. Thus, in the high frequency (660 MHz)
r containing 1% acetic ultrasonic degradation of 2,4-D, effective oxidation takes place

V O L. 37, N O . 9, 2003 / E N VIR O N M E N T A L S CIE N C E & T E C H N O L O G Y 9 1927

 degradation

TiO2(h) or

FIGURE 3. Sonolysis of 0.22 mM 2,4-D solution using O2 as the

sparging gas. The breakdown of (a) 2,4-D (9) and (b) formation/ The herb
degradation of the intermediate 2,4-DCP (b). ucts during
was relative
Figure
3
shows
that
the
intermediate
2,4‐DCP,
is
almost
instantaneously
degraded,
 one observe
to form 2,4-DCP. This, in turn, is quickly oxidized to various
so
it
can
be
seen
that
sonolysis
is
advantageous,
in
terms
of
time
as
well.
2,4‐DCP
and
2,4,6‐ lifetime for
other intermediate compounds. The additional compound difference i
under study, 2,4,6-TCP, reacted in the same manner under
TCP
had
decay
lifetimes
of
11
and
12
min.
respectively
when
their
samples
were
tested. be seen in t
sonolytic conditions, with a lifetime of 12 min. DCP, which
Whereas the sonolytic degradation lifetimes for the four and 2,4-DP
chlorinated aromatic compounds are very similar and period of tim
relatively short, the decrease in total organic carbon occurs the photoc
at a remarkably slow rate. The decrease in TOC in the photocataly
sonolysis experiments is depicted in Figure 4A. Even though which is mo
the parent compounds were short-lived, mineralization was The 2,4,6-tr
typically less than 50% after 4-5 h of high frequency is also less
ultrasound. After subjecting a 0.20 mM 2,4-D solution to herbicides.
high frequency ultrasound for 5 h, only about 50% reduction certain orga
in the total organic carbon was seen. As indicated in our resistance t
5
previous study, low molecular weight organic acids (e.g., solutions. S
oxalic acid) accumulate in solution during sonolysis, and a water trea
their degradation occurs with an extremely slow rate. Being out to be m
polar in nature, these carboxylic acids are repelled from the Whereas
hydrophobic cavitation bubble surface, which decreases the efficiently
probability of interaction with OH radicals. Their resistance powerful in
to sonolytic oxidation makes the overall process of miner- a short per
alization of organic compounds very slow. more polar
Photocatalytic Degradation. The photocatalytic degra- mineralizat
 other intermediate compounds. The additional compound difference in comparison with the sonolysis experiment can
dations of 2,4-D
under study, 2,4,6-TCP, and
reacted other
in the samemodel compounds
manner under were carried
be seen in the formation carbon
of the chemical intermediate 2,4- in the ph
sonolytic conditions, with a lifetime of 12 min. DCP, which accumulates during the photocatalysis of 2,4-D
out inWhereas
the thesamesonolyticcell thatlifetimes
degradation wasforemployed
the four for solutions
and 2,4-DP sonolysis.
and remains in solution forcompounds,
The a substantial illustra
chlorinated aromatic compounds are very similar and
illumination was
relatively short, the done
decrease externally
in total organic carbonby placing
occurs the mercury
the photocatalysis of 2,4-Dlampis shown in FigureAll four
period of time. The formation/breakdown of 2,4-DCP during
5. The compounds
close to the solution cell that was which
at a remarkably slow rate. The decrease in TOC in the
sonolysis experiments is depicted in Figure 4A. Even though
used
photocatalyticfor sonolysis.
degradation lifetime of 2,4-DCP completely
is 20
is more than twice the degradation lifetime of 2,4-D.
min, minerali
Compared to sonolysis,
the parent compounds a different
were short-lived, mineralization
typically less than 50% after 4-5 h of high frequency
was pattern of reactivity
The 2,4,6-trichlorophenol mineralization
molecule, with a lifetime of 18 min, (less
is also less prone to photocatalytic degradation than the
emerged for
After the chlorinated aromatic compounds
TOC:
One
downside
to
sonolysis
is
the
length
of
time
required
to
reduce
the
amounts
ultrasound. subjecting a 0.20 mM 2,4-D solution to herbicides. in the
These experiments in the
clearly demonstrate thatsonolysis ex
high frequency ultrasound for 5 h, only about 50% reduction certain organic compounds, which show a higher degree of
photocatalytic
in the total organic studies using
carbon was seen. TiO2 and
As indicated in our UV light.toPhotoinduced
resistance TiO photocatalysis, tend to accumulate 2 To in achieve effe
of
total
organic
carbon.
Though
the
lifetimes
of
the
source
compounds
were
short
(11
and

5
previous study, low molecular weight organic acids (e.g., solutions. Such longer survival of chemical intermediates in
charge separation
oxalic acid) accumulate in in TiO
solution 2 issonolysis,
during followed and by charge
a water treatment transfer
process can be at problematicexperiments,
if they turn it is n
the12
min.),
mineralisation
had
reached
only
50
%
in
4
‐
5
hours
Figure
4A
{below}
shows
a

interface, depicted in reactions 3-5.
their degradation occurs with an extremely slow rate. Being
polar in nature, these carboxylic acids are repelled from the
Both valence band
out to be more toxic than the parent compounds.
the TiO surface. S
Whereas TiO photocatalysis is slow in its ability to 2
2

holes and surface hydroxyl radicalsefficiently

hydrophobic cavitation bubble surface, which decreases the
probability of interaction with OH radicals. Their resistance
contribute
break down chlorinated
powerful in its ability to induce complete mineralization in
plot
to sonolytic oxidation makes the overall process of miner-
alization of organic compounds very slow.
Photocatalytic Degradation. The photocatalytic degra-
dations of 2,4-D and other model compounds were carried
out in the same cell that was employed for sonolysis. The
illumination was done externally by placing the mercury lamp
close to the solution cell that was used for sonolysis.
Compared to sonolysis, a different pattern of reactivity
emerged for the chlorinated aromatic compounds in the
photocatalytic studies using TiO2 and UV light. Photoinduced
charge separation in TiO2 is followed by charge transfer at
the interface, depicted in reactions 3-5. Both valence band
holes and surface hydroxyl radicals contribute to the
to the phenols,oxidation
it is quite
by the ph
a short period of time. As soon as 2,4-DCP is oxidized to
more polar compounds, further oxidation to the point of
mineralization is fairly rapid. The change in total organic
carbon in the photocatalytic breakdown of the model
compounds, illustrated in Figure 4B, supports this argument.
All four compounds transformed by TiO2 photocatalysis were
completely mineralized in 2-3 h, compared to the incomplete
mineralization (less than 50% during the same period) noted
in the sonolysis experiments.
To achieve effective oxidation in the photocatalysis
experiments, it is necessary for substrates to interact with
the TiO2 surface. Such surface interactions lead to a faster
oxidation by the photogenerated holes and surface hydroxyl

FIGURE 4. (A) Change in total organic carbon content (TOC, ppm) of model compound solutions when subjected to 660 kHz ultrasonic
FIGURE
waves in4.O -sparged
(A) Change
2 system over a in total(B) Change
4 h period. organic carbon
in TOC (ppm) of modelcontent (TOC,
compound solutions usingppm) of model
TiO photocatalysis compound solu
(500 mg/L
2
solution and CuSO filter solution). (a) 2,4-D; (b) 2,4-DP; (c) 2,4-DCP; and (d) 2,4,6-TCP.
waves in O2-sparged system over a 4 h period. (B) Change in TOC (ppm) of model compound s
4

solution
1928
and CuSO4 filter solution). (a) 2,4-D; (b) 2,4-DP; (c) 2,4-DCP; and (d) 2,4,6-TCP.
9 E N VIR O N M E N T A L S CIE N C E & T E C H N O L O G Y / V O L. 37, N O . 9, 2003

1928 9 E N VIR O N M E N T A L S CIE N C E & T E C H N O L O G Y / V O L. 37, N O . 9, 2003

 TABLE 1. Degradation Lifetimes of Chlorinated Aromatic Compounds
de
sonolysis
PHOTOLYTIC
DEGRADATION:
compound sonolysis UV photoly
2,4-dichlorophenoxyacetic acid (2,4-D) 12
The
degradation
lifetimes
of
2,4‐D
and
2,4‐DP
were
observed
to
be
8
and
6
minutes,
 11
2,4-dichlorophenol (2,4-DCP) 11 11
~50
%
faster
than
under
sonolysis.
However,
the
effect
was
opposite
on
the
intermediates,

2,4-dichlorophenoxypropionic acid (2,4-DP) 11 10
2,4,6-trichlorophenol (2,4,6-TCP) 12 10
2,4‐DCP
and
2,4,6‐TCP;
their
lifetimes
were
observed
to
be
as
high
as
~20
min.
and
~18

a Degradation lifetim es (τ ) 1/ k) w ere obtained fro m the first-order kinetic fit of the 2

min.

FIGURE 7. Ox
FIGURE 5. Photocatalysis of 0.24 mM 2,4-D solution with O2-sparged (9), (b) sono
system. The breakdown of (a) 2,4-D (9) leads to the longer-lasting sonolysis, PS
(b) 2,4-DCP (b), with a lifetime (20 min) more than twice that of for the comb
2,4-D (8 min).
Combin
TOC:
Photolysis
redeems
itself

by
performing
far
better
than
sonolysis
as
far
as
TOC

mental resu
is
concerned.
The
results
would
suggest
that
it
is
a
powerful,
rapid
technique
for
 degradation
(Figures 3-5
mineralisation. of the indivi
are establis
experiment
(chlorinated
degradation
these defici
FIGURE 6. Adsorption of (a) 2,4-D and (b) 2,4-DCP (moles × 10-6) processes.
in the dark for 24 h per gram of TiO2 plotted against the equilibrium approach w
concentration (µm). the degrada
We have
radicals. The type of chemistry that ensues may also be to establish
 high frequency ultrasound for 5 h, only about 50% reduction certain organic compounds, which show a higher degree of
ght. Photoinduced Towasachieve
in the total organic carbon effective
seen. As indicated in our oxidation
resistance in the tend
to TiO photocatalysis, photocatalysis
to accumulate in 2
5
previous study, low molecular weight organic acids (e.g.,
charge transfer at experiments, it is necessary
oxalic acid) accumulate in solution during sonolysis, and for substrates to interact with
solutions. Such longer survival of chemical intermediates in
a water treatment process can be problematic if they turn
oth valencetheir
band the TiO2 surface. Such surface
degradation occurs with an extremely slow rate. Being
polar in nature, these carboxylic acids are repelled from the
interactions
out to be more lead
toxic than the parent to a faster
compounds.
Whereas TiO photocatalysis is slow in its ability to 2

ontribute toprobability
hydrophobic oxidation
the of interaction
cavitation bubble by the photogenerated
surface, which decreases the
with OH radicals. Their resistance
holes
efficiently break
down chlorinated
to sonolytic oxidation makes the overall process of miner-
alization of organic compounds very slow.
Photocatalytic Degradation. The photocatalytic degra-
dations of 2,4-D and other model compounds were carried
out in the same cell that was employed for sonolysis. The
illumination was done externally by placing the mercury lamp
close to the solution cell that was used for sonolysis.
Compared to sonolysis, a different pattern of reactivity
emerged for the chlorinated aromatic compounds in the
photocatalytic studies using TiO2 and UV light. Photoinduced
charge separation in TiO2 is followed by charge transfer at
the interface, depicted in reactions 3-5. Both valence band
holes and surface hydroxyl radicals contribute to the
and surface
phenols, hydroxyl
it is quite
powerful in its ability to induce complete mineralization in
a short period of time. As soon as 2,4-DCP is oxidized to
more polar compounds, further oxidation to the point of
mineralization is fairly rapid. The change in total organic
carbon in the photocatalytic breakdown of the model
compounds, illustrated in Figure 4B, supports this argument.
All four compounds transformed by TiO2 photocatalysis were
completely mineralized in 2-3 h, compared to the incomplete
mineralization (less than 50% during the same period) noted
in the sonolysis experiments.
To achieve effective oxidation in the photocatalysis
experiments, it is necessary for substrates to interact with
the TiO2 surface. Such surface interactions lead to a faster
oxidation by the photogenerated holes and surface hydroxyl

FIGURE 4. (A) Change in total organic carbon content (TOC, ppm) of model compound solutions when subjected to 660 kHz ultrasonic
n content (TOC,wavesppm) of model
in O -sparged system overcompound
2 solutions
a 4 h period. (B) Change in TOC (ppm) when subjected
of model compound to 660
solutions using kHz ultrasonic
TiO photocatalysis (500 mg/L 2
solution and CuSO filter solution). (a) 2,4-D; (b) 2,4-DP; (c) 2,4-DCP; and (d) 2,4,6-TCP.
(B) Change in TOC (ppm) of model compound solutions using TiO2 photocatalysis (500 mg/L
4

b) 2,4-DP; (c)1928
2,4-DCP; and (d) 2,4,6-TCP.
E N VIR O N M E N T A L S CIE N C E & T E C H N O L O G Y / V O L. 37, N O . 9, 2003
9

Mineralisation
(removal
of
TOC)
was
complete
by
~3
hours
compared
with
only

/ V O L. 37, N O . 9, 2003
50%
by
~5
hours
under
sonolysis.

Mechanism:
the
substrates
must
interact
with
TiO2
surface
for
efaicient
oxidation,
as

photogenerated
holes
and
surface
hyrdoxyl
radicals
bring
about
quick
oxidation.
The
type
of

chemistry
that
ensues
may
also
be
dependant
on
the
extent
of
adsorption
[ref.
1.14].

2,4­D
and
2,4­DCP
compared
further:
Since
their
reactivities
(lifetimes)
we
starkly

different,
this
was
explored
further.
The
adsoprtion
results
are
as
follows:
 FIGURE
FIGURE 5. Photocatalysis of 0.24 mM 2,4-D solution with O2-sparged (9), (b
system. The breakdown of (a) 2,4-D (9) leads to the longer-lasting sonoly
(b) 2,4-DCP (b), with a lifetime (20 min) more than twice that of for the
2,4-D (8 min). FIGURE 7. Oxidative d
FIGURE 5. Photocatalysis of 0.24 mM 2,4-D solution with O2-sparged (9), (b) sonolysis (2)
system. The breakdown of (a) 2,4-D (9) leads to the longer-lasting sonolysis, PS (b). Co
TiO2
(b) 2,4-DCP (b), with a lifetime (20 min) more than twice that of mentas
for the combination
2,4-D (8 min).
degrad
Combined Sono
mental results(Figur
obtain
degradation ofthe
of 2,4i
(Figures 3-5)are
demon es
of the individual pro
experi
are established in
(chlor
experiments exhibi
(chlorinateddegrad
pheno
degradation. The o
thesebd
these deficiencies
FIGURE FIGURE
6. Adsorption of of(a)(a)2,4-D and(b)(b) 2,4-DCP -6)
6. Adsorption 2,4-D and 2,4-DCP (moles(moles
× 10-6) × 10
processes. proces
The me
in the dark for 24 h per gram of TiO22 plotted against the equilibrium
in the dark for 24 h per gram of TiO plotted against the equilibrium approach were
approdem
concentration (µm). the degradation of
concentration (µm). the de
We have employe
radicals. The type of chemistry that ensues may also be
As
per
the
isotherm
shown
above,
the
equilibrium
constant
value,
K,
is
360
L/mol
 to establish the We ben
radicals. dependent
The type uponof thechemistry
extent of adsorption (14).
that ensues may alsooxidation
be processes
to esta
for
2,4‐D
and
110
L/mol
for

2,4‐DCP,
one‐third
that
of
its
precursor.
In
light
of
the
mecha‐
Earlier studies aromatic compound
dependent upon thehave
extent employed Langmuir-Hinshelwood
of adsorption (14). oxidat
oxidative degradat
analyses to follow the degradation of chlorinated phenols in
nism
cited,
this
can
be
explained
by
the
greater
afainity
of
2,4‐D
for
the
surface
of
TiO
Earlier studies slurries
UV-irradiated have (employed
14, 33, 34). Such Langmuir-Hinshelwood
analyses point to the 2.
photocatalysisaroma
and s
fact The degradation
oxidat lif
analyses tothat the adsorption
follow the degradationof molecules oftochlorinated
the TiO2 surface is
phenolsas in
compared to th
the limiting factor in dictating the overall rate of degradation.
UV-irradiated slurries (14,that 33, 34 photo
Other studies indicate no ).strong
Suchcorrelation
analyses existspoint toindividual
the photocat
fact that the adsorption ofadsorption
molecules and to thethe TiO Table 1 The
summa d
between the strength of initial 2 surface
rate of is
chlorinatedas com
aromat
the limiting factor(35,
degradation in36 ). Since thethe
dictating reactivities
overallofrate 2,4-Dofand 2,4-
degradation.
catalysis, and combi
DCP in the photocatalysis experiments proved to be blatantly
Other studies indicate individ
different, we probed thethat no strong
adsorption behaviorscorrelation
of these two exists
lifetimes for the chlo
between the strength
compounds. Variousofconcentrations
adsorption inand 100 the
mL initial
sample rate in the
of combination Tab
degradationvolumes(35, of 2,4-D
36).and Since 2,4-DCP
the were stirred with
reactivities of200 mg ofand either
2,4-D 2,4-
the chlori
photoca
example, 2,4-DCP,
breakdown,catalys
TiO2 in the dark for 24 h. After removal of the TiO2 by
DCP in centrifugation,
the photocatalysis experiments
the equilibrium proved
concentrations todeter-
were be blatantly has a lif
different, minedweand probed
graphed the adsorption
against the number behaviors
of moles of of these system
solute two lifetimt
compared
sonolysis and in phot
the
compounds. adsorbedVarious
per gram ofconcentrations
TiO2. The adsorption results in 100 are shown
mL sample enhancement of 2,
volumes
in Figure 6. The adsorption isotherm for 2,4-DCP yielded an
of 2,4-D and 2,4-DCP were stirred with 200 mg either
of degradatio
observed
equilibrium constant value, K, of 110 L/mol, while the K value
TiO2 inforthe 2,4-Ddark for 24ath.
was calculated 360After removal
L/mol. While of the TiO2rate
both compounds
examp
byenhancement o
are considered to be weakly adsorbing species (36),were the deter- breakd
centrifugation, the equilibrium concentrations ko
herbicide 2,4-D exhibits a three times greater adsorption system
mined ability
and graphed against
than the 2,4-DCP. Thethe number
greater adsorption of ofmoles
2,4-D toof solute
sonoly
adsorbed the per gram
catalyst of TiO
surface, though 2. The adsorption
moderate, providesresults
an explana-are shown
where the k values
tion6.for the higher degradation rate observed for 2,4-D inyielded
the determined enhan
from the
in Figure The adsorption isotherm for 2,4-DCP an
photocatalytic experiments. degradationobserv
proces
equilibrium constant value, K, of 110 L/mol, while the K value
rate en
 
SONOLYSIS
+
PHOTOLYSIS
COMBINED:­

Summary:
the
rate
of
oxidative
degradation
was
signiaicantly
enhanced
when
the


both
techniques
were
carried
out
simultaneously;
the
degradation
lifetimes
measured
were

lesser
than
those
measured
under
one
technique
only.
Table
1
summarises
the
degradation


lifetime
magnitudes
under
sonolysis,
photolysis
and
under
the
combination:

TABLE 1. Degradation Lifetimes of Chlorinated Aromatic Compounds

degradation lifetime, ((1) mina
sonolysis + TiO2 combined sonolysis
ted Aromatic Compounds compound sonolysis UV photolysis photocatalysis and photocatalysis
2,4-dichlorophenoxyacetic acid (2,4-D) 12 11 8.0 6.6
2,4-dichlorophenol (2,4-DCP)degradation lifetime,
11 ((1) mina 11 20.0 7.7
2,4-dichlorophenoxypropionic acid (2,4-DP) 11 10 6.2 5.9
sonolysis
2,4,6-trichlorophenol +
(2,4,6-TCP) TiO
12
2
10 combined18sonolysis 8.2
s of Chlorinated Aromatic
sonolysis Compounds
a
Degradation UV
lifetim photolysis
es (τ ) 1/k) w ere obtained fro mphotocatalysis and photocatalysis
the first-order kinetic fit of the 2,4-decay.

degradation lifetime, ((1) min a

12 11 8.0 6.6
2,4‐DCP,
the
toxic
intermediate
has
a
lifetime
of
only
7.7
min.
under
the
combination,
con‐
11 11sonolysis + 20.02
TiO combined 7.7
sonolysis
-DP) 11 sonolysis UV photolysis
10 photocatalysis
6.2 and photocatalysis
5.9
acid (2,4-D) 12 12 10 11 18 8.0 6.68.2
siderably
lesser
than
under
any
one
technique
only.
This
is
exempliaied
by
the
following

P) 11 11 20.0 7.7
ed
nic fro
acidm(2,4-DP)
the first-order kinetic
11 fit of the 2,4-decay.
10 6.2 5.9
graph:
TCP) 12 10 18 8.2
w ere obtained fro m the first-order kinetic fit of the 2,4-decay.
FIGURE 7. Oxidative degradation of 2,4-DCP using (a) photocatalysis
FIGURE 5. Photocatalysis of 0.24 mM 2,4-D solution with O2-sparged (9), (b) sonolysis (2), and (c) the combined photocatalysis and
system. The breakdown of (a) 2,4-D (9) leads to the longer-lasting sonolysis, PS (b). TiO2 loading was 125 mg/L for photocatalysis and
(b) 2,4-DCP (b), with a lifetime (20 min) more than twice that of for the combination system.
2,4-D (8 min).
Combined Sonolysis and Photocatalysis. The experi-
mental results obtained from the sonolytic and photocatalytic
degradation of 2,4-D, 2,4-DP, and chlorinated phenols
(Figures 3-5) demonstrate both the strengths and weaknesses
of the individual processes. Whereas slow mineralization rates
are established in sonolysis experiments, photocatalysis
experiments exhibit a build-up of a toxic intermediate
(chlorinated phenol) during the course of 2,4-D and 2,4-DP
degradation. The obvious strategy would be to overcome
these deficiencies by combining the two advanced oxidation
FIGURE 6. Adsorption of (a) 2,4-D and (b) 2,4-DCP (moles × 10-6) processes. The merits of such an advanced oxidation
in the dark for 24FIGURE
h per gram 7. Oxidative degradation
the equilibrium of 2,4-DCP using
of TiO
FIGURE 2 plotted against
7. Oxidative degradation of approach were
2,4-DCP using (a)(a) photocatalysis
demonstrated
photocatalysis in our preliminary study on
tion with O 2-sparged
mM 2,4-D solution concentration
with O2-sparged (µm).
(9), (b)(9),sonolysis
(b) sonolysis (2),(2),and and(c)(c)the
the degradation
the combined
combined
of an azo
photocatalysis
photocatalysis
dye, Naphthol Blue Black (9).
and
andsonolysis/photocatalysis
We have employed simultaneous
to
-D the longer-lasting
(9) leads to theradicals.
longer-lasting
sonolysis,
The type of chemistryPS that
sonolysis, (b).ensues
PS TiO2 loading
(b). TiOmay
2 loading
also bewas 125
was 125 mg/L for
mg/L
to establish for photocatalysis
of combiningand
photocatalysis
the benefits and these two advanced
e(20than
min) twice
more than
that twice
of that
dependent upon of extent
forthethe for the combination
of adsorption
combination (14).system.
system. oxidation processes in the degradation of the four chlorinated
Earlier studies have employed Langmuir-Hinshelwood aromatic compounds. In the case of all four compounds, the
analyses to follow the degradation of chlorinated phenols in oxidative degradation was significantly enhanced when
Combined Sonolysis and Photocatalysis.
UV-irradiated slurries (14, 33, 34). Such analyses point to the
The experi-
photocatalysis and sonolysis were carried out simultaneously.
Combined
fact that the adsorptionmentalof molecules
Sonolysis
results obtained
to the
and
from
TiO2 surface
Photocatalysis.
is the sonolytic and photocatalytic
The degradation lifetimes Theof all experi-
the compounds decreased
mental
the limiting factor results obtained from
degradation of 2,4-D, 2,4-DP,individual
in dictating the overall rate of degradation. the sonolytic
as compared and
and chlorinatedto thephotocatalytic
lifetimes obtained in either of the
phenols
Other studies indicate(Figuresthat no strong correlation exists photocatalysis or sonolysis experiments.
degradation of
3-5) 2,4-D,
demonstrate
between the strength of adsorption and the initial rate of
2,4-DP,
both theand chlorinated
strengths and weaknesses phenolslifetimes of the
Table 1 summarizes the degradation
degradation (35, (Figures of the
3-5)
36). Since the individual
demonstrate
reactivities processes.
of 2,4-D andboth Whereas slow mineralization
2,4- the strengths and weaknesses
chlorinated aromatic compounds rates in the sonolysis, photo-
DCP in the photocatalysis are established
experiments proved into besonolysis
blatantly catalysis, and combined
experiments, oxidation processes. The degradation
photocatalysis
of the individual
different, we probed theexperiments
processes.
adsorption behaviors of these
Whereas
two
slow
lifetimes mineralization
for the chlorinated phenolsrates are significantly shorter
exhibit a build-up ofcombination
a toxic intermediate
compounds. Variousare established
concentrations inin 100sonolysis
mL sample experiments,
(chlorinated phenol) during theeither
in the
course the of
photocatalysis
experiments
2,4-D and 2,4-DP
photocatalysis
than the ones observed in
or sonolysis experiments. For
volumes of 2,4-D and 2,4-DCP were stirred with 200 mg of
The
observed
degradation
rate
follows
approximately
an
additive
rate
enhancement
of
the
in­

dividual
rates
[ref.
1]
as
per
the
following
equation:

kobsd
=
ksono
+
kphotocat

where
the
k­values
are
quasi‐airst
order
rate
constants,

calculated
from
the
reciprocal
lifetimes
of
the
corresponding
degradation
processes
[ref.
1]

TOC
factor:
the
reduction
in
TOC
was
also
improved
upon;
the
addition
of
ultrasonic

waves
reinforce
the
rate
of
mineralisation
under
photolysis,
already
adept
at
reducing
TOC.


Overall,
an
improvement
is
obvious.

the effectiv
phenyltriflu
observe syn
frequency
the effectiveness of remediat s
tion approa
phenyltrifluoromethyl ketone
observe synergy using simultan
frequency (
frequency sonolysis of TiO2 su
tion approachozonolysis,
was only effec
frequency (30improving
kHz). By comb t
ozonolysis, Hoffman and c
orange solu
improving the mineralization r
of from
orange solutions ozone.20% to m
of ozone.
The resu
The results described in th
the advantage the advant
of combinin
FIGURE 8.FIGURE
Mineralization ofof2,4-D
8. Mineralization solutions
2,4-D solutions usingusing photocatalysis
photocatalysis
frequency
frequency sonolysis for the s m
(9), sonolysis (b), and
(9), sonolysis thethecombination
(b), and system
combination system (2) as(2) as inchange
change in compounds. It is we
aromatic
total organic carbon in ppm. aromatic co
total organic carbon in ppm. high-frequency ultrasound is
high-freque
nonpolar compounds (5, 7, 39
TABLE 2. Effect of TiO2 Loading on the Degradation Rate of nonpolar
chlorinated aromatic compoun co
2,4-Dichlorophenol
TABLE 2. Effect of TiO2 Loading on the Degradation Rate datively of
strengthens our argument th
chlorinated
transformed at the
2,4-Dichlorophenol degradation lifetime, ((1) min
strengthens
Chlorinated aromatics all hav
combined sonolysis bubble surface, which provide
TiO2, g/L degradation lifetime,
photocatalysis ((1) min
and photocatalysis datively tra
The hydroxyl radicals produ
0.5 20 7.7
Chlorinated
bubble interface initiate the o
0.25 combined
7.4 sonolysis bubble surfa
more polar compounds. Since
TiO2, g/L 0.125 photocatalysis
21.5 and7.4photocatalysis
becomes less effective in furth
The hydrox
0.064 25.6 8.1 we do not observe complete m
0.5 0.034 20 49.0 8.2 7.7 bubble
oxidized compounds intein
formed
0.020 8.8
0.25 0.010 >60 8.8 7.4 morecavitation
for the hydrophobic polar
mations take place. Hence, son
0.125 0 21.5 only 9% degradation 11.0 7.4 becomes
for the complete mineralizatioles
after 90 min
 ozonolysis, Hoffm
improving the min
orange solutions fr
of ozone.
The results des
the advantage of
FIGURE 8. Mineralization of 2,4-D solutions using photocatalysis
TiO2
control:
the
variation
of
degradation
lifetimes
as
affected
by
different
TiO frequency
2
 sonolys
(9), sonolysis (b), and the combination system (2) as change in
aromatic compou
total organic carbon in ppm.
loadings
is
shown
here: high-frequency ul
nonpolar compou
TABLE 2. Effect of TiO2 Loading on the Degradation Rate of chlorinated aroma
2,4-Dichlorophenol strengthens our a
degradation lifetime, ((1) min datively transform
Chlorinated arom
combined sonolysis bubble surface, wh
TiO2, g/L photocatalysis and photocatalysis The hydroxyl rad
0.5 20 7.7 bubble interface in
0.25 7.4 more polar compo
0.125 21.5 7.4 becomes less effec
0.064 25.6 8.1 we do not observe
0.034 49.0 8.2 oxidized compoun
0.020 8.8 for the hydrophob
0.010 >60 8.8
mations take place
0 only 9% degradation 11.0
after 90 min for the complete m
complimentary n
apparent, since it
An interesting observation in these experiments is the
The
amount
of
catalyst
is
systematically
halved
at
regular
intervals.
When
the
cata‐ the point of comp
fact that the decrease in total organic carbon was expedited
in the combination experiments. Although photocatalysis is
lyst
loading
is
small,
an
all
too
signiaicant
difference
is
seen
between
the
sole
and
combined
 Suggestions hav
quite effective in mineralizing organic compounds, the prevents the catal
techniques.
The
combination
techniques
remains
efaicient
even
at
low
loadings,
whereas

addition of ultrasonic waves augments the speed of min- transfer of molecu
eralization. Figure 8 shows the decrease in organic carbon While this argume
the
sole
photolysis
technique
utterly
fails.
of aqueous solutions of 2,4-D during the individual and alone cannot expla
combined systems. A significant benefit in mineralization tion experiments.
rate is noted when the combined system is compared to the
The
results
concur
with
the
hypothesis
that
higher
degration
rates
at
higher
TiO facilitates the bre
2

high-frequency ultrasound results. suspensions. For t
We also independently assessed the role of direct UV-
loadings
is
due
to
an
additive
effect
of
two
techniques.
Other
factors
such
as
better
mass
 was performed usi
irradiation in the combined experiment. The degradation the TiO2 suspens
transfer
are
of
lesser
importance
under
standard
conditions,
but
may
be
a
factor
at
lower

lifetimes of the four model compounds were determined frequency ultrasou
using sonolysis under ultraviolet irradiation, without any flowing to finely d
TiO2
loadings.added TiO2 catalyst. No difference was realized by the turned off, solute
presence of UV light during the sonolysis experiments. The catalysis experimen
absorption
TOC
under
TiO band of these compounds lies in the range of of 2,4-DCP in th
2
control:
with
low
catalyst
loadings,
there
is
still
efaicient
minerali‐
281-287 nm and tails off around 310. Since the light filtering degradation lifetim
sation
under
the
combination.
Mineralisation
of
2,4‐DCP,
complete
at
~3
hours,
is
unaffect‐
solution used in the photolysis experiments cuts off wave- without sonolysis
lengths below 315 nm, the tested compounds should not be treatment of the ca
ed
by
catalyst
loadings
of
≥10
mg/L;
affected directly by the therate
UVof depletion of carbon is, however, lower.effects but canno
light. 2,4,6-Trichlorophenol
showed a slight decrease in lifetime of the compound. This observed in the co
small difference, noted in Table 1, is within the experimental ment. Similar fin
error of ( 1 min. These control experiments confirm that the loadings.
additive effect seen in the combination experiment arises We further eva
from the photocatalytic activity of the TiO2 nanoparticles photocatalysis and
and not the UV light. loadings. These re
 tocatalysis s
of toxic inter
in thesimultan
tocatalysis comb
of toxic intermediat
in theAcknowledg
combination
We thank Dr
Acknowledgments
the Departm
We thank Dr. K. Vin
for providin
the Department of C
The work d
for providing the fac
the Basic
The work En
described
the Basic Energy Sc
This is contr
This isLaboratory.
contribution
Laboratory.
Literature
Literature Cited C
FIGURE 9. Change
FIGURE 9. Changein in
thethetotal
totalorganic carbonofof2,4-DCP
organic carbon 2,4-DCP solutions
solutions (1) D.Ollis, D.
(1) Ollis, F.; Al-Ek
in photocatalysis or the
in photocatalysis combined
or the combined photocatalysis/sonolysis experi-
photocatalysis/sonolysis experi- ment om fW enatterofa
ments using various loadings of TiO : (a) photocatalysis,
ments using various loadings of TiO22: (a) photocatalysis, 10 mg/L; 10 mg/L; (2) Jeworski, M.;
(2) Jeworski He
(b) photocatalysis,6464mg/L;
(b) photocatalysis, mg/L; (c)
(c) photocatalysis,
photocatalysis, 500500mg/L; (d) (d)
mg/L; 196. 196.
photocatalysis + sonolysis, 10 mg/L; (e) photocatalysis + sonolysis, (3) Hoigne, J. Chem
photocatalysis + sonolysis, 10 mg/L; (e) photocatalysis + sonolysis,
250 mg/L; (f) photocatalysis + sonolysis, 500 mg/L.
(3) Hoigne,
Pollutants by Oz
250 mg/L; (f) photocatalysis + sonolysis, 500 mg/L. The HaPollutan
ndbook o
of the two processes, as described above. Additional factors, T he H an
Springer-Verlag:
Under
sole
photolysis,
if
the
TiO
of thesuch
twoasprocesses,
improved 2
loading
is
less
then
10
mg/L,
the
change
in
TOC
is
severe.

as described
mass transfer, are above. Additional
less important factors,
under
(4) Springer
Andreozzi, R.; C
1999, 53 ,
(4) Andreoz51.
suchstandard
as improved conditionsmassbut transfer,
may play are aless important
larger
Quantitatively,
after
~3
hours,
only
less
than
40%
of
TOC
is
resolved.
role in theunder (5) Peller, 1999,
J.; Wiest, 53
degradation at lower TiO loadings.
standard conditions but 2may play a larger role in the 3176.
The degradation results for 0.2 mM solutions of 2,4-DCP (5) Peller,
(6) Hart, E. J.; Fische J.
degradation at lower TiO2 loadings. 284. 3176.
with varying TiO2 loading are summarized in Table 2. In
The
thesedegradation
experiments,results
the amountfor 0.2 mM solutions
of catalyst of 2,4-DCP (7) Serpone,
was systematically
(6) Hart, E.
N.; Terz
with decreased
varying TiO 2 loading
in half, are summarized
over several cycles. With small in Table 2. In
catalyst
1994, 284.
98 , 2634.
(8) Destaillats,
(7) SerponeH.; C
theseloading,
experiments,
a major the amount
difference of catalyst
is prevalent was systematically
between the inde- Phys. C1994,
hem. A98 2
pendentinphotocatalysis
decreased half, over severaland the cycles.
combinationWithprocess.
small TiOcatalyst
2 (9) Stock, N. L.; Pelle
e(8)
chnoDestailla
loadings
loading, as small
a major as 10 mg/L is
difference of TiO 2 are sufficient
prevalent between the inde- (10) TColarusso,
to maintain l. 2000, 3
PhysP.; . CSeh
an effective degradation rate in the combination experiment.
pendent photocatalysis and the combination process. TiO2 (11) Vinodgopal, (9) Stock,K.;NP
Conversely, in the photocatalysis experiments, (no sonolysis)
loadings as smallofas2,4-DCP
10 mg/L of TiO2at are sufficient to maintain 1998, 32 Te, c3646.
hnol.
the lifetimes lengthen TiO 2 loadings smaller (12) Kamat, P. V. C he
an effective (10) Colaruss
than 125degradation
mg/L. With a rate loading in the
of 34combination experiment. (13) Liu,
mg/L, the performance G.; Li, X.; Z
(11) Vinodgo
Conversely, in thefor
is maintained photocatalysis
the combination experiments, (no sonolysis)
process (lifetime ) 8.2 Technol. 2000, 3
1998, 32
min) and of
the lifetimes diminishes
2,4-DCP substantially
lengthen atinTiO the2 loadings smaller (14) Li,
photocatalysis X.; Cubbage,
C(12)
hem. Kamat,
2001, 143P
thanexperiment With a )
125 mg/L.(lifetime 49 ( 2 min).
loading of 34Thus,
mg/L, it is
theclear that the
performance (13) C.;
(15) Nasr, Liu, G.;
Vinodg
combination approach remains very effective for degradation
is maintained for the combination process (lifetime
of 2,4-DCP even at very low levels of TiO2, a trend not present
) 8.2 padhyay, TecA.hnK.; olK.
(16) Hoffman, M.
(14) Li, X.; Cu R.;
min)inand diminishesphotocatalysis.
the independent substantially in the photocatalysis Chem. Rev. 1995
experiment (lifetime )process
The combination 49 ( 2also min). Thus,
offers clear that the (17) Malato,CS.;
it is mineraliza-
effective
h em . 2
Blan
combination
tion ratesapproach remains
with low catalyst very At
levels. effective for degradation
TiO2 loadings of 10 Environ. 2002,C.3
(15) Nasr,
padhyay
(18) Naffrechous, E.;
 eralization. Figure 8 shows the decrease in organic carbon While this argument is certainly valid in a general sense, it
of aqueous solutions of 2,4-D during the individual and alone cannot explain the synergetic effects seen in combina-
combined systems. A significant benefit in mineralization tion experiments. We tested the hypothesis that sonolysis
rate is noted when the combined system is compared to the facilitates the break-up of TiO2 aggregates in aqueous
high-frequency ultrasound results. suspensions. For this purpose, a photocatalysis experiment
We also independently assessed the role of direct UV- was performed using sonolytically treated TiO2 catalyst. First,
irradiation in the combined experiment. The degradation the TiO2 suspension (no solute) was subjected to high
lifetimes of the four model compounds were determined frequency ultrasound waves for 30 min with the oxygen gas
using sonolysis under ultraviolet irradiation, without any flowing to finely disperse the TiO2. The ultrasound was then
turned off, solute was added, and the independent photo-
Opresence 

SUMMARY
of UV :‐
added TiO2 catalyst. No difference was realized by the
VERALL light during the sonolysis experiments. The catalysis experiment was completed. The degradation lifetime
absorption band of these compounds lies in the range of of 2,4-DCP in this case was 18 min as compared to a
281-287 nm and tails off around 310. Since the light filtering degradation lifetime of 20 min (Table 2) using the catalyst
without sonolysis treatment. These results show that pre-
_________________________________________________________________________________________________________
solution used in the photolysis experiments cuts off wave-
treatment of the catalyst with sonolysis has limited beneficial
lengths below 315 nm, the tested compounds should not be
affected directly by the UV light. 2,4,6-Trichlorophenol effects but cannot account fully for the enhancement
showed a slight decrease in lifetime of the compound. This observed in the combined photocatalysis/sonolysis experi-
small difference, noted in Table 1, is within the experimental ment. Similar findings were also noted at different TiO2
error of ( 1 min. These control experiments confirm that the loadings.
additive effect seen in the combination experiment arises We further evaluated the synergy effects by carrying out
from theThe
following
table
compiles
a
summary
of
the
main
characteristics
of
the
two
tech‐
photocatalytic activity of the TiO2 nanoparticles photocatalysis and combination experiments at different TiO2
and not the UV light. loadings. These results are consistent with the hypothesis
Earlier efforts have been made to combine sonolysis with that the main explanation for the enhancement in rate of
niques
and
their
synergy.
either ozonolysis (8, 37) or photocatalysis (38) to improve degradation at the higher TiO2 loadings is the additive effect

TABLE 3. Comparison of Salient Features of Different Advanced Oxidation Processes

feature sonolysis photocatalysis combined sonolysis and photocatalysis
degradation of nonpolar co m pounds good variable very good
degradation of polar co m pounds poor good very good
mineralization poor good very good
avoidance of toxic interm ediate good poor very good
need for a catalyst no yes yes, in sm aller quantity

1930 9 E N VIR O N M E N T A L S CIE N C E & T E C H N O L O G Y / V O L. 37, N O . 9, 2003

Rapid
decay
and
mineralisation
of
the
chlorinated
aromatic
organic
compounds
is
brought


about
under
simultaneous
sonolysis
+
photolysis.
The
lack
of
long‐lived
accumulation
of


more
toxic
intermediates
is
also
a
major
achievement.
SECTION
2: ON‐LINE
ANALYSIS
OF
THE
SIZE
DISTRIBUTION
OF
FINE

AND
ULTRA­FINE
AEROSOL
PARTICLES
IN
FLUE
AND


STACK
GAS
OF
A
(GERMAN)
MUNICIPAL
WASTE
INCINER

ATION
PLANT:
EFFECT
OF
DYNAMIC
PROCESS
CONTROL


MEASURES
AND
EMISSION
REDUCTION
DEVICES [ref.
2]

PRELUDE:

__________________________________________________________________________________________

There
has
been
intensive
research
in
the
past
decade
that
citing
the
adverse
health


effects
of
particulate
emissions.
Fine
particles
(d
<
2.5
μm)
and
ultra­Vine
particles
(d
<
0.1


μm)
can
penetrate
the
lungs
upto
the
alveolar
region
if
inhaled,
thus
are
of
great
concern
to


human
health.
Particulate
emission
control
legislations,
effectively,
do
not
factor
ultra­Vine


particles;
and
total
particle
mass
is
an
incomplete
measure
of
lung‐penetrating
power
since

the
bulk
is
made
of
particles
of
>2.5
μm
diameter,
which
precipitate
in
the
nose
or
throat
if


inhaled.
 An
appropriate
measure
would
be
fraction
of
particles
in
the
size
range
of
PM2.5


and
PM1.0
(particulate
matter
with
diameters
less
than
2.5
μm
and
1.0
μm
respectively).
To

this
end,
such
emissions
of
a
German
municipal
waste
incineration
plant
are
investigated.

1. Scheme of the 23 MW waste-incineration plant. The measuring points are indicated.

FIGURE 1. Scheme of the 23 MW waste-incineration plant. The measuring points are indicated.
ne particle formation and emission of a German The main objectives considered within this stu
ultrafine particle formation and emission of a German The main objectives considered within th
pal waste incineration plant was investigated.
municipal waste incineration plant was investigated.
follows: follows:
ste incineration represents a favorable
Waste incineration technique
represents for technique
a favorable (i) The
for investigation of the impact
(i) The investigation of proces
of the impact of p
ng the volume ofreducing
waste thestreams and recovering its
volume of waste streams and recovering measures its onmeasures
the particle-size distribution
on the particle-size in thei
distribution
content for generation
energy contentof electricity
for generationandofdistrict
electricity and district µm0.017-10
0.017-10 in the raw µm influe
thegas: Togas:
raw flue develop new
To develop
heating. However, in the past,
g. However, in the past, municipal waste incinerators municipal waste incinerators integrated and flue-gas cleaning
integrated and flue-gas cleaning measures for red measures f
(MWI) had a bad reputation due to the emission of toxic particlefrom
emissions from combustion
had a bad reputation due to the emission of toxic particle emissions combustion plants plants
a betta
combustion byproducts (including polychlorinated dibenzo- edge of generation mechanisms of particles d
stion byproducts (including polychlorinated dibenzo- edge of generation mechanisms of particles during
p-dioxins/-furans, PCDD/F and polycyclic aromatic hydro- combustion processes is required.
ns/-furans, PCDD/F andPAH
carbons, polycyclic
as well asaromatic hydro-
heavy metals, combustion
such as mercury and processes is required.
s, PAH as well ascadmium),
heavy metals, (ii) The study of the course and the va
whichsuch as amercury
exhibit and
serious hazardous potential.
(ii) The study
emittedofparticle-size
the course and the variabil
distribution: This info
um), which exhibit a the
Within serious hazardous
past decade numerous potential.
efforts have been under-
emitted particle-size distribution:
quired as basis, This informat
e.g., for evaluation of the amo
the past decade taken
numerous efforts
by several Europeanhave been under-
countries to reduce toxic emissions
quired as basis,inhalable particles.
e.g., for evaluation of the amount o
from MWI in order to achieve the
y several European countries to reduce toxic emissions very tight emission levels
set by thethe
national inhalable particles.
(iii) The observation of the impact of flu
MWI in order to achieve very environmental
tight emission protection
levels authorities. For devices on the emitted particle-size distribu
example, the emission limit of PCDD/F (measured (iii) as
The observation of the impact of flue-gas
he national environmental protection authorities. For
international toxicity equivalent) was set to 0.1devices ng/m3 inon the The recent flue-gas cleaning technology needs
le, the emissionGermany
limit of PCDD/F (measured as withemitted
respect toparticle-size distribution
fine and ultrafine particle pres
(5). Due to these efforts, waste incineration in
ational toxicity equivalent)
Germany nowadayswas set to 0.1 ng/m
represents
3 in
a relatively
The recent flue-gas
clean process, potential cleaning technology
new formation needs partic
of inhalable to be
ny (5). Due to these
equippedefforts, waste
with some incineration
of the in with
most recent emission-reduction respect to fine and ultrafine particle precipit
devices, such
ny nowadays represents a as wet scrubbers,
relatively cleanfabric dust filters, potential
process, absorbers, new Experimental
formationSectionof inhalable particles.
ed with some of or
theelectrostatic
most recent dustemission-reduction
precipitators (ESP). (A) Measurement of the Particle-Size Dis
However, the fine and ultrafine
s, such as wet scrubbers, fabric dust filters, absorbers, particle Experimental
precipitation Section aerosol in the waste gas of the inc
combustion
characteristics of most of the flue-gas cleaning devices are a scheme of which is shown in Figure 1,
trostatic dust precipitators (ESP). (A) Measurement ofitsthe Particle-Size Distribu
not yet characterized. Furthermore, the formation of particles regarding particle-size distribution using o
wever, the fine and ultrafine
in industrial scaleparticle
combustion precipitation combustion aerosol
processes itself is not yet well in the waste
sizing techniques. gas of measurement
The aerosol the incinerats
INTRODUCTION:

__________________________________________________________________________________________

Combustion
of
aerosols
in
model
systems
e.g.
laboratory
burners
[ref.
2.6
‐
.8]
has


been
much
studied,
whereas
little
or
no
detailed
data
is
available
on
the
properties
of
com­

bustion
aerosols
in
the
state
of
formation
from
industrial
incineration
plants
[ref.
2].
Aerosols

formed
of
industrial
combustion
exhibit
residence
times
in
the
tens
of
seconds
before
being

emitted.
This
allows
for
the
gas
and
the
particle
phases
to
interact
strongly.
Therefore,
a
dif‐

ferent
behaviour
as
compared
to
that
in
the
lab
settings
in
expected.

The
purpose
of
the
study
were
as
follows:

(1) Investigate
the
effect
of
process
control
measures
on
the
particle‐size
distribution

in

the
range
of
0.017
μm
‐
10
μm.

(2) Reinforce
and
encourage
the
presence
of
scrubbers

(3) The
consequence
of
alue‐gas
cleaning
methods/devices.
EXPERIMENTAL
INTRO:

__________________________________________________________________________________________

The
equipment
setup
is
comprised
of
an
aerodynamic
particle
sizer
(APS)
for
parti‐

cles
with
diameters
of
0.5
‐
30
μm,
a
scanning
mobility
particle
sizer
(SMPS)
for
diameters


of
0.017
‐
0.6
μm,
a
condensation
particle
counter,
a
home­made
sampling
system
[ref.
2]


and
heavy‐duty
statistics
in
the
processing
of
data.
{A
diagram
is
shown
below.}
 FIGURE 3. C
FIGURE 2. Particle sampling and measuring system: (a) scheme averaging dh a
of the on-line particle sampling and analysis system; (b) photograph size distribut
of the sampling and dilution system (1/10 000); and (c) photograph and after the
of the particle measurement unit in mobile rack. statistics, the
below 600 nm
sampling and analysis scheme as well as photographs of the drops drama
sampling system and the measurement cabinet are depicted
in Figure 2. 3b). In prac
The SMPS measures the mobility of charged aerosol by two instr
particles in a high voltage electric field. The mobility is in backup f
inversely proportional to the volume-equivalent diameter d
 The
APS
measures
the
volume
equivalent
diamater,
d,
whereas
the
SMPS
measures


the
aerodynamic
diameter,
dae,
a
slight
difference,
which
is
compensated
for
by
the
applica‐

tion
of
heavy‐duty
statistics.
An
overall
particle‐size
distribution
graph
is
shown
here:

FIGURE FIGURE
3. Combination
3. Combination ofofAPS
APS and SMPS
and SMPS data.
data. (a) Algorithm
(a) Algorithm for for
system: (a) scheme
ng and measuring system: (a) scheme averaging dh anddhdhand
averaging ae from idealized
dhae from SMPS
idealized SMPS and
and APSAPS
data.data. (b) Particle-
(b) Particle-
ystem; (b) photograph
ing and analysis system; (b) photograph
size distribution
size distributionfromfrom real measurements
real of SMPS
measurements of SMPS and APSandbefore
APS before
n system (1/10 000); and (c) photograph and after the combination of both spectra. Due to poor particle
); and (c) photograph
nt unit in mobile rack. and after the combination of both spectra. Due to poor particle
statistics, the SMPS measurements stopped at 650 nm. APS channels
ack. statistics, the
below 600 SMPS measurements
nm were rejected because stopped
the APSat 650 nm.
counting APS channels
efficiency
heme as well as photographs ofbelow the 600
drops nmdramatically
were rejected at thesebecause the APS counting efficiency
particle sizes.
measurement cabinet
photographs of theare depicted
drops dramatically at these particle sizes.
abinet are depicted 3b). In practice, one individual particle cannot be analyzed
the mobility ofThe
y‐axis
represents
number
of
particles
per
size
intervals.
Since
the
no.
of
particles
count­
charged aerosol by two instruments simultaneously as particles are trapped
age electric field. The mobility 3b).
is In in
practice,
backup filters, one and individual
the densityparticle
cannot be cannot
calculated be for
analyzed
ofthecharged
volume-equivalent
aerosol diameter d
ed
by
the
instrument
is
done
so
in
discrete
size
bins
with
varying
intervals
(logarithmically
in­
e APS measures the particle velocity
by two all sizes as the simultaneously
instruments overlapping range isassmall. Thus, are
particles some trapped
d. The mobility is
tream, which is a function ofin
assumptions have to be made about the particle population
thebackup filters, and the density cannot be calculated for
to achieve a solution for eq 1:
uivalent diameter dvelocimetry
creasing
with
diameter),
the
no.
per
size
bin
is
normalised
to
a
bin
width
(size
interval)
of
1

dae, by laser-scattering all sizes (1) as Thetheshape overlapping range is small. Thus, some
factor κ is assumed to be constant and
he particle velocity assumptions
close to 1have for allto be made
particles. The about the is
shape factor particle
defined as population
the
ata were combined according to a
μm
[ref.
author].
a function of the
d (15) into one single distribution to achieve a solution for eq 1:
ratio of the drag force on the particle and the drag force on
tering velocimetry
le density in the overlapping size an ideal sphere with identical properties. κ is 1 for water
ts and by calculating the geometric(1) The droplets shape
and close factor is assumed
κ atmospheric
to 1 for to be
particles constant
which have and
nnels.according to a
ned close to 1 for all particles. The shape factor is defined as the
undergone condensation processes. It deviates from 1 for
nm ofaggregates fibers (17).
ze range between 500 and 1000ratio
single distribution the dragand force on the particle and the drag force on
re the same particle population and (2) It is assumed that both instruments sample an identical
eenumber
overlapping an ideal
size However,
concentration. sphere with identical properties. κ is 1 for water
particle population, and therefore the measurement results
e plotted
ating thewithin droplets
the same diagram,
geometric in and close to
an identical 1 for atmospheric
concentration particles
in the overlapping which
range. In have
ping particle population appears undergonepractice, condensation
this assumption processes. It deviates
is met by carefully minimizingfrom the 1 for
erent diameters) due to the different sampling errors of both instruments and correction of the
nFrom
500the and 1000
shift nm
of the aggregates and fibers (17).
overlapping resulting data for transmission losses in the sampling lines
cle population
anges (see Figure 3a) andthe particle(2) Itand
is assumed
coincidence that both
errors instruments
using standard methodssample fromanlit-identical
ed as both diameters are related by
ntration. However, erature (18 ).
particle population, and therefore the measurement results
dthe
) ) same
F0dae2C(diagram,
dae)
(3) The number concentration graphs of both instruments
in(1)an identical concentration in the overlapping range. In
have to be monotonic. If data show peaks in the overlapping
opulation appears practice, this assumption is met by carefully minimizing the
 It
should
be
noted
that
aluctuations
in
the
combustion
conditions
gave
rise
to
aluctu‐

ations
in
the
measurements
of
the
particle
concentration
in
the
alue‐gas
duct
(std.
dev.
of


30%).

Apart
from
the
particle‐size
distribution,
the
chemical
composition
of
the
alue‐gas


was
also
analysed
(concentration
of
volatile
and
semi‐volatile
organic
compounds
or
VOC's


and
SVOC's)
[ref.
2.20,
.21
for
further
details].
 EXPERIMENTAL
MAIN:

__________________________________________________________________________________________

Typical
particle‐size
distribution
is
shown
here,
data
was
collected
from
the
700
...


(2)
(2)
(3)
N (3)
mum of SMPS)
mum of of
minimum APS).
SMPS)
m eq 1 for
maximum the
of APS).
.from
Assuming Fj tothe
eq 1 for
hAPS
d ae. Assuming
size range, Fj to
the APS size
channels andrange,
a
(Figure 3b). For a
PS channels and
edSMPS
he (Figure 3b). For
system
of the SMPS system
ize-distribution
e size-distribution
tition frequency
epetition
recorded frequency
every
um recorded every
SMPS data, nine
nd SMPS data, nine
btain the same
o obtain the same
S.
datedby bymeansmeans of of
ied particle-size
rtified particle-size
eres, DuSkceiSecniteinfitcific
s, D u k e
lngeern rarto(Model
aeto r (Model FIGURE
FIGURE4.4. Change
Changeof of particle-size distributionupon
particle-size distribution uponthe
thetravel
travel
of of
biasbias
ent of the
of thetwo two thetheflue
fluegas
gasthrough
through thethe boiler section ofof the
boiler section theincinerator
incineratorplant.
plant.
w
elow 10%.10%. Due Dueto to Particle-size distribution measured in the flue gas (a) at 700 °C°C
Particle-size distribution measured in the flue gas (a) at 700
enduring
during normal
normal (above)
(above)andand(b) 300 °C
(b)atat300 °C (below).
(below).
entration in in
ncentration thethe
dard deviation
d deviation 30- 30- wasperformed
was performed via via external
external calibration.
calibration. The TheVOCsVOCswere were
oughly
hly an an order
order of of analyzed by th e r m al d e so r pt io n
analyzed by thermal desorption gas chromatography-m ga s ch r o m ato gr a ph y - m assass
spsepcetcrtormetertyry(TD-GC/MS,
om (TD-GC/MS, Perkin-Elmer
Perkin-Elmer ATD ATD400 400thermal
thermal
to desorption unit coupled to a HP 5890 series II-GC with a SSQ
hethe particle-size
particle-size desorption unit coupled to a HP 5890 series II-GC with a SSQ
position (aromatic 7000/Varian 3400/ITS 40 tracker as mass-selective
7000/Varian 3400/ITS 40 tracker as mass-selective detector). detector).
ition (aromatic
pling points along
ng points along
Forfurther
For furtherdetails
details of of the
the analytical
analytical procedures
proceduressee refs2020
seerefs
g of volatile organic and 21. All flue-gas concentrations are given with respect to
volatile organic and 21. All flue-gas concentrations are given with respect to
normalized conditions (dry flue gas, 273 K, 1013 hPa, and 11
...
and
300
oC
points
in
the
alue‐stack.
A
broad
maximum
at
0.08
μm
can
be
seen
in
aigure
4a,

the
max.
at
0.04
μm
was
unstable
and
is
to
be
excluded.
The
max.
in
aigure
4b
(300
oC,
end


of
boiler)
is
larger,
it
is
at
0.14
μm.
The
enlargement
of
particles
further
in
the
bolier
sug‐

gests
a
reactive
relation
of
gas
phase
species
and
coagulation
processes
[ref.
2].

Chemical
composition:
The
concentration
of
major
gas‐phase
chemical
species
de‐

creases
further
up
the
alue‐gas
duct
(800
‐
300
oC)
due
to
condensation
and
chemical
bond‐

ing
[ref.
2.24
‐
.27].

This
can
shed

much
light
on
the
dynamics
of
particle
growth
in
the


alue‐gas
chamber.

Figure
5
depicts
the
concentrations
of
some
detected
aromatic
compounds
as
they


vary
with
temperature.
At
1100
oC,
the
concentration
seem
to
be
commonly
low;
this
may


be
explained
by
thermal
decomposition
(high
rate)
and
oxidation
by
the
residual
oxygen.
At

lower
temperatures,
formation
reactions
overtake
the
rate
of
decomposition
and
so
the


concentration
rises.
Evaluation
of
the
600
‐
200
oC
range
is
quite
complex
[ref.
2];
more
im‐

portantly,
ultra‐trace
compounds
of
the
highly
toxic
poly‐chlorinated
dibenzo‐p‐dioxins
/
‐

furans
(PCDD/F)
is
detected.
 trations of several aromatic flue-gas constituents along the flue-gas duct. The highest concentrations

s the coagulation, however, is TABLE 1: Concentrations [ng/Nm3] of Several Aromatic

e small particles are consumed Flue-Gas Constituents along the Flue-Gas Ducta
diffusion coefficient.
and coagulation effects have sampling temperature
based flame experiments (see, compound 1100 °C 800 °C 600 °C 400 °C 200 °C
In case of laboratory flames,
of flame and waste-gas con- benzene 1952 71230 30532 27454 2388
nd time scale and so does the toluene 242 2832 5541 2233 269
o -xylene 57 1607 2854 376 4
ticles, whereas the cooling of naphthalene 355 23009 57384 22642 1965
mperatures down to ambient biphenyl 31 131 212 21 18
line of the waste incineration dibenzofuran 1 799 1440 32 22
seconds. diobenzo- p -dioxin 1 85 314 9 5
the concentration of the major phenanthrene 93 11474 2438 6991 1240
the raw gas tends to decrease pyrene 10 7662 3550 4336 634
ue-gas duct (800-300 °C) (24- chrysene 2 37 1223 792 123
sumption of gas-phase species benzo[ b ]fluoranthene 5 43 1358 559 59
benzo[ a ]pyrene 9 33 1165 18 23
to condensation and chemical
benzo[ g,h,i]perylene 3 57 1954 453 48
se concentration of organic
a Sa m pling te m peratures w ere 1100 °C, 800 °C, 600 °C, 400 °C, and
meter for understanding the
n the flue-gas channel. There- 200 °C.
cle-size distribution the con-
nt aromatic species along the peratures, e.g. in the flame zone (28), the very high decom-
igated too. Larger aliphatic position rates are limiting the surviving concentration of
y a significant role because of complex organic molecules. However, when approaching
emperatures, while the small lower temperatures, the concentration of all investigated
ndensed on particles at these compounds increases considerably reaching maximum
aken at five different positions concentrations at 800 or 600 °C. In this temperature range,
ampling temperatures of 1100 the formation reactions dominate over decomposition reac-
zzles), 800 °C (first draw of tions. The results given in Table 1 and depicted in Figure 5
(second draw of combustion show that the concentrations of gas-phase species are
/economizer), and 200 °C (inlet decreasing again with further decreasing temperatures. This
e 5, the spatial course of the is in line with results from preceding investigations (24-27)
matic species in the flue-gas and the conclusions drawn from the particle-size changes
epresent the average of three during the travel of the flue gas through the duct. An increased
a at 1100 °C which result from reactive gas- to particle-phase transfer rate is expected in
this temperature range, and larger PAH structures as well as
nic gas-phase species is rela- inorganic compounds begin to condense onto particles with
temperature supports thermal decreasing temperature.
ell as oxidation by the residual The chemical processes taking place on the particles
as. Although the formation of between 600 and 200 °C are of particular complexity. For
takes place at very high tem- example, an increase of certain chlorinated ultratrace

V O L. 37, N O . 20, 2003 / E N VIR O N M E N T A L S CIE N C E & T E C H N O L O G Y 9

FIGURE 5. Course of the concentrations of several aromatic flue-gas constituents along the flue-gas duct. The highest concentrations
FIGURE 5. Course of the concentrations of several aromatic flue-gas constituents along the flue-gas duct. The highest concentrations
are observedareforobserved
800 orfor
600800°C.
or 600 °C.

and coagulation processes.

and coagulation As theAscoagulation,
processes. the coagulation, however,
however, isis
TABLE
TABLE 1: Concentrations
1: Concentrations [ng/Nm3] [ng/Nm 3] Aromatic
of Several ofa Several Aromatic
a diffusion-driven
a diffusion-driven process,process, the small
the small particles
particles areare consumed
consumed Flue-Gas Constituents along the Flue-Gas Duct
first because of their higher diffusion coefficient. Flue-Gas Constituents along the Flue-Gas Ducta
first because of their higher diffusion coefficient. sampling temperature
Comparable condensation and coagulation effects have
Comparable condensation and coagulation effects have sampling temperature
been observed in laboratory-based flame experiments (see, compound 1100 °C 800 °C 600 °C 400 °C 200 °C
been observed in laboratory-based
for example, refs 8 and 23). Inflame experiments
case of (see,
laboratory flames, compound 1100 °C 800 °C 600 °C 400 °C 200 °C
for example, refs 8significant
however, and 23).cooling
In case of laboratory
of flame and waste-gasflames,
con- benzene 1952 71230 30532 27454 2388
stituents occurs on a subsecond toluene
benzene 242 2832 5541
1952 71230223330532
269 27454 2388
however, significant cooling of flametime and scale and so doescon-
waste-gas the
o -xylene 57 1607 2854 376 4
correlated growth of soot particles, whereas the cooling of toluene 242 2832 5541 2233 269
 Process
control:
Changes
in
combustion
conditions
can
cause
drastic,
dynamic


changes
in
the
composition
of
the
alue‐gas
[ref.
2.38
‐
.40].
The
impact
of
using
the
back‐up


oil
burners
and
cleaning
of
the
grate
with
pressurised
air
is
cited
here.
Reasons:
the
oil


burners
are
expected
to
affect
soot
and
organic
compound
particles
(very
small
particles)


and
residual
mineral
particles
(larger
particles)
by
the
cleaning.

The
effects
of
Viring
up

the
back‐up
oil
burners
are
presented
here:

FIGURE 6. FIGURE
Influence of6. Influence
the back-up of the
oil burners at theback-up oil burners
flue-gas measuring point at 700at
°C:the flue-gasdistribution
(a) particle-size measuring at 700 °C: (a) particle
pointswitched
with burners
on (above)on
and (above) and(b)off
off (below) and (below)
3D plot and course
of the temporal (b) 3Dof the
plot of the distribution.
particle-size temporal course of the particle-size distributi
compounds in this temperature range is observed. This conditions (38-40). As gas-phase species represent the
includes compounds in
highly toxic polychlorinatedthis temperature
dibenzo- p-dioxins/- range
feedstockis observed.
for particle formationThis effects (38-40). A
conditions
and growth, transient
furans (PCDD/F or dioxins). However, as carbonaceous are assumed to have a major impact on the particle-size
includes
particulate highly
matter has been toxic
identified polychlorinated
to play a major role dibenzo-
spectrum p-dioxins/-
too. In this work two types of transientfeedstock
processes for particle for
furans (PCDD/F or dioxins). However,
in the PCDD/F formation pathways (de novo-synthesis
30)), primary measures for particle reduction in the flue gas
( 29, were as carbonaceous
investigated, the influence of the oil are assumed
burner
particle-size spectrum of the flue gas and the effects of the
on the to have a
particulate matter has been
may also be motivated by their potential impact on PCDD/F identified to play a major role spectrum
grate cleaning with pressurized air. These two cases were too. In this w
abatement.in the PCDD/F formation pathwaysfractions (de novo-synthesis
selected because they are (29,
suspected of were investigated, the
influencing
of the aerosol. While the oil burner is likely
different
A deeper understanding of the chemical processes oc-
curring on30the)), primary
particles measures
will require a chemicalfor particle reduction
characteriza- influencing the insootthe flueand
particles gasorganic gas-phase
particle-size
con- spectrum
may also be motivated by their potential
tion of the particle ensemble on a single-particle basis. Up impact on PCDD/F
stituents (i.e. the very small particles) the grate cleaning with pre
cleaning
grate should predominantly increase the amount of resus-
of the
to now, such information is only accessible by on-line aerosol
abatement.
laser mass spectrometry, which enables a simultaneous size selected because they a
pended mineral particles (i.e. the larger particles).
 The
burners
are
used
during
the
starup
and
shutdown
of
the
waste
incineration
process,


and
during
instabilities
in
combustion
conditions
(e.g.
temperature
drop
below
850
oC).
A


new
stable
max.
at
0.04
μm
can
be
clearly
seen,
this
was
not
seen
before.
The
particles
are


most
likely
soot;
even
though,
most
of
the
particles
shall
coagulate
during
their
travel
fur‐

ther
through
the
chamber,
this
whole
scenario
is
of
concern
since
the
formation
of
PCDD/

F's
is
inaluenced
by
carbonaceous
particles
[ref.
2].

Figure
7
shows
the
result
of
pneumatic
cleaning
of
the
grate
on
the
particle‐size


distribution.

FIGURE 7. Effect of cleaning-flap

FIGURE operation
7. Effect of cleaning-flap to remove
operation the the
to remove ashes from
ashes fromthe grateonon
the grate particle-size
particle-size distribution
distribution (APS) at (APS) at the
the flue-gas flue-gas measuring
measuring
point at 300 °C:point
(a)atAPS spectra
300 °C: (a) APSatspectra
normal operation
at normal (b, (b,
operation green)
green)and
andduring flapoperation
during flap operation ([,and
([, red) red)(b)and (b) of3Dtheplot
3D plot of thecourse
temporal temporal course
of the particle-size distribution.
of the particle-size distribution.
of fine dust particles which may be predominantly composed Precipitator) and Possible Regeneration of Ultrafine Par-
of fine dust particles which may be predominantly composed
of inorganic material. They are periodically reintroduced into
Precipitator) and Possible Regeneration of Ultrafine Par-
ticles in the Stack. In the previous section, the effect of
of inorganic material. Theychamber
the combustion are periodically
by openingreintroduced into
the cleaning flaps and ticles in the Stack.
primary process control In the previous
measures on the section,
particle-sizethe effect of
the combustion chamber
blowing by opening
pressurized air throughthethemcleaning
from theflaps
ash-binand
side primary
distributionprocess
of the fluecontrol
gas was measures
considered. The on particle
the particle-size
of the grating
blowing pressurized (see Figure
air through them1). This
fromcleaning procedure
the ash-bin sideis emission of industrial
distribution of the combustion
flue gas was plants, however, also
considered. The particle
performed every 30 min for a time span of approximately 20 depends on the so-called secondary flue-gas cleaning
of the grating (see Figure 1). This cleaning procedure
s. The increased air flow induced by the cleaning procedure
is emission of industrial combustion plants,
measures such as wet scrubbers, fabric filters, or electrostatic
however, also
performed every 30 min for a time span of approximately
may also discharge additional particles from the fuel bed. 20 depends on the so-called secondary
dust precipitators. With respect to the health relevance of flue-gas cleaning
s. The increased
Duringairthis
flow induced
cleaning by the
procedure, cleaning
a very procedure
different particle-size measures such as wet
inhalable particulate matterscrubbers, fabricimportant
it is particularly filters, ortoelectrostatic
distribution
may also discharge was observed.
additional The reintroduced
particles from the particles
fuel bed. are evaluate
dust flue-gas cleaning
precipitators. measures
With regarding
respect to thethehealth
efficiencyrelevance of
much larger than newly formed soot particles as demon- of fine and ultrafine particulate matter precipitation. The
During this cleaning procedure, a very different particle-size
strated in Figure 7. This is consistent with the assumption
inhalable particulate matter it is particularly
actual design of flue-gas cleaning devices is optimized for
important to
distribution that
waspredominantly
observed. The agedreintroduced
mineral particlesparticles are
are additionally evaluate flue-gas cleaning measures
the precipitation of particulate mass which is not anregarding the efficiency
much larger released.
than newly Because formed soot
of the very particles
short as demon-
cleaning procedure only of fine and
appropriate ultrafine
measure particulate
for the efficiency of matter precipitation. The
fine and ultrafine
APS spectra
strated in Figure 7. This(sizeisdistribution
consistent above
with1 µm)
thecould be obtained,
assumption particle removal.
actual design Within this study
of flue-gas the particular
cleaning case is
devices of the
optimized for
since one SMPS scan lasts 90 s. Figure 7a shows the particle- wet electrostatic dust precipitator is considered. The entire
that predominantly aged mineral particles are additionally
size distribution obtained by the APS during normal operation
the precipitation of particulate mass
flue-gas cleaning system of the investigated MWI plant
which is not an
released. Because
(b) as wellthe
of very the
as during short cleaning
cleaning procedure
procedure only
([). During the appropriate measure for the efficiency of
consists of a spray absorbing unit (slurry of active carbon/ fine and ultrafine
The
aine
dust
particle,
which
comprise
the
large
amounts
of
ash
loosed,
causes
a
rise
in


multiple
orders
of
magnitude.
The
graph
on
the
right
shows
the
live
changes
as
the
cleaning

is
paused
and
resumed.

Wet
ESP
in
the
stack
chamber:
beneait
of
a
wet
electro‐static
dust
precipitator.
A


signiaicant
reduction
in
particulate
matter
is
seen,
though
it
in
not
uniform:
two
orders
of


magnitude
lesser
around
the
0.1
μm
diameter
and
one
from
0.017
to
0.07
μm.
shift of the size-dist
The high efficiency
of fine particles can
of the wet-ESP (swi
electrode). In Figur
typically measured
ESP is shown. It ca
precipitates fine an
approximately 0.05
magnitude is visib
particle diameter o
slightly weaker. In F
on the wet-ESP on
plot of a 48 min
measurement sequ
was deactivated tw
some 10 s. The graph
gained by the APS.
It
can
be
seen
that
the
w‐ESP
is
quite
effective
down
to
0.05
μm,
causing
a
reduction
of
one

In Figure 9a, two
order
of
magnitude;
it
effectiveness
drops
off
below
0.05
μm. the stack gas with ac
(i.e. over 80% of the
one depicted in the
ized by a broad ma
drastically altered
casionally. In these
creased concentrati
present. The typica
ranges from several
size distribution du
upper graph of Figu
ultrafine particle re
magnitude.
At the lower si
equipment (17 nm
 particlediameter
particle diameteroo
slightlyweaker.
slightly weaker.In InF
on the wet-ESP
on the wet-ESP on on
plot of
plot of aa 4848 min
min
measurementsequ
measurement sequ
was deactivated
was deactivated tw tw
some 10 s. The
some 10 s. The graph grap
gained by
gained by the
the APS.
APS
InFigure
In Figure9a, 9a,two
tw
thestack
the stackgas
gaswith
withac a
(i.e.over
(i.e. over80%
80%of ofthe
the
one depicted
one depicted in the in the
ized by
ized by aa broad
broad ma ma
drastically altered
drastically altered
casionally. In
casionally. In these
thes
creased concentrat
creased concentrat
present. The
present. The typica
typic
rangesfrom
ranges fromseveral
severa
size distribution
size distribution du du
upper graph
upper graph of Figuof Fig
ultrafine particle
ultrafine particle re r
magnitude.
magnitude.
At the
At the lower
lower ss
equipment (17
equipment (17 nm
nm
FIGURE8.8. Effects
Effectsofofshutting
shuttingdown
downthe thewet
wetelectrostatic
electrostaticprecipitator
precipitator concentration
concentration withwith
FIGURE
(ESP) onon particle-size
particle-size distribution:
distribution: (a)(a) particle-size
particle-size distribution
distribution inin small particles
small particles in
in gg
(ESP)
the stack gas (80 °C) with ESP operating (b, green) and ESP shut gas- to
gas- to particle-pha
particle-ph
the stack gas (80 °C) with ESP operating (b, green) and ESP shut
off ([,
off ([, red)
red) and
and (b)
(b) 3D
3D plot
plot of
of the
the temporal
temporal course
course ofof the
the particle-
particle- centrations of
centrations of ultra
ultra
size distribution
size distribution in
in the
the APS
APS range.
range. with new formation
with new formation

As
before,
the
real‐time
stark
contrast
between
ESP‐on
and
ESP‐off
can
be
seen.

Inadvertently
promoting
ultra­Mine
particles
(UFP):
Fine
particles
serve
as
nucle‐

ation
sites,
which
are
removed
by
the
w‐ESP,
and
so
in
the
absence
of
potential
coagulation


partners,
the
consequence
is
an
increased
lifetime
of
the
newly
generated
UFP
[ref.
2,
.42].
IN
THE
END:

__________________________________________________________________________________________

The
study
proves
the
sensitivity
of
particle
concentration
and
size
proaile
to
process


control
measures,
combustion
conditions
and
so
on.
And
so,
process‐integrated
and
alue‐

gas
cleaning
methods
need
reainement
in
order
to
periodically
exacerbate
UFP.

_________________________________________________________________________________________________________

_________________________________________________________________________________________________________
[ref. 1]: Peller, Wiest, and Kamat, Environ. Sci. Technol. 2003, 37, pg 1926
[ref. 2]: Maguhn, Karg, Kettrup and Zimmermann, Environ. Sci. Technol. 2003, 37, pg 4761