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Ultrasonics Sonochemistry
journal homepage: www . elsevier . com/locate/ultson
a,
School of Urban and Environmental Engineering, Ulsan National Institute of Science and Technology (UNIST), Ulsan 44919, Republic of Korea
School of Applied Biosciences, Kyungpook National University, Daegu 41566, Republic of Korea
article info
Article history:
Received 8 February 2016
Received in revised form 22 April 2016 Accepted 22 April 2016
Available online 23 April 2016
Keywords:
Sludge
PAHs
Ultrasonic treatment
Sonication
Leaching
comp
ound
s, and
carbo
1. Introduction
hydra
tes
Sludge is generally produced from[2]. It
wastewater treatment pro-cesses, andalso
its amount has increased with the rapid conta
growth of industrialization andins
urbanization [1]. Sludge contains high tracelevel
frac-tions of water and solids
toxic
containing microorganisms and their
organ
extracellular polymeric substances
ic
(EPS) such as proteins, humic
chem
abstrac
t
Ultrasonic
treatment for
sludge
reduction in
wastewater
treatment
plants
(WWTPs) can
substantially
affect the fate
of
trace
pollutants.
However, their
fates in the
different
phases
of
sludge
and
mass balances
have
rarely
been reported.
In this study,
wastewater
sludge
samples were
ultrasonicated
at 600 W for
16
[12],
ultrasonic
treatment [8],
Correspond
ing author.
E-mail
address:
sdchoi@unist.ac.kr
(S.-D. Choi).
h
t
t
p
:
//dx.doi.org/
10.1016/j.ul
tsonch.2016
.04.027
1350-4177/
2016
Elsevier
B.V. All
rights
reserved.
of
anddewaterability
sludge
can
be
microwave treatment [16].
improved
[17],
Among them, ultrasonic
resulting in cost
treatment has been used
reduction for the
widely because of its
final dis-posal of
relatively low processing
sludge
through
cost and high effi-ciency of
landfilling,
reduction [1720].
incineration,
and
ocean
dump-ing.
Sludge reduction afterPreviously, studies
ultrasonic treatment ishave been carried
based
on
ultra-soundout to find optimum
cavitation
phenomenonprocessing
that
destroysconditions for high
microorganism flocs andremoval efficiencies
sludge.
For
microbial
cell
wallsof
both
[1,20,21].
Ultrasonicexample,
pretreatment can enhanceultrasonic irradiation
not only direct reduction oftime and intensity
sludge, but also digestionsignificantly
removal
of biosolids in sludgeimprove
of
[22].
Furthermore,efficiencies
o-flotation
highpress
ure
homo
geniz
ation
[13],
ozon
e
treat
ment
[8],
electr
ochem
ical
treat
ment
[14],
electr
[15],
sludge [21,23,24].
Studies
have
shown that PAHs in
water
[25,26] and
62
pore
size,
Whatman,
England). Note that there
were suspended solids in the
supernatant
even
after
centrifugation.
Before
extrac-tion,
surrogate
standards (100 ng each of
naphthalene-d8,
acenaphthene-d10,
phenanthrene-d10, chrisened12, and perylene-d12) were
added to all the samples.
The
PAHs
in
the
dissolved phase of the
supernatant (i.e., filtrate)
were liquidliquid extracted
for 10 min with 100 mL of a
mixed
solvent
(dichloromethane:methanol
= 9:1, v/v). This extraction
procedure was repeated three
times. The extract was
concentrated to 5 mL by a
Turbo Vap II (Biotage,
Sweden) and cleaned up
using a column consisting of
10 g of anhydrous sodium
sulfate (Na2SO4) to remove
moisture from the samples.
Finally, the samples were
con-centrated to 1 mL by a
nitrogen evaporator (MGS2200, Eyela, Japan).
The
PAHs
in
the
particulate phase of the
supernatant (i.e., GFF) were
extracted using 20 mL of nhexane/acetone (9:1, v/v)
mixture in an ultrasonic bath
operated for 15 min. This
was repeated three times.
The extract was concentrated
to 5 mL by the Turbo Vap II
and purified using a column
consisting of 5 g each of
silica gel and Na2SO4 with
60
mL
of
dichloromethane/hexane
(1:1, v/v). Finally, the
purified
samples
were
concentrated to 1 mL by the
nitrogen evaporator.
For the analysis of the
PAHs in the sludge sediment,
0.5 g of dried samples were
mixed with 2 g of Na2SO4
and then Soxhlet extracted
for 20 h with 350 mL of nhexane/acetone (9:1, v/v).
The extract was concentrated
to 5 mL by the Turbo Vap II
and cleaned up using a silica
gel column with 2 g of
Na2SO4, 2 g of alu-mina, 5 g
of activated silica gel, and 2
g of Na2SO4. The samples
were eluted with 120 mL of
detection
limits
were
represented as non-detects
(ND).
63
microorganisms
[30], resulting in an
increased soluble chemical oxygen
demand (SCOD) [31].
The levels of TSS and VSS decreased
as the ultrasonic irradiation time increased
20
Concentration (g/L)
25
15
10
treatment [30].
from petroleum
[36].
Therefore, the high fraction
of Nap in the sludge sample
seems to be related directly
to
the
production
of
terephtha-late
and
its
isomers.
PAHs, Sweden: 3
The concentration of 16
PAHs in the dissolved phase
of the supernatant increased
almost twofold after 15 min,
and then it decreased and
The
reasons
for
the
unexpected decrease of 16
PAHs in the dis-solved phase
after
20
min
of
ultrasonication are suggested
as fol-lows. First, an abrupt
elution of biomaterials from
disintegrated microbial cells
may
have
induced
a
migration of dissolved PAHs
into the particulate phase,
i.e., less soluble biomaterials
could act as the adsorption
media. Second, a sampling
artifact for dissolved
(a)
64
(b)
Nap Acy
Ace Flu Phe
Ant Flt Pyr
BaA Chr
BbF BkF
BaP Ind
DahA BghiP
t major distribution
r pattern of the PAHs
e in the sed-iment.
PAHs may exist.a For the PAHs in the
The pores of thet supernatant (both in
GFFs seemed tomthe dissolved and
become
cloggede particulate phases),
with microbial celln Nap accounted for
debris
as
thet more than 50% of
sonication
time the 16 PAHs, and
increased.
There-d increasing trends of
fore, the passage ofi Nap clearly were
dissolved
PAHsd observed
with
through the filter increased sonication
may have beenn
time ( Fig. 3a and
hindered by cello
t
debris accumulation b). The PAHs with
three rings also
on the filter. Note
showed
similar
s
that the decreasing
patterns to those of
i
trend of TSS with
Nap. This result
increased sonicationg
n indicates that light
time ( Fig. 1) isi and more water
opposite to the timef soluble PAHs were
trend of particulatei dominantly released
- to the liquid phase
PAHs ( Fig. 3b).
c from the solid phase
The fractions ofa of
sludge. The
PAHs with differentn fractions of 2-, 3-,
ring numbers cant and 4-ring PAHs
give insight intol increased until 15
how
the
PAHsy min, whereas 5- and
behaved
after 6-ring
PAHs
ultrasonic treatment.a generally decreased
The fractions off in the dissolved
PAHs
in
thef phase, except at 15
sediment
weree min. It seems that
constant during thec heavier PAHs (those
dif-fering sonicationt with five and six
times (030 min) rings) with higher
and dominated by 3-t
KOW values in the
and 5-ring PAHs (h dissolved
phase
Fig. 3c), implyinge quickly
were
that
ultrasonic adsorbed
to
mixture
(1:49, v/v);
3.4. Mass balance of PAHs
ultrasonic
treatment at
The amounts and mass600 W for 0,
fractions of the 16 PAHs for10, and 20
and
each phase of the sediment andmin;
the dissolved and particulateinitial
phases of the supernatant are concentratio
ns
of
shown in Figs. S2 and 4,individual
respectively. The amounts ofPAH
PAHs in each phase werestandards of
ng/L
calculated by multiplying the100
1.6
concen-trations of PAHs by the(i.e.,
volumes of each phase. Thelg/L in total,
is
decreasing trend of PAHwhich
to
amounts in the sediment was similar
clearly observed. Whereas thethe level of
amounts of PAHs in the16 PAHs in
particulate phase of thethe
supernatant increased withdissolved
sonication time, those in thephase of the
dissolved phase decreased aftersupernatant)
Other
20 min. As the total amounts of.
PAHs in the sludge samplesexperimenta
were rather constant regardlessl conditions
the
of sonication time (one-waywere
same
as
ANOVA, p > 0.05) with a
those of the
relative standard deviation of
sludge
4% ( Fig. S2d), it seems that samples.
there was no significantAccording
sonodegradation of PAHs.to the result
this
Therefore, we assumed thatof
some of the PAHs in the sed- degradation
iment simply moved to theexper-iment
(n = 3),
supernatant.
there was no
statistical
difference in
To
confirm
this
assumption, we conducted antotal ( 16
additional experiment forPAHs) and
degradation of PAHs by usingindividual
500 mL of an acetone:water concentratio
ns after the
different
sonication
times (oneway
ANOVA, p
>
0.05).
Namely, no
discernible
degrada-tion
of the PAHs
was
observed
during
ultrasonic
treatment,
even
if
sonodegrada
tion
occurred.
This
result
contrasts
those
in
previous
studies
[2527] that
reported
high
removal
efficiencies
of
PAHs
(>90%) in
water
or
wastewater
with
increased
sonication
time (up to
150
min).
The
100%
80%
60%
40%
20%
0%
0
(g/L)
15
12
5 rings 6 rings
Fraction
Concentratio
n (g/L)
65
10
20
30
1
0
8
0
Concentration
9
6
3
0
0
(c) Sediment
3.0
10
Fraction
15
60%
40%
20%
0%
Concentration (g/g)
100%
2.4
1.8
1.2
0.6
0.0
0
20
25
30
Fraction
80%
60%
40%
20%
0%
5
10
15
20
25
30
Time (min)
100%
Fraction
80%
60%
40%
10
15
20
25
30
Time (min)
Sediment
l
e
d
p
s
t
u
d
i
e
s
c
h
h
i
g
h
e
w r
Time (min)
e (
r a
F
i
e p
p
m r
u o
o
u
s
s
t
u
d
i
e
s
w
att
ern
o
f
Fig. 5.
Mass
balances
Supernatant
(i.e.,
Dissolved relative
fractions
phase
among the
(5.9%)
three
phases) of
the 16
Sediment
PAHs in
the sludge
samples
before and
30 min
Before ultrasonic
treatment
after
ultrasonic
treatment.
66
[8]
C. Bougrier, C.
Albasi, J.P. Delgens, H.
Carrre, Effect of ultrasonic,
4. Conclusions
In this study, we first reported the
overall fate of PAHs in sludge after
ultrasonic treatment by separately
analyzing PAHs in each phase of sludge.
The ultrasonication resulted in an increase
and a decrease of PAHs in the supernatant
and sludge sediment, respec-tively. The
temporal change of the levels and patterns
of PAHs caused by sonication suggested
that light and more water soluble PAHs
were released preferentially to the
supernatant until the full disintegration of
the microorganisms occurred. In contrast,
heavy and more hydrophobic PAHs were
bound strongly to particles and mainly
leached after the substantial disintegration
of the microorganisms.
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This work was supported by research
funds of UNIST (1.110052.01) and the
National Research Foundation of Korea
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