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SONOCHEMISTRY

ELSEVIER Ultrasonics Sonochemistry 4 (1997) 153 156

An investigation into the ultrasonic treatment of polluted solids

A.P. Newman, J.P. Lorimer, T.J. Mason *, K . R . H u t t
School of Natural and Environmental Sciences, Coventry University, Coventry, CV1 5FB, UK
Received 15 October 1996

Abstract

Granular pieces of brick impregnated with copper oxide were used as a model for contaminated soil. Washing this model
substrate by passing water across the substrate on an ultrasonically shaken tray irradiation afforded a 40% reduction in copper
content. This was compared with only a 6% reduction when the sample was treated under otherwise identical conditions but using
a tray shaken conventionally. The majority of the copper was removed as a result of the removal of surface materials which were
more heavily contaminated with the copper oxide. © 1997 Elsevier Science B.V.

Keywords: Ultrasound; Soil washing; Decontamination

1. Introduction which tend to be attached to coarser sand and gravel

The utilisation of ultrasound for the treatment of
waste materials is a growing area of sonochemical
research. The majority of this work has been confined
to small scale studies and although some work has been
carried out in areas such as sludge dewatering and
filtration [1-5], the most widely researched area of
'environmental sonochemistry' has been the destruction
of organics in aqueous solution. However, the develop-
ment and availability of ultrasonic apparatus capable of
sonicating relatively large volumes of slurry has allowed
for more extensive investigations to be performed in the
area of solid waste treatment.
As yet, no significant work involving the ultrasonic
treatment of waste solids has been carried out in the
UK, but some trial work has been performed in the
USA by Fairbanks et al. [6]. It was found that ultra-
sound was able to enhance a precious metal recovery
process in several ways. Firstly the cleaning action of
ultrasound removed an unwanted clay coating from raw
ore, and this gave rise to the secondary affects of
accelerated leaching of minerals from the ore and
improved filtration rates.
Conventional soil washing processes are based on the
principle that m a n y pollutants adsorb onto the fine
fractions of soil such as silt, clay and humic matter
* Corresponding author. E-mail: 077@coventry.ac.uk; fax: + 4 4 1203
838173.
particles which make up the majority of the soil content.
Therefore the primary aim in soil washing is to separate
these fine components from the bulk soil. Isolation of
the fine materials will result in a 'concentrated' volume
of polluted soil which may be treated or disposed of,
and a large volume of residual soil which requires
relatively little treatment and can be returned to the site
as back fill. In this study we examine the use of
ultrasound as a means of soil washing wherein the
abrasive action of ultrasound in a heterogeneous envi-
ronment is harnessed to separate the different fractions
of soil.
The efficiency of a soil washing process can be
expressed in terms of both the volume reduction attained
and to what degree the clean fraction meets specified
clean-up standards.
2. Experimental
Soil washing is itself an innovative land treatment
technique enjoying success in the Netherlands, Germany
and the U.S.A. [7-10]. As this was a relatively new area
of research all experimental parameters were kept as
uniform as possible in our experiments. The bulk soil
was represented by crushed house brick sieved to 2-5
m m and the fine particulate parts of the soil which are
normally attached to the coarse fraction were repre-
sented by the surface of the brick pieces. The 'pollutant'

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154 A.P. Newman et aL / Ultrasonics Sonochemistry 4 (1997) 153-156
introduced to the crushed brick was copper oxide pro-
duced by impregnation with aqueous copper sulphate,
treatment with sodium hydroxide followed by washing
and drying. Analysis of copper content in the detached
sample was relatively simple using Atomic Absorption
(AA) and Inductively Coupled Plasma (ICP-AES).
Sonication of the brick pieces was achieved using
an ultrasonic vibrating tray. This piece of apparatus
consists of a stainless steel tray (surface area 21.5 cm x 58
cm) the base of which is fitted with a 20 kHz magneto-
strictive ultrasonic transducer such that sound nodes
and anti-nodes are generated in a standing wave pattern
along the surface of the tray. The most intense area of
ultrasound will be produced directly above the trans-
ducer where it is welded to the tray with the ultrasonic
field weakening towards the extreme ends.
The 'standard' conditions used as a comparison with
conventional technology comprised of a steel tray of
equal dimensions to that used under ultrasonic condi-
tions which was attached to a sieve shaker as the source
of agitation. The experimental set-up is as shown in
Fig. 1, de-ionised water was passed over the tray contain-
ing 750 g of copper contaminated brick. Gentle mechan-
ical mixing during sonication ensured that all the brick
pieces had some exposure to the most intense area of
ultrasound in the centre of the tray. The resulting
particle rich wash water was collected and underwent
centrifugation to separate out the brick fines. The brick
remaining in the tray was wet sieved at 20 mesh to
collect particles under this size which was considered as
detached particulates. The remaining brick pieces, the
majority of the sample, were retained for analysis.
All of the different brick fractions were dried, ground
(where appropriate) and subjected to microwave diges-
tion. The resulting solutions along with the wash water
were analysed for copper content by AA.
1._~.__constanthead
device
---1 shakingtray
ing device
/ as acoustic streaming can result in inter-particle colli-
pump . ~
[ ~...wash
reservoir . "~-- water
ofwater.
Fig. 1. Experimental apparatus for soil washing.
3. Results and discussion
3.1. Copper removal
Analysis of the brick pieces before and after 30 min
sonication revealed an average reduction in copper
content of some 40% (Table la and lb). Under conven-
tional shaking for 30 min the corresponding figure was
only 6% (Table 2a and 2b).
3.2. Mass balance
Having established the extent of copper loss from the
brick pieces it was important to be able to demonstrate
a mass balance relating to the removal of copper from
the bulk brick pieces and the quantities identified in the
> 20 micron particulate material, fines and water given
by:
Cu(on brick before treatmentl--CU(on brick after treatment)
= Cu(on fines) Jr- Cu(on < 20 mesh) q- Cu(in water)"
The results show that good agreements between the
two totals can be achieved for both the ultrasonic and
conventional shaking trays (Table 3). Interestingly, the
distribution of copper between the fines, < 20 mesh and
water fractions differs according to which form of wash-
ing was used. In the case of ultrasonic washing 96% of
the total copper removed was found in the fine particu-
lates carried in the wash water, only 1% was 'solubilised'
and appeared in the wash water and the remaining 3%
resided in the particles < 20 mesh wet sieved from the
remaining brick (Table 3a). In contrast (Table 3b) when
the non-ultrasonic shaking tray was used the majority
of copper was again removed in the fines (68%) but in
this case a larger proportion was in the particles <20
mesh (31%) with a similar amount (1%) 'solubilised' in
the wash water.
3.3. The action of ultrasound
Sonication of an heterogenous system can have a
number of physical and/or chemical effects which have
been well reported, particularly in areas such as sonoca-
talysis. The collapse of cavitation bubbles near a solid
can produce microjets which on impact cause the solid
surface to pit and erode [11 ]. Furthermore effects such
sions which can also contribute to particle size reduction.
The extreme agitation caused by sonication is likely
to account for the improved copper removal levels
observed in this study. Sonication resulted in higher
masses of copper in the fine fraction of brick particulates
(Table 3), which indicates that more of the brick surface
was dislodged than with conventional shaking. Indeed,
a study carried out by Coles et al. [12] on the removal
 A.P. Newman et al. / Ultrasonics Sonochemistry 4 (1997) 153-156 155

Table 1
Results of ultrasonic 'soil washing'

Run Original mass Mass of brick Mass of brick Volume of water

No. of brick (g) < 2 0 mesh (g) fines (g) collected (1)

(a) Massesofthe various brickfragments obtained and water used

1 750.44 3.27 1.95 14.01
2 750.37 3.19 1.70 13.92
3 750.26 3.19 2.02 13.44
4 750.30 3.81 1.88 12.95
5 750.40 3.73 1.92 13.16
Average 750.35 3.44 1.89 13.51

Run Residual copper conc. on Copper conc. Copper conc. Copper conc.
No. treated brick i.e. > 20 mesh on < 20 mesh on fines in water

(b) Concentration ofcopper(ppm) in the var&usfract&ns obtained

1 31.79 104.50 2772.09 0.50
2 28.69 108.51 5135.40 0.54
3 27.23 90.61 5253.29 0.54
4 30.47 87.58 5308.36 0.43
5 35.72 87.30 6330.88 0.44
Average 30.78 95.70 4690.00 0.49

Copper concentration on doped brick prior to washing under ultrasound = 51.41 ppm.
Average reduction in copper concentration on treated brick =40%.

Table 2
Results of conventional vibrating tray 'soil washing'

Run Original mass Mass of brick Mass of brick Volume of water

No. of brick (g) < 2 0 mesh (g) fines (g) collected (1)

(a) Masses of the various brick.fragments obtained and water used

1 750.57 4.38 0.56 13.14
2 750.43 4.47 0.44 12.72
3 750.56 3.98 0.95 11.60
4 750.10 0.98 0.57 12.74
5 750.34 0.88 0.61 12.70
Average 750.40 2.94 0.63 12.58

Run Residual copper conc. on Copper conc. Copper conc. Copper conc.
No. treated brick i.e. > 20 mesh on < 20 mesh on fines in water

(b) Concentration of copper (ppm) in the various fractions obtained

1 50.34 304.09 3351.16 0.25
2 50.82 374.78 5731.99 0.29
3 47.67 189.96 1754.90 0.23
4 46.79 193.29 2999.13 0.17
5 45.84 505.15 2153.85 0.14
Average 48.29 313.45 3198.21 0.22

Copper concentration on doped brick prior to ultrasound = 51.41 ppm.

Average reduction in copper concentration on treated brick = 6%.

of organic pollutants from sandy soil revealed that 5
min of sonication in conjunction with 0.75% aqueous
surfactant was equivalent to stirring for 60 min with the
same solution. This promising result was attributed to
the improved interaction of the surfactant brought about
by the mechanical effects of ultrasound expressed in
terms of:
(a) Ultrasonically induced high fluid-solid shear
stresses, which promote mechanical detachment and
removal of contaminants and
(b) Ultrasonically promoted mass transfer of surfac-
tant monomer between the bulk fluid phase and the
soil/substrate interface.
These improvements might be expected to occur in
all ultrasonically agitated extractive soil washing and
would thus offset the problems identified in conventional
156 A.P. Newman et al. / Ultrasonics Sonochemistr) 4 (1997) 153 156

Table 3
Mass balance of copper from washing experiments

Run No. Mass of copper (rng)

On brick before u (s) On brick after u (s) Total removed On < 20 mesh In water On fines Total removed

(a) Ultrasonic washing

1 38.58 23.69 14.98 0.342 7.078 5.397 12.82
2 38.58 21.39 17.19 0.346 7.531 8.718 16.59
3 38.57 20.29 18.28 0.289 7.204 10.636 18.13
4 38.58 22.69 15.88 0.334 5.543 9.957 15.83
5 38.58 24.71 13.88 0.325 5.830 10.430 16.59
Average 38.58 22.55 16.04 0.327 6.637 9.028 15.99

Run No. Mass of copper (rag)

On brick before shaking On brick after shaking Total removed On < 20 mesh In water On fines Total removed

( b ) Con yen tional shaking

1 40.34 37.54 2.80 1.33 3.26 1.88 6.47
2 40.34 37.89 2.45 1.68 3.70 2.49 7.87
3 40.34 35.54 4.80 0.76 2.68 1.66 5.10
4 40.32 35.02 5.30 0.19 2.18 1.71 4.08
5 40.23 34.33 5.90 0.44 1.83 1.32 3.59
Average 40.31 36.06 4.25 0.88 2.09 1.81 5.42

i n v e s t i g a t i o n s w h i c h s e e m to be a s s o c i a t e d w i t h p o o r
p o l l u t a n t r e m o v a l rates a n d p r e v e n t such m e t h o d s f r o m
b e i n g c o m m e r c i a l l y v i a b l e [ 13 17].
In this study, u l t r a s o n i c i r r a d i a t i o n c a u s e d o v e r twice
the m a s s o f c o p p e r to e n t e r t h e a q u e o u s p h a s e ( T a b l e 3)
w h i c h suggests t h a t u l t r a s o u n d was a b l e to p r o m o t e t h e
l e a c h i n g o f c o p p e r f r o m t h e b r i c k to the w a s h w a t e r .
H o w e v e r as w i t h all u l t r a s o n i c a p p a r a t u s s o m e d e g r e e
o f h e a t i n g w a s o b s e r v e d a n d this is also likely to
influence c o p p e r solubilities.
4. Conclusions
Ultrasound improves the removal of copper oxide
c o n t a m i n a t i o n f r o m b r i c k pieces via a p r o c e s s i n v o l v i n g
the d e t a c h m e n t o f s u r f a c e m a t e r i a l u p o n w h i c h the
m a j o r i t y o f p o l l u t i o n resides. T h i s suggests t h a t the
m e t h o d o l o g y m a y be s u i t a b l e for the r e m e d i a t i o n o f
soils c o n t a m i n a t e d w i t h i n o r g a n i c p o l l u t a n t s . H o w e v e r
in o r d e r to m a k e a p r o p e r c o m p a r i s o n b e t w e e n the
u l t r a s o n i c v i b r a t i n g t r a y a n d the n o n u l t r a s o n i c s h a k i n g
e q u i v a l e n t t h e a m o u n t o f e n e r g y t h a t e a c h s y s t e m uses
a n d t h e i r r e l a t i v e efficiencies m u s t be t a k e n i n t o a c c o u n t .
S t u d i e s i n v o l v i n g electrical p o w e r i n p u t , c a l o r i m e t r i c
a n d c h e m i c a l d o s i m e t r y are c u r r e n t l y in h a n d .
References
[1] H.S. Muralidhara, N. Senapati, D. Ensminger, S.P. Chauhan,
Filtration and Separation 23 (1986) 361.
[2] E. Kowalska, K. Chmura, J. Bien, Ultrasonics 17 (1978) 184.
[3] L. Bjorno, S. Gram, P. Steenstrup, Ultrasonics 17 (1978) 103.
[4] J. Bien, Filtration and Separation 25 (1988) 425.
[5] J.C. Lozier, R.A. Sierka, J. Am. Water Works Assoc. 77 (1985) 60.
[6] H. Fairbanks, W. Morton, J. Wallis, Precious Met. Proc. Met.
Inst. Conf. 9th, Int. Precious Met. Inst. 305 (1986).
[7] M.F. Pruijn, 5th Forum on Innovative Hazardous Waste Treat-
ment Technologies: Domestic and International, Chicago, IL
(1994) p. 57.
[8] Warren Spring Laboratory Review of Innovative Contaminated
Soil Clean-up Process, 60.
[9] M.E. Fristad, C. Jones, 5th Forum on Innovative Hazardous
Waste Treatment Technologies: Domestic and International, Chi-
cago, IL (1994) p. 62.
[10] J.W. Assik, 1st Int. TNO Conf. on Contaminated Soil (1986)
p. 655.
[11] T.J. Mason, J.P. Lorimer, Sonochemistry: Theory Applications
and Uses of Ultrasound in Chemistry, Ellis Horwood,
Chichester, 1988.
[12] E.T. Coles, B. Rubin, R. Gaire, Haztech Int. 90, Houston Waste
Conf. and Exhib., Houston (May 1990).
[13] B.J.W. Tuin, M. Tels, Environ. Technol. 11 (1990) 541.
[14] B.J.W. Tuin, M. Tels, Environ. Technol. ll (1990) 935.
[15] B.J.W. Tuin, M. Tels, Environ. Technol. 12 (1990) 178.
[16] B.J.W. Tuin, M. Tels, Environ. Technol. 11 (1990) 1039.
[17] J.E. Van Benschoten, B.E. Reed, M.R. Matsumoto, P.J. McGar-
vey, Water Environ. Res. 66 (1994) 168.