Effects of Microwave Radiation on Extraction of

Heavy Metals from Sludge by Organic Acids

Leaching

l l 2*
Jiancheng Tu , Qingliang Zhao , , Qianqian Yang I
1. School of Municipal & Environmental Engineering,
Harbin Institute of Technology
2. State Key Laboratory of Urban Water Resources and Environment (SKLUWRE)
Harbin, China

Abstract-The effects of radiation time, power and energy on time and high removal efficiency. Extraction efficiency of
microwave-assisted extraction of heavy metals from sewage heavy metals depends on pH, temperature, contact time, and
sludge by using HEDTA and oxalic acid were investigated. The extracting agent type. Previous studies showed that low pH,
heavy metal fractions in raw and extracted sewage sludge high temperature, and long contact time can improve heavy
samples were analyzed by the application of tessier's sequential metal extraction, inorganic acids [15], organic acids [16] and
extraction procedure. The results showed the concentration of
chelating agents [17], have been proposed as effective
extractable fraction of Cu, Ni and Cr in sludge were increased by
extracting agents. Nevertheless, high extraction efficiency
the increasing of microwave time, power intensity and energy
requires a large number of dosages, which results in high
density and the extractable fraction of Zn has no obvious
processing costs and difficulty in pH adjustment of the sludge
improvement. After the microwave-assisted chemical extraction
compost [18). Thus, it is necessary to reduce the dosages of
procedure, the contents of organic fraction of Cu, Cr and Ni
extracting agents.
were decreased. However, the contents of exchangeable and
carbonate fractions were slightly increased; the speciation of Zn Microwave as assisted extraction method can efficiently
in sludge was hardly changed. release heavy metals from sludge, shorten extraction time and
reduce agent dosages[19,20). In this paper, Microwave was
Keywords-sludge; heavy metals; microwave assisted; extraction;
utilized to enhance HEDTA-Oxalic extraction efficiency of
fraction
heavy metals. The advantages of heavy metal extraction by
l. INTRODUCTION HEDTA-Oxalic acid over extraction by other inorganic acids
is the fact of the organic content in HEDTA-Oxalic acid acted
Over 4479 WWTPs have been built m china, these
as a nutrient source for fertilizers. Additionally, the changes of
WWTPs produce large amounts of surplus sludge, over
heavy metal fractions before and after microwave assisted
constitutes a serious problem of pollution when they are
extraction are also discussed.
discharged on the environment. Proper waste treatment and
final disposal methods are important for reducing excess II. MATERIALS AND METHODS
sewage sludge. Traditional sludge disposal methods include
landfilling, incineration, and agricultural use [1-3). Compared A. A. Sewage Sludge
with landfilling and incineration, agricultural use for sludge as The dewatered sludges were collected from Taiping
organic fertilizer is a more sustainable alternative [4]. Unlike wastewater treatment plants in Harbin city, China. The
organic pollutants, heavy metals are persistent environmental sludges were dried at 40°C firstly, and then ground and
contaminants, which cannot be destroyed [5]. Their potential homogenized in an agate mortar, sieved through a sieve (mesh
accumulation in human tissues and bio-magnification through size 250), finally stored in polyethylene bottles at 4°C until
the food-chain cause both human health and environmental needed. The characteristics of sludge were as follows:
concerns [6,7). These considerations are usually based on total moisture 84.5%, pH 6.9, conductivity 2085 �s'cm-l ,organic
heavy metal content in sludge. Thus, the extraction of heavy matter 44.2%, TN 3.25%, TP 0.94%, TC 25.98%; K 9057
metals in sludge before land application is a necessity for mg'kg-1 and Ca 23509 mg'kg-l ; Cu 116.8 mg'kg- \ Zn 475.3
achieving more sustainable sludge treatment. l
mg'kg-l , Cr 94.7 mg'kg-1 and Ni 25.5 mg·kg' .

In recent years, effective methods for heavy metal removal B. B. Microwave Assisted Extraction Procedure
from sludge, including chemical extraction [8], thermal
To investigate the effect of time on extraction of heavy
treatment [9], bioleaching extraction [10], phytoextraction [11],
metals in sludge, sludge samples of 1.00g with 50 ml
electro-reclamation [12], supercritical fluid extraction [13] and
HEDTA-Oxalic acid (10 mmol'L-1 oxalic, 75 mmol'L-1
ion exchange [14], have been extensively studied.
HEDTA) were radiated by the microwave at constant
Conventional chemical extraction of heavy metals has received
microwave power density for 7.7 W'mr1 and the microwave
extensive attention due to its simple operation, short extraction
radiation time respectively for 30 s, 60 s, 90 s, 120 s, 150 s,

The authors gratefully acknowledge funding from Project 50821002 (National

Creative Research Groups), Key Projects in the National Science & Technology
Pillar Program during the Eleventh Five-Year Plan Period (2006BACI9B04), and
partial supports by State Key Laboratory of Urban Water Resource and
Environment, Harbin Institute of Technology (No. 20IODXI7).

978-1-61284-340-71111$26.00 ©2011 IEEE

1607
180 s, and 210 s. Moreover, the effect of microwave power increased along with the rise of microwave power density. In
density on extraction of heavy metals in sludge was also particular, an obvious improvement on extraction of heavy
investigated; sludge samples of 1.00g with 50 ml metals from sludge was observed when the microwave power
! !
HEDTA-Oxalic acid were radiated by the microwave at density is varied from 8 W'mr to 10 W'mr , the balance of
constant microwave radiation time for 60s and the microwave extraction procedure was reached at the microwave power
! !
power density respectively for 2.5 W·mr , 4.6 W'mr \ 7.7 density for 10.8 W'mr It was observed from Fig.2 that the
! ! !
W'mr , 10.8 W'mr and 14 W·mr . Sludge samples after rise of extraction ration of heavy metal from sludge is not
microwave pretreatment were then shaken for 16 h at room continual; this is related with the released organic matter can
temperature. The solution and solid phases were separated by reabsorbed heavy metals at microwave power density for 4.6
centrifugation at 4000 rpm for 20 min. Subsequently, the W'mr I, reabsorbed ability of the released organic matter is
suspension was filtered through a 0.45 !lm membrane filter and destroyed along with the rise of microwave power density and
stored in a polyethylene tube at 4 "c. The rinsed residue with also related with the nature of sludge.
10 ml deionized water was shaken for 15min, removing the --0- C u --t>- Z n --0- C r ---*- N i
centrifuged. The supernatant were determined by an 100
inductively coupled plasma atomic emission spectrometer 0"-
80
(ICP-AES). Each experiment was conducted in four replicates. c:
°
t5 60
C. C. Analytical methods .£:
.sl 40
"0

The moisture, organic matter, pH and electric conductivity �

u

>< 20
(EC) of the sludge samples were measured according to the w

China Standard Methods (CJ/T 221-2005). Total nitrogen (TN)

30 60 90 120 150 1 80 210
was determined by an elemental analyzer (Vario EL cube, Radiation time (s)
Elementar). Total contents of phosphorus (TP) and potassium, Figure 1. Effects of microwave time on extraction of heavy metals from
calcium and magnesium were determined by ICP-AES sewage
(Optima 5300DV, Perkin Elmer) after the microwave assisted
digestion (MARS-5, CEM) on sealed PTFE vessels with 0.3 g C. Effect ofEnergy Density
sludge sample and 10 ml aqua regia (ISO 11466) for 30 min
The effect of energy density on extraction of heavy metals
at 180°C and 10 min at 20°C.
in sludge was showed in Fig.3, the extractable ratio of heavy
Total metal concentrations were determined by ICP-AES metals from sludge with HEDTA-Oxalic acid was improved
after the digestion as follows: 2.5 g of sieved sludge sample with the increase of microwave energy density. The extraction
was digested with 50 ml aqua regia (ISO 11466) for 24 h at ratio of Cu, Cr, and Ni was rising when microwave energy
room temperature, and then for 2h in open reflux condition at density varied from 100 to 1400 J'ml-l, then was stead. It can
180 °C . The cooled residue was dissolved in 20 ml 10% be concluded that organics, fatty acid, carbohydrate and
HN03, the dissolved solution was filtered, and then diluted to protein was dissolved completely at microwave energy
100 ml with deionized water for determination. The speciation density for over 1400 J·ml-l. It was worthy mentioned that Zn
of heavy metals in sludge were analyzed by Tessier's in sludge has no obvious effects by microwave radiation,
sequential extraction [20]. The analysis of the residual which showed release of Zn in sludge has no related with the
fractions for an internal check on the procedure was dissolving procedure of organic matters in sludge. The forms
supplemented as additional step. of heavy metals in sludge may be responsible for individual
effects by microwave treatment.
III. RESULTS AND DISCUSSION
D Fractions ofHeavy Metals
A. Effects of Microwave Time
Tessier's sequential extraction is an efficient approach to
The effect of time on extraction of heavy metals in sludge analyze the forms heavy metals in sludge, fractions of heavy
was showed in Fig.l, the extraction concentration of heavy metals in sludge can be classified as Fl fraction (exchangeable
metals in sludge with HEDTA-Oxalic acid was improved fraction), F2 fraction (bound to carbonate) , F3 fraction (bound
along with microwave radiation time's increase. It can be seen to Fe and Mn oxides) , F4 fraction (bound to organic matter)
from Fig.l that different heavy metal elements shows their and F5 Fraction (residual fraction). Extractable fraction of
individual enhanced extraction effects, the order is: heavy metals in sludge by microwave assisted HEDTA-Oxalic
Zn>Cu>Ni>Cr; when the microwave radiation time reached extraction was expressed as extracted fraction in Fig.4.
180s, the extraction rate has no longer obvious rises. Hamers
[22] believed that the cell membrane and rRNA is destroyed at The content of Fl fraction, F2 fraction, F3 fraction and F5
45�65 DC, DNA is destroyed at 50�70°C and the cell wall is fraction of Cu was low in raw sludge sample (Fig. 4), the
broken at 65�90 °C and protein was denatured, which lead to concentration of Cu in F2 was higher than that of Fl and F3,
release the heavy metals complicated with these matter. indicating that the content of Cu in raw sludge sample were
associated by dissolved organic matter of municipal sludges. It
E. Effects of microwave power density is noteworthy that majority of Cu was existed in the form of
Figure 2 showed that the rise of microwave power can oxidizable fraction and residual fraction, accounting for about
enhance extractable concentration of heavy metals in sludge by 78.3% of the bulk Cu in raw sludge, F3 fraction of Cu rise
HEDTA-Oxalic acid, when microwave power density reached after the microwave-assisted procedure was completed;
!
4.6W·mr , the extraction ratio slightly declined, then otherwise, F4 fraction of Cu was reduced.

1608
 -O-Cu -f>- Z n -o-Cr_Ni
100 IV. CONCLUSIONS
Microwave assisted HEDTA-Oxalic acid procedure can
� 80
<::
0
release heavy metals from sludge in short time and showed
:g 60 great different extraction efficiency on individual heavy metals
�
in sludge. The results showed the optimal operation of
� 40
"C

� microwave assisted HEDTA-Oxalic acid procedure is 60s

X
w 20 microwave radiation at 10.8 W·ml-l of microwave power
density. Fractions of heavy metals in sewage sludge can
2 4 6 8 10 12 14 16
influence the dissolved concentration of heavy metals by
Radiation power density (W mr')
microwave assisted HEDT A-Oxalic acid procedure.
Figure 2. Effects of microwave power on extraction of heavy metals from Experiment showed that the fraction complicated with organic
sewage
matters is key to the release procedure of heavy metals from

-O-Cu -f>-Zn -o-Cr_Ni

sludge by microwave assisted HEDT A-Oxalic acid procedure.

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