Wat. Res. Vol. 30, No. 4, pp.

932-938, 1996
Pergamon Copyright © 1996ElsevierScienceLtd
0043-1354(95)00227-8 Printed in Great Britain.All fights reserved
0043-1354/96$15.00+ 0.00

RELEASE BEHAVIOR OF CHROMIUM FROM

TANNERY SLUDGE

M. C. CHUAN and J. C. LIU *@

Department of Chemical Engineering, 43 Keelung Road, Section 4, National Taiwan Institute of
Technology, Taipei 10672, Taiwan, Republic of China

(First received November 1994; accepted in revised form October 1995)

Abstract--The release behavior of chromium from tannery sludge was assessed in this study. Fundamental
properties of sludge were characterized. Total Cr content was 17,200mg/kg. Trivalent chromium, Cr(III),
was the predominant species in the sludge. The total Cr and Cr(VI) concentrations in the leachate of TCLP
were 5.02 and 0.25 mg/dm3, respectively. Solubility of Cr from sludge was the lowest in the neutral range.
Both pH and redox potential significantlyaffected release of Cr from the sludge. When sludge suspension
was continuously aerated with oxygen for 600 hours, pH increased from 7.1 to 7.3, and redox potential
increased from -300 to 295 mV, respectively. Dissolved Cr concentrations were lower than 7 mg/kg
during the aeration period. The equilibrium solubility experimentswere first conducted when the pH value
was maintained at 4.2, and varied redox potential (0, 150, 250, 320, 470 mV), dissolved Cr concentrations
decreased with increased redox potential. When the pH value was maintained at 8.0, and varied redox
potential (-220, -100, 0, 150, 250mV), dissolved Cr concentrations were relatively low. A linear
correlation was observed between dissolved concentrations of Cr and Fe. Combining with results from
sludge fractionation experiment, we can conclude that precipitation-dissolution reactions controlled the
release behavior of Cr.

Key words--chromium, precipitation, dissolution, pH, redox potential, tannery sludge

INTRODUCTION Cr when wastewater and sludge are applied to the

In November 1985, the Taiwan Environmental Pro-
tection Administration, based on the Amendment of
Waste Disposal Act, classified leather-tanning sludge
from chrome processing as a potential hazardous
waste. Approximately 100 tanneries are currently
operating throughout the country with an annual
processing capacity of 9 million skins and hides.
Seven million metric tons of wastewater and 93,000
metric tons of sludge (dry weight) are estimated to be
generated annually. Approximately 332 metric tons
of chromium are annually discharged into the en-
vironment. Wastewater and sludge generated by these
plants had once caused serious environmental pol-
lution since illegal dumping was a common practice.
Nowadays, sludge treatment and disposal remains a
problem due to the lack of facilities and landfill sites.
Considering the content of highly toxic Cr, proper
disposal of tannery sludge has therefore persisted to
be an important local environmental issue. The ur-
gency has also been raised to assess migration of Cr
from tannery sludge in uncontrolled disposal sites.
Release behavior of Cr from sludge must be carefully
examined in light of the fact that potential threat to
soil and groundwater is governed by the mobility of
*Author to whom all correspondence should be addressed.
environment. Additionally, toxicity, bioavailability,
and mobility of trivalent and hexavalent Cr differ
significantly, thereby making it necessary to under-
stand what the major species are. In this work, a
characterization is made of the fundamental proper-
ties of tannery sludge along with an assessment of the
release behavior of Cr from sludge. Also, both pH
and redox potential, i.e. the two most critical factors,
effects on Cr speciation and solubility are studied.
Two major sources of Cr contamination are
sludge-treated soil (Dreiss, 1986) and uncontrolled
disposal of wastes (Montclair Environmental Man-
agement Team, 1990; Cajuste et al., 1991; Makdisi,
1992; Sturges Jr et al,, 1992; Zotter and Liesko, 1992).
In Taiwan, the latter is believed to be the major
source for Cr pollution, since land application of
sludge has not been widely practiced. Chemical reac-
tions that influence Cr mobility in the natural en-
vironment are extremely complex. Precipitation,
complexation, redox, absorption, and diffusion pro-
cesses are all involved. Besides, different Cr species
show quite different chemical behaviors. Cr(III) is
stable at moderate pH and redox potential and exists
mostly in cationic forms. On the other hand, Cr(VI)
is stable under a more oxidizing environment in
anionic forms (McGrath and Smith, 1990; Dreiss,
1986). The mobility of Cr(III) is expected to be
limited in slightly acidic to basic waters by the low

932
 Release behavior of chromium from tannery sludge 933

100
i l Ill[~ IIIIII 40
90
II) i I I)l, ll tlllll • S=0.015 g/L
80
70
60
I I',11 IIIIII
I Illll ~. zo I = 0 , 1 N NaCIO,

50 I Illlll itiJi)
Illll I 1J/l[lll I I[Irl ~ o
40
,YI IIII rJJHi
30
20
10 •j/I/it
i Illllll
]_,H-44+f~ I I []llll]
10 100
I[1111
IIIII
111111
tooo
~-za

P a r t i e l e size ( u r n )
-40

Fig. I. Size distribution of tannery sludge.

-6C
4 6 8 10
pH

solubility of Cr(OH)3(s) a n d (Fe,Cr)(OH)3(s), while

t h a t o f Cr(VI) is expected to be controlled by adsorp-
tion a n d desorption reactions (Rai et al., 1987; Eary
a n d Rai, 1987; W e n g et aL, 1994). Since the import-
ance of waste recycle a n d m i n i m i z a t i o n has been
widely acknowledged, some works have investigated
the recovery o f Cr from sludge (Macchi et al., 1991;
R a j a m a n i et al., 1992). This work could facilitate in
identifying factors t h a t determine C r reactions at
sludge--water interfaces, as well as be beneficial
t o w a r d studies o n b o t h fate modelling a n d resource
recovery.
MATERIALS AND METHODS
Tanner), sludge composition
The sludge sample was obtained from a tannery factory
in Pingtung, Taiwan. The factory, using pig hide as raw
material, is representative of tannery plants in Taiwan. The
factory is equipped with a coagulation-precipitation pri-
mary treatment unit and a secondary biological treatment
unit (activated sludge process) that handles wastewater of
220 metric tons per day. The amount of sludge generated is
4 ~ metric tons (dry weight) monthly. Sludge sample was
taken from the primary precipitation tank in February 1993.
Sludge was air-dried for i week, and then ground with a
mortar. Fractions that passed through a 20-mesh sieve were
collected and stored in polyethylene bottles for experiments.
The pH of sludge was 7.26. The size distribution of tannery
sludge sample (Fig. l) was analyzed by a particle counter
(Malvern 2600-C). The average particle size was 57 #m. The
BET specific surface area measured by an instrument
(Quantachrome AV-14) was 2.2 m2/g. Zeta potential was
measured by a zeta meter (Photal Leza-600) and shown
Fig. 2. The zero-point-of-charge (ZPC) was found to be
5.24. Total organic carbon was measured to be 0.91% by a
TOC analyzer (O.I. Anal. 700). The cation exchange
capacity was found to be 2.98 meq/100 g.
Fig. 2. Zeta potential of tannery sludge: solid concentration
(S) = 0.015 g/l, ionic strength (I) = 0.1 N NaC104.
Chromium determination
In order to analyze total metal content, 2.5 g of sludge
was put into a 250 cm 3 pyrex flask. 5 cm 3 of 4 N HNO 3 was
added to the sludge, and then placed on a heating plate
(Coming PC-320) for digestion. A small amount of nitric
acid was added intermittently to prevent sludge from total
dry-out; until the supernatant became clear and a brownish-
colored fume no longer generated. The suspension was
cooled and filtered through a 0.45/1m membrane filter
(MFS), and then measured by atomic absorption spec-
troscopy (GBC 904). Those results are summarized in
Table 1. The determination of Cr(VI) was by the s-diphenyl
carbazide method (Bartlett and Kimble, 1976). In order to
examine the toxicity of tannery sludge, TCLP (Toxicity
Characteristic Leaching Procedures, Taiwan, EPA) exper-
iment was conducted. 100g of sludge sample was first
weighed and placed in a 2-dm 3 polyethylene bottle. Appro-
priate amount of extractant (acetic anhydride solution at pH
value of 2.88 _+ 0.05) was added and then placed on a rotary
shaker (ATCS DC-20S) to be rotated 18 h at 30 r.p.m. The
sludge suspension was then filtered through a 0.6-0.8 #m
membrane filter (MFS). The concentrations of total Cr and
Cr(VI) in filtrate were determined to be 5.02 and
0.25 mg/dm 3, respectively.
Experimental set-up and procedure
To study the pH effect on Cr solubility of sludge, 10 g of
sludge and 70 cm 3 of distilled water were put into each
125 cm 3 polyethylene bottle, pH of suspension was adjusted
with 1 N NaOH and 1 N HC1, and then placed on a shaker
(Firstek B603). After shaking for 48 h, pH values of suspen-
sion were measured, and then filtered through 0.45/~m
membrane filters (MFS). The Cr concentration was deter-
mined by atomic absorption spectroscopy.
In the Cr fractionation experiment, sequential extrac-
tion (gessier et al., 1979) procedures were utilized. The
scheme is displayed in Table 2. Cr was partitioned into

Table 1. Main chemical composition of tannery sludge (mg/kg)

Ca Cr A1 Mg Fe Zn Pb
1.2 x 105 1.7 x 104 1.6 x 10' 1.3 x 104 1.9 x 103 1.1 x 102 4.9 x 10~

Table 2. Sequential extraction procedures

Fraction Extractant Extraction condition
Exchangeable 10 ml 1 M MgCI2 Shaken 1 h at pH 7
Carbonates-bound I0 ml 1 M NaOAc Shaken 5 h at pH 5
Fc--Mn oxides-bound 20 ml 0.04 M NH2OH.HCI Shaken 5 h at 85°C
Organic-bound 20 ml 30% H202 and Shaken 2 h and 3 h, respectively, at 85°C
10 ml conc. H2SO4
Residual 20 ml conc. H2SO4 Mildly boiled for 1 h

WR 30/~-L
934 M.C. Chuan and J. C. Liu

b I
] j O.gen or
Solenoid valve Nitrogen

.-j1.Acid s u p p l y
2.Metering pump
3.Metering pump
4.Alkali s u p p l y
5.Alkali i n l e t
6.Acid s u p p l y
7.pH e l e c t r o d e
Sludge suspension
8.Septum
9.Platinum electrode
1 2 3 4 10.Gas i n l e t
11 . S t i r r e r

Fig. 3. Diagram of apparatus for controlling redox potential and pH of sludge suspensions.

exchangeable, carbonates-bound, Fe-Mn oxides-bound,
organic-bound, and residual fractions. Results are shown in
Table 3. The Fe--Mn oxides-bound Cr is the predominant
fraction. The other four fractions comprise less than 7% of
total Cr in the sludge.
Next, pH/redox effects on release behavior of Cr from the
tannery sludge were assessed by utilizing an apparatus
(Fig. 3) based on modification of the pH/redox control
system (Patrick Jr et al., 1973). The first experiment involved
examining the dissolution of Cr under continuous oxygen
aeration. Mix 250 g of sludge and 1750 cm3 of distilled water
in the 2-dm 3pyrex reactor. Oxygen was bubbled through the
sludge suspension. The sludge suspension was continuously
stirred. Redox potential and pH were on-line measured and
recorded. Samples were taken at a certain time interval.
50 cm 3 of sludge suspension was regularly sampled, filtered
through a 0.45 #m filter paper (MFS) under nitrogen atmos-
phere. Dissolved concentrations of Fe and Cr were analyzed
by atomic absorption spectroscopy. Additionally, Cr(VI)
and TOC were analyzed by methods described above. In the
second experiment, sludge suspensions were equilibrated
under controlled redox potential and pH. The automatic
pH/redox control apparatus allowed either oxygen or nitro-
gen to flow into the reactor to adjust redox potential at
preset value. Meanwhile, 1 N HC1 and 1 N NaOH aqueous
solution were automatically pumped into the sludge suspen-
sion to maintain pH at the preset value. Equilibrium
conditions were assumed when both pH and redox potential
were maintained at constant values for 3 d. Since minimum
320, 470 mV) was first investigated. Additionally, release of
Cr under slightly alkaline condition (pH 8.0) and five
different redox potentials (-220, -100, 0, 150, 250mV)
was also examined. Since 320 mV was the highest achievable
redox potential by oxygen bubbling, an oxidizing reagent,
Na2S2Os, was added to raise redox potential to 470 mV. The
sohibilizing effect of Na2S20 s on Cr through complexation
was calculated on the basis of stability constants (Smith
and Martell, 1976) and proved to be negligible. Samples
were not taken until both redox potential and pH reached
preset values for at least 3 d. The error of redox potential
was within +10mV, and of pH, +0.1 unit. Electrodes
were calibrated intermittently during the period of each
experiment.
RESULTS AND DISCUSSION
The Cr released from the sludge as affected by p H
is shown in Fig. 4. Solubility decreased as p H in-
creased and showed minimum values in the p H range
of 5.5-7.5. The dissolution pattern was similar to Cr
4,0-
3.5

8.0
\
amounts of released Cr were found in the pH range of
5.5-7.5, as will later be shown (Fig. 4), both acidic (pH 4.2) 2.5
and slightly alkaline (pH 8.0) conditions were chosen for O
investigation. In addition, taking into account the prevailing 2.0
acidic precipitate in Taiwan (Cheng, 1990), mostly ranging
from pH value of 4.09-4.36, the potential leaching of Cr 1.5
from tannery sludge under acidic condition ought to be
examined. The amount of Cr released under acidic condition
(pH 4.2) and five different redox potentials (0, 150, 250,
1.0

0.5
/
0.0
10
Table 3. Fractions of Cr in tannery sludge
pH
Concentration Percentage
Exchangeable 27.8 0.24
Carbonates-bound 10.7 0.09 ---x-- Cr(total)
F e - M n oxides-bound 10,996.0 93.14
Organic-bound 706.2 5.98 Fig. 4. Cr solubility as affected by pH: 10 g sludge in 70 cm3
Residual 654.0 0.55
H20.
 Release behavior of chromium from tannery sludge 935

3oo pH=4.2
1000 10,000
m Cr~otal) ~ Fe(total) ~ TOC
-200 m
o)
784 792.4 "o
= 800 8000 .~
-lO0

~ 600 0ooo "~

t -0
E '1o "o
o o
--100 E 400"-- • 4000 ¢~
Q _o
0 o
n- er
*-200
"~ 200" --" 2000 O
o o
I-
--300

0 150 250 320 470

-40O
1~0 260 3~0 460 560 60O Redox Potential (mV) (oxidant)
Tirne(hrs)
Fig. 7. Dissolved Cr, Fe, and TOC of sludge suspension at
pH ~ Eh(rnv)
pH 4.2 and five different redox potentials.

Fig. 5. Changes of pH and redox potential of sludge

suspension under continuous oxygen aeration.
hydroxide (Richard and Bourg, 1991). When the
sludge-water suspension system was continuously
aerated by oxygen, the initial redox potential of
sludge suspension was - 3 1 0 m V (Fig. 5). Redox
potential rapidly increased to 63 mV within 6 h, and
to 90 mV within 24 h under aeration. It then gradu-
ally increased to 300 mV within 23 d. The changes of
redox potential during aeration represented oxidation
reactions of some reducing reagents by oxygen.
Chemicals with higher oxidation potential than oxy-
gen may be required to raise redox potential even
higher. Meanwhile, pH increased from initial value of
7.0-7.7, and then stabilized at 7.3. Both microbial
metabolism and purge of carbon dioxide during
aeration could affect pH value. In addition, consider-
ing the complicated chemical composition of tannery
sludge, it is unclear why pH values fluctuated slightly
during aeration. At present, it is found that pH value
8386
8092 ,o,~ 770n
65s4
30-
"(3 4683467
20-
:E 10-
0 to Cr(VI) ratio was over 200 and of low mobility
o o.o6 o a o4 7 a6 12o a16
Time(hrs)
Cr(total) ~ TOC
Fig. 6. Dissolved Cr and TOC of sludge suspension under
continuous oxygen aeration.
does not deviate from neutral condition very signifi-
cantly during aeration. Cr(III) was the only species in
the aqueous phase. No dissolved Cr(VI) was detected.
Total dissolved Cr concentrations during oxygen
aeration decreased from 6.3 to 1.3 mg/kg as aeration
proceeded (Fig. 6). Total dissolved organic carbon
(TOC) content was initially 8386 mg/kg, decreased to
6594 mg/kg after 7 h, and then stabilized at approx.
4700 mg/kg.
Equilibrium solubility experimental results under
acidic condition (pH 4.2) are shown in Fig. 7. Dis-
solved Cr concentration (330 mg/kg) at 0 mV was the
highest. The figure indicated that dissolved Cr con-
centration decreased when redox potential became
more oxidizing. A similar pattern of dissolved Fe
concentration, as affected by redox potential, was
found. Dissolved TOC concentration decreased from
492 mg/kg at 0 mV to 126 mg/kg at 320 mV. Notably,
the abrupt increase of TOC was brought on by the
addition of sodium peroxodisulfate. When under
slightly alkaline condition (pH 8.0), dissolved Cr
concentrations were very low in reducing environ-
ment (Fig. 8). It increased to 40.8 mg/kg at 0 mV and
10000
then decreased as redox potential became more oxi-
dizing. No clear effect of pH or redox potential
sooo "~ occurred. Concerning the dissolution of Fe, the pat-
tern was quite similar to that of Cr. Again, no clear
"~
effect of pH and redox potential occurred. Addition-
~, ally, dissolved Cr concentration was obviously much
e 4~ EE lower under alkaline conditions than under acidic
conditions at an identical redox potential.
¢D
Under moderately oxidizing to reducing con-
ditions, Cr(III) precipitates are known to be signifi-
0 cant controls for dissolved chromium (Richard
and Bourg, 1991). In a leather-tanning facility in
California, U.S.A., a survey showed that the Cr(III)
~ 6sl
(Makdisi, 1992). No oxidation reaction of Cr(III) was
detected during our experiment. This could be ac-
counted for by the fact that oxidation of Cr(III) by
dissolved 02 is very slow and became negligible at
room temperature and normal pressure (Eary and
936
Rai, 1987). Similar behaviors have been found that
only negligible Cr(III) oxidation occurred in flood-
water spiked with Cr(VI) (Masscheleyn et al., 1992).
In activated sludge system no Cr(III) oxidation to
Cr(VI) would occur, contrary to thermodynamic
prediction, has also been observed (Imai and Gloyna,
1990). Nevertheless, Cr(III) oxidation by potassium
permanganate has been reported among solidified
wastes (Dusing et al., 1992). It has also been observed
that Cr(III) was readily oxidized to Cr(VI) under
certain soil conditions if manganese oxide is present
(James and Bartlett, 1983). In this work, however,
Cr(III) was not oxidized when redox potential was
raised to 320 mV by oxygen aeration. Notably, oxi-
dation did not occur when redox potential was raised
to 470 mV by sodium peroxodisulfate. This was in
conformity with thermodynamic prediction of Eh/pH
diagram (Fig. 9) that Cr(IlI) is thermodynamically
more stable throughout the redox potential and pH
range that was studied here. Both thermodynamic
prediction and actual experimental results confirmed
that Cr(III) is the predominant species in the system
that was examined in this work.
Release behavior of Cr from tannery sludge could
be discussed in terms of Cr aqueous chemistry.
Trivalent chromium is generally expected not to mi-
grate significantly in natural systems because Cr(III)
minerals [Cr(OH)3(s), FeCrzO4(s), (Fe,Cr)(OH)3(s)]
readily precipitate and maintain low Cr(III) dissolved
concentrations (Dreiss, 1986; Richard and Bourg,
1991). Both precipitation and adsorption are mechan-
isms that remove Cr(VI) in the dissolved form
(Stollenwerk and Grove, 1985). In the activated
sludge, adsorption reaction plays a key role in Cr
removal (Imai and Gloyna, 1990, 1993). As other
cationic metals, Cr(III) is strongly adsorbed by Fe
and Mn oxides and clay minerals through specific
interaction (Wehrli et al., 1990; Charlet and
Manceau, 1992; Fendorf et al., 1994; Fendorf and
pH=8.0
500-
0
"0
400"
-I
6573
2 3oo
6251
._. ,r,*~ - -
E g
...........
20o
i !
~ loo
-220 -100 0 150
Redox Potential (mV)
Cr(total) a m Fe(total) ~
Fig. 8. Dissolved Cr, Fe, and TOC of sludge suspension at
pH 8.0 and five different redox potentials.
M.C. Chuan and J. C. Liu
30 ~-1.73
[Cr]T=a.Sgxto-~
20 Cr,O,'-,.,0 ~ 1.23
10.
_,. I I ~ ~-0.z3 ;>
~ 0
-10-
-20.
Cr(,) ~ --1.27
-30 11 2I0' ~31' l4' 1
l '5~1'6l '2l7' l1'St ' l39' ~1' ~ 1' 1 4' -1'77
pH
Fig. 9. Eh/pH diagram for Cr. [Cr]r = 8.29 × 10 3M.
Sparks, 1994). In exploring Cr release from contami-
nated sediment (Gambrell et al., 1991), no apparent
pH or redox potential effects were found. However,
more Cr was leached from solidified wastes when
redox potential was raised by sodium permanganate
(Dusing et al., 1992). Organic compounds are found
to affect Cr mobility in a mangrove ecosystem
(Lacerda et al., 1991). It has been reported that
organic matter significantly affected Cr(VI) leaching
from ore waste. However, it did not change the
leaching behavior of Cr(III) and Fe (Weng et al.,
1994). The dissolved concentration of Cr(III) appears
to be controlled by a solubility process rather than an
adsorption-desorption reaction, since experimental
results of solubility (Fig. 4) are near the theoretical
solubility proposed by other works (Sass and Rai,
1987; Weng et al., 1994). Concerning complexation
by organic compounds, dissolved Cr concentration
decreased as dissolved TOC concentration decreased
in the first stage of oxygen aeration (Fig. 6). Yet, it
is difficult to make any conclusion based on that
correlation. When dealing with equilibrium solubility
.IOOO0
experiment, organic compounds were not expected to
significantly affect release of Cr from tannery sludge.
This could be attributed to the fact that dissolved
"o
TOC concentrations were relatively low under acidic
conditions (Fig. 7), or the long equilibration period
7~" SO00 had rendered biodegradable fraction of soluble TOC
non-existent (Fig. 8). Besides, since Cr(VI) was not
i found in the tannery sludge that we examined, ad-
sorption and complexation by organic compounds
therefore would not be expected to influence release
o behavior of Cr as significantly as precipitation-
dissolution.
Whereas effects of adsorption and complexation
250
0 cannot be totally ruled out, data presented here
would suggest that precipitation-dissolution reac-
tions are of primary significance that govern release
TOC
behavior of Cr from tannery sludge. Actually, co-
precipitation of Cr with Fe(III) hydroxide to form
mixed solid phase [CrxFel _x)(OH)3](s) has been well
 Release behavior of chromium from tannery sludge
400
Eh=O
300
~ E h = = 1 5 0
~200 Eh=25~
1 CONCLUSIONS
loo
Eh=470 mY
O~ I I I I I I I I I I I I I [ I I ' I I ' ' I I
200 400 600 800
Fe Released ( m g / k g sludge)
Fig. 10. Relation between the amount of Fe and the amount
of Cr released into the aqueous phase.
documented (Sass and Rai, 1987; Rai and
Szelmeczka, 1990; Macchi et al., 1991; Weng et al.,
1994). Eary and Rai (1988) have reported a Fe/Cr
ratio of 3.0 and concluded that the x value is 0.25, i.e.
giving the C r - F e precipitate as Cr0.25Fe0.75(OH)3.
Besides, these co-precipitates were less soluble than
pure Cr hydroxide. Thus, Cr(III) mainly either pre-
cipitated as Cr(OH)3(s) or co-precipitated with Fe to
form mixed oxides. The dissolution of oxides and
hydroxides under reducing conditions caused the
release of Cr. Based on the experimental procedures
of this work, it is difficult to differentiate between
Cr(OH)3 and CrxFej_x(OH)3(s). However, stoichio-
metry of dissolved Cr and Fe from tannery sludge of
this work would yield the x value of 0.28, which is
quite close to reported value. This precipi-
tation-dissolution model is supported by the results
that demonstrated a linear correlation (~, = 0.981)
between dissolved Cr concentration and dissolved Fe
concentration when pH was at 4.2 (Fig. 10). Further-
more, according to the Cr fractionation analysis,
F e - M n oxides-bound fraction was the predominant
form of Cr in the sludge (Table 3). Though interpret-
ation of sequential extraction results must be cautious
(Clevenger, 1990), fractionation analysis was in con-
formity with our proposed mechanisms for Cr release
from sludge. Therefore, results from this work indi-
cated that precipitation-dissolution reactions are
major mechanisms that control release behavior of Cr
from tannery sludge.
It is acknowledged that compositions of industrial
sludge, affected by process type, operational skill,
chemicals utilized, and raw materials, vary signifi-
cantly. What have been observed and proposed in the
current study do not necessarily apply to all tannery
sludge. However, some interesting phenomena and
their implications are pointed out in summary.
Though trace amount of Cr was released from the
tannery sludge under neutral pH range. It should be
noted that any changes in the environmental con-
937
ditions could enhance Cr release, as evidenced in the
present study. In modelling fate of Cr in the natural
mV
environment, interactions found among Cr, Fe,
and organic compounds are believed to be critical.
Mobility of Cr as affected by various factors could
also facilitate studies on Cr fixation and extraction.
mY
Further investigation will delineate Cr reactions at
sludge-water interfaces.
The release behavior of Cr from tannery sludge
into the aqueous phase was examined in this work.
Basic characterizing experiments, e.g. TCLP and
1000 sequential extraction, indicated low mobility of Cr.
This is attributed to the predominance of Cr(III)
species. Sludge-water suspension released less than
7 mg/kg of Cr when under continuous oxygen aera-
tion. In the equilibrium solubility experiment, when
under acidic conditions, amount of Cr released was
found to increase as the system became reduced.
However, no clear effect of pH and redox potential
was found when the system was under slightly alka-
line conditions. We suggest that mixed oxides of
C r - F e co-precipitates are the primary form of Cr in
the sludge. Precipitation-dissolution reactions are
major mechanisms that control Cr release from
tannery sludge.
Acknowledgements--The authors would like to thank the
National Science Council of Taiwan for the financial
support of this work under Contract No. NSC-84-2215-E-
011-012.
REFERENCES
Bartlett R. J. and Kimble J. M. (1976) Behavior of chro-
mium in soils: I. Trivalent forms. J. environ. Qual. 5,
379-386.
Cajuste L. J. R., Carrillo G. E., Cota G. and Laird R. J.
(1991) The distribution of metals from wastewater in the
Mexican valley of Mezquital. Wat. Air, Soil Pollut. 57-58,
763-771.
Charlet L. and Manteau A. A. (1992) X-ray absorption
spectroscopic study of the sorption of Cr(lII) at the
oxide-water interface. J. Coll. Interface Sci. 148, 443-458.
Cheng F. T. (1990) Survey of acidic precipitate in Taiwan.
Graduate Institute of Environmental Engineering,
National Taiwan University, Report No. 255 (in
Chinese).
Clevenger T. E. (1990) Use of sequential extraction to
evaluate the heavy metals in water treatment sludges.
Wat. Air, Soil Pollut. 50, 241-250.
Dreiss S. J. (1986) Chromium migration through sludge-
treated soils. Ground War. 24, 312-321.
Dusing D. C., Bishop P. L. and Keener T. C. (1992) Effect
of redox potential on leaching from stabilized/solidified
waste materials. J. Air. Waste. Manage. Assoc. 42, 56~52.
Eary L. E. and Rai D. (1987) Kinetics of chromium(Ill)
oxidation to chromium(VI) by reaction with manganese
dioxide. Environ. Sci. Technol. 21, 1187-1193.
Fendorf S. E., Lamble G. M., Stapleton M. G., Kelley M. J.
and Sparks D. L. (1994) Mechanisms of cbromium(III)
sorption on silica. 1. Cr(IlI) surface structure derived by
extended X-ray absorption fine structure spectroscopy.
Environ. Sci. Technol. 28, 284-289.
938 M. C. Chuan and J. C. Liu
Fendorf S. E. and Sparks D. L. (1994) Mechanisms of
chromium(III) sorption on silica. 2. Effect of reaction
conditions. Environ. Sci. Technol. 28, 290-297.
Gambrell R. P., Wiesepape J. B., Patrick Jr W. H. and Duff
M. C. (1991) The effects of pH, redox, and salinity on
metal release from a contaminated sediment. Wat. Air,
Soil Pollut. 57-58, 359-367.
Imai A. and Gloyna E. F. (1990) Effects of pH and oxi-
dation state of chromium on the behavior of chromium
in the activated sludge process. Wat. Res. 24, 1143-1150.
Imai A. and Gloyna E. F. (1993) Cr(IlI) in activated sludge.
J. environ. Engng 119, 137-158.
James B. R. and Bartlett R. J. (1983) Behavior of chromium
in soils: V. Fate of organically complexed Cr(III) added
to soil. J. environ. Qual. 12, 169-172.
Lacerda L. D., Rezende C. E., Aragon G. T. and Ovalle
A. R. (1991) Iron and chromium transport and accumu-
lation in a mangrove ecosystem. Wat. Air, Soil Pollut.
57-58, 513-520.
Macchi G., Pagano M., Pettine M., Santori M. and
Tiravanti G. (1991) A bench study on chromium recovery
from tannery sludge. War. Res. 25, 1019-1026.
Makdisi R. S. (1993) Tannery wastes definition, risk assess-
ment and cleanup options, Berkeley, California. J.
Hazard. Mater. 29, 7946.
Masscheleyn P. H., Pardue J. H., Delaune R. D. and Patrick
Jr W. H. (1992) Chromium redox chemistry in a lower
Mississippi Bottomland Hardwood Wetland. Environ.
Sci. Technol. 26, 1217-1226.
McGrath S. P. and Smith S. (1990) Chromium and Nickel.
In Heavy Metals in Soils (Edited by Alloway B. J.),
pp. 125-146. Blackie, London.
Montclair Environmental Management Team (1990)
Management plan for chromium-contaminated soil. Int.
J. environ. Stud. 35, 263-275.
Patrick Jr W. H., Williams B. G. and Moraghan J. T. (1973)
A simple system for controlling redox potential and pH
in soil suspensions. Soil Sci. Soc. Am. Proc. 37, 331-332.
Rai D., Sass B. M. and Moore D. A. (1987) Chromium(Ill)
hydrolysis constants and solubility of chromium(IIl)
hydroxide. Inorg. Chem. 7,,6, 345-349.
Rai D. and Szelmeczka R. W. (1990) Aqueous behavior of
chromium in coal fly ash. J. environ. Qual. 19, 378-382.
Rajamani S., Gupta S. N., Mitra R. B., Schaapman J. E.
and Pelckmans H. H. A. (1992) Chrome recovery and
reuse in India. Wat. environ. Technol. 4, 60-63.
Richard F. C. and Bourg A. C. M. (1991) Aqueous geo-
chemistry of chromium: a review. Wat. Res. 25, 807-816.
Sass B. M. and Rai D. (1987) The solubility of amorphous
Cr(Ill) Fe(III) hydroxide solids solutions. Inorg. Chem.
26, 2228 2232.
Smith R. W. and Martell A. E. (1976) Critical Stability
Constants, Vol. 4, Inorganic Complexes, Plenum Press,
New York.
Stollenwerk K. G. and Grove D. B. (1985) Adsorption
and desorption of hexavalent chromium in an alluvial
aquifer near Telluride, Colorado. J. environ. Qual. 14,
150-155.
Sturges Jr S. G., McBeth Jr P. and Pratt R. C. (1992)
Performance of soil flushing and groundwater extraction
at the United Chrome superfund site. J. Hazard. Mater.
29, 59 78.
Tessier A., Campbell P. G. C. and Bisson M. (1979)
Sequential extraction procedures for the speciation of
particulate trace metals. Anal. Chem. 51, 844-851.
Wehrli B., Ibric S. and Stumm W. (1990) Adsorption
kinetics of vanadyl(IV) and chromium(III) to aluminium
oxide: evidence for a two-step mechanism. Coll. Surf. 51,
77-88.
Weng C. H., Huang C. P., Allen H. E., Cheng A. H-D. and
Sanders P. F. (1994) Chromium leaching behavior in soil
derived from chromite ore processing waste. Sci. Total
Environ. 154, 71-86.
Zotter K. and Licsko I. (1992) Removal of chromium(VI)
and other heavy metals from groundwaters in neutral and
alkaline media. Wat. Sci. Technol. 26, 207-216.