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h i g h l i g h t s
Humic substances (HS) from compost showed good surfactant properties.
HS effectively removed Cu and Cd from contaminated soil.
Cu and Cd removal efciency was higher for sandy clay loam than for clay.
Soils washing with HS enable decrease of Cu and Cd ecological risk (on Er index).
a r t i c l e
i n f o
Article history:
Received 30 August 2014
Received in revised form 5 March 2015
Accepted 24 March 2015
Available online 15 May 2015
Handling Editor: Jrg E. Drewes
Keywords:
Soil washing
Cu
Cd
Humic substances
ER index
a b s t r a c t
Although commercially available biosurfactants are environmentally friendly and effectively remove
heavy metals from soil, they are costly. Therefore, this study investigated whether inexpensive humic
substances (HS) from sewage sludge compost could effectively remove copper (Cu) and cadmium (Cd)
from highly contaminated sandy clay loam (S1) and clay (S2). The optimum HS concentration and pH
were determined, as well process kinetics. Under optimum conditions, a single washing removed
80.7% of Cu and 69.1% of Cd from S1, and 53.2% and 36.5%, respectively, from S2. Triple washing increased
removal from S1 to almost 100% for both metals, and to 83.2% of Cu and 88.9% of Cd from S2. Triple
washing lowered the potential ecological risk (Eir) of the soils, especially the risk from Cd. HS substances
show potential for treating soils highly contaminated with heavy metals, and HS from other sources
should be tested with these and other contaminants.
2015 Elsevier Ltd. All rights reserved.
1. Introduction
Soil washing is one of the most effective forms of remediation
because it allows rapid cleanup of a contaminated site, it reduces
or eliminates long-term liability, and it is cost-effective. This process is based on the desorption of pollutants from contaminated
soils through the action of various agents. Washing agents that have
been commonly used include inorganic acids, such as sulfuric and
hydrochloric acids, organic acids, including acetic and citric acids,
and chelating agents like ethylenediaminetetracetic acid (EDTA)
and nitrilotriacetic acid (NTA) (Mulligan et al., 2001).
Interest in biosurfactants derived from microbes and plants has
been increasing, mainly because of their high capacity to bind with
metal ions, which allows them to effectively remove heavy metals.
Most studies on biosurfactants have been done with microbial
rhamnolipids (Wang and Mulligan, 2009a; Elouzi et al., 2012;
Corresponding author.
E-mail address: dorotak@uwm.edu.pl (D. Kulikowska).
http://dx.doi.org/10.1016/j.chemosphere.2015.03.083
0045-6535/ 2015 Elsevier Ltd. All rights reserved.
43
Table 1
Physicochemical characteristics of experimental soils.
Characteristic
Unit
Soil S1
Soil S2
Sand content
Silt content
Clay content
Texture
Organic matter
CEC
pH (H2O)
Total Cu
Total Cd
%
%
%
%
cmol (+) kg1
mg kg1
mg kg1
64
16
20
Sandy clay loam
1.6
12.3
7.1
36
0.3
6
33
61
Clay
10.3
53.3
6.1
95
1.1
CuSO45H2O and 3CdSO48H2O salt were added to 500 g of airdried soils at concentrations of 2000 and 50 mg L1, respectively.
The samples were mixed for homogeneity by shaking overnight
(100 r min1), left at room temperature for one month with
frequent thorough mixing, then dried at 10305 C to a constant
mass, and nally ground manually and passed through a 1 mm
sieve. Total metal concentrations in articially contaminated soils
were: for Cu 1984.1 mg kg1 (S1) and 2042.2 mg kg1 (S2); and
for Cd, 49.8 mg kg1 (S1) and 55.2 mg kg1 (S2).
2.3. Compost the source of HS
Mature compost from sewage sludge and lignocellulosic
materials (wood chips, grass, rape straw) was the source of humic
substances (after 170 days of composting). Compost came from the
Department of Environmental Biotechnology at the University of
Warmia and Mazury (project No. N523455036). The compost had
a relatively high content of organic matter (47.9%), total organic
carbon (TOC) (22.65%), nitrogen (1.68%) and phosphorus (0.93%).
The concentration of HS was 162.3 g C kg1 OM. Importantly, the
concentrations of all heavy metals were below the permissible
values for heavy metals in organic and organo-mineral fertilizers
and organic and organo-mineral plant conditioner, as given in
the Ordinance of the Ministry of Agriculture and Rural
Development (OMARD 2004, 2008) on the implementation of
certain provisions of the Act on Fertilizers and Fertilization.
Because the concentrations of metals in the compost were low
(Cd 0.93 mg kg1, Cr 50.7 mg kg1, Cu 48.6 mg kg1, Fe
10.79 g kg1, Mn 294 mg kg1, Ni 24.2 mg kg1, Pb 25.3 mg kg1,
Zn 270 mg kg1, Hg 0.055 mg kg1, based on dry mass), it can be
concluded that only a negligible amount of metal was introduced
to the soil during washing with humic substances extracted from
the compost.
2.4. Washing agents
As washing agent, HS derived from compost were tested.
Additionally, for comparison studies, the effectiveness of heavy
metals removal with commercial HA (Fluka) and two plant biosurfactants, tannic acid (TA) and saponin (SAP) were evaluated.
HS extraction followed the methodology described in Jouraiphy
et al. (2005) and Amir et al. (2006). Before HS extraction, compost
was washed with distilled water to eliminate soluble non-humic
substances (e.g. sugars and proteins), which can interact with HS.
Then, the samples were defatted with a chloroform:methanol
(2:1) mixture in a microwave oven. After ltering, the defatted
samples were evaporated to eliminate the solvents. Next, HS were
extracted with 0.1 M NaOH. In order to nd out the concentration
of HA and the fulvic fraction (FF) in the solution of HS, humic substances were fractionated into HA and FF as follows. First, the solution of HS was acidied to pH 1 with H2SO4. Next, the precipitate
(HA) was allowed to coagulate for 24 h at 4 C. Then, HA were
redissolved in 0.1 M NaOH, and in the HS and HA, TOC was
44
(Fig. 1). Despite the fact that studies that have determined the CMC
and surface tension of HS and HA are not numerous, the ones that
are available in the literature conrm that HS and HA exhibit surfactant properties.
For example, Montoneri et al. (2009) reported that the CMC of
HA like substances from green waste composted for 60 days was
730 mg L1 and surface tension at CMC was 38.1 mN m1; both
these values were lower than those of HA commercially available
from Aldrich (CMC, 1530 mg L1; surface tension, 47.48 mN m1).
In our study, the value of c was higher than in Montoneri et al.
(2009). This may be because the surface tension of HS obtained
from different sources can vary signicantly depending on their
origin and molecular properties. Moreover, whereas HS isolated
from natural samples (soil, peat, sediments, sewage sludge) were
found to decrease surface tension as their concentration increased,
many industrially produced humic materials had little or no effect
on the surface tension of their solutions (Klavins and Purmalis,
2010). Similarly, our data indicates that HS show better surfactant
properties than HA. These ndings indicate that biomass or compost can be a good source of HS, natural biosurfactants.
3.2. The effect of HS and HA on the efciency of Cu and Cd removal
from soils
The efciency of removal of both Cu and Cd depended on HS
and HA concentration (Fig. 2). Removal of Cd from soil S2 was
not affected by the kind of washing agent. However, HS at
concentrations above 2500 mg C L1 did remove Cd slightly more
effectively from soil S1 (Fig. 2b).
HS were more effective than HA at removing Cu; this was
evident at all concentrations with soil S1 (Fig. 2a), but only at
concentrations above 2000 mg C L1 with soil S2 (Fig. 2c). The
effectiveness of Cu removal with HS from soil S1 increased quickly
up to a concentration of 1500 mg C L1, when it reached 50.5%,
(a)
-1
80
70
60
50
y1 = -20.068x + 108.59
40
y2 = -2.9412x + 57.62
30
20
10
CMC
0
0.0
0.8
1.6
2.4
3.2
log C
-1
(b)
60
y1 = -13.883x + 100.51
30
20
10
CMC
0
0.5
1.0
1.5
2.0
dq1
k qe qt 2
dt
y2 = -0.552x + 56.364
0.0
70
40
then slowly up to 3000 mg C L1 (64.5%), and then only 1% as concentration was increased to 4000 mg C L1. Cu removal with HS
from soil S2 followed a similar trend. Therefore, a HS concentration
of 3000 mg C L1 was adopted as optimum for determination of
process kinetics and of the effect of pH on metal removal efciency.
80
50
45
2.5
3.0
3.5
4.0
log C
Fig. 1. Plot of surface tension (c) as a function of washing agent concentration (as
log C) (a) HS; (b) HA.
1
1
1
t
qt k q2e qe
46
(b)
60
50
40
30
20
10
HS
HA
S1
60
50
40
30
20
10
HS
HA
concentration (mg C
500
L -1)
(c)
(d)
70
70
S1
70
S2
60
50
40
30
20
HS
10
HA
(a)
70
S2
60
50
40
30
20
10
HS
HA
-1
concentration (mg C L )
Fig. 2. Cu and Cd removal efciency in dependence on washing agents (HS, HA) concentrations (a and b) soil S1; (c and d) soil S2.
2000
1600
-1
Qe (mg Cu kg d.m.)
(a)
Cu and Cd removal
efficiency (%)
3000
2500
80
2000
60
1500
40
1000
20
500
Cu
Cd
HS
0
2
10
12
14
(b)
S2
3000
2500
80
2000
60
1500
40
1000
20
Cu
Cd
500
HS
SH concentration after
washing (mgC/L)
Cu and Cd removal
efficiency (%)
100
10
12
14
pH
400
0
120 240 360 480 600 720 840 960 1080 1200
time (min)
-1
pH
800
S1-experimental data
pseudo 2. order kinetic
(b)
1200
Qe (mg Cd kg d.m.)
S1
100
SH concentration after
-1
washing (mg C L )
(a)
S2-experimental data
50
40
30
20
10
0
120
240
360
480
600
720
840
time (min)
S1-experimental data
pseudo 2. order kinetic
Soil
q e*
Cu
k **
S1
S2
1667
1111
2.25 10
.
-4
1.37 10
S2-experimental data
r ***
-4
624.838
169.520
q e*
Cd
k **
.
r ***
-3
3.89 10
.
-3
19.8 10
5.64
7.56
Fig. 4. Kinetics of Cu (a) and Cd (b) washing from soil S1 and S2.
r k q2e
Table 2
Efciency of Cu and Cd removal in a single*, duplicate** and triple*** soil washing.
Washing agent
HS
Soil S2
Cu
Cd
Cu
Cd
80.7
69.1
53.2
36.5
HSHS
HSSAP
HSTA
Soil S2
Cu
Cd
Cu
Cd
94.4
89.4
87.7
89.0
85.0
76.8
72.6
66.8
60.3
57.2
54.0
40.8
HS
*
Soil S2
Cu
Cd
Cu
Cd
97.7
98.2
83.2
88.9
1
47
The high efciency of metal removal in our study may be connected with the fact that both the HA and FA in HS are known to
strongly affect the mobility and bioavailability of heavy metals in
soils (Stevenson, 1994). Both have many functional groups which
are involved in the formation of metalhumic complexes, mainly
carboxylic COOH and phenolic OH groups. In our study, the HS
concentration was 3000 mgC L1, and the concentrations of HA
and FA were 2160 mg C L1 and 840 mg C L1, respectively.
Despite the relatively low FA concentration, their role in heavy
metals removal may have been large because FA contain more
functional groups of an acidic nature, particularly COOH. The total
acidities of FA (9001400 meq 100 g1) can be considerably higher
than those of HA (400870 meq 100 g1). Donisa et al. (2003)
found that Cu, Cd and 9 other elements were bound more to the
fulvic than to the humic fraction in natural soils (andosol, podzol,
cambisol). In contrast, Laborda et al. (2008) found that in general,
both FA and HA contribute to binding Cu, whereas Cd preferentially associates with HA.
3.5.2. Efciency of Cu and Cd removal in duplicate soil washing
The effectiveness of heavy metals removal by HS was compared
to the effectiveness of SAP and TA in the 2nd step of soil washing.
Although SAP and TA are known to effectively remove Cu and Cd
(Chen et al., 2008; Gusiatin, 2014), their high price is a disadvantage. Thus, in this study SAP and TA were only used for the 2nd step
of washing. With both soils, HSHS washing was most effective
(Table 2) and HSTA washing was least effective. Regardless of
the combination of washing agents used, heavy metals were more
efciently removed from soil S1 than from soil S2. This means that
regardless of the type of washing agents, soil with low organic
matter (S1) can be more effectively remediated mainly because
the metals are less strongly sorbed to the soil.
3.5.3. Efciency of Cu and Cd removal in triple soil washing
With HS as a washing agent in triple washing, Cu and Cd was
almost completely removed from soil S1 (Table 2). In soil S2,
removal of both metals was lower, but also high.
Similarly, SAP very effectively removed heavy metals during triple washing, with 6597% Cu and 89100% Cd efciency from
three types of soils (sandy clay loam, loam, clay) (Gusiatin and
Klimiuk, 2012). However, heavy metals were removed much less
efciently from a real polluted construction site in Canada and lake
sediment from Japan (Mulligan et al., 2007; after Mulligan, 2009).
They used different biosurfactants (rhamnolipids, saponin and
mannosylerytritol lipids (MEL)) to remove heavy metals from soil
in a ve-step washing process. The authors showed that saponin
(30 g L1) removed zinc (88%, pH 3.0) and nickel (76%, pH 5.0) most
effectively from the construction site, 2% rhamnolipids (pH 6.5)
were best for removing copper (46%), and 4% MEL (pH 5.6)
removed contaminants least effectively (17% of the zinc and nickel
and 36% of the copper). From the sediment, 30 g L1 saponin (pH 5)
removed zinc (33%) and lead (24%) most effectively, and 2% rhamnolipids (pH 6.5) were again best for removing copper (84%).
Mulligan et al. (2001) stated that multiple washings may be more
effective because they can remove the easier metal phases rst
(e.g. exchangeable) and then the more difcult ones (e.g. carbonate
and reducible). It can be important especially for real pollution
caused many years ago, which is much more difcult to remove
than spiked pollution because the metals are included in minerals
and soil aggregates.
3.5.4. The distribution and environmental risk of heavy metals in
treated soils
Total Cu and Cd concentrations, their distributions and
ecological risks (as Eir) in contaminated and treated soils are given
in Table 3.
48
Table 3
Chemical form of Cu and Cd in contaminated soils and soil after three step washing with HS (W/V = 1/40, HS = 3000 mg C L1, pH 5 for soil S1 and pH 7 for soil S2).
Parameter
Unit
Total Cu
F1
F2
F3
F4
ECu
r
Total Cd
F1
F2
F3
F4
ECd
r
mg kg1 d.m.
mg kg1 d.m.
mg kg1 d.m.
mg kg1 d.m.
mg kg1 d.m.
mg kg1 d.m.
mg kg1 d.m.
mg kg1 d.m.
mg kg1 d.m.
mg kg1 d.m.
Soil S1
Soil S2
Contaminated
After washing
% removal
Contaminated
After washing
% removal
1984.1
1242.1
433.1
57.9
251.0
26.5
49.8
42.6
6.8
0.0
0.4
159.4
44.8
23.1
9.3
12.4
5.1
0.6
0.9
0.7
0.2
0.0
0.0
2.9
97.7
98.1
97.8
78.6
97.9
98.2
98.3
97.0
0.0
100
2042.2
273.2
735.9
864.5
168.7
20.4
55.2
19.1
35.6
0.6
0.0
154.6
341.9
124
18.4
111.5
86.0
4.0
6.1
1.6
4.5
0.0
0.0
14.1
83.2
54.6
97.5
87.1
49.0
88.9
91.6
87.3
100
0.0
Eir T ir
C iD X
C iR
49
Laborda, F., Bolea, E., Grriz, M.P., Ruiz, M.P.M., Ruiz-Begueria, S., Castillo, J.R., 2008.
A speciation methodology to study the contributions of humic-like and fulviclike acids to the mobilization of metals from compost using size exclusion
chromatographyultraviolet absorptioninductively coupled plasma mass
spectrometry and deconvolution analysis. Anal. Chim. Acta. 606, 18.
Li, W., Peters, R.W., Brewster, M.D., Miller, G.A., 1995. Sequential extraction
evaluation of heavy-metal contaminated soil: how clean is clean? In:
Proceedings of the 88th Annual Meeting and Exhibition of Air and Waste
Management Association. San Antonio, USA. June 1823.
Li, X., Shen, Z., Wai, O.W.H., Li, Y.S., 2001. Chemical forms of Pb, Zn and Cu in the
sediment proles of the Pearl River Estuary. Mar. Pollut. Bull. 42, 215223.
Meng, D., Wan, J., Zhang, S., Yao, H., Lin, Y., 2014. Simultaneous removal of lindane
and heavy metals from contaminated soils by rhamnolipids enhanced washing.
Huanjing Kexue Xuebao/Acta Sci. Circumst. 34, 229237.
Montoneri, E., Boffa, V., Savarino, P., Perrone, D.G., Musso, G., Mendichi, R., Chierotti,
M.R., Gobetto, R., 2009. Biosurfactants from urban green waste. ChemSusChem.
2, 239247.
Mulligan, C.N., 2009. Recent advances in the environmental applications of
biosurfactants. Curr. Opin. Colloid In. 14, 372378.
Mulligan, C.N., Yong, R.N., Gibbs, B.F., 2001. Heavy metal removal from sediments
by biosurfactants. J. Hazard. Mater. 85, 111125.
Mulligan, C.N., Oghenekevwe, C., Fukue, M., Shimizu, Y., 2007. Biosurfactant
enhanced remediation of a mixed contaminated soil and metal contaminated
sediment. In: Proceedings of the 7th Geoenvironmental Engineering Seminar,
JapanKoreaFrance, Grenoble, France.
Ochoa-Loza, F.J., Noordman, W.H., Jannsen, D.B., Brusseau, M.L., Miller, R.M., 2007.
Effects of clays, metal oxides, and organic matter on rhamnolipid sorption by
soil. Chemosphere 66, 16341642.
OMARD, 2004. Ordinance of the Minister of Agriculture and Rural Development on
fertilizers and fertilization. J. Law. 236, 1683416839 (in Polish).
OMARD, 2008. Ordinance of the Minister of Agriculture and Rural Development on
fertilizers and fertilization. J. Law. 119, 65156520 (in Polish).
Ostrowska, A., Gawlinski, S., Szczubiaka, Z., 1991. Methods of Analysis and
Assessment of Soil Properties and Plants. Institute of Environmental
Protection. Warsaw, Poland. 5195.
Pueyo, M., Mateu, J., Rigol, A., Vidal, M., Lopez-Sanchez, J.F., Rauret, G., 2008. Use of
the modied BCR three-step sequential extraction procedure for the study of
trace element dynamics in contaminated soils. Environ. Pollut. 152, 330341.
Qingjie, G., Jun, D., Yunchuan, X., Qingfei, W., Liqiang, Y., 2008. Calculating pollution
indices by heavy metals in ecological geochemistry assessment and a case study
in parks of Beijing. J. China Univ. Geosci. 19, 230241.
Shaker, A.M., Komy, Z.R., Heggy, S.E.M., El-Sayed, E.A., 2012. Kinetic study for
adsorption humic acid on soil minerals. J. Phys. Chem. 116, 1088910896.
Steelink, C., 1985. Implications of elemental characteristics of humic substances. In:
Aiken, G.R., McKnight, D.M., Wershaw, R.L., MacCarthy, P. (Eds.), Humic
Substances in Soil, Sediment and Water. Wiley, New York, pp. 457476.
Stevenson, F.J., 1994. Humus Chemistry, Genesis, Composition, Reactions. John
Wiley Sons Inc., Canada.
Thawornchaisit, U., Polprasert, C., 2009. Evaluation of phosphate fertilizers for the
stabilization of cadmium in highly contaminated soils. J. Hazard. Mater. 165,
11091113.
Tsang, D.C.W., Yip, A.C.K., 2014. Comparing chemical-enhanced washing and
waste-based stabilisation approach for soil remediation. J. Soils Sediments.
14, 936947.
Tsang, D.C.W., Yip, T.C.M., Lo, I.M.C., 2011. Conceptual model and sensitivity
analysis for simulating the extraction kinetics of soil washing. J. Soils
Sediments. 11, 12211233.
Wang, S., Mulligan, C.N., 2009a. Rhamnolipid biosurfactant-enhanced soil ushing
for the removal of arsenic and heavy metals from mine tailings. Process
Biochem. 44, 296301.
Wang, S., Mulligan, C.N., 2009b. Effect of natural organic matter on arsenic
mobilization from mine tailings. J. Hazard. Mater. 168, 721726.
Wang, M., Liao, L., Zhang, X., Li, Z., 2012. Adsorption of low concentration of humic
acid from water by palygorskie. Appl. Clay Sci. 6768, 164168.
Zhu, H.N., Yuan, X.Z., Zeng, G.M., Jiang, M., Liang, J., Zhang, C., Yin, J., Huang, H.J., Liu,
Z.F., Jiang, H.W., 2012. Ecological risk assessment of heavy metals in sediments
of Xiawan Port based on modied potential ecological risk index. Trans.
Nonferrous Met. Soc. China (english edition) 22, 14701477.