Chemosphere 91 (2013) 415–420

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Chemosphere
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A novel organo-zeolite adduct for environmental applications: Sorption

of phenol
V. Leone a, S. Canzano a, P. Iovino a,b, S. Salvestrini a,b, S. Capasso a,b,⇑
a
Department of Environmental Science, Second University of Naples,Via Vivaldi 43, 81100 Caserta, Italy
b
Interuniversity Consortium ‘‘Chemistry for the Environment’’ (INCA), Via delle Industrie, 21/8, 30175 Venezia, Marghera, Italy

h i g h l i g h t s

" A stable humic acids-zeolitic tuff adduct has been synthesized by a heating procedure.
" The adduct has good adsorbing properties for phenol.
" The adduct is easy to prepare, has a low cost and is environmentally friendly.

a r t i c l e i n f o a b s t r a c t

Article history: A novel organo-zeolite adduct has been synthesized by sorbing humic acids (HA) onto zeolitic tuff and
Received 20 June 2012 then heating the resulting complex at 330 °C for 1.5 h. Desorption tests showed that this procedure effec-
Received in revised form 27 November 2012 tively immobilized HA on the tuff. The crystal structure of the zeolitic tuff and the chemical structure of
Accepted 30 November 2012
HA were not altered during the preparation. Phenol sorption analysis demonstrated that the HA–zeolite
Available online 18 February 2013
adduct had good sorbing properties; moreover, the sorbed amount markedly decreased with increased
ionic strength. These results point to prospective application of the HA–zeolite adduct as a low-cost
Keywords:
and environmentally friendly sorbent for water purification from phenol and possibly other neutral
Sorption
Zeolitic tuff
organic pollutants.
Humic acids Ó 2013 Published by Elsevier Ltd.
Organic pollutants
Phenol

1. Introduction Natural polymers deriving from the biological decomposition of

The removal of inorganic and organic pollutants from wastewa-
ter is a matter of increasing interest. Many different techniques
have been employed, in dependence on the type of pollutant.
Among these, sorption is one of the most popular approach due
to its simplicity and relatively low cost. The most widely used sorb-
ing materials are activated carbon (Corwin and Summers, 2011)
and alumino-silicates such as clays and zeolites (Wang and Peng,
2010) and their surface-modified derivatives (Dìaz-Nava et al.,
2009). Prominent among these are natural zeolites because of their
high cation-exchange ability (Wang and Peng, 2010). Natural zeo-
lites modified with cationic surfactants have also been employed
for sorbing neutral and anionic organic contaminants, possibly
via a partitioning mechanism and ionic interaction with surfactant
bilayers, respectively (Krajišnik et al., 2011).
⇑ Corresponding author at: Department of Environmental Science, Second
University of Naples, Via Vivaldi 43, 81100 Caserta, Italy. Tel.: +39 0823 274623;
fax: +39 0823 274605.
E-mail address: sante.capasso@unina2.it (S. Capasso).
organic matter from plants and other organisms, humic substances
(HS) are the major organic fraction in soil and surface water. HS
consist of a skeleton of aromatic blocks and alkyl chains bearing
a diversity of functional groups, notably carboxylic, phenol, hydro-
xyl and quinone groups (Brigante et al., 2008). HS usually are clas-
sified according to their solubility in aqueous media: humic acids
(HA) are soluble at neutral and basic pH, fulvic acids are soluble
also at acidic pH, while humin is the insoluble fraction at any pH
value.
HS are able to sorb both cations and hydrophobic organic com-
pounds, including several common pollutants (Poerschmann et al.,
1999). Cation binding is mainly due to electrostatic interactions
with deprotonated carboxylic and phenol groups; hydrogen bonds,
dipole interactions and hydrophobic effects have a dominant role
in the interaction of HS with neutral organic molecules. Covalent
binding with functional groups of HS has also been observed for
some compounds (Berns et al., 2005). The magnitude of non-cova-
lent binding, expressed as the partition coefficient Koc (Joo et al.,
2008), depends on the structure of the specific HS analyzed and
the hydrophobicity of the ligand. The water solubility of HA can

0045-6535/$ - see front matter Ó 2013 Published by Elsevier Ltd.

http://dx.doi.org/10.1016/j.chemosphere.2012.11.079
416 V. Leone et al. / Chemosphere 91 (2013) 415–420
be markedly reduced by heating at high temperature, possibly due
to a moderate loss of ACOOH and AOH groups (Seki and Suzuki,
1995). Heat-treated HA retain the ability to adsorb cations and or-
ganic pollutants (Klavins et al., 2006). Phillipsite/chabazite-rich
tuffs are able to bind HA through the action of surface extra frame-
work exchangeable cations, and the binding ability is markedly en-
hanced when the zeolitic material is enriched with divalent
cations, especially Ca2+ (Capasso et al., 2007; Leone et al., 2012).
Starting from this background, an investigation has been carried
out with the aim to prepare an organo-zeolite material by linking
HA to a zeolitic tuff in an irreversible way, and to test its potential
sorbing capacity for organic pollutants. Zeolitic tuffs are rocks of
volcanic origin widespread throughout the world, and HA can eas-
ily be extracted from soil and surface water.
The prospective sorbent should have a low cost and be easy to
prepare. Sorption tests have been carried out in batch using phenol
as the sorbate, because this and related compounds are considered
priority pollutants due to significant toxicity and carcinogenicity
(Calace et al., 2002).
2. Experimental methods
2.1. Materials
The sample of humic acids used in this study was purchased
from Sigma–Aldrich and purified as previously reported (Capasso
et al., 2007): dissolution at basic pH, precipitation at acidic pH
and dialysis against deionised water (nominal molecular cutoff
3500 Da). The zeolitic-tuff material employed was obtained from
a quarry near Naples (Italy) and was rich in phillipsite and chabaz-
ite (phillipsite–chabazite tuff, PCT). The mineralogical and chemi-
cal composition of this tuff have been reported elsewhere
(Buondonno et al., 2007).
2.2. Synthesis of the organo-zeolite adduct
A sample of raw tuff was gently crashed and sieved in order to
obtain particles in the 0.5–1.0 mm size range and then repeatedly
washed with deionised water (5 mL water per 1.0 g tuff) until the
rinse water showed no significant increase in conductivity after 1-
d contact with tuff. The tuff sample was enriched in calcium ions in
a chromatographic column (height = 52.7 cm, diameter = 2.5 cm)
using 2.0 L of 1.0 mol L1 CaCl2 solution followed by repeated rins-
ing with deionised water. The exchangeable calcium ions in the
calcium-enriched tuff (Ca–PCT), as determined by the ammonium
acetate method (Hendershot et al., 2008), was 2.54 meq g1.
In order to bind HA to the tuff, a Ca–PCT sample in a column
was rinsed with a solution of purified HA (HA concentra-
tion = 100 mg L1, flow rate = 1.8 mL h1) up to saturation: outlet
concentration equal to inlet concentration. The tuff–humic acids
adduct (PCT–HA) was then washed with a few mL of water and
dried at 40 °C. The amount of HA sorbed, determined by extraction
with pyrophosphate (Tonelli et al., 1997), was 6800 mg HA kg1
tuff. Heating a PCT–HA sample in an oven at 330 °C for 1.5 h (Seki
and Suzuki, 1995) yielded immobilization of the HA sorbed (no re-
lease in water at neutral pH). The effect of heating on the crystal
phases in the resulting material (PCT–ImHA-I) was checked by X-
ray powder diffraction. A sample of PCT–ImHA-I was introduced
in a chromatographic column and rinsed again with the HA solu-
tion. The first pore volume contained no measurable amount of
HA. The sorbing material was subjected to a second heating treat-
ment according to the protocol described above, obtaining a new
adduct (PCT–ImHA-II) with a higher HA content. The organic car-
bon content, determined by oxidation with K2Cr2O7 and back titra-
tion of the excess dichromate ion by ferrous ion (Hendershot et al.,
2008), in the PCT–ImHA-I and PCT–ImHA-II was respectively 0.31%
and 0.56%.
The HA solution used in the experiments above was prepared
adding the desired amount to 0.01 mol L1 KCl water solution
and, under stirring, adjusting the pH to 7.4 with high-strength
TrisH+/Tris buffer [Tris = 2-amino-2-(hydroxymethyl)-1,3-propan-
diol]. After 1-d stirring, the pH was tested again and re-adjusted
to 7.4 with Tris base solution if necessary. Afterwards, the solution
was centrifuged at 13 000 rpm for 1 h.
2.3. Preparation of immobilized tuff–free HA
Few milliliters of a 1.0 mol L1 CaCl2 solution were added to a
100 mg L1 HA solution, pH 7.4 (obtained by Tris base) until com-
plete precipitation of humic substances. After 1 d, the precipitate,
calcium humate (Ca–HA), was collected by centrifugation, washed
with deionized water and dried at 40 °C. Afterward, the Ca–HA was
kept in an oven at 330 °C for 1.5 h (Seki and Suzuki, 1995), in order
to obtain an insoluble form of the HA salt (ImCaHA). The sample
was characterized by IR spectra.
2.4. Desorption tests of HA
One hundred fifty mg of the immobilized (PCT–ImHA-I) and
non-immobilized (PCT–HA) adduct were suspended in 15 mL of
0.01 M TrisH+/Tris buffer, pH 6.0 or 8.4, and the mixture was stirred
in a shaker for 1 d. The liquid phase was then collected by centri-
fugation and analyzed by UV–Vis spectrometry for HA concentra-
tion. The desorbing procedure was repeated with new solutions
of TrisH+/Tris buffer until no HA was detected in the eluate.
2.5. Sorption experiments in batch
Fifty milliliter aliquots of phenol in deionized water, concentra-
tion range 10–150 mg L1, were added to 150 mg of the organo-
zeolite derivatives (PCT–ImHA-I, PCT–ImHA-II), or Ca–PCT, or to
10 mg of ImCaHA, in a glass bottle and kept at room temperature
on a shaker at one oscillation per second. At programmed times,
aliquots were centrifuged at 13 000 rpm for 15 min and analyzed.
The pH of the solutions at the beginning of the sorption was 6.5
and did not change during the sorption tests. All the sorption
experiments were carried out at 25 °C.
2.5.1. pH and ionic strength effects on the sorption
For analyzing the pH effect, sorption experiments were carried
out in 0.01 M KCl solutions at pH 4.0, 6.0 and 8.0, obtained using
the Tris/CH3COOH buffer, concentration of the base Tris = 0.001 M.
The effect of ionic strength was investigated using solutions at pH
6.0, 0.001 M buffer, containing 0.01, 0.02 and 0.04 M KCl.
2.6. Analytical procedures
The concentrations of HA in solution was determined by UV–Vis
spectrometry at 450 nm, on a Perkin Elmer Lambda 40 spectrome-
ter, using as extinction coefficient e = 7.24 10–3 L mg1 cm1, ob-
tained from standard HA solutions prepared adding buffered
water solution, pH 7.0, to known masses of HA.
The IR spectra were recorded in the range of 500–4000 cm1
using pellets of 0.5 mg of the sample in 100 mg KBr. Measurements
were carried out on a Perkin Elmer Spectrum GX (FT-IR System).
Phenol concentration in water was determined by gas chroma-
tography performed by a Dani GC 1000 model equipped with a
spit/splitless capillary inlet system and a FID detector. The injector
and detector temperatures were 280 and 300 °C, respectively. Sam-
ples (1.0 lL) were injected in the split mode with a split ratio of
1:20 and analyzed on an ELITE 1 capillary column (60 m  0.32 mm
 V. Leone et al. / Chemosphere 91 (2013) 415–420 417

I.D., 5 lm film thickness; Perkin Elmer, USA). The GC–FID analysis

was conducted according to the following temperature program:
2.0 min at 110 °C, increased at 15 °C min1 to 210 °C, increased at
5 °C min1 to 260 °C; and 10 min at 260 °C. The flow-rate of nitro-
gen was 2 mL min1.
The X-ray powder spectra were recorded on pulverized samples

Intensity
using a Bruker D8 Advance diffractometer, Cu Ka radiation
(k = 1.54 Å).

3. Results and discussion

3.1. Synthesis of the organo-zeolite adduct

For this study we have used a zeolitic-tuff sample rich in phil-

5 10 15 20 25 30 35 40 45 50 55 60
lipsite and chabazite, enriched in calcium by cation exchange
2 teta
(Ca–PCT) and with particle size of 0.5–1.0 mm. Although smaller
particles have a higher capacity to sorb HA (Daifullah et al., Fig. 2. X-ray powder spectra of PCT–ImHA-I (lower spectra) and PCT–HA (upper
2004), we used particles of relatively large sizes in order to avoid spectra): k = 1.54 (Cu Ka).
excessive resistance to liquid flow in column tests (Cooney,
1999) to be carried out in prospective experiments. In line with
previous work (Capasso et al., 2007), Ca–PCT bound HA with a rel-
used for PCT–ImHA-I. The IR spectra of Ca–HA and of its immobi-
atively good capacity, giving a PCT–HA adduct (at pH 7.6, at equi-
lized form (ImCaHA) are very similar, indicating that heating did
librium with 100 mg L1 HA flowing solution, the amount sorbed
not appreciably change the chemical structure of HA (see Supple-
was 6800 mg kg1). The thermal treatment of PCT–HA markedly
mentary material).
reduced HA release in water (Seki and Suzuki, 1995). Fig. 1 reports
the result of HA desorption tests for PCT–ImHA-I at two pH values
and, for comparison, for the sample before the immobilization 3.3. Sorption in batch of phenol onto the organo-zeolite adduct
treatment (PCT–HA).
The amounts of HA released by PCT–ImHA-I were remarkably The ability of PCT–ImHA-I and PCT–ImHA-II to sorb organic pol-
lower than for PCT–HA at both pH tested. The X-ray powder spec- lutants was tested using as sorbate hydroxybenzene (phenol). This
tra of PCT–ImHA-I and PCT–HA (Fig. 2) showed no significant var- is a very common water pollutant of moderate lipophilicity. The
iation, indicating that the thermal treatment did not alter the octanol–water partition coefficient is 101.47 (Makovskaya et al.,
structure of the crystal phases of Ca–PCT. 1995).
The IR spectrum of PCT–HA showed no peaks attributable to an
organic component (spectrum not shown), therefore the thermal 3.3.1. Sorption kinetics
stability of the humic component was checked on HA in the form Fig. 3 reports typical sorption kinetics for two sorbate concen-
of solid calcium salt. trations. For comparison the figure also includes the sorption data
Samples of PCT–ImHA-I (organic carbon content 0.31%), put in a relative to Ca–PCT subjected to the same heating protocol as for the
chromatographic column and rinsed with a HA solution, sorbed immobilized organo-zeolite adduct. In all kinetic runs, the equilib-
further amounts of HA and produced, after immobilization by heat, rium was reached within few days. The curves were obtained by
a sorbent (PCT–ImHA-II) with a higher content of organic carbon fitting the experimental data with a pseudo-first-order sorption ki-
(0.56%). netic equation (Plazinski et al., 2009):

qt ¼ qe ð1  ekt Þ ð1Þ
3.2. Immobilization of tuff–free HA
1
where qt is the amount (mg kg ) sorbed at the time t, qe is the
The calcium salt of humic acid (Ca–HA) was immobilized by amount sorbed at equilibrium, and k is a first-order kinetic
heat (Seki and Suzuki, 1995) under the experimental conditions constant.

5000 5000

4000 4000
q (mg kg ) release

q (mg kg ) release

3000 3000
-1
-1

2000 2000

1000 1000

0 0
0 5 10 15 20 25 0 5 10 15 20 25

number of washes number of washes

Fig. 1. Cumulative amounts of HA desorbed from a PCT–ImHA-I (N) and from a PCT–HA (d) at pH 6.0 (left) and at pH 8.4 (right), versus number of washes with fresh solution.
418 V. Leone et al. / Chemosphere 91 (2013) 415–420

8000 4
1.6 10

7000 4
1.4 10

6000 4
1.2 10

5000 4
q (mg kg )

1 10
-1

q (mg kg )
-1
4000 8000
t

3000

t
6000

2000 4000

1000 2000

0 0
0 10 20 30 40 50 60 0 10 20 30 40 50 60
time (hour) time (hour)

Fig. 3. Sorption kinetics of phenol, 75 mg L1 (left) and 150 mg L1 (right), onto 150 mg of PCT–ImHA-II (d) and of Ca–PCT (N): pH 6.0, 25 °C.

3.3.2. Sorption isotherms

5
Fig. 4 reports the sorption isotherms of phenol onto the ther- 2 10
mally-treated HA-zeolite adducts PCT–ImHA-I and PCT–ImHA-II
and, for comparison the sorption isotherm onto Ca–PCT subjected
to the same thermal treatment. 5
1.5 10
The sorption capacity of the organo-zeolite adducts is markedly
higher than for the simple zeolitic tuff. Fig. 4 also shows that the
q e (mg kg )
-1

phenol-sorption capacity increases with the amount of HA bound

5
to the sorbent. Since phenol, among neutral organic pollutants, 1 10

has a relatively low octanol/water partition coefficient, this result

appears to be at odd with the notion that the distribution coeffi-
cient in HA/water systems increases with the hydrophobicity of 5 10
4

the sorbate (Balcke et al., 2005). The sorption isotherm of phenol

onto insoluble HA (ImCaHA) is shown in Fig. 5.
Good descriptions of the experimental data were obtained by
0
the Langmuir equation: 0 50 100 150
Kqm C e C e (mg L )
-1
qe ¼ ð2Þ
1 þ KC e
Fig. 5. Sorption isotherms of phenol onto ImCaHA: 150 mg of sorbent, pH 6.0, 25 °C.
where qm is the maximum sorbate capacity (mg kg1), Ce the equi- Ce, phenol concentration. Data recorded after 3 d of contact between the phases.
librium concentration of the sorbate (mg L1), and K an equilibrium
constant related to surface-binding energy (Zhou et al., 2005); qe
has been descripted in Section 3.3.1. The parameters obtained by
least-square fits are reported in Table 1. As can be seen in the table, the two organo-zeolite adducts
exhibited much higher qm values than the zeolitic tuff alone (Ca–
PCT); moreover, qm increased with the percent of organic carbon
in the sample (0.31% for the first sample and 0.56% for the second
4
1.6 10 sample). The constant K had, within the experimental error, an
4
identical value, as expected considering that this parameter is re-
1.4 10
lated to the energy of the binding, which obviously does not de-
1.2 10
4 pend on the amount of sorbing material. The Langmuir
parameters for Ca–PCT were lower than for Jordanian phillipsite
4
1 10 rich-tuff with the same sorbate: at pH 6.0, the values reported
qe (mg kg )
-1

were qm = 0.447 mmol g1 and K = 20.1 L mmol1, corresponding

8000
respectively to 4.21  104 mg kg1 and 0.21 L mg1 (Yousef et al.,
2011). The qm value of the Langmuir equation determined in this
6000
work for the immobilized HA (ImCaHA) was relatively high,
4000 although lower than the value reported for activated carbon of
0.8 mm particle size: qm = 309.7 mg g1 (Roostaei and Tezel,
2000 2004). However, despite its good sorbing properties, ImCaHA can-
not be used as a sorbent in column experiments because of its
0
0 20 40 60 80 100 120 140
powder consistence. It is worth noting that the value of qm for
PCT–ImHA-I and for PCT–ImHA-II not only is higher than for pure
C e (mg L -1 )
tuff, but largely exceeds the value predicted when assuming a pro-
Fig. 4. Sorption isotherms of phenol onto PCT–ImHA-I (d), PCT–ImHA-II (N) and
portional relation between qm and the relative amount of HA in the
onto Ca–PCT (.): 150 mg of sorbent, pH 6.0, 25 °C. Ce, phenol concentration. Data sample. This points to increased sorbing efficiency of HA when
recorded after 3 d of contact between the phases. bound to tuff than in the form of calcium salt.
 V. Leone et al. / Chemosphere 91 (2013) 415–420 419

Table 1
Langmuir parameters for the sorption of phenol.

Sample pH KCl conc. (M) K (L mg1) qm (mg kg1) r2

2 2 3 3
PCT–ImHA-I 6.0 0.00 5  10 ± 1  10 15  10 ± 1  10 0.99
PCT–ImHA-II 6.0 0.00 4.3  102 ± 0.9   102 18  103 ± 1  103 0.99
4.0 0.01 1.5  102 ± 0.1  102 9.2  103 ± 0.3  103 0.99
6.0 0.01 3.8  102 ± 0.4  102 7.3  103 ± 0.3  103 0.99
8.0 0.01 0.58  102 ± 0.02  102 11.4  103 ± 0.3  103 0.99
6.0 0.01 3.8  102 ± 0.5  102 7.3  103 ± 0.3  103 0.99
6.0 0.02 0.7  102 ± 0.3  102 6  103 ± 2  103 0.98
6.0 0.04 0.1  102 ± 0.1  102 9  103 ± 8  103 0.98
ImCaHA 6.0 0.01 20  102 ± 3  102 17  103 ± 6  103 0.99
Ca–PCT 6.0 0.01 1.3  102 ± 0.6   102 6  103 ± 1  103 0.99

7000 made of naturally-occurring materials, it is environmentally

friendly. Because the sizes of the granules of this organo-zeolite ad-
KCl 0.01 M duct characterized in the present study virtually coincide with the
6000
sizes of the tuff particles employed, it is anticipated that selecting
5000 the right granulometry of the starting zeolitic material will permit
optimization of sorption performances.
q e (mg kg )
-1

4000

KCl 0.02 M
3000 Acknowledgements

2000 The authors wish to thanks Dr.ssa Consiglia Tedesco, Depart-

KCl 0.04 M
1000
0 and useful comments and suggestions about prospective research.
0 50 100 150
-1
C e (mg L )
Fig. 6. Sorption isotherms of phenol onto PCT–ImHA-II: Tris/CH3COOH buffer, pH
6.0, KCl concentration indicated on the plot. Ce, phenol concentration. Data recorded
after 3 d of contact between the phases.
3.3.3. Ionic strength and pH effects on sorption
The effect of the ionic strength on the sorption of phenol was
analyzed recording the sorption isotherms for solutions containing
different amounts of KCl (Fig. 6). The Langmuir parameters for the
sorption isotherms are also reported in Table 1.
As can be seen, the ionic-strength increment markedly reduced
the sorption ability: the sorbent PCT–ImHA-II, containing, for
example, 1000 mg kg1 of phenol, is in equilibrium with less than
5 mg L1 of phenol in a 0.01 M KCl solution, or with about
90 mg L1 of phenol in a 0.04 M KCl solution. This reduction of
the sorbitivity is possibly related to the reduction of the hydrody-
namic radius of HA molecules associated with increased ionic
strength (Avena et al., 1999).
The dependence of sorbitivity on pH, in the range 4–8, was
found to be not significant. The Langmuir parameters of the iso-
therms are also reported in Table 1. It is worth noting that the buf-
fer used (Tris/CH3COOH) ensures a sufficient buffer capacity in the
pH range analyzed. Moreover at these pH values the ionization of
the phenol is negligible (pKa = 10.2).
4. Conclusion
The results obtained in this study show that the material ob-
tained by heat-mediated irreversible binding of HA to zeolitic tuff
has good potential application in water purification from organic
pollutants. Indeed, this composite material has good sorbing char-
acteristic as can be judged by the sorption isotherm curves. The
sorbitivity markedly decreases increasing the ionic strength, sug-
gesting a way to regenerate the sorbent, and then for its reuse.
Moreover, this sorbent is easy to prepare, has a low cost and, being
ment of Chemistry and Biology of the University of Salerno (Italy),
for XRD analysis.
Moreover, we thank an anonymous Reviewer for constructive
200
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/
j.chemosphere.2012.11.079.
References
Avena, M.J., Vermeer, A.W.P., Koopal, L.K., 1999. Volume and structure of humic
acids studied by viscometry pH and electrolyte concentration effects. Colloids
Surf. A 151, 213–224.
Balcke, G.U., Georgi, A., Woszidolo, S., Kopinke, F.D., Poerschmann, J., 2005. In:
Perminova, I.V., Hatfield, K., Hertkorn, N. (Eds.), Use of Humic Substances to
Remediate Polluted Environments: From Theory to Practice, vol. 506. Springer,
Zvenigorod, Russia.
Berns, A., Vinken, R., Bertmer, M., Breitschwerdt, A., Schäffer, A., 2005. Use of 15N-
depleted artificial compost in bound residue studies. Chemosphere 59, 649–
658.
Brigante, M., Zanini, G., Avena, M., 2008. On the dissolution kinetics of humic acid
particles. Effect of monocarboxylic acids. Chemosphere 71, 2076–2081.
Buondonno, A., Colella, A., Colella, C., Coppola, E., de’ Gennaro, B., de’ Gennaro, M.,
Gargiulo, N., Grilli, E., Langella, A., Rubino, M., 2007. Modeling pedogenization of
zeolitized tuff. II: medium–term weathering of phlegraean yellow tuff and red
tuff with black scoriae by water and humic acids. Stud. Surf. Sci. Catal. 170,
2092–2097.
Calace, N., Nardi, E., Petronio, B.M., Pietroletti, M., 2002. Adsorption of phenols by
papermill sludges. Environ. Pollut. 118, 315–319.
Capasso, S., Coppola, E., Iovino, P., Salvestrini, S., Colella, C., 2007. Sorption of humic
acids on zeolitic tuffs. Microporous Mesoporous Mater. 105, 324–328.
Cooney, D.O., 1999. Adsorption Design for Wastewater Treatment. Lewis Publishers,
Boca Raton, FL.
Corwin, C.J., Summers, R.S., 2011. Adsorption and desorption of trace organic
contaminants from granular activated carbon adsorbers after intermittent
loading and throughout backwash cycles. Water Res. 45, 417–426.
Dìaz-Nava, C., Olguìn, M.T., Solache-Rìos, M., Alarcòn-Herrera, M.T., Arguilar-
Elguezabel, A., 2009. Phenol sorption on surfactant-modified Mexican zeolitic-
rich tuff in batch and continuous systems. J. Hazard. Mater. 167, 1063–1069.
Daifullah, A.A.M., Girgis, B.S., Gad, H.M.H., 2004. A study of the factors affecting the
removal of humic acid by activated carbon prepared from biomass material.
Colloids Surf. A 235, 1–10.
Hendershot, W.H., Lalande, H., Duquette, M., 2008. In: Corte, M.R., Gregorich, E.G.
(Eds.), Soil Sampling and Methods of Analysis, vol. 1224. Broken Sound
Parkway, NY.
420 V. Leone et al. / Chemosphere 91 (2013) 415–420
Joo, J.C., Shackelford, C.D., Reardon, K.F., 2008. Sorption of nonpolar neutral
compounds to humic acid-coated sands: contributions of organic and mineral
component. Chemosphere 70, 1290–1297.
Klavins, M., Eglite, L., Ziemanis, A., 2006. Immobilized humic substances as sorbents.
Chemosphere 62, 1500–1506.
Krajišnik, D., Daković, A., Milojević, M., Malenović, A., Kragović, M., Bogdanović, D.B.,
Dondur, V., Milić, V., 2011. Properties of diclofenac sodium sorption onto
natural zeolite modified with cetylpiridium chloride. Colloids Surf. B 83, 165–
172.
Leone, V., Canzano, S., Iovino, P., Capasso, S., 2012. Sorption of humic acids by a
zeolite-feldspare bearing tuff in batch and fixed-bed column. J. Porous Mater..
http://dx.doi.org/10.1007/s10934-011-9493-6.
Makovskaya, V., Deam, J.R., Tomlinson, W.R., Comber, M., 1995. Octanol–water
partition coefficients of substituted phenols and their correlation with
molecular descriptors. Anal. Chim. Acta 315, 193–200.
Plazinski, W., Rudzinski, W., Plazinska, A., 2009. Theoretical models of sorption
kinetics including a surface reaction mechanism: a review. Adv. Colloid
Interface Sci. 152, 2–13.
Poerschmann, J., Kopinke, F.-D., Plugge, J., Georgi, A., 1999. Interaction of organic
chemicals (PAH, PCB, triazines, nitroaromatics and organotin compounds) with
dissolved Humic organic matter. In: Ghabbour, E.A., Davies, G. (Eds.),
Understanding Humic Substances Advanced Methods Properties and
Applications. RCS, Cambridge, U.K., pp. 223–240.
Roostaei, N., Tezel, F.H., 2004. Removal of phenol from aqueous solutions by
adsorption. J. Environ. Manage. 70, 157–164.
Seki, H., Suzuki, A., 1995. Adsorption of heavy metal ions onto insolubilized humic
acid. J. Colloid Interface Sci. 171, 490–494.
Tonelli, D., Seeber, R., Ciavatta, C., Gessa, C., 1997. Extraction of humic acids from a
natural matrix by alkaline pyrophosphate. Evaluation of the molecular weight
of fractions obtained by ultrafiltration. Fresenius J. Anal. Chem. 359, 555–560.
Wang, S., Peng, Y., 2010. Natural zeolites as effective adsorbents in water and
wastewater treatment. Chem. Eng. J. 156, 11–24.
Yousef, R., EI-Eswed, B., AI-Muhtaseb, A., 2011. Adsorption characteristics of natural
zeolites as solid adsorbents for phenol removal from aqueous solutions:
kinetics, mechanism and thermodynamics studies. Chem. Eng. J. 171, 1143–
1149.
Zhou, A., Tang, H., Wang, D., 2005. Phosphorus adsorption on natural sediments:
modeling and effects of pH and sediment composition. Water Res. 39, 1245–
1254.