J. Baham et G. Sposito, ADSORPTION OF DISSOLVED ORGANIC-CARBON EXTRACTED FROM SEWAGE-SLUDGE ON MONTMORILLONITE AND KAOLINITE IN THE PRESENCE OF METAL-IONS, Journal of environmental quality, 23(1), 1994, pp. 147-153
The adsorption of dissolved organic carbon extracted from sewage sludg
e (SSDOC) and its complexes with Cu, Pb, and Cd by montmorillonite and
kaolinite was measured at 283, 298, and 308 K. Experiments were condu
cted at 2 g L(-3) clay suspension concentration in an ionic background
of 50 mM NaCIO4. Sufficient metal ion con centrations were present to
saturate the clays (92 and 5 cmol(c) kg(-1) for montmorillonite and k
aolinite, respectively). The pH value of the suspensions was adjusted
to 5.5 prior to initiation of the adsorption experiments. Kinetic stud
ies conducted under aseptic conditions indicated that within 2 h the a
dsorption of the SSDOC by the clays reached an equilibrium value. Adso
rption of SSDOC was found to be reversible with respect to small chang
es in the concentration of the adsorbate thus meeting the criteria for
thermodynamic equilibrium. Rapid adsorption of the SSDOC suggests tha
t adsorption was restricted to the external surfaces of the layer sili
cates. Statistical analysis of the data showed that all of the isother
ms were described by a linear isotherm model. The average isosteric he
at of adsorption <(Delta H)over bar>(qc)) was estimated to be O +/- 2
kJ mol(-1) SSDOC, within experimental error, for each of the clay meta
l combinations. The low values for <(Delta H)over bar>(qc) suggests th
at adsorption of SSDOC by montmorillonite and kaolinite is the result
of an increase in the configurational entropy of the clay-metal-SSDOC
system. Pooled adsorption data across temperatures yielded a single re
gression line for each clay-metal-SSDOC system with the following orde
r of slopes and calculated average free energy of adsorption <(Delta G
)over bar>(ads)): Pb > Cu > Cd. The observed order of the values for <
(Delta H)over bar>(ads) follow the same trend for the formation consta
nts of metal humic complexes. This observation suggests that the favor
able increase in <(Delta G)over bar>(ads) is the result of changes in
the conformation of the SSDOC making adsorption more favorable. When
the value for <(Delta G)over bar>(ads) was computed on the basis of ex
ternal clay surface area the differences between the two clays decreas
ed markedly, suggesting that adsorption was restricted to the external
surfaces of the minerals.