Particle size• Ions molecular clusters nanocrystals

colloids bulk minerals• Small particles can have a significant % of

molecules at their surface– Thermodynamics are different (surface free

energy)– Surface area per mass is huge and charged

through interaction with water– Sorption of ions to these surfaces can be critical

part of contaminant mobility

Surface area• Selected mineral groups often occur as colloids /

nanoparticles:– FeOOH SA up to 500 m2/g, site density 2-20/nm2

– Al(OH)3 SA up to 150 m2/g, site density 2-12/nm2

– MnOOH SA hundreds m2/g, site density 2-20/nm2

– SiO2 SA 0.1 – 300 m2/g, site density 4-12/nm2

– Clays SA 10-1000 m2/g, site density 1-5/nm2

– Organics SA up 1300 m2/g, site density 2/nm2

DEFINITIONS• Sorption - removal of solutes from solution onto mineral

surfaces.• Sorbate - the species removed from solution.• Sorbent - the solid onto which solution species are sorbed.• Three types of sorption:

– Adsorption - solutes held at the mineral surface as a hydrated species.

– Absorption - solute incorporated into the mineral structure at the surface.

– Ion exchange - when an ion becomes sorbed to a surface by changing places with a similarly charged ion previously residing on the sorbent.

Mineral Surfaces• Minerals which are precipitated can also

interact with other molecules and ions at the surface

• Attraction between a particular mineral surface and an ion or molecule due to:– Electrostatic interaction (unlike charges attract)– Hydrophobic/hydrophilic interactions– Specific bonding reactions at the surface

Inner Sphere and Outer Sphere

• Outer Sphere surface complex ion remains bounded to the hydration shell so it does not bind directly to the surface, attraction is purely electrostatic

• Inner Sphere surface complex ion bonds to a specific site on the surface, this ignores overall electrostatic interaction with bulk surface (i.e. a cation could bind to a mineral below the mineral pHzpc)

Charged Surfaces

• Mineral surface has exposed ions that have an unsatisfied bond in water, they bond to H2O, many of which rearrange and shed a H+

• ≡S- + H2O ≡S—H2O ≡S-OH + H+H+

OH

OH

OH

OH

H+OH2

OH

OH

Surfaces as acid-base reactants

• The surface ‘SITE’ acts as an amphoteric substance it can take on an extra H+ or lose the one it has to develop charge

• ≡S-O- + H+ ↔ ≡S-OH ↔ ≡S-OH2+

• The # of sites on a surface that are +, -, or 0 charge is a function of pH

• pHzpc is the pH where the + sites = - sites = 0 sites and the surface charge is nil

OH2+

OH

OH

OH

O-

O-

OH2+

pHzpc• Zero Point of Charge, A.k.a: Zero Point of Net

Proton Charge (pHZPNPC) or the Isoelectric Point (IEP)

• Measured by titration curves (pHzpc similar to pKa…) or electrophoretic mobility (tendency of the solids to migrate towards a positively charged plate)

• Below pHzpc more sites are protonated net + charge

• Above pHzpc more sites are unprotonated net - charge

POINT OF ZERO CHARGE CAUSED BY BINDING OR

DISSOCIATION OF PROTONS

Material pHpznpc Material pHpznpc Material pHpznpc-Al2O3 9.1 -Fe2O3 8.5 ZrSiO4 5-Al(OH)3 5.0 Fe(OH)3 8.5 Feldspars 2-2.4-AlOOH 8.2 MgO 12.4 Kaolinite 4.6CuO 9.5 -MnO2 2.8 Montmorillonite 2.5Fe3O4 6.5 -MnO2 7.2 Albite 2-FeOOH 7.8 SiO2 2 Chrysotile >10

From Stumm and Morgan, Aquatic Chemistry

ION EXCHANGE REACTIONS

• Ions adsorbed by outer-sphere complexation and diffuse-ion adsorption are readily exchangeable with similar ions in solution.

• Cation exchange capacity: The concentration of ions, in meq/100 g soil, that can be displaced from the soil by ions in solution.

• Also anion exchange capacity for positively charged surfaces

ION EXCHANGE REACTIONS

• Exchange reactions involving common, major cations are treated as equilibrium processes.

• The general form of a cation exchange reaction is:

nAm+ + mBX mBn+ + nAX• The equilibrium constant for this reaction

is given by:mB

nA

nA

mB

NN

aaK

CATION EXCHANGE CAPACITIES OF MINERALS AND SOILS

SORPTION ISOTHERMS - I• The capacity for a soil or mineral to adsorb a solute

from solution can be determined by an experiment called a batch test.

• In a batch test, a known mass of solid (S m) is mixed and allowed to equilibrate with a known volume of solution (V ) containing a known initial concentration of a solute (C i). The solid and solution are then separated and the concentration (C ) of the solute remaining is measured. The difference C i - C is the concentration of solute adsorbed.

Kd

• Descriptions of how solutes stick to the surface

• What would the ‘real’ behavior be you think??

Kd

SORPTION ISOTHERMS - II• The mass of solute adsorbed per mass of dry solid is

given by

where S m is the mass of the solid.• The test is repeated at constant temperature but

varying values of C i. A relationship between C and S can be graphed. Such a graph is known as an isotherm and is usually non-linear.

• Two common equations describing isotherms are the Freundlich and Langmuir isotherms.

m

i

SVCCS

FREUNDLICH ISOTHERMThe Freundlich isotherm is described by where K is the partition coefficient and n 1.

nKCS

When n < 1, the plot is concave with respect to the C axis. When n = 1, the plot is linear. In this case, K is called the distribution coefficient (Kd ).

C (mg L-1)0 10 20 30 40

S (m

g g-1

)

0

10

20

30

40

50

60

S = 1.5C1.0

S = 5.0C0.5

FREUNDLICH ISOTHERMS

LANGMUIR ISOTHERMThe Langmuir isotherm describes the situation where

the number of sorption sites is limited, so a maximum sorptive capacity (S max) is reached.

C (mg L-1)0 10 20 30 40

S (m

g g-1

)

0

10

20

30

40 LANGMUIR ISOTHERMS

CCS

1.011.030

CCS

5.115.130

The governing equation for Langmuir isotherms is:

KCKCSS

1max

Sorption of organic contaminants

• Organic contaminants in water are often sorbed to the solid organic fractions present in soils and sediments

• Natural dissolved organics (primarily humic and fulvic acids) are ionic and have a Koc close to zero

• Solubility is correlated to Koc for most organics

solutionin g/mlC organic solidadsorbed/g gKoc

Measuring organic sorption properties

• Kow, the octanol-water partition coefficient is measured in batches with ½ water and ½ octanol – measures proportion of added organic which partitions to the hydrophobic organic material

• Empirical relation back to Koc:

log Koc = 1.377 + 0.544 log Kow

ADSORPTION OF METAL CATIONS - I

• In a natural solution, many metal cations compete for the available sorption sites.

• Experiments show some metals have greater adsorption affinities than others. What factors determine this selectivity?

• Ionic potential: defined as the charge over the radius (Z/r).

• Cations with low Z/r release their waters of hydration more easily and can form inner-sphere surface complexes.

ADSORPTION OF METAL CATIONS - II

• Many isovalent series cations exhibit decreasing sorption affinity with decreasing ionic radius:

Cs+ > Rb+ > K+ > Na+ > Li+

Ba2+ > Sr2+ > Ca2+ > Mg2+

Hg2+ > Cd2+ > Zn2+

• For transition metals, electron configuration becomes more important than ionic radius:

Cu2+ > Ni2+ > Co2+ > Fe2+ > Mn2+

ADSORPTION OF METAL CATIONS - III

• For variable-charge sorbents, the fraction of cations sorbed increases with increasing pH.

• For each individual ion, the degree of sorption increases rapidly over a narrow pH range (the adsorption edge).

Exchange reaction and site competition

• For a reaction: A + BX = B + AX

• Plot of log[B]/[A] vs. log[BX]/[AX] yield n and K

• When n and K=1 Donnan exchange, exhange only dependent on valence, bonding strictly electrostatic

• When n=1 and K≠1 Simple ion exchange, dependent on valence AND size, bonding strictly electrostatic

• When n≠1 and K≠1 Power exchange, no physical description (complicated beyond the model) and unbalanced stoichiometry

][][loglog

][][log

BXAXnK

AB

ex

n

ex BXAX

ABK

][][

][][

Electrostatic models

• Combining electrostatic interactions and specific complexation using mechanistic and atomic ideas about the surface yield models to describe specific sorption behavior