6e. Aquatic Geochemistry
6e. Aquatic Geochemistry
6e. Aquatic Geochemistry
Natural Waters
Aquatic Geochemistry
A. Koschinsky
Aquatic Geochemistry - Introduction
Some general definitions
Excercise: 1. Express „5 µmol/l Pb“ in the unit mg/l (atomic weight Pb = 207).
2. Express „60 mg/l CO2“ in the unit mmol/l (molecular weight CO2 = 44).
Activity a = c(concentration) x f
(activity coefficient, also called )
a. hydrated radius of
ion ()
c. ionic strength of
solution ()
= 1/2 cizi2
Aquatic Geochemistry - Introduction
Speciation
Importance of Speciation
Speciation
1. Oxidation State
2. pH
3. Composition of Inorganic Ligands (OH-, CO32-, HS-)
4. Composition of Organic Ligands (Humic and Fulvic Acids, others)
5. Pressure and Temperature
Importance of pH in Speciation
Central ion (metal) - ligands (ions or molecules that surround, or coordinate, the
central ion)
The simplest complexes are those formed between metals and water: aquo
complexes (Water molecules are the ligands). Aquo-complexes are ubiquitous:
all charged species will have a solvation shell. Truly “free ions” do not exist.
pH
size of the central ion
charge of the central ion.
Complexation - Other complexes
Complexation - Other complexes
With respect to complex formation, the elements can be divided into four classes:
1. non-metals (forming anions), ligand formers.
2. “A-type” or “hard” metals. These metals have spherically symmetric,
inert-gas type outer electron configurations. Their electron shells are not readily
deformed by electric fields and can be viewed as “hard spheres”.
Dependence on pH and
temperature
Complexation - Speciation Calculation
Dependance on ligand concentration and temperature
Pb 0 0 4
Zn
1
4 2
2
3
3
1
Pb 1
2 Zn 2
1 3
0 4
Solid - Solution Interactions
Mineral surface - interface - solution
The processes at the interface govern equilibria between solids and solutions.
Solid - solution interactions: Adsorption
Important: Many minerals have large active surface areas (strong sorptive
properties)!
Example: In natural marine solids, the following specific surface areas were measured:
Surface complex
formation: The formation
of coordinative bonds
between metals and
ligands at the surface
(similar to the formation of
complexes between
dissolved components).
Reactions between these surface groups and dissolved species are influenced
by the proximity of surface groups to each other. For example, the surface
charge will change systematically as the adsorbed surface concentration of a
positive species such as H+ increases. This change in surface charge will
decrease the attraction between H+ ions and the surface. As a result, the
equilibrium constant for the surface protonation reaction will change as the
surface concentration of H+ increases.
- - - -H - -H
Oxide + H -->
+
Oxide + H -->
+
Oxide …
- - - - - -H
(pK = -logK)
Surface complexation
Stable surface complexes are most likely to be formed at surface irregularities
such as kinks and steps (see scheme below, formation of copper complexes
on calcite surface). The presence of other metal ions may lead to the
incorporation of these ions into the crystal lattice, or to the inhibition of the
calcite crystal growth. Both processes involve the substitution of Ca by these
ions at the surface complexation sites.
Adsorption: oxide surfaces in water
Oxygen and metal atoms at an oxide surface are
incompletely coordinated; i.e., they are not
surrounded by oppositely charged ions as they
would be in the interior of a crystal (Fig. a).
Consequently, mineral surfaces immersed in
water bind water molecules (Fig. b), which can
then dissociate, leaving a hydroxyl group bound
to the surface metal ion:
Adsorption on a mineral
surface may occur when
Multidentate adsorption
2-
involves more than one
surface site (e, f).
pH dependence of adsorption
Since surface bound protons and OH groups are almost inevitably involved in
adsorption, adsorption of metals and ligands is strongly pH dependent. This strong
dependence on pH certainly reflects protonation of the surface, but it also reflects
the extent of hydrolysis of the ion in solution.
Surface charge of particles
Mineral surfaces develop electrical charge for several reasons:
Complexation reactions between the surface and dissolved species, including
protonation and deprotonation. Because these reactions depend on pH, this aspect
of surface charge is pH dependent.
Thus there are several contributions to surface charge density. We define net as
the net density of electric charge on the solid surface, and can express it as:
net = 0 + H + SC
where 0 is the intrinsic surface charge due to lattice imperfections and
substitutions,
H is the net proton charge, i.e., the charge due to binding H+ and OH–,
SC is the charge due to other surface complexes.
is usually measured in coulombs per square meter (C/m2).
Surface charge of particles
Sorbed ions may be incorporated into the host structure via dissolution and
recrystallization.
Surface precipitation and solid solution
In surface precipitation, cations (or anions) which adsorb to the surface of a mineral,
may form a precipitate of the cation (anion) with the constituent ions of the mineral
at high surface coverage.
Cations at the solid-water interface are treated as surface species, while those not
in contact with the solution phase are treated as solid species forming a solid
solution. The formation of solid solution implies isomorphic substitution.
Precipitation of ions as
insoluble (low solubility) minerals
is a major mechanism by which
metal concentrations are limited
in groundwater and other natural
waters.
than PbSO4
The presence of minerals such as CaCO3 and CaSO4 can suppress the solubility
of metals such as Pb and Cd via the common ion effect.
Dissolution/precipitation - solubility calculations
2,7,9 ?
Because they are strong bases, the solubilities of hydroxides, sulfides and
carbonates will depend on the pH.