1

Chapter 5

PHASE INTERACTIONS IN AQUATIC

CHEMISTRY

Environmental Chemistry, 9th Edition

Stanley E. Manahan
Taylor and Francis/CRC Press
2010

For questions, contact:

Stanley E. Manahan
manahans@missouri.edu
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5.1 Chemical Interactions Involving Solids, Gases,

and Water (Figure 5.1)

5.2 Importance and Formation of Sediments

Sediments are
Layers of relatively finely divided matter
Cover bottoms of various bodies of water
Generally mixtures of clay, silt, sand, organic matter
Various organisms
Pollutants including heavy metals, organics
Transfer to organisms directly or through pore water
Formation of sediments
Physical transfer of material
Chemical precipitation
Biochemical processes such as photosynthesis producing
biomass and solid CaCO3, action of anoxic bacteria
producing solid FeS

Figure 5.2 Alternate layers of CaCO3(s) and FeS(s) in lake

sediment

Organic and Carbonaceous Sedimentary Materials

Particularly important for binding organic pollutants
Organics may be held for many years
Black carbon from combustion

5.3 Solubilities
Solubilities of solids
From solubility products (see calculation of solubility of
BaSO4 in text
Intrinsic solubility, example of CaSO4
S=
[Ca2+]
+
[CaSO4]
From solubility product

From intrinsic solubility

Solubilities of ionic solids affected by several factors,

example of PbCO3 (see Section 3.15)
Increased by chelation of metal: Pb2+ + T3- PbT Increased by reaction of anion:
PbCO3 + H+ Pb2+ + HCO3 Presence of common ion:
HCO3- H+ + CO32-

Solubilities of Gases
Henrys law: At constant temperature the solubility of a gas
in a liquid is proportional to the partial pressure of the gas
in contact with the liquid
X(g) X(aq)
[X(aq)] = KPX
Increased by acid-base reactions
NH3(g) + H+ NH4+(aq)
SO2(g) + HCO3-(alkalinity) HSO3-(aq) + CO2

Concentration of O2 in water in contact with air at

25C

The Clausius-Clapeyron equation for gas solubilities C1 and

C2 at absolute temperatures of T1 and T2 where R is the gas
constant and DH is the heat of solution

C2
log
C1

H
1
1
=
T2
2.303R T1

5.4 Colloidal Particles in Water

Size range of 0.001 1 micrometers
Include
Minerals Microorganisms Organic matter
Proteinaceous material
Important characteristics
Light scattering (Tyndall effect) High area
High interfacial area High surface/charge density ratio
Important, widespread in natural waters and wastewaters
Colloid-facilitated transport of pollutants
Colloids are widespread in water and wastewater
Kinds of colloids
Hydrophobic Hydrophilic Association

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Figure 5.3 Charged hydrophobic colloidal particles

surrounded by counter-ions
+

+ -+
+

+
+
+
+
- - - +
+
+ - - - - + --- ++ - - - +
- +
+ -- - + +
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
- - +
+
++ + + +
- + -- - - +
+
-- + + - - +
-- - - +
+ + -- + +
+
+
- +
+
-+
+
+
+
+
+
+ +
+
+
+
+

Figure 5.4 Colloidal soap micelle particles

HHHHHHHHHHHHHHHHHO
+
H C C C C C C C C C C C C C C C C C C O Na
HHHHHHHHHHHHHHHHH
Represented as

- Na+

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Colloid stability
Stabilized by attraction to water and by surface charge
Colloidal particles acquire charge by
Surface chemical reaction, often involving H+ (see Figure
5.5, next slide)
Ion absorption
Ion replacement (such as Al(III) for Si(IV)) in clays

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Figure 5.5 Acquisition of surface charge by

H
H
colloidal MnO2 O
O
O
H
Mn

O Mn O

O
O Mn

O
O Mn

O
Mn

O Mn
H
Hydration
+H 2 O

O Mn

O
O Mn

O Mn O

O Mn

O
H

Loss
of H

O Mn O

O Mn
H

O Mn O

O Mn

O Mn O

O Mn O

O
II

Gain of H
+

O
-

HO M n

OH

O
O Mn
HO M n

O M n OH

OH

H
-

O Mn
H

O
O M n OH
-

O
III

O M n OH
O

O M n OH
O

O Mn O

O
H

HO M n

O Mn O

H
O

HO M n

O Mn O

O
O Mn

O Mn

O
-

O Mn O

H
O

OH
IV

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5.5 The Colloidal Properties of Clays

Clays are widespread as colloidal particles in water and as
solids in sediments
Secondary minerals
Hydrated aluminum and silicon oxides
Common clays include
Kaolinite: Al2(OH)4Si2O5
Montmorillonite: Al2(OH)2Si4O10
Nontronite: Fe2(OH)2Si4O10
Hydrous mica: KAl2(OH)2(AlSi3)O10
Unit layers in clay structures
Clays acquire charge usually by substitution of Al(III) for
Si(IV)
Exchangeable cations, such as H+, K+, NH4+
Cation exchange capacity

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Aggregation of Particles
Important in water
Example: Settling of waste biomass in wastewater
treatment
Example: Formation of sediments from river water
entering oceans
Mechanisms of aggregation
Coagulation from reduction of surface charge repulsion
Flocculation with bridging compounds that produce floc
networks
Flocculation is facilitated by synthetic and natural
polyelectrolytes

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Figure 5.6 Aggregation and restabilization of

charged colloidal particles

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Figure 5.7 Surface sorption by solids

Many of the effects of colloidal and sedimentary solids in
contact with water have to do with their sorption of solutes
Metals are sorbed by solids, particularly metal oxides
Nonspecific ion exchange adsorption
Complexation with surface OH groups
Coprecipitation with the metal oxide
Discrete oxide or hydroxide sorbed to metal
Hydrated manganese(IV) and iron(III) oxides are good
sorbents, especially when freshly precipitated
Freshly precipitated MnO2 may have a surface area of
several hundred square meters per gram
Anions are also sorbed by solids
Usually with less specific bonding than metals

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5.8 Solute Exchange with Bottom Sediments

Bottom sediments are important sources and sinks of
inorganic and organic matter in streams, fresh-water
impoundments, estuaries and oceans
Generally anoxic (reducing conditions)
Generally high levels of organic matter
Cation exchange capacity (CEC) expresses the capacity of a
sediment to sorb cations
Expressed as milliequivalents per 100 g solid
Exchangeable cation status (ECS) refers to specific ions
held by sediments
Common cations held by sediments are H+, K+, NH4+, Ca2+,
Mg2+, Fe2+, Mn2+, Zn2+, Cu2+, Ni2+
Sediments act as buffers by exchanging H+

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Trace-Level Metals in Suspended Matter and

Sediments
Trace metals held in sediments and colloidal suspensions
include cadmium, chromium, cobalt, copper, manganese,
molybdenum, and nickel
Metals held in suspended particles less available than those
in solution but more so than those in sediments
pE is an important factor
High pE (oxic, oxidizing): Oxides, hydroxides, and
carbonates such as HgO, C(OH)2CuCO3
Low pE (anoxic, reducing): Sulfides predominate such as
CdS, PbS

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Phosphorus Exchange with Bottom Sediments

Important in algal growth eutrophication
Forms of phosphorus in sediments
Phosphate minerals, Ca5OH(PO4)3
Nonoccluded phosphorus such as PO43- held on mineral
surfaces
Occluded phosphorus with orthophosphate ions contained
within mineral matrix, such as in aluminosilicates
Organic phosphorus in biomass (usually algal or bacterial)

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Organic Compounds on Sediments and Suspended

Matter
Sediments as sinks and repositories of organic matter
Colloids may transport organic matter
Sorption affects degradation of organic matter
Common sorbents are clays, humic substances and
complexes between clays and humic substances
Sorption generally proportional to water solubility

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Bound residues of organics

Bound residues of persistent organic pollutants form during

humification of organic matter
Immobilization
Detoxification

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Bioavailability of Sediment Contaminants

The facility with which a substance may be taken up by
organisms
May be direct or through water (Figure 5.7 below)

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5.9 Interstitial Water

Water held in voids and pores in sediments
Reflects chemical and biochemical conditions in sediment
Products of decomposition and mineralization of
planktonic biomass
Largely through activity of anoxic bacteria in sediments
Gases in interstitial water
Usually virtually no O2
N2 usually stripped by action of anoxic bacteria producing
CO2 and CH4

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5.10 Phase Interactions in Chemical Fate and Transport

Hydrosphere is particularly important in fate and transport
Rivers move dissolved and suspended substances long
distances
Water bodies are repositories, but movement still occurs
Figure 5.8 Relatively more mixing involved with sediment in
chemical fate and transport occur in a shallow water body
(left) compared to a deeper, stratified body (right)
Wind flow
Wind drift
Return current

Wind flow
Wind drift
Epilimnion layer
Return current
Quiescent hypolimnion

Disturbed sediment
Undisturbed sediment

Exchange with the Atmosphere

Gases from air to water
Oxygen required by fish
Carbon dioxide required by algae
Air pollutants including acid gases and particles
Gases from water to air
O2 from algal photosynthesis
CO2 from microbial degradation of organic matter
H2S from anoxic microbial reduction of SO42 Volatile organic water pollutants

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Exchange with Sediments

2000

10

1980
Replacement of leaded
gasoline with unleaded

20
30

Rise in use of leaded

gasoline

40
50

Gradually increased industrial

use, lead paint

1960
1940
1920
1900

60

1880

70

1860
0

100 200 300 400 500 600 700 800

Lead concentration in sediment, mg/kg

Year of deposition

Depth into sediment, cm

Pollutants are incorporated with particles as they form and

settle in water and are placed in sediments
Figure 5.9 Sediment record of environmental lead

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