Environmental Mineralogy

Dr. Doni P E Putra

 Basic Mineralogy
 Mineral  a naturally occurring inorganic
substance with a characteristics internal
structure and a chemical composition that is
either fixed or varies within certain limits
 Environmental Mineralogy
 Interdisciplinary field dealing with systems at, or
near, the surface of the Earth where geosphere
comes into contact with the hydrosphere,
atmosphere and biosphere.

 It deals with those systems containing minerals

that constitute key environments; both pure
systems and those contaminated through human
activities.
Ta ble 7-1. Mineral cl asses

Class Chemical characteristics Examples

Borates Vario us elements in co mbination with boron Borax [Na2 B4 O 7 

10H 2 O]

Carb onates Metals in co mbination with carb onate Calcite [CaCO 3 ]

2
( CO 3 ) Cerrusite [Pb CO 3 ]

Halides Alkali metals or alkaline earths in Halite [NaCl]

co mbination with halogens (F, Cl, Br, I) Fluorite [CaF 2]

Hydro xides Metals in co mbination with hyd ro xyls (OH -) Brucite [Mg(OH) 2]

Native elements Pure co mpound of a metallic or non metallic Gold [Au]

element Graphite [C]

O xid es Metals in co mbination with o xygen Hematite [Fe 3O 4 ]

Phosphates, arsenates, Vario us elements in co mbination with the Apatite [Ca5 (PO 4 )3 (F,Cl,OH)]
vanadates, chro mates, ZO 4 radical where Z = P, As, V, Cr, W , M o Carnotite [K 2(UO 2 (VO 4) 2 
3H 2 O]
tungstates & molybdates Scheelite [CaWO 4 ]

Silicates Metals in co mbination with silica tetrahedra Quartz [SiO 2 ]

4
( SiO4 ) for ming three d imensional Forsterite [MgSiO 4]
networks, sheets, chains and isolated Orthoclase [KAlSi 3O 8 ]
tetrahedra

Sulfates Alkaline earths or metals in co mbinatio n with Barite [BaSO 4 ]

2
sulfate ( SO 4 ) Epso mite [MgSO 4 
7 H 2O]

Sulfides One or more metals in co mbination with Pyrite [FeS2 ]

reduced sulfur or chemically similar elements Galena [PbS]
(As, Se, Te) Skutterudite [CoAs3 ]
 Type of Element Bonding

 Covalent  electrons share between atoms

 Ionic  electrons transfer from one atoms to another
 Metallic  electrons freely shared among all the atoms
 Hydrogen  weak electrostatic bond with other ions
 Electronegativity

• Ability of an atom or molecule to attracting an electrons

• The smaller the electronegativity  the smaller is the

likelihood of the atom attracting an electron

• Note: the bond between the same element; C-C, do not

have an ionic character, electronegativity is zero
Ta ble 7-2 . Electroneg ati vities
Electro- Electro- Electro-
Z Ion negativity Z Ion negativity Z Ion negativity
1 H+ 2.2 0 33 As5 + 2.18 65 Dy 3+ 1.22
+ 2- 3+
3 Li 0.9 8 34 Se 2.55 67 Ho 1.23
2+ - 3+
4 Be 1.5 7 35 Br 2.96 68 Er 1.24
3+ + 3+
5 B 2.0 4 37 Rb 0.82 69 Tm 1.25
4+ 2+ 3+
6 C 2.5 5 38 Sr 0.95 70 Yb ---
5+ 3+ 3+
7 N 3.0 4 39 Y 1.22 71 Lu 1.0
2- 4+ 4+
8 O 3.4 4 40 Zr 1.33 72 Hf 1.3
- 5+ 5+
9 F 3.9 8 41 Nb 1.6 73 Ta 1.5
+ 6+ 6+
11 Na 0.9 3 42 Mo 2.16 74 W 1.7
2+ 2+ 7+
12 Mg 1.3 1 43 Tc 2.10 75 Re 1.9
3+ 2+ 6+
13 Al 1.6 1 44 Ru 2.2 76 Os 2.2
4+ 2+ 6+
14 Si 1.9 0 45 Rh 2.28 77 Ir 2.2
5+ 2+ 4+
15 P 2.1 9 46 Pd 2.20 78 Pt 2.2
2- + +
16 S 2.5 8 47 Ag 1.93 79 Au 2.4
- 2+ 2+
17 Cl 3.1 6 48 Cd 1.69 80 Hg 1.9
+ 3+ 3+
19 K 0.8 2 49 In 1.78 81 Tl 1.8
2+ 2+ 2+
20 Ca 1.0 0 50 Sn 1.96 82 Pb 1.8
3+ 5+ 3+
21 Sc 1.3 6 51 Sb 2.05 83 Bi 1.9
4+ 2- 4+
22 Ti 1.5 4 52 Te 2.1 84 Po 2.0
3+ - 5+
23 V 1.6 3 53 I 2.66 85 At 2.2
3+ + +
24 Cr 1.6 6 55 Cs 0.79 87 Fr 0.7
2+ 2+ 2+
25 Mn 1.5 5 56 Ba 0.89 88 Ra 0.9
2+ 3+ 3+
26 Fe 1.8 3 57 La 1.10 89 Ac 1.1
2+ 3+ 4+
27 Co 1.8 8 58 Ce 1.12 90 Th 1.3
2+ 3+ 4+
28 Ni 1.9 1 59 Pr 1.13 91 Pa 1.5
+ 3+ 6+
29 Cu 1.9 0 60 Nd 1.14 92 U 1.7
2+ 3+ 3+
30 Zn 1.6 5 62 Sm 1.17 93 Np 1.3
3+ 3+ 4+
31 Ga 1.8 1 64 Gd 1.20 94 Pu 1.3
4+
32 Ge 2.0 1
Ta ble 7-3. Percent ionic character of a single chemical bon d

Difference in Ionic Difference in Io nic

electronegativity character, % electronegativity character, %
0.1 0.5 1.7 51
0.2 1 1.8 55
0.3 2 1.9 59
0.4 4 2.0 63
0.5 6 2.1 67
0.6 9 2.2 70
0.7 12 2.3 74
0.8 15 2.4 76
0.9 19 2.5 79
1.0 22 2.6 82
1.1 26 2.7 84
1.2 30 2.8 86
1.3 34 2.9 88
1.4 39 3.0 89
1.5 43 3.1 91
1.6 47 3.2 92
Example:

The mineral fluorite has the chemical composition CaF2,

calculate the ionic character of the bond between Ca-F!

From Table 7.2.

Electronegativity Ca2+ = 1,00, F- = 3,98
Differenet electronegativity = (F-) – (Ca2+) = 3,98 – 1,00 = 2,98
From Table 7.3, the bond is 89% ionic.
 Coordination Number

• Most crystal structures can be viewed as polyhedra of

anions

• The number of anions fit around cations depend on the

relative size of the cations and anions
 sin θ = Ra/(Ra + Rc)

Radius Ratio = Rc/Ra

Figure 7-1. Packing of anions around a cation for a coordination number of 4. The
minimum radius ratio can be calculated from the geometry of the packing. Ra and
Rc are the radii of the anion and cation, respectively. In this case,  = 45o. See text
for calculation.
Figure 7-2. Possible arrangement of
ions in crystals for particular
coordination numbers (CN). Radius
ratio range is listed for each CN. From
Faure (1998).
 Ionic substitutions
1. Ions of one element can substitute for those of another in
a crystal structure if their radii differ by less than about
15%.
2. Ions that differ by one charge unit substitute readily for
each other as long as charge neutrality is maintained.
3. When two occupy the same site in a crystal structure, the
ion with higher ionic potential preferentially enters the
site
4. Even if the size and charge of the minor and major ion are
similar, substitution may be limited for the minor ion if it
has a very different electronegativity
 X-ray Crystallography

sin θ = BC / AC

BC = d sin θ

λ = 2BC = 2 d sin θ

n λ = 2 d sin θ

Figure 7-3. Diagram illustrating Bragg’s law.  = angle of incidence and

diffraction when Bragg’s law conditions are met. d = interplanar spacing.
X-ray Crystallography
 Basic Silicate Structures

Figure 7-4. Arrangement of silica tetrahedra in the various classes of silicate minerals. See text for further
discussion. From Brownlow (1996).
Table 7-4. Properties of the silicate crystal classes

# shared Che mical

Class Tetrahedral arrangement corners unit Si:O Example
4
Nesosilicate Independent tetrahedra 0 SiO4 1:4 Olivine
6
Sorosilicate Two tetrahedra sharing a corner 1 Si2 O 7 1:3.5 Melilite
3
Cyclosilicate Three or more tetrahedra sharing two 2 SiO3 1:3 Beryl
co rners, fo rming a ring
3
Inosilicate Single chain of tetrahedra sharing two 2 SiO3 1:3 Augite
co rners
6
Double chain of tetrahedra alternately 2.5 Si4 O 11 1:2.75 Hornblende
sharing two or three corners
2
Phyllosilicate Sheet of tetrahedra sharing three co rners 3 Si2 O 5 1:2.5 Kaolinite

Tektosilicate Framework of tetrahedra sharing all four 4 SiO2 1:2 K-feldspar

co rners
 Clay Minerals
One of the important mineral;
- A common product of the weathering of silicate minerals
- Play an important role in the sequestering of metals via
ion exchange
- Have a number of engineering use such as liners for
landfills

Clay Mineral:
“fine grained hydrous silicate composed of layers of
tetrahedrally and octahedrally coordinated cations”
Figure 7-5. Structure of the octahedral and tetrahedral layer. Mg2+ in the octahedral layer =
brucite. Al3+ in the octahedral layer = gibbsite. Al3+ can substitute for Si4+ in the tetrahedral
layer.
T able 7-5. Su m mary of the princi pal characteristics of the layere d clay miner al gr ou ps

Kaolinites Illites S mectites Ver miculites

Structure 1:1 2:1 2:1 2:1

Tetrahedral:
Octahed ral

Octahed ral layer Di-octahedral Mostly di- Di- or tri- Mostly tri-
octahedral octahedral octahedral

Interlayer cations Nil K Ca , Na Mg

Interlayer water Only in halloysite So me in Ca , two layers Ca , two layers
hydro muscovite Na, one to many K, one layer to nil
layers

Basal spacing 7.1  10  Variable Variable

most ~15  14.4  when fully
hydrated

Ethylene glycol Only taken up by No effect Two glycol la yers, One glycol layer,
halloysite 17  14 

Cation e xchange Nil Lo w High High

capa city (C EC) in 3 - 15 10 - 40 80 - 15 0 100 - 1 50
meq/10 0 g clay
Formula Al 2Si 2O 5 (OH)2 , K 0 .5-0.75 Al 2(Si,Al)2 M + 0 .7( Y3+ , Y2+ ) 4-6 M 2 + 0.6 6( Y2+ , Y3 + )6
little variation O 1 0(OH) 2 (Si,Al)8 O 20 (O H)4  n (Si,Al)8 O 20 (O H)4  8
H2 O H2 O
Dilute a cids Scarcely soluble Re adily attacked Attacked Re adily attacked

Heating 200 oC Except hallo ysite, No marked change Co llapse to Exfoliation,

unchanged appro xi mately 10 shrinkage o f layer
 spa cing
Exa mples Kaolinite, dickite, Illite, hydrous Mo ntmo rillonite , Ver miculite
nacrite , ha lloysite micas, phengite , beidellite,
bra mmallite , nontronite,
glauconite, hectorite , sap onite,
celadonite sauc onite
Figure 7-6. Structure of kaolinite. Each structural unit consists of a gibbsite layer and a tetrahedral
layer. Note that only two out of three octahedral sites in the octahedral layer are occupied.
Ta ble 7-6 . Su bstituti ons for smectite grou p cl ay minerals

M ineral Tetrahedral cations Octahedral cations Exchangeable cations

Di-octahedral

M ont morillonite Si8 Al3.3M g 0.7 (0.5 Ca,Na) 0.7

Beidellite Si7 .3Al0.7 Al4 (0.5 Ca,Na) 0.7
3
Nontronite Si7 .3Al0.7 Fe4 (0.5 Ca,Na) 0.7

Tri-octahed ral

Sapo nite Si7 .2Al0.8 Mg 6 (0.5 Ca,Na) 0.8

Hectorite Si8 Mg 5 .3Li0 .7 (0.5 Ca,Na) 0.7

Sauconite Si6 .7Al1.3 Zn 4-6(Mg,Al,Fe3 + )2-0 (0.5 Ca,Na) 0.7

Figure 7-7. Structure of montmorillonite, a 2:1 clay. The octahedral layer is a gibbsite layer.
Substitution of Mg2+ for Al3+ in the octahderal layer is charge balanced by the addition of Na+ or
Ca2+ cations (exchangeable cations) in the interlayer position.
Clay minerals - Ion Exchange Properties

Ta ble 7 -7. Permanent negati ve surface charge of 2:1 cl ay mineral

M ineral gro up Charge ( mol sites kg -1)2

Kaolinite 0.02 - 0.2

Illites 0.1 - 0.9

S mectites 0.7 - 1.7

Vermiculites 1.6 - 2.5

CEC (meq/100 g) = Nsm (mole sites /g) x 1.0 x 105

Clay minerals - Ion Exchange Properties

Table 7-8. Surface area per unit mass of illite with a density of 2600 kg m-3-3

Length of side ( m) Number of cubes Surface area of cube (m2 ) Surface area ( m2 g -1)

1 1 6 2.3 x 10 -6
1 x 10 -2 (cm) 1 x 10 6 6 x 10 -4 2.3 x 10 -4

1 x 10 -6 (1 µm) 1 x 10 1 8 6 x 10 -12 2.31

1 x 10 -7 (0.1 µm) 1 x 10 2 1 6 x 10 -14 23.1
1 x 10 -8 (0.01 µm) 1 x 10 2 4 6 x 10 -16 231
 Zeta Potential

• A measure of the potential energy difference between a

bulk solution and the boundary between the free solvent
and the solvent adhering to the surface.
• The zeta potential varies as a function of pH
• Positive zeta potential  adsorb negative ions
• Negative zeta potential  adsorb positive ions
 PZC

• Lower pH of PZC  net surface charge positive

• Higher pH of PZC  net surface charge negative
Ion Exchange Properties – Determination

Figure 7-8. Representation of a typical adsorption isotherm showing the distribution of a species between
an aqueous phase and a solid (sorbent). At very low concentrations, the distribution behaves ideally and can
be represented by a unique value, Kd. At higher concentrations, the partitioning deviates from ideality. If
precipitation occurs, the concentration of the species in solution will remain constant; i.e., the solution is
saturated with respect to the particular species.
 Batch Method

Linear isotherm
Cads = Kd.Csoln

Freundlich Isoterm
Cads = Kd. Csolnn
Log Cads = Log Kd + n Log Csoln

Langmuir Isoterm QoKCsoln

Cads =
1 + KCsoln
Figure 7-9. Plot of the log of the concentration of the substance adsorbed on a particle
(Cads) versus the log of the concentration of the substance in water (Csoln). Linear plots
indicate that the partitioning can be represented by a Freundlich isotherm. The slope
of the line gives the exponent, n, and the intercept gives the value for log K.
Figure 7-10a. Langmuir isotherms for Qo = 40 mg g-1 and K =
0.1, 0.5, and 2.

Figure 7-10b. Linearized form of the isotherms plotted in Figure 7-

10a. The y-intercept is 1/Qo and the slope = 1/KQo.
Figure 7-C2-1. Adsorption isotherms for sepiolite. Adsorbent dose = 10 g L-1, agitation time = 3 h,
pH = 4, and T = 22oC. The Langmuir equation provided the best fit to the adsorption isotherms.
From Sanchez et al. (1999).
Figure 7-C2-2. Effect of pH on the adsorption of metal cations by sepiolite. Adsorbent dose = 5 g L-1,
initial cation concentration = 50 mg L-1, agitation time = 2 h. With increasing pH the adsorption of the
metal ions increases. From Sanchez et al. (1999).
 Column Test Method

Ci – Cf V
Kd =
Cf M

Where:
Kd Distribution coefficient
Ci Initial concentration of sorbate
Cf Final concentration of sorbate
V Volume of solution passed through column
M Mass of sorbent in the column
Example:

Ten grams of montmorilonite are placed in a column and 100 ml

of solution are passed through the column. The initial solution
had a zinc concentration of 20 mg/L. After passing through the
column, the solution had a zinc concentration of 14.1 mg/L.
Calculate the Kd for zinc!
 ZEOLITES

• A crystalline substance with a structure characterized by a

frame work of linked tetrahedra, each consisting of four O
atoms surrounding a cation.
• This framework contains open cavities in the form of
channels and cages

MxDy[Alx+2ySin-(x+2y)O2n].mH2O
Where:
M Na, K and other monovalent cations
D Mg, Ca, Sr, Ba and other divalent cations
 ZEOLITES
Ta ble 7-9 . Chemical formulas an d various pro perties of representati ve natural zeolites

Void
M ineral Representative chemical for mula Si:(Si+Al) space Free aperture size

Erionite NaK 2 Mg Ca1.5 (Al8 Si28 )O 72·28 H 2O 0.75-0.78 0.36 3.6Å x 5.2Å
8-rings  (0 01)

M ordenite Na3 KCa2 (Al8 Si4 0)O 96 ·8 H 2O 0.80-0.85 0.26 6.7Å x 7.0 Å
12-rings (001)
2.9Å x 5.7Å
8-rings (010)

Clinoptilo lite (Na,K)6 (Al6Si30 )O 72·20 H 2O 0.74-0.84 0.34 3.5Å x 7.9Å

10-rings (001)
3.0Å x 4.4Å
8-rings

Phillipsite K 2(Ca 0.5,Na) 4(Al6Si10 )O 3 2·12H 2 O 0.54-0.75 0.30 4.2Å x 4.4Å

8-rings (100)
2.8Å x 4.8Å
8-rings (010)
3.3Å diameter
8-rings (001)

Chabazite Ca2 (Al4 Si8 )O 2 4·12H 2 O 0.59-0.80 0.48 3.7Å x 4.1Å

8-rings
Figure 7-11. The structure of mordenite viewed (a) down the c-axis and (b) obliquely down the c-axis. Note
the presence of two sets of channels, one consisting of 12-membered rings and the other of 8-membered rings
(count the tetrahedra around the large and small channels). From Bish and Guthrie (1993).
Ta ble 7-10. Theoretical cation-exchange ca pacity for selected zeolite minerals

CEC
Zeolite Typical Unit-Cell Formula ( meq/10 0 g)
Analci me Na16(A L16Si32 O 96 )
16H 2 O 4 50

Chabazite Ca2(Al4Si8O 2 4)

1 2H 2O 3 90
Clinoptilolite (Na,K) 6(AL6 Si3 0O 7 2)
20 H 2O 2 20

Erionite NaK 2M gCa1 .5(Al8Si28 O 72) 

28H 2 O 2 80
Faujasite Na20 Ca12 Mg 8 (Al6 0Si1 32 O 38 4)
2 35H 2 O 3 60
Ferrierite (Na,K)Mg 2 Ca0 .5(Al6Si3 0O 7 2)
20H 2 O 2 30

Heuland ite (Na,K)Ca4 (Al9 Si2 7O 7 2)

24 H 2O 3 20
Lau montite Ca4(Al8Si16 O 48) 
16H 2 O 4 30
M ord enite Na3K Ca2(Al8Si40 O 96) 
28H 2 O 2 20
Natrolite Na16(Al16 Si2 4O 8 0)
1 6H 2O 5 30

Phillipsite K 2(Ca0 .5,Na) 4(Al6 Si1 0O 3 2)

12H 2 O 4 50
Wairakite Ca8(Al16 Si32 O 96 )
16 H 2) 4 60
 ASBESTOS MINERALS

Ta ble 7-11. Chemical formulas an d pro perties of as bestos minerals

Mineral Chemical for mula Crystal system Hardness Specific gravity

Chrysotile M g 3[Si2 O 5](OH)4 Mono clinic 2.5 

2.55
Actinolite Ca2(Mg,Fe2+ ) 5[Si8 O 22](OH,)2 Mono clinic 5-6 3.0 - 3.2

A mosite (Fe 2+ ,M g) 7[Si8 O 22](OH) 2 Mono clinic 5.5 - 6.0 3.1 - 3.25
Anthophyllite (Mg,Fe2+ ) 7[Si8 O 22](OH) 2 Orthorho mbic 5.5 - 6.0 2.85 - 3.1

Crocidolite Na 2Fe3+ 2(Fe2+ ,Mg) 3[Si8 O 22 ](OH) 2 Mono clinic 5 3.15 - 3.5
Tremolite Ca2M g 5[Si8 O 22 ](OH) 2 Mono clinic 5-6 2.9 - 3.2

• Two Types of Asbestos Mineral; Serpentine Minerals and

Fibrous Amphiboles.
Figure 7-12. Crystal structure of chrysotile, a 1:1 layer silicate
consisting of a tetrahedral layer and an octahedral layer in which
Mg2+ ions are surrounded by four OH molecules and two oxygens.

Figure 7-13. Simplified clinoamphibole structure looking

down the c-axis. The gray areas are the tetrahedral chains, the
cyanide area is the octahedral layer, and the filled circles
indicate the M4 cation positions.
 Type of Asbestos and their use

• Resistance to heat, friction and acid conditions

• Asbestos used  95% chyrsotile (white asbes) and 5%
amphibole asbes – crocidolite (blue asbes) and amosite
(brown asbes)
• Health impact to human
Figure 7-C4-1. Schematic diagram showing the various factors that affect the relationship among
exposure-dose-effect. Adapted from Johnson and Mossman (2001).
 Crystalline and Amorphous Silica

• There are six silica

polymorphs
• Same chemical
composition but
different crystal
structures
• Amorphous silica
(opal, SiO2.nH2O)
• A common
constituent of soil
dust
• Quartz 
Figure 7-15. Phase diagram for the silica system Adapted from MANUAL
OF MINERALOGY, 21/e by C. Klein and C. S. Hurlbut, p. 681. Copyright © carcinogen
1993. This material is used by permission of John Wiley & Sons, Inc.
Example:
Calculate the Ksp for quartz and amorphous silica at pH =
5.5 and T = 25oC , which form of silica is more soluble?
 Mineral-Microorganism Interactions

• Role microorganism in the dissolution and precipitation of

minerals:
1. Dissolution and release of metal ions by acid and
complexing compounds produced by autotrophic and
heterotrophic.
2. Oxidation and reduction reactions promoted by
microorganisms that can lead to either increased and
reduced solubility of particular metals.
3. Changes in Eh and pH due to uptake and release of
different compounds or ions, which change the solubility
of various compounds.
Figure 7-16. Various pathways for the dissolution and weathering of minerals by soil
microorganisms. Note both the energy sources and products of the various pathways. See text
for further discussion. From Berthelin et al. (2000).