Chemically Precipitated Minerals

Chapter 8 deals with a wide range of everyday and "exotic" chemical ppts.
Many of the minerals come from same geologic and chemical processes.
Water-solubility is a very big issue
(1) allows build-up of dissolved constituents and eventual precipitation
(2) accounts for the need for fertilizer for plants
(3)causes the susceptibility of such precipitates/minerals to leaching

Geologically:
Basin forms, seawater becomes isolated, water evaporates, brine forms.
Saturation is reached, and one or more minerals precipitate

Evaporites are sedimentary deposits consisting of layers of individual

minerals, i.e., chemical precipitates.

Development of
Evaporite Deposits
Evaporation faster than water
influx Possible isolation
from influx Possible
desert environment
Concentration of dissolved ions
increases Saturation is reached
Nucleation of tiny crystals
occurs Sequential
precipitation of minerals

Chemically: seawater becomes increasingly

concentrated (brine) and finally reaches
saturation.

Cations (Na+, Ca2+) and anions (Cl-, SO42-)

build up; exceed solubility (i.e., no more can
dissolve).
Seawater
Sequence of minerals ppt. from evaporating
Evaporation seawater:
CaCO3 7 CaSO4 7 NaCl 7 Mg & K sulfates
7 Mg & K chlorides

Much limestone forms/formed this way.

Seawater NaCl (halite) and CaSO4 (anhydrite) common
1,000,000 grams
100%
1 metric ton
(tonne)

%
%
%

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 FERTILIZER AND CHEMICAL MINERALS

Introduction
Fertilizer and chemical minerals are part
of the nonmetallic mineral resources

Minerals processed for the

nonmetallic elements within them or
for the chemical or physical processes
they possess

Most of these are used as trace

amounts within other materials thus
are not widely known

There are hundreds of nonmetallic

elements and compounds used in tens
of thousands of combinations for
modern products and processes

Fertilizer as Example of
Important Chemical Mineral

Large tonnages of rock mined for fertilizer

Chemically intense processing

Strong (+, -) environmental implications of mining, processing, and use

N, P, K (nitrogen, phosphorus, potassium) are essential plant nutrients

Incorporation into essential molecules such as proteins and DNA

Act as catalysts to important biochemical reactions

Minerals for Fertilizers

Food crops require ~10 essential chemical elements

Hydrogen, oxygen, carbn -98% of living plant,

acquired from water and air mostly

Nitrogen, phosphorus, potassium, sulfur, calcium,

iron, magnesium
only 2% total needed but are vital for growth
process

extracted by plants from minerals or organic

matter in soils or in groundwater

many soils either dont naturally have all these

elements, or become exhausted in them with
repeated crop growths on same soil

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 Goals of Fertilizer
Application
Apply nutrients to (poor/depleted)
soil in water- soluble form that
plant roots can take up.

Bioavailability (ability to be drawn

into and used by plants) is the issue
with fertilizers, bioavailability is
essential.

Note: with other chemicals, such

as toxins, bioavailability is the fear
(undesired).

N, K, P:
Essential Elements for Plants
For centuries, we used biological products as fertilizer: manure, guano, dead
fish, bones, wood ash. Now have gone back to geological sources.

N: not much nitrogen in typical rocks (air has 78%)

Natural nitrate (NO 3) deposits form from evaporation of water,
but nitrate is so water-soluble that minerals typically dissolve away again
Manufacture of nitrogen fertilizer from nitrogen (from air) plus methane
(natural gas, CH4)

K: potassium is a geochemically abundant element

Major component in some feldspar (pink mineral in granite)
Evaporite minerals, such as KCl

P: phosphorus is essential in DNA, ATP, ADP (energy cycles of cells)

Often the life-limiting element
Bad aspect is eutrophication

Eutrophication
Entry of too much
nutrient material into a
lake causes algae to
bloom (covering the
water and blocking light)
and then die (consuming
oxygen from the water
during their decay).

Liberty Lake, WA, in the 1970s, while

suffering from eutrophication. Algae
completely cover the surface.

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 Minerals for Fertilizers
Historical Overview

use of natural fertilizers (manure, guano etc.) known for 1000s years
increased use of fertilizers from minerals and other processed sources in
last 100 years mostly

Minerals for Fertilizers

Historical Overview
has allowed huge increases in crop areas and yield and allowed feeding of
much larger world population than would be possible without extensive use
of fertilizers

Minerals for Fertilizers

Historical Overview

http://www.fertilizer101.org/facts/

World
population

Change in world population vs. fertilizer use Since 1950, population ~doubled, but
fertilizer use increased 10-fold.
CVS4, Fig. 9.3

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 Minerals for Fertilizers
Nitrogen (N)
essential part of all proteins and many amino acids in plants and
essential to photosynthesis process
not naturally abundant in most soils and rocks in soils, naturally
comes from breakdown of dead vegetation in soils over long periods

Nitrogen (N) Minerals for Fertilizers

early addition as fertilizer was from animal wastes spread on fields

still common
also guano (huge accumulations of bird dung mostly from arid coastal
islands)
very rich in both nitrogen and phosphate
almost all mined today from Nauru in south Pacific for Australia and
New Zealand

Nitrogen (N) Minerals for Fertilizers

99.8% of nitrogen now used for fertilizer is synthesized

Main method is Haber-Bosch process
Use to make ammonia (NH3)
Basic reaction of hydrogen with air and a iron catalyst
nitrogen from air binds with hydrogen to make ammonia
ammonia gas easily processed to make nitrogen-releasing
powder fertilizers

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Nitrogen (N) Minerals for Fertilizers

U.S. India and Canada are largest producers (and some of largest users)
air is 78% N2 so abundant supply
main control on price is cost of making Hydrogen from natural gas

Minerals for Fertilizers

Phosphorus (P)
Indispensable for lifeforms as vital in DNA and RNA and in
molecules involved in energy cycle in living cells

Usually considered as Phosphate (P2O5)

Phosphorus (P) Minerals for Fertilizers

Largest mineral source is Apatite - Ca5(P04)3(F, Cl, OH)2

occurs in mineable quantities in some igneous rocks and some marine
sedimentary rocks
Apatite is also the main natural constituent of bone material
ground bone was main source of phosphate fertilizer for 100s years
and still widely use

6
Phosphorus (P) Minerals for Fertilizers

can concentrate phosphate from apatite or bone by chemical processes

mostly involves reaction with strong sulfuric acid
results in very phosphate-rich superphosphate
apply as liquid form or powders to soils as fertilizer

Phosphorus (P) Minerals for Fertilizers

Many large deposits of apatite-bearing rock around world

>80% from marine phosphorites
Formed as apatite rich muds, nodules and crusts in some shallow
marine and coastal lagoon environments
Largest mines in U.S China, Morocco, Russia

Phosphorus (P) Minerals for Fertilizers

Large reserves exist

enough for foreseeable world demand for future
probably lots more deposits to be found if needed

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Phosphorus (P)
Need Phosphate in More Soluble Form
Phosphorite rock requires extensive chemical processing, e.g.,

Ca 3(PO4)2 + 2H2SO4 + 6H2O CaH4(PO4)2 + 2H2O + 2(CaSO4 2H2O) .

phosphate rock acid water monocalcium phosphate water gypsum

Production of phosphate fertilizer accounts for huge use of sulfuric

acid

Keep processing to get higher concentrations of phosphate in more

soluble form.

Hitchhiker elements (solid solution): uranium (0.01 - 0.03 wt. % U3O8),

vanadium, cadmium, selenium occur in natural phosphate deposits.
Unfortunately, they can become concentrated in the fertilizer (spread
on fields) or in the waste products (as in Florida) from phosphate
fertilizer production.

Problems with Mining, Processing, and

Use of Fertilizer
o Disruption of huge expanses of Phosphogypsum stack in Florida
coastal/environmentally sensitive land
o Waste gypsum (phosphogypsum)
Uranium release from crushed material
o Heavy-metal residues in the waste products

o Eutrophication due to use of phosphate

fertilizer

Ca3(PO4)2 + 2H2SO4 + 6H2O

CaH4(PO4)2 + 2H2O + 2(CaSO4 2H2O)

fertilizer gypsum

Flat-lying phosphate deposits in Florida and

N. Carolina are mined by mobile drag-lines.
Overburden removed, phosphate mined,
then land returned to approx. original state.
CVS4, Fig. 9.10

Minerals for Fertilizers

Potassium (K)

K+ is vital in plants as a catalyst in numerous plant functions

Nitrogen metabolism, synthesis of proteins, etc.

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Potassium (K) Minerals for Fertilizers

abundant in Earths crusts (8th most abundant) and widespread in many

rocks and soils
mostly as very common mineral potassium feldspar (KAlSi3O8)
weathers to common clay minerals containing K such as Illite
but difficult to recover K directly from feldspar and not really economic

Potassium (K) Minerals for Fertilizers

most K recovered from evaporate minerals common in some

evaporate deposits
most important are Sylvite (KCl) and several others
huge evaporate deposits formed in past in restricted marine basins

Potassium (K) Minerals for Fertilizers

huge evaporate deposits formed in past in restricted marine

basins

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Potassium (K) Minerals for Fertilizers

most K recovered from evaporate minerals common in some

evaporate deposits
mostly consist of simple salt Halite (NaCl) but also significant other
evaporative mineral layers as well including Sylvite and other K-
bearing minerals

Potassium (K) Minerals for Fertilizers

most K recovered from evaporate minerals common in some

evaporate deposits
very soft and ductile rocks tend to slowly flow upward as
Salt Diapirs with time
make large shallow deposits easily mined by open pit mining
or shallow underground mines
huge Permian age deposits in southern U.S. New Mexico
Texas Oklahoma Kansas
also giant Devonian deposits in Saskatchewan Canada

Potassium (K) Minerals for Fertilizers

huge deposits known and probably lots more

if needed
near endless world resource for future

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 Minerals for Chemicals
many minerals contain elements used in many industrial processes
and for other uses in society
only a few of more important or common are discussed here

Minerals for Chemicals

Sulfur (S)
abundant on Earths surface as native sulfur
also abundant in many sulfide minerals and in evaporate mineral
Gypsum

Sulfur (S) Minerals for Chemicals

sour gas (hydrogen sulfide) is a common byproduct of natural gas in

some fields
is increasingly the main source of raw sulfur

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Sulfur (S) Minerals for Chemicals

known as brimstone in ancient world

and used for many purposes,
including medicine and rituals

Sulfur (S) Minerals for Chemicals

also many industrial uses

sulfuric acid used in many chemical processes
trace amounts in many manufactured goods (e.g. soaps, rubber,
plastics, explosives, bleaches, paints etc etc)

Sulfur (S) Minerals for Chemicals

as a resource is very abundant

reserves very large - should never be a shortage

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 Minerals for Chemicals
Halite (NaCl)
common table salt and additive to many
processed foods

Halite (NaCl) Minerals for Chemicals

Na and Cl commonly based for other important chemicals

e.g Soda ash (Na2CO3); hydrochloric acid (HCl) and caustic soda
(NaOH)
also very important as de-icing component for roads, airplanes
etc.

Halite (NaCl) Minerals for Chemicals

naturally occurs in seawater and saline lakes

can be recovered by forced evaporation

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Halite (NaCl) Minerals for Chemicals

ancient deposits of evaporites formed ocean shores and in

restricted basins
can be 100s m thick and are dominated by Halite but with other
evaporate minerals too

Halite (NaCl) Minerals for Chemicals

if deeply buried commonly

flow upward in vertical Salt
Diapirs to make Salt Domes
mines in salt domes are
common mine by simple
water dissolution commonly

Halite (NaCl) Minerals for Chemicals

large salt mines in southeast U.S. (Texas etc.) but many

others as well

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Halite (NaCl) Minerals for Chemicals

abundant availability and supply for future

concerns about environmental effects of water and soil
contamination from overuse for road de-icing has lessened
demand as substitutes developed.
up to 1 kg of salt spread for each 1 m2 of road in parts of
Quebec

Minerals for Chemicals

Soda Ash (Na2CO3) and Sodium Sulfate (Na2SO4)

common minerals used as part of ingredients for many
manufactured products
widely used in manufacture of glass, soaps, dyes, detergents, paper, water
treatment
also used as common baking soda sodium bicarbonate (NaHCO3)

Soda Ash (Na2CO3) and Sodium Sulfate (Na2SO4) Minerals for Chemicals

can form artificially but large natural deposits available and cheaper to use
occur as evaporate minerals that form in some arid region lakes
e.g. Mono Lake in California (many others)
forms as trona natural soda ash bearing deposits

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Soda Ash (Na2CO3) and Sodium Sulfate (Na2SO4) Minerals for Chemicals

large deposits known and 100s of years supply available

U.S. largest producer but lots elsewhere too

Minerals for Chemicals

Boron (B)

Used as trace additive in many glass products, insulation, detergents,

food preservatives, fire retardants, ceramic glazes and enamels, pesticide
Known for >1000 years in China and one of earliest non-metallic
minerals traded (except salt)

Boron (B) Minerals for Chemicals

Boron-bearing minerals mostly from volcanic fluids

Most famous are Borax mineral deposits in Death Valley and other deposits in
Nevada/California
Largest deposits in U.S. but also major production from countries of former
Soviet Union

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 Minerals for Chemicals

Fluorine (F)

Used as important trace element in production of steel, aluminium and

uranium fuel rods
Also used for water fluoridation (reduces cavities) and in ceramics, Teflon
for cooking pans and other industrial uses

Fluorine (F) Minerals for Chemicals

Most comes from Fluorite (CaF2)

common but minor mineral in many hydrothermal ore deposits
also common with Miss. Valley Type Pb-Zn deposits

Fluorine (F) Minerals for Chemicals

world reserves are large and probably plentiful for future needs
Mexico is a particularly large producer of fluorine at moment

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