Geochemistry for Chemists

John D. Hosteffler San Jose State Universi'

,. San Jose. CA 95192

semester upper division elective by the Chemistry Department of the University of Colorado a t Colorado Springs (UCCS) in 1982183 and also in 1983184. Both courses were taught as three-credit lectures. The only prerequisite for Chem 421 was general chemistry. Chem 421 served as prerequisite for Chem 422. The course was desiened to anneal to chemistrv and eeolo" .. gy majors and to local high school science teachers. Most of the students actually taking the course were chemistry majors, but geologists and science teachers were also represented. The ~articioationof eeoloeists in the eeochemistrv course u,o;tld undoul,ted~~ greater at an i n s t ~ u t i o n be which offers a reolorv maior ( U C W do~.snot). Enrollments varied from 5-i0 studentiper semester. Three geochemistry texts (2-4) have recently been published. Each of these texts have their individual merits and weaknesses, but no one was judged sufficient for our course. Students were asked to nurchase one of these texts (Brownlow's in 1982183 and ~ r a u s k o p f in 1983/84), and the other s texts were made available in the lihrarv on reserve. The format of the course consisted of assigned readings,
w

Theabsenceof geochemistry fromour chemistry curricula seems inex~licahleon hasis of the maturitv ofthesubiect the or its re1e;ance to the rest of chemistry. I& absence may simply he amatter of tradition and imorance. The traditional geochemistry course has been taught by and for geologists. Geology departments usually offer such courses as upper division or graduate electives with mineralogy and petrology prerequisites which in turn have a physical geology prerequisite. Thus, geochemistry has been buried in the geology curriculum, and chemists have remained relatively ignorant of its subiect matter. This a k c l e describes a geochemistry course for chemists. Some eeneral course information is urovided. and then its subject matter is outlined topic by topic. he concluding section considers the uses of geochemistry in a chemistry curriculum including geochemical "real world" examples ( I ) , geochemistry in general chemistry, and geochemistry as an elective. Geochemistry (Chem 421 and 422) was offered as a two-

Primary m a t e d Figwe 1. The rack cycle. Reservoirs tor primary material entering Me cycle from the earth's interior are shown as rectangles. Geological processes which carry rock material from one reservoir to another are indicated by arrows. Diagenesls includes all changes which occur as sediment becomes rock including compaction. cementation, recrystallization, and replacement. Anatexis refers to the melting of rock to form a magma (Fig. 12.4, fmm "Principler,of Geochemistry" by 6. Mason and C. 8. Moore. 4th ed.. 1982. Reprinted by permission of John Wiley and Sons.Inc.)

Volume 62

Number 10 October 1985

,823

Table 1. Syllabus o the Geochernlstry for Chernlsts Course f

I. Minerals and Racks Crvstal chemistrv: comoosition and structure of crvstals - ,-~ Systemat c monera ogy: e assificatlan and description of Common minerals ntrOdUCtm to rocks. thtl rock cycle. class tical on and description of common rocks 11. F m t i o n of Me Earth
~~ ~~~~~

Nuclear chemistrv: nuclear stabllitv and nuclear reactions ~ - - isotope geocnemootry: n~clsar clocks, wacer Isotopes E emental aoLndanceo. in the earth, metwrotes, and me dn.vase Orig n of the elements: the Big Bang, stars and nlrc wsymhssir The solar system: description and evolulion Differentiationof the earth: into care, mantle, crust, amsphere, hydm Sphere and biosphere Ill. The Rock Cycle
~ ~ ~~ ~~

arranged according to three major themes: 1) minerals and rocks, 2) the formation of the earth, and 3) the rock cycle. The minerals and rocks topics provided the mineralogy and petrology needed to understand the rest of the course. The formation of the earth included the origin of the earth's elements, the formation of the solar system, and the suhsequent differentiation of the earth into core, mantle, crust, atmosphere, hydrosphere, and biosphere. The rock cycle topics dealt with the geological processes which produce igneous, sedimentary, and metamorphic rocks on the earth ) as i t now exists (see Fig. 1. The chemical topics-crystal chemistry, nuclear chemistry, thermodynamics, aqueous and organic chemistry-appeared a t the appropriate point in the course to support related geological topics. Mlnerals and Rocks
Crystal Chemistry (2- 12)

Thermodynamics: principles, calculations, and phase diagrams Magmatic processes: formation of magma, Igneous rocks, hydrothermal fluids, and volcanic gases Water chemisby: acid base, redox and solubility equilibria In the hydrologic cycle Chemical weatherinn: reactions formino clavs. soils. and natural waters - . Sedimentation: formation of detrital, biogenic and chemical sedimenb Organic geochemistry: natural organics, toss11 fuel genesis, and the carbon cycle Economic mineral deposits: genesis of deposits, occurrence of the elements

lecture notes, transparencies, problem sets, and exams. Lectures incorporated material from a wide variety of sources. These sources were referenced in a bibliography (2-50) which was made available to students to facilitate further research. The pictorial nature of geochemistry made transparencies a very desirable and important feature of the course. The problem sets were designed to challenge students' understanding of the readings, lectures, and transparencies and also to serve as practice exams. Library exercises adapted from the CLEAR materials (51)were used to introduce students to the geochemical literature. Students were required to research this literature on a geochemical topic of their own choosing and to present the results in oral and written form. The content of the course was divided into chemical and geological topics (see Tahle 1).The geological topics were

Crystal chemistry began with a review of the comuositions and modes of bonding b f substances forming crystals. Five types of crystals were then distinguished on the basis of the particles present and the bonding between the particles: metallic, atomic, molecular, covalent (network), and ionic ( n e t w r k ) crystals. The characteristic physical properties (luster, melting point, density, hardness, malleability, conductivity) as.ioriated with each crystal type were described and related to the crystal composition and structure. Descriptions of crystal structures inevitablv involve some crysrallugraphic concepts. Our course made use of unit cells, Rravais lattices, Miller indices, symrnetrv elements and nuerations, and ~ermann-Mauguin symbofs. No group the& and no X-ray diffraction was included. Some information on crystal morphology was provided so that students might perceive the correlation between the external form or habit of a crystal and its internal symmetry. The crystal chemistry topic concluded with a consideration of the compositions and crystal structures of 21 nonsilicate minerals (see Tahle 2). Models were distributed to small groups of students, and they were asked to determine coordination numbers, find and classify unit cells, count formula units per unit cell, and draw floor plans. Models of metallic crystals were examined first and then models of

Table 2. Cornposltlons and Structures o Nonslllcate Mlnerals f

Crystal Type Metallic Particle Packing* ccp atoms bcc atoms hcp atoms Mineralb gold a-iron lridwmined a-sulfur Ice i methane diamond graphite halite Sphalerite spinel nlccolite brucite gibbsite hematite wurtzite C5CIe fluorite rutlle calcite aragonite

Z,Formula, CNsC
4AuXt1 2Fev'l1 2(lr.O~)~" 18Sa 4(H# 4(CH4IX" 8ClV 4C"'

Unit Cell cubic cubic hexagonal orthorhomblc hexagonal cubic cubic hexagonal cubic cubic cubic hexagonal hexagonal monoclinic hexagonal hexagonal Cubic Cubic tetragonal hexaqonal orthorhombic

Molecular
CCP

m~lecule~

Covalent lonid -ccp anions -ccp anions -ccp anions -hcp anions -hcp anions -hcp anions -hcp anions - h ~ p anions -simple cubic anions -simple cubic anions

'The symbol

denotes approximately. bThe lawen-temperahlrepolymwph is dealgnsfed o,the nen lowest 8, stc. <Thefwmula unit. per "nil cell (4 me number precedlw the brmula. lh8 omdlnetlon numbers (CNs)of particles are lndlcatedwith Roman numeral superonlpt.. Is d A M~Y~BIIY occurrino sllw 01 05 and ir. . . 'While CsCI dmo not occur In nature and, thus, Is not a mineral. It la Includedto Illustrate the body-centersd cublc armaure.

824

Journal of Chemlcal Education

Table 3. Classlflcatlon, CornpooRlons and Structures 01 Slllcate Mlnerals Class Name

(anion)
Group

Name olivine garnet

Formula Y,[ZO,l XSY~[ZO&

Example Name forsterile grossularite lawsonite beryl

Species Formula Ms.[SiO,l CasAI.[SiO& CaA12[Si,0,](OH)~.H~0 Be~Al~[SiO& CaMg[SiO& CanMgr[Sl~Otrlr(OHk MgdSirOrl(0H)r A12[Si~O&Y~ MgdSi20ddOH)* K(Mg.Fe)s[AlSi~Orol(OHk KAlr[AISisOla](OH)2 Si01 K[AiSls081 Na[AISirOa] Ca[AldirOa] K[AiSi2O8] (Na.K)[AISiO,]

Nesmilicate (isolatedtetrahedra) Sorosilicate (dimers) Cyclosiiicate (rings) lnosilicate (chains) Phyilosilicate (sheets)

pyroxene amphibole serpentine clay mica

XY[ZO& X~Yr[&OdzWz YS[Z~OSIWI

YdZ2051W~

~2-~[z~O5l~W2 XYa-&OdzW2
202

Tectosilicate (network)

SiOf feldspard feldspathoids

dioposide tremolite antlgorlte kaolinite talc biotite muscovite

8-quanr

X[Zo& x[Z02lp

K-spars albite anotihlte leucite nepheline

(slbne to anamits).

'The SiO,

grwp contsins me nlne cryotalline polymapha of sillca and also -1, w i I amorphaua. hm s 'Fddswr8 display two imWmnt solid solvtion series: the alkali telds~ar (K-s~ar albls)and plagiodto 'K-spar i. a generic term whlch encompasses microchne, wmodsse, and ssnidine.

molecular. covalent. and ionic crystals were investigated in that order. Lectures attemvted to simvlify and rationalize the model structures. The &portance-of hexagonal and cubic close vackine was stressed, and many structures were described as distorted andlor stuffed deriGatives of hcp or ccp atoms, molecules, or anions. Pauling's rules were applied to rationalize the structures of ionic crystals. The phenomena of isomorphism, polymorphism, and substitution were discussed with mineral examples of each. Crystal chemistry was the longest and most difficult topic in the course. I t consumed 6 weeks of class time and vresented unique conceptual challenges for students. ~ a n d s - o n erperience with models proved absolutely essential for the mastery of geometrical concepts. Fortunately, excellent models of crystal structures were available.'J
~ ~~~

Systematic Mineralogy (11) The second topic in Chem 421 was the system for classifying and describing minerals. The system was defined and illustrated by applying i t to the nonsilicate minerals whose crystal chemistry had already been studied (see Table 2). Theseminerals were classified by anion (or lack thereof) into families (the native elements, the halides, the sulfides, the oxides. or the carbonates) and by crvstal structure into , . groups (e.g., the spinel, hematite, and rutile groups in the oxide familv). The common characteristics of these families and some df their groups were discussed, and detailed descrivtions of a few individual minerals species were presented, he detailed descriptions oteach sp&ciesincluded inforn~atiun its rrystnllo~raphy, m physical properties, compoiition and structure, diagnostic features, occurrence, and uses. The systematic minrralugv of the silicate family was exnlnred next (see Table 31.The maior classes ol'silicate minerals were named and their characteristic silicate anions described. The names and formulae of some silicate groups . . were prt,sented along with example species, and their crystal structures were invcstipated nith models.'l'he solid solution series which occur within some silicate groups (e.g., the pla~ ~

gioclase series in the feldspar group) were explained in terms of cation substitutions in the group's crystal structure. Silicate compositions were related to structures via the general formula X,Y,[Z,O,]W, where X represents a cation with coordination number greater than six (e.g., K+, Ca2+,Na+), Y denotes a six-coordinate cation (e.g., Mg2+, Fez+, Fe3+, AP+), Z is a four-coordinate cation (A13+ or Si4+),[ZpOy]is the silicate anion repeat unit (SiOa4-, Si20++, etc.), W refers to extra anions (e.g., OH-, F-), and the subscripts m, n, p, q, and r are integers varying from zero upward. Students who had mastered crystal chemistry had little difficulty reading and understanding systematic mineralogy. In problems and on exams they were able to classify minerals. describe crvstal structures. rationalize comnositions, calculate densities, and interpret physical prop&ties and uses. Students could not, however, understand descriptions of mineral occurrences without petrology. Descriptions of mineral occurrences were postponed until the rock cvcle had been thoroughly studied' Introduction to Rocks (2-7, 12, 13) The introduction to rocks topic consisted of a brief discussion of the rock cycle and some practice in classifying and describing rocks. The origin (i.e., genesis) of the major rock tvves and the relations between them were clarified via the ". rock cycle (see Fig. 1).The genesis, compositions, and textures of the major rock types were described along with a classification scheme based on these properties (see Table 4). Problems and tests emphasized the classification and des(ripti(,nofcomm~n rocks, their relation to the rockcycle, and calculations or their elemental and mineralogical rompositions.
Formation of the Earth

Crystal structure models of silicateand nonsillcate minerals may be ordered from Klinger Scientific, 110120 Jamaica. Richmond Hill.
NY
IlAlR

'

..

Mayer (52, 53 has described an ingenious method for modeling 53 nonsilicate crystal structures.

Nuclear Chemistry (14, 15) Nuclear chemistry was the first topic in the sequence on the formation of the earth (see Table 1).The nuclear chemistry was necessary to support the isotove geochemistrv and n&leosynthesis topics.- ~ r a n s ~ a r e n c i e s jepictiug niclear composition and stability were used to rationalize radioactive decay, fission and f&on reactions. Problems and tests required students to balance and classify nuclear reactions and to verform calculations related to the kinetics of radioactive decay.
~~ ~~ ~

Volume 62

Number 10 October 1985

825

Isotope Geochemistry (2-6, 16-20) The use of isotopes to date andlor trace geological processes was considered next. T h e nuclear clocks studied were
Table 4.
Rock Type igneous plutonica granite diorite gabbro perldotite dunite Sedimentary detritaib shale sandstone biogenica limestone chemicalb salt beds Metamorphic foliateds slate Schist gneiss nOnfoliatedC chlorite. quanz. mica chlorite, quartz, mica, amphibole quartz, feldspar, mica, amphibole gypsum, halite calcite, dolomite clays, quartz quam, feldspars voicanica rhyolite andesite basalt quanz, alkali feldspar, mica, amphibole piagiociase. pyroxene, amphibole piagioclase, pyroxene pyroxene, olivine olivine

Classlflcatlon ot Rocks
Characteristic Minerals

W/'4N, 4oK/40Ar, 87Rb/87Sr, 23sU12mPh,235U/2WPh, and 232Th/208Ph. Lectures on each dating technique included information on the decav scheme and kinetics..the eeochemiatry of parent and daughter, analytical methods, and appli'. cations.The fracrivnatio~~ofstable isotoocs t2H11H.'"0( 0 W/12C, and 34S/32S)was explained a i d related to trace; studies.

Elemental Abundances (2-6, 21-25) The first topic in Chem 422 was the abundance and distrit~tltion the earth's elements. 'I'ransparencies were used to of show the earth's internal structure (i.e., crust, mantle, inner and outer core) and geophysical properties (seismic wave velocities. densitv. oressure. and temoerature variations with depth). hen th'e comp&itions of earth's various zones and s ~ h e r e swere described. The earth was crudelv described as an iron core surrounded by a peridotite &tle with a granite-basalt crust under a 0.5 M NaCl ocean and an oxygen-nitrogen atmosphere. Abundance data on the distribution of the elements (see Table 5) was handed out and comparisons were made. In problems and on exams students were asked to describe the structure, properties and composition of the earth and to calculate atomic abundances from compositions expressed as parts by weight or volume of elements, minerals or rocks. Origin of the Elements (3-6, 26-29) The story of the origin of the elements began with the origin of the universe. The synthesis of H and He in the Big Bang and the nature of the expanding universe which resulted were briefly discussed. Various star types were distinguished (first or later generation, light or massive), and their properties and life cycles were described. The synthesis of atoms heavier than H by nuclear reactions in stars-i.e., stellar nucleosynthesis-was outlined and related to the cosmic abundances of the elements (see Table 5). Exam questions required students to devise nucleosyntheses, correlate nucleosyntheses with star types and stages in the star's life cycle, and give nucleosynthetic explanations of cosmic abundances.

horntels
granulite marlie quartzite

variable quartz, feldspar. pyroxene calcite, dolomite quartz

'Cenetiotwms. Plutonicmcks crystallized at depth. Valcanicrackscrystallizedonthe

surface of me earth

%nellc terms. htrital sediments were deposited mechanically. Biwgenic dspmns were produced by living organisms. Chemical sediments precipitated from a dissolved state. 5 T e ~ 1 ~ ~ I~oliatim terms. Implies ~isntation minerals in parallel layem. of

Table 5.

Abundance Data on the Dlstrlbution of the Elements (Atomic Abundances In ppma)

ON

Cosmic (4

Whole E*h (4)

%W(W

w t l e (3)

D u s t (d)

Avg. River Water (2)

Seawater

(2)
661.633 14 331.553

Atmosphere 14)

H
He
C

N 0 F
Ne Na Mg Al Si P S Ci Ar

K
Ca Ti Cr Mn Fe Co Ni Cu Zn

936.000 63.000 391 81 647 0.03 91 2 37 3 35 0.2 18 0.2 4 01 . 2 0.08 0.4 0.3 32 0.08 2 0.02 0.04

1.200

...

1,500b

29.000

666,647 6 333,341

...
588,000 350 29 603,000 690

1,000 3 490,000 40

5 3 170 784,380 210.740 9

...
6.400 124.000 13,000 140.000 1,000 10,000 450 0.008 600 4.600 300 1.000 500 189,000 490 10,000 7.900 166.000 13,000 172.000 1,000 99,700

...
21,000 20.000 62.000 208.000 710 170 77 2

1 1
0.7 1 0.4 2

2,890 326

...

175 3,270 4.690 60 63

829,000 3,600 67.400

600 9.000 300 1,600 1.300 38,000

... ...

11,000 20,000 2,500 40 350 20.000 9 27 18 23

0.07

nCaic~iated ham data in refs. (2-q as indicated for each oobmn. 'Calculated from data in ref. (4).

826

Journal of Chemical Education

Discontinuous react~on serles Structure tvpes SI Si

Continuous reactlon series

Mlneralr

Na, K

AI

Minerals

Olivlne

Pyroxene

Isolated SiO, groups

rn

Bytcwnite

Amphibole

Single chains Double

\ \

Labradorite

Anderme

1 I

Blotite

1 I
K Feldspar

Hvdrothermal minerals

'"i"'

Figure 2. Bowen's reaction series. The continuous reaetion series gives the sequence of crystallizationhom cooling magmaof feldspar mlnerals from Bytownite(Carich plagioclase)to oligoclase (Na-rich plagioclase). Thediscontinuous does the same for aher mlneralsas indicated.The two series may occur simultaneously (Fig. 5.13, from "Principles of Geochemistry" by B. Mason and C. 3.Moore. 4th ed.. 1982. Reprinted by permission of John Wiley and Sons. Inc.)

The Solar System (3-6, 30-33)

Our solar svstem was described as it currently exists, and its evolution was traced using the nebular hypothesis. Particular attention was paid to the evolutionary processes (solar ignition, condensation, cold accretion) which may have influenced elemental abundances in the terrestrial and Jovian planets. In exams students were expected to provide plausible explanations of solar system facts.
Differentiation of the Earfh (2-6, 16, 30-34)

lations were reviewed a t the general chemistry level, and then the phase rule and phase diagrams were presented usine transoarencies. Unarv ohase diagrams of nonsilicate minerals add of SiOz were ieiated to crystal structure and volvmorohism. Binarv and ternary vhase diagrams of siliiatk minmals were reiated to euteitics, solid solution series (e.g., alkali feldspar, plagioclase, olivine), peritectics, and Bowen's reaction series (see the next topic).
Magmatic Processes (2-7, 13, 35-37)

The differentiation of the orimitive earth was the last topic in the formation of the earth sequence. Processes which may have occurred sometime in the earth's first billion years (the pregeological eon, roughly 4.5 to 3.5 X lo9 y B.P.) were discussed first: heating and partial melting of the earth; separation of a dense molten iron core from a lighter to peridotite mantle; de~assing form a reducing atmosphere; nnd cooliuz with suh&ue& crvstallization of a basalt crust and conde&ation of an'acid ocean. The changes in the ensuing Precambrian (-3.5 to 0.58 X 109y B.P.) andPhanerozoic (580 X 106 y B.P. to date) eons were described next: the growth, drifting, collisions, and rifting of granitic continents; uplift; erosion, and sedimentation; evolution of life; formation of an oxidizing atmosphere and an alkaline ocean. A geological ralendar'has handed out t o help students understand and rcmemher the maior events in the history of the earth.
~ ~ ~~~~~

The Rock Cycle Thermodynamics (2-6, 12-14,35)

The first topic in the rock cycle sequence was thermodynamics (see Table 1).Thermodynamic functions and calcu-

The formation of magma, igneous rocks, hydrothermal fluids, and volcanic gases was the next topic. The partial melting of mantle peridotite parent rock to form a basaltic magma and of crustal rocks to form a granitic magma were described first. Then the changes which may occur as the magma rises toward the surface were considered: decreases in temperature and lithostatic pressure, crystallization to igneous rocks, increases in magma water content, retrograde boiling to form a hydrothermal fluid, precipitation of ore deposits, and release of volcanic gases. The equilibrium sequence of crystallization of minerals from a cooling magma (see, e.g., Bowen's reaction series, Fig. 2) was emphasized and related to igneous rocks previously discussed (see Table 4). Precipitation of metal ores from hydrothermal fluids was discussed in terms of volatility, solubility, and crystal chemistry. The compositions of volcanic gases (primarily Hz0 with minor GOa GO, SOz, HnS, HCI, Nz, H2) was related to the reducing atmosphere and acidic ocean of the early earth. On tests students were expected t o compare and contrast basaltic and granitic magmas, state the effects of changing temperature and lithostatic pressure on magmas, use Bowen's reaction series, classify hydrothermal ores, and identify the common components.of volcanic gases.
Volume'62 Number 10 October 1965 827

Water Chemistry(2-4, 38-41) Considerable aqueous chemistry was required to support the study of weathering and sedimentation. Analytical data on natural waters (rain, river, lake, and seawater; soil, hog, and groundwater) was presented and related to the hydrologic cycle. Carbonate equilibria were treated in some detail. Acid-base, redox, and solubility equilibria were portrayed in Eh-pH diagrams ( 3 8 4 1 ) on transparencies. Problems and exams stressed Eh, pH and solubility calculations, interpretation of Eh-pH diagrams, and balanced equations for geochemically important aqueous reactions. Chemical Weathering (2-4) Chemical weathering was defined as the approach of rocks, air, and water to chemical equilibrium. Weathering reactions involving various rocks, weathering agents (HzO,

COz, and 02) and products (aqueous solutes, clays, and insoluble oxides) were expressed with balanced chemical equations. The sequence of weathering of minerals was contrasted with their sequence of crystallization from magmas (i.e., Bowen's reaction series). The develonment of different soils in different environments was related to variations in weathering patterns due to climate, topography, and vegetation. Sedimentation (2-7, 13, 42) Detrital sediments (class and sands) were distineuished from hiogmic deposits rcnrhonntes, silica, organics, and sulfur) and cheinicalsedimenrs. Chemicnlsediments werecharacterized as hydrolysates (e.g., A1203). oxidates (e.g., Fez03, Mn02), reductates.(e.g., metal sulfides, UOz), replacement deposits (dolomites and phosphates), and evaporites (gypsum, halite, and epsom salts).

Atmophile: N Lithophile: Na Chalcophile: Zn Siderophile Fe

H e
B Al
Zn

C Si

N P As Sb Bi

O S Se Te

N CI Br

e Ar

K
Rb Cs

Ca Sr Ba

Sc

Ti Zr

V
Nb Ta

Cr

Mn

Fe Ru

Co

Ni Pd Pt

C J ~

Ga
In TI

Ge
Sn
~ ~

Kr Xe -

Y
La-Lu

Mo - -

Rh
Ir

Ag Au

Cd ~-

Hf
Th

Re

0s

Hg

Pb

Figure 3. Goldschmidt's geochemical classification of the elements. Atmophilesare elements that tendlo concentrate in the atmosphere. Lithophiles concernrate in silicate racks in the mantle and crust. Chaicophiles form sulfides, and siderophiles dissolve in iron. Both chalcophiles and siderophiles are believed to be concentrated intheearWs wre(Tbl.3.12, from "Principlesof GeochemisW'by B. MasonandC. 6. Moore.4thed.. 1982. Reprintsd by permissionofJohn Wiley and Sons. Inc.)

Table 6. Origina Magmatic chromite Pt Ni-CU sulfide magnetite ilmenite carbonatite pegmatite
skarn

Econornlc Mlneral Deposits: Metal Ores Typical Minerals O C e % F ,. Pt (alloyed), RAs2, (Pt. Pd, NOS. PtAsS (Fe. Nil&, CuFeS2 ~e.04 FeTiOl (Ca. NaMNb, TaLOdO, OH. F). (La. Ce. Y, Th)PO, Be.AIdSiOd6, LiAI(Si0.h. Ai20s, Sn02, UOt. (Fe. MnHTa. NbhO.. (Fe. Mn)WO,, CaWO,. (La,Ce, Y. Th)PO, graphite, Fe104, F e 2 0 ~ FeTi03. AI2O3. SnO*. CaWO,. (Fe, Mn)WO,. Cu sulfidess, Mas.. ZnS, PbS Au. F , , e O Fe203.FeTiOa. Sn02. (Fe, Mn)W04, Most, CwAg s ~ l f i d e s , ~ PbS, 2"s. Sb2S3.HgS, Hg, Ag CU ~ulfides.~ZnS, PbS hydrous Mn oxides AlrOrlh. A 203.H20. Fe20rmi90. (hi.MgllS rO,rOro, Fe,Ol.rCI,O. MnO,. Cu. CL,O. CuO. C.,C0,1Orll,. CudCOd~Orl),. ZnCO,. ZndS ,O,llOhwH~O, PoCOs. PoSO,. AgCI. Ag. A". rlg

Deposit

hydrothermal5

massive Sulfide Mn nadules Weathering

supergene sulfide Sedimentary placer ironstone banded iron formation U-V-sandstone massive sulfide Au. Pi. Cu,diamond. 3 . SnO*. U02. (Fe, Mn)W04.FeCrz04. 0. Falo,. FeTiO.. (La, Ce, Y, Th)P04. ZrSiO, Fe20rnH20,FeC03 FeA. U O , USiOmH,O. VO(0H) Cu sulfides, ZnS, PbS

.me aigin a any given ore deposit is very often a matter of oomroversy.
'Tb wwceolthe hotwater from whichthearedepo~namay magma but couldalso be heated meteoric, gound. or connate waters, Tb hydramermaloredepasns we lIae.5roughly be In l ader of l b l r appearance from deepest and honest (i.e. hypolbrmailto ohallowest and coldeat (1.e. spithermall. Then, are many exceptions to mia sequence. b 'Cu sulfides Include Curs. CUS.CueSr, CuFeSn. CurFe4. CusAsS.. andlor Cu&b,S,,. AQ svllldes include AQsS.AgoArSp. AgaSbSs. ~ g s s b s , ,AQ,.s~~s,, volcanic activity may be (or have been) submarine.

828

Journal of Chemical Education

Table 7.
Origin Magmatic

Economic Mineral Deposits: Industrial Materlalsa

Typical Chemicals. Minerals, or Rocks granite, basalt diamond limestone. Cas(POJ3(F, CI. OH), CaF2. BaSO. feldspar, quartz, mica. NalAIFs, LiAI(SiOs)2.A , I. , O Be3Al*(SiO&, aquamarine, topaz Fe sulfides4 CaFs, BaSOa graphite, garnet. A1,03, emery pumice S8 dtsmond, &by, rapphore. garnet m ca, clay. rand. mmeral p gments shale. limestone. dolomite, magnesite, sandstone, gravel chalcedony. =hen, flint, opal, diatomite Ca$POddF, CISOH) gypsum, NaCI. potash. Na2SOrtOH.0, Na2C0s10H20, Na2COsNaHCOs2H20.NaNOs, barates slate, marble, quartzite coal, peat, ail-shale, tar sands, oil, natural gas. S8, He mica, asbestos, graphite. garnet, emery. A0 I. . A, O 1S . i soapstone

Deposit igneous rock kimberlite pipe carbonatite pegmstites hydrothermal skam

Volcanogenic Weathering

rock Sulfur
placer residua rock8 silica phosphate evaporite

Sedimentary

rocks
fossil fuels other groundwater brines Seawater Atmosphere air

talc.

, . N2. 0 Ne, Ar, Kr, Xe

s m lndu~trial materials are also mined horn metal we depann (see Table 6).
OFe sulfides include F e , 3 . FeS,. CuFeS.. Cu.FeS, and/or FeArS.

r-Jnr--J.n=m
solf~des
oxides

....... ....,,..
.......

C f r o m coal carbonates B from borax Figure 4. Natural sources of the elements Elements are coded accordmg to their chemical f w m in economic mineral depos~te (Fg 7 6, from ref 50)
occur uncombined
halide sails phosphates sthcates

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Organic Geochemistry (2-4, 14.43-45) The organic geochemistry topic began with a review of organic a t the general chemistry level. A lecture on chemical evolution was used to introduce the important biopolymers. The alteration of biopolymers to geopolymers (humic substances, sapropel, and kerogen) and the metamorphosis of these to fossil fuels was outlined next. The organic geochemistry topic concluded with a consideration of the carbon cycle. Metamorphism was not included in our course. This topic of was sacrificed to make more time available for t o ~ i c s greater interest to chemists. I t is, of course, a serious omission from the geologist's perspective. Economic Mineral Deposits (46-50) The last topic in the course, economic mineral deposits, was hoth a summary and a climax. The topic began with a review of the distribution and abundances of the elements. Then Goldschmidt's geochemical classification of the elements was introduced to show where in the earth periodic groups of elements tended to concentrate (see Fig. 3). The further concentration of elements into economic mineral deposits by rock cycle processes was described next (see Tables 6 and 7). The tendencv of some elements to occur as the native element (e.g., noble metals and inert gases, C, N2, 0 2 , and SS) and of others to occur as sulfides, oxides, ~ h o s phates, carbonates, and halides (see Fig. 4) was related to the crystal chemistry and geology of these minerals. Metal ore deposits (Table 6) were distinguished from deposits of industrial materials (Table 7). The metals recoverable from ore deposits were characterized by use as precious (Au, Ag, and the P t group), ferrous (V, Cr, Mo, W, Mn, Fe, Co, and Ni). nonferrous (Al and the base metals Cu. Zn. Sn. and Ph). minor (Cs, Mg, da, Ti, Zr, Nb, Ta, Cd, Hg, ktc.j, a i d fission: able metals (U and Th). The uses of industrial materials as fertilizers, building materials, refractories, abrasives, ceramics, fuels, raw chemicals, and gems were also described. Conclusions Geochemical "Real World" Examples Geochemical examples which relate to the "real world" experienced by our students are far too numerous to list here. Perham it will be enough to indicate brieflv the main connections.hetween and the more traditional chemistry courses so that instructors interested in such examples will know where to search. The most obvious connection between physical and geochemistry is thermodynamics. Thermodynamics is used in geochemistry to describe the formation of natural materials like granite, basalt, various economic minerals, volcanic gases, sands, clays, soils, river, and seawater. Virtually all the common types of phase diagrams and many kinds of thermodynamic calculations can be illustrated with "real world" eeocbemical examoles. Of the many connections between inorganic and geochemistrv, three deserve special mention. First, the treatment in i~mrganic slructure and bonding in solids is very similar to of that of vrystnl chemistry in ceochemistrs. The usual inor. . ganic treatment, however, contains more-theory with fewer examples. Crystal chemistry can provide many interesting and sophisticated "real world" examples of solid state principles. Secondly, there is considerable overlap between descriptive inorganic chemistry and systematic mineralogy. The advantage of systematic mineralogy is that the cbemistrv is daced in a .. eeoloeical context so that the distribution. " . " occurrence, and uses of elements and compounds make more sense. Thirdlv. aaueous eeochemistrv makes use of Eh-DH .. . diagrams (see refs. (2-4, j8-41,54)) summarize very c & -

plex acid-hase, precipitation, complexation, and redox behaviors of elements in natural waters. In the author's opinion these diagrams should be employed routinely to illustrate descriptive inorganic chemistry in aqueous solution (55). Topics in geochemistry may also he linked to analytical, organic, and biochemistry. The analyses of natural samples -minerals, rocks, organics, and waters of various kinds -very often involve complicated procedures and state of the art instrumentation. The analytical methods used in isotope geochemistry for dating minerals and rocks are good examples. The principles of multiple equilibria which are taught in analytical chemistry may he illustrated with the geochemical systems like the carbonates. Chemical evolution and biogeochemical cycles like the carbon cycle can provide "real world" examples to stimulate student interest in organic and hiochemistrv. Geochemistry in General Chemistry In the opinion of the author, the relationship between geochemistry and general chemistry is so intimate and profound that it merits special consideration. There are some signs alreadv of a arowina interest in this relationshin. Geochemical examplei are geing used more frequentl; in the general chemistrv course, and isolated c h a ~ t e r s a eeoof ihemical nature are now appearing in leading tests (seeref. (14), Chaps. 10,18, and 22). The impact of geochemistry on general chemistry could, however, he far greater than this. Geochemistry could provide hoth a context and a coherent theme for general chemintry topics. I t could unite these apparently ;isparate topics and make them more loeical and interestine. I t is a wav to introduce descriptive chLmistry into the "I&world" of"our students in diaestible form. The interested reader should consult refs. (5659) (especially ref. (59)) for examples of this approach. Geochemistry a s an Elective Of the interdisciplinary chemistries only geochemistry has no status in typical chemistry curricula. Physical chemistry has, of course, long been a requirement in a chemistry major. Biochemistry has become a t least a respected elective and in some instances a requirement in a biochemical option or maior. Geochemistrv. on the other hand. is an uDoer division .. tt, kraduate electiv~infrequentlytaught by geologists for peolopists. Its atatus is comnarable to that of biorhemistrv 30 . . years ago. This article has attempted to show that geochemistry is a mature subject, that it is intimately related to the rest of chemistry, and that i t deserves serious consideration as an undergraduate elective in our chemistry curricula. Our experience with geochemistry for chemists has been very positive. I t is hoped that others will be encouraged to make similar attempts and, if these are successful, geochemistry will become a permanent feature of undergraduate chemistry curricula. LHerature Clted (1) Hmstettler, J.D., J. CHZM EDUC..60,1031(19831.
(21 Krauskopf.K.B.,"IntroduetionfoGeochemistry,"2ndd.,McGraw-HiU,NewVork,
1979.

13) Mason, B.,andMaare, C.B.."PrineipleaofGeoehemia~y,"4fhed., John Wiley.New

14) Bmunlov. A. H .'"Geochemistry," . Prentice-Hall, Englewood Cliffs, NJ. 197% ( 5 ) Turekian. K K., "Chemistry of thcEarth." Holt. Rinehsrt, and Winston, New York, .
York, 1982.

~, , I91 B1ms.F. D., "CrystsUography and Crystal Chemistry,"Holt,Rincharf and Winston,

New York, 1971. (101 Evans, R C.. "IntroduNon to C N l Chemistry," Cambridge University Press, Cambridge. 1964. (111 Hurlbut. C. S., and Klein, C.. "Manual of Mineralogy," 19th ed.. Wiley, New York,

. .."".

to

(121 Ernst, WG. " M h Msfetials," Prentice-Hall, E n g l e w d Cliffs, NJ. 1969. . . (13) Ehlen. E. G., and Blatt, H., "Peuolagy: Igneoua, Sedimentary and Metamorphic," Freeman, Sen Francisco, 1982.

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(141 Brown.T.L..andl.e~ey,~.E.."~hemi.try:~heCentral~denee."2nded.,~ret~fieeI381 Stumm,W.,sudMo~~gan,J.J.,'~AquatiiChemiit'y:2ndddd,WiI~yYN~wY~~k,l98l. (39) Ganels. R. M., and Christ, C. L.. "Solutions, Minerals, and Equilibria." Harper and Hall, Englewaod Ciiffs. NJ. 1991. Row,New York, 1965. (151 Seahurg.G.T., J.C~~M.E~~~.,46,626(19691. (401 Bsmum, D. W., J. CHEM.EDUC.. 59,809 (19821. 116) Eicher, D. L., "Geologic Time: 2nd ed., Prenlice-Hall, Englewod Cliffs, NJ, 1976. (411 Campbell. J.A.,and WhiBker,R. A,, J.CHEM.E~~~..46,9n(19691. 1171 Faure, G., "Principles of lrutope Geology," Wiley, New Ynrk. 1977. (42) Bernor, R. A,. "Principles of Chemical Sedimentology." MeGraw-Hill, New Yurk, 1181 York, D., and Ferquhar. R. M.. "The Earth's Age and Geahronology: Pergamon, Oxford. 1972. 1971. (411 Egiinton. G., and Murphy. M. T J.. (Editom!. "Orgnnic Geahemistry:' Sprinpr1191 Hods. J.,"StablelrutopeGeuchemi~try:' Springer-Verlsg.NewYork. 1973. Vcriag. New York, 1969. 120) Clark. S. P., Jr.,"Structure of the Earth,"Prentiee-Hall, Englewood Cliffs,NJ. 1971. I441 Breger, I. A,, (Editor). "Organic Geoehemiatry." Pergsmon Preaa, New York, 196C (211 Alier. L. H., "The Abundance ofthe Elements," Wiley Interaeience. New York. 1961. (45) Garrels, R. M.. Maekenaie, F. T., and Hunt, C., "Chemical Cycles snd the Global I221 Ahrens.L..H.."DidributionoftheElemenlsinourPlsnet,"MeGrsw~Hill,NewYork. Environment: Wm. Kaufmann, Inc, LasAltos. CA, 1975. 1965. (461 Jensen. M. L., and Batoman, A. M., "Economic Mineral De!mils: 3rd ed., Wiley, l2Jl Fairbridge, R. W., (Editor). '"The Eneyelopediaaf Geuchamistry and Environmentd New York, 1981. Sciences," Duwden, Hutchinsan and Ross. Svoudshun, PA. 1972. (47) Park, C. F., Jr., and MacDiamid, R. A,, "Om Depoaiu:' 3rd ed., Freeman, San (24) Wedepohi. K. H., (Edilor), ('Hsndbook 01 Gemhemistry:' Springer-Verlq, Berlin. 196974. Francisco. 1975. I481 Stanton, R. L.,"Ore Petrology,(. McGrar-Hill, New York, 1972. (25) Hamnel, C. A.. (Miforl. "The Encyclopedis of the Chemical Elamenls: Van Nm(491 Evens. A.M.. "An Invoduction t o o r e Geology: Elsevier, New York. 1980. trand Reinhold, New York, 1968. (50) MssteMn,W.,andSlowinski,E..'ChemicslPrinciple~,"4thhdddSssdddddPhiI~ddl(261 Trimble, V., Amor. Scientist. 65.76 (19771. phia, 1977. (271 Fowler, W. A,, C h e m Engr.News, 42 (11). 90 (Mar. 16,19641. (51) Hwletfler, 3. D.. and W o k , M. B., J. CHEMEDUC..61. 622 (19841. (19731. (261 Selbin,J.,J.CHeM.EouC.,50.306,380 I521 Mayer, L., J . Coll. Sri. Tmch.. 6 (31.192 (19771. (291 Viols,V.E., Jr., J. C H E M . E D U C . . ~ O(1973). ,~~I I531 Meyer,L..U.S. Ps~nlNo.4.014.110I19771. (301 Lewis, J. S., Sei. Amer., 230,51 (Mar. 19741. I541 Pourbaix, M., "Atlas of Electrahemieal Equilibria in Aqueous Solutian," (Tramlo(31) Hartmann. W. K.. '"Moons and Planefs: An Introduction to Planetary Science:' l o r Franklin. J. A.1, Pergsmon, Landon, 1966. Wsdsworth, Belmont, CA, 1972. (551 Hoafeftler,J. D., J.CHEMEDUC..~S, (19811. 17 (32) Wmd. J. A., "The Solar System." Prenfice-Hall, E n g l e w d Cliffs, NJ, 1979. (561 Gymer, R. G.. "Chemistry: An Ecalogiesl Approach: Harper and Row. Now York. I331 Sci. Amer., 233 (SepL. 19751, (entire iasuel. 1973. ( 1 ) Eichor,D.L., and MeAlester, A. L.,"Hislory oftheEarth:Preotia-HsU, Englewood (57) Barrow, G., "General Chemistry," Wsdsworth, Belmont CA, 1972. Cliffs, NJ, 1980. (58) Moore, J. W., and Moore. E. A,. "Enviranmental Chemistry: Academic Press. New (35) Ernst, W. G., "Petrologic Phase Equilibria: Freeman, Ssn Francism. 1976. Yark, 1976. (361 Ringwood, A. E.,"Camposition and Petrologyafthe Earthla MsnUe:' McCraw-Hill. (59) Weil, D.R.,III, J.CH~M.EDUC..EO,~O~~ (19831. New York, 1975. (37) Wyllie, P. J., '"The Dynamic Earth:' Wiley, New York, 1971.

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October 1985

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