Trations especially so since their electrode potentials are lower than that of the Au-AuCl4_ couple.

Againn we find that dissolution of gold is possible, but that it requires such a special set of circum
stances that is should be noted only rarely in nature.

All the rection just described for dissolving gold have been demonstrated in the laboratory
ekcept the reaction with free oxygen.agreement is excellent between the laborotary results
thermodynamic predictions, and geologic observations. Laborotary work confirms also theoretical
prediction that other solvents suggested in the literature-notably Al2(SO4)3 and Fe(SO4)2 without
Cl- can have no effect on gold

In contrast to acid solutions, theoretical data on alkaline solutions are meager.several

experimenters have reported that gold dissolves appreciably in NaHS solutions at room
temperature, adifficult reaction to undrstand because NaHS seems to contain no oxidizing agent of
sufficient power to attack gold. Conceivably hydrogen might be liberated,

Au + HS Aus_ + H2

But this would be possible only if Aus- ( or some similir complex sulfide or hydrosulfide ion ) is
exceptionally stable, and on this point we have no independet evidance. The transportation of gold
in neutral or alkaline vein slutions, therefore,remains a mystery, but the bahavior of the metal in
acid soluctions of the oxidizd zone is well understood

18-6. oxidation of uranium ores

a discussions of oxidation processes could be extended to ores of many other metals. S particularly
interesting one is uranium , whose complex and varicolored oxidation products have become well
know as a result of the intesive search for uranium deposits after the second world war.

The cheif primary compound of uranium in vein deposits is the dioxide, UO2< which occurs
in the well-crystallized variety uranite and the microcristalline form pitchblende. Incipient oxidation
and loss of uranium by radioactive decay may increase the oxygen-uranium ratio, so that uraninite
and pitchbelnde seldom show precisely the compositon UO2, often approaching a composition
sybolized by U3O8. In the zone of weathering,pitchbelnde and uraninite are converted to one or
more of the bright-oloredd oxidized uranium minerals,such as carnotite
[K2(UO2)2(VO4)2.3H2O].tyuyamunite [Ca(UO2)2(VO4)2 .nH2O],autunite [Ca(UO2)2(PO4)2.nH2O],
and rutherfordine (UO2CO2). These minerals arenslightly soluble, so that their uranium can be
carried by surface water or ground water into reducing environments ( a bed of lignite or black
shale, for example ) and precipitated as pitchblende or coffnite ( USiO4.nH2O).

Thus uranium, like iron or copper, is an element showing changes from one oxidation state
to another in geologic enviroments. Details of its chemistry provide an explanation for much of its
behavior. Uranium has many valence states (+2,+3,+4,+5,+6 ), but only the +4 and +6 states are of
geologic interest. In is two lowst valences uranium is such a powerful reducing agent that it can
libarate hydrogen from water, and the +5 valence in the presence of water is unstable with respect
to +4 and +6 :

U4 +2H2O UO2+++ 4H++2e- E = +0.33 volt

So we would expect to find compounds of these two valences in nature.
Uranous ion, U4+, reacts with bases to form an extremely insoluble hydroxide, U
(OH)4. The low ionization constant, about 10-46 at 25, means that in neutral solution the U4+
concentration is negligibly small and even at a pH of 4 would be only 10-6M. The hydroxide is
somewhat unstable with respect to dehydration,
U(OH) UO2 + 2H2O delta F = -8.4 kcal
So that the maximum concentrations of U4+ in equilibrium with UO2 are even smaller than
for the hydroxide. Small wonder that pitchblende and uraninite are so stable in reducing
environments !
The uranyl ion, UO2++, on the other hand, forms a considerably more soluble
hydroxide :

RUMUS
In a solution at pH 7 the concentration of UO2OH+ would be 10-5.1 M, and of UO2++ 10-8.0 M.
At a pH of 4 the concentration of each ion would rise to about 10-2M , which gives a total of nearly 5
g/liter of uranium. In this case the hydroxide is more stable than the oxide :

UO2(OH)2 UO3 + H2O deltaF = +13.2 kcal

At least two other hydrates or hydroxides of UO3 are know, all having roughly similar stabilities. In
nature, hydrates of UO3 are somerimes found as minerals, but more commonly the uranyl ion unites
with other anions : carbonate, phospate , and vanadate more often than others. The number of
know complex minerals of uranium in the sexivalent state is enormous.

Urayl hydroxid is slightly soluble in alkaline solutions as well as in acid :

RUMUS

( these are the diuranate and uranate ions,respectively,often wrriten without H2O as HUO4- and
UO4= ) . the low values of the constants mean that solubilities become appreciable only in strongly
alkaline solutions. Minerals containing uranium in these anions are not known.

In solutions cintaining carbonate ion,the solubility of compounds of sexivalent uranium is

greatly increased by the formation of carbonate complexes :

Rumus

The first equation means,for example, that a solution at pH 7 with 0.01 M total carbonat would
contain about 10.00 times as much UO2 (CO2) 2= as UO2++. From the calculation above for above for a
carbonate-free solution, we can estimate that the total dissolved uranium would now consist of
about 10-5M UO2OH+, 10-8M UO2++, and 10-4 M UO2 (CO3)2==, ot then times as much as we estimated
for the carbonate-free solution. The contribution of the carbonate complex would inscreased,either
by dissolving more carbonate complex becomes significant only in strongly alkaline solutions

The general geochemistry of uranium in near-surface enviroments,therefore, can be redily

described. Primary minerals are oxidized to uranyl ion, which is somewhat mobile in weakly acid
solutions , and also in neutral and alkaline solutions if CO3== is present . surface watrs in contact with
uranium mineral should contain a few parts per million of uraniumordinarily, and up to a few
thousand parts per million in exceptional situations. From such solutions uranium may be
precipitayed in the sexi valent state by a variety of anions,forming the familiar oxidized minerals : or
it may be reducedd by any one of a number of reducing agents,notably by organic matter,
commonly forming UO2 or one of its hydrates. Processes of these general kinds are probably taking
place ,or have taken place reecetly,in the famous uranium deposits of the Colorado plateau and
central Wyoming where oxidized minerals are desseminated in sandstones near the surface,and at
lower levels black unoxidized ore is found in sedimentasi containing much organic material.
Especially conspicuous is the concentration of uranium minerals around buried logs, fragment of
bone, and isolated lenses of dark shale.

Note,however, that an understanding of the chemistry of the uranium occurrences does not
in itself give an explanation of the origin of these deposits. As far as cheistry is concerned, it is
equally plausible to regard the surface ore as derived by oxidation pf original deposits in the
organic-rich sediments, or to think of the unoxidized ore as derived by downward leaching and
reduction from original deposits of oxidized material in the sandstone. The mechanisme of
oxidation,dissolution,prcipitation,and reduction is explained by the chemistry of uranium, but the
sequence of events must be worked out from geologic relations.

To gie a complete account of the oxidation of uranium ores in deposits like those of the
colorado plateau requires consideration of the geochemistry of vanadium,since this element is
intimately associated with uranium in the plateau deposits. In its chemical behavior vana dium
somewhat resembles uranium, but details are more complicated,since vanadium has three valences
states rather than two which are stable in the normal range of geologic enviroments, and since the
element forms a bewildering variety of complex ions. Rather than discuss the geochemistry of
vanadium in detail, we reproduce an Eh-pH diagram worked out by Garrels and his colleagues
(fig.18-2),showing the relations of some uranium and vanadium compounds in contact with water at
25 and 1 atm total pressure ( Garrels and Christ, 1965). For the specified concentrations of
vanadium ( total dissolved = 10-3M), carbonate (total = 0.1 M ) and potassium ( total = 10-3M), the
diagram shows that unoxidized ores should contain uraninite and montroseite,minerals with both
metals i their lowest naturally occuring valences. This agress with experience,for these minerals are
common in the lower parts of many Colorado Plateau deposits,especially in the vicinity of organic
matter. Increasing oxidation changes the uranium to uranyl compounds and vanadium to
compounds in which it shows a valences of 4. Maximum oxidation gives carnotite, in which both
elements have their highest valences; this mineral occupies most of the upper part of the diagram,
corresponding with its widespiread occurence in oxidized ores. At both sides of the diagram uranium
shows a total solubility exceeding 10 -4M, one the acid side taking the form chiefly uranyl ion and on
the alkaline side appearing chiefly in the carbonate complexes. The diagram shows general
relationship of the oxidatin states clearly, but it includes only a handful of the compounds found in
natural occurrences.

These various examples illustrate how simple chemical ideas can be applied in explaning the
reactions that occur when ore deposits are exposed to oxidation. This is one place in geochemistry
where prediction from thermodynamic data accord beatifully with observed mineral associations. It
should be emphasized once more ,however,that our chemical explanations are largely ex post
facto: given a mineral assemblage, we can consructuct plausible hypotesis for its derivation from
other assemblages. But we are still a long way from being able to select the only possible hypothesis
of origin, and still father from being able to predict just what mineral assemblage must follow from
a given set of geologic conditions. The oxidized and unoxidizeed ores of the Colorado Plateau, for
example, are apparently related by simple chemical rection, but these reactions do not tell us
whether the dominant process has been in the direction of oxidation or of reduction. And they
certainly cannot tell us with any degree of certainty whether in similar environments elsewhere we
may expect to find other deposits of uranium and vanadium minerals.

PROBLEMS

1. In the oxidized zone of lead deposits, it is common to find a crystal of galena surrounded
by a layer of anglesite, and the anglesite sorrounded by an outer layer of cerussite. Suggest
an explanation.
2. The metal cadmium often occurs as a minor constituent of sphalerite in primary sulfide ores.
In pertially oxidized ores the sulfide of cadmium ( greenockite, CdS) is sometimes found as
tiny yellow crystals on the surface of sphalerite. Suggest an explanation
3. Using free energies from appendix VIII, show how the line separating the PbO2 and PbCO3
fields in fig. 18-1 is located
4. Construct a diagram similar to fig.18-1 showing the stability field of the zinc minerals
sphalerite, smithsonite, and zincite. Include countor lines showing concertations of Zn++ in
the part of the diagram representing acid ,oxidizing conditions. Use any resonable figures for
total dissolved carbonate and total dissolved sulfur
5. Explain why supergene sulfide enricment is more important for copper than foir iron,and
more important for silver hen for nickel.
6. Calculate the conceration of all dissolved species containing uranium in a solution having a
pH of 6,an Eh of 0,0 volt and total dissolved carbonate equal to 10-3M.
7. Using the oxidtion potentials in appendix IX,investigate the possibility of oxidizing and
dissolving the metal palladium in the oxidized zone of ore dposits.
8. Several ferrous sulfate and ferric sulfate minerals are known [e.g. melanterite, Fe(SO4 )
39H2O]. Under what geologic conditions would you expect these minerals to form ?
9. One of the minerals found in the oxidized zone of cobalt deposits is the
hydroxide,stainierite. A controversy has arisen as to wheter this minerals is cobaltic
hydroxide, Co (OH)3, or cobaltous hydroxide, Co (OH)2. Using free energies or electrode
potentials, see if Co (OH)3 would be stable under geologically reasonable conditions.
10. A common method of geochemical prospecting is to analyze soil for traces of metals
released to soil solutions during the xidation of concealed sulfide deposits below. Such
analyses in areas known to have deposits of chalcopyrite,spalerite, and galena often show
anomalously large concentrations of copper and zinc in the soil, but seldom unusual
concentrations of lead. Suggest an explanation.
11. At some ore deposits oxidized minerals have been the principal source of the metals
recovered, the wethering process apparently having concentrated the methals from low-
grade primary ores. Suggest what geologic,topographic,and climatic conditions might lead
to such concentrations in the oxidized zones. Would the same conditions neces sarily favor
supergene sulfide enrichment ?