Metalliferous Duricrusts (Orecretes) - Markers of Weathering .. Supergene Pb-Zn-Cu-Sb-P PDF

N. Jb. Miner. Abh. (J. Min. Geochem.
) 190/2, 123 –195 Article

Stuttgart, April 2013
Metalliferous duricrusts (“orecretes”) – markers of

weathering: A mineralogical and climatic-geomorphological
approach to supergene Pb-Zn-Cu-Sb-P mineralization on
different parent materials
Harald G. Dill, Berthold Weber, Reiner Botz
With 17 figures and 5 tables
Table of contents 6.2 Climate and the formation of orecretes . . . . . . . . . . . . 155

6.2.1 Temperature of oxidation versus palaeoclimatic
Abstract . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
temperature. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
1. Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
6.2.2 Physico-chemical regime of oxicretes . . . . . . . . 157
!"# $%&'()*+*,-#.)/#0+.11(23.4(*) . . . . . . . . . . . . . . . . . . . . . 126
6.2.3 Physico-chemical regime of carbocretes . . . . . . 159
3. Methodology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141
6.2.4 Physico-chemical regime of silicacretes . . . . . . 161
4. Geographic and Geological Settings. . . . . . . . . . . . . . . . . . 146
6.2.5 Physico-chemical regime of halcretes . . . . . . . . 167
5. Results. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147
6.2.6 Physico-chemical regime of sulcretes . . . . . . . . 167
5"6# #7*8# 4*# /(13*9%&# *&%3&%4%1# ()# 4:%# 2%+/# .)/# 4:%# +.;*-
6.2.7 Physico-chemical regime of phoscretes. . . . . . . 168
ratory. The outward appearance of supergene mineral
assemblages on different bedrocks . . . . . . . . . . . . . . . 147 6.2.8 Physico-chemical regime of arseno- and vana-
5.1.1 Supergene Se mineralization in siliceous sedi- docretes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 171
mentary rocks. . . . . . . . . . . . . . . . . . . . . . . . . . 147 6.2.9 Physico-chemical regime of orecretes-(Se-Mo-
5.1.2 Supergene Cu mineralization in siliceous mag- oxalate). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 171
matic rocks . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147 6.3 Landforms and the formation of orecretes. . . . . . . . . . 171
5.1.3 Supergene Cu mineralization in basic magmat- 6.3.1 Geomorphology . . . . . . . . . . . . . . . . . . . . . . . . . 171
ic rocks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149 6.3.2 Hydrology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 172
5.1.4 Supergene Cu mineralization in siliceous sedi- 6.3.3 Pedology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 173
mentary rocks. . . . . . . . . . . . . . . . . . . . . . . . . . 149 6.4 Parent material and the formation of orecretes . . . . . . 175
5.1.5 Supergene Cu mineralization in calcareous 7. Summary and Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . 178
sedimentary rocks . . . . . . . . . . . . . . . . . . . . . . 151 7.1 First order lithosphere-atmosphere . . . . . . . . . . . . . . . 178
5.1.6 Supergene Pb-Zn mineralization in siliceous 7.2 Second order lithosphere-atmosphere-hydrosphere. . . 178
magmatic rocks . . . . . . . . . . . . . . . . . . . . . . . . 151 7.3 Third order atmosphere-hydrosphere-pedosphere . . . . 178
5.1.7 Supergene Pb-Zn mineralization in siliceous 8. Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 180
sedimentary rocks . . . . . . . . . . . . . . . . . . . . . . 151 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 180
5.1.8 Supergene Pb-Zn mineralization in calcareous
sedimentary rocks . . . . . . . . . . . . . . . . . . . . . . 151 Supplementary material related to economic geology and ore
5.1.9 Supergene Sb-(Pb-Zn) mineralization in sili- deposits . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189
ceous magmatic rocks . . . . . . . . . . . . . . . . . . . 151 1. Supergene mineral assemblages across the globe. . . . . . . . 189
5.1.10 Supergene Sb mineralization in siliceous and 1.1 North America . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189
calcareous sedimentary rocks . . . . . . . . . . . . . 151 1.2 Central America . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189
5.1.11 Supergene P-S mineralization in magmatic 1.3 South America . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189
rocks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151 1.4 Northern and western Europe . . . . . . . . . . . . . . . . . . 191
5.1.12 Supergene P-S mineralization in sedimentary 1.5 Central Europe . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 192
rocks. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153 1.6 Southern Europe. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 192
5.2 Oxygen isotopes and the temperatures of formation of 1.7 Northern and Central Africa. . . . . . . . . . . . . . . . . . . . 192
carbocretes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153 1.8 Southern Africa . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193
6. Discussion of the origin of orecretes . . . . . . . . . . . . . . . . . 155 1.9 Middle East (Western Asia) . . . . . . . . . . . . . . . . . . . . 194
6.1 The origin of orecretes as a result of morphoclimatic 1.10 Southeast Asia and Australia . . . . . . . . . . . . . . . . . . . 194
processes and parent material . . . . . . . . . . . . . . . . . . . 155 2. Supergene ore mineralization as an ore guide . . . . . . . . . . 195
© 2013 E. Schweizerbart’sche Verlagsbuchhandlung, Stuttgart, Germany www.schweizerbart.de

DOI: 10.1127/0077-7757/2013/0235 0077-7757/2013/0235 $ 18.25
124 H. G. Dill et al.
Abstract: <&%3&%4%1#.&%#/%2)%/#()#4:%#3=&&%)4#14=/-#.1#.#1>%3(.+#4->%#*?#/=&(3&=141#@3:%'(3.+#&%1(/=%1A#8(4:#:%.9-#'%4.+1B#.33='=-
+.4%/#)%.&C1=&?.3%B#;=4#%D3+=/(),#/%%>%&#>.&41#4:.4#/%9%+*>%/#=)/%&#&%/=3(),#3*)/(4(*)1"#E*&%#4:.)#FG#14=/-#.&%.1#.3&*11#4:%#,+*;%B#
1*'%#*?#8:(3:#3*)4.()(),#'*&%#4:.)#*)%#'()%&.+(H%/#1(4%B#:.9%#;%%)#1%+%34%/#/=&(),#4:(1#,%*'*&>:*+*,(3.+#14=/-#4*#3*9%&#4:%#9.&(-
*=1#'*&>:*3+('.4(3#H*)%1#?&*'#>*+%#4*#>*+%"#$:%#1=>%&,%)%#'()%&.+#.11%';+.,%1#8%&%#()9%14(,.4%/#;-#'%.)1#*?#IJKB#LMECMKLB#
MENO#@%+%34&*)#'(3&*>&*;%#.).+-1(1AB#*>4(3.+#'%4:*/1#.)/#*D-,%)#(1*4*>%#.).+-1(1#*?#3.&;*).4%1"#P:(+%#4:%1%#'%4:*/1#&%'.()#
()3*'>+%4%B# '*&>:*3+('.4(3# 14=/(%1# 1=>>+%'%)4%/# ;-# /.4.# ?&*'# +(4%&.4=&%# 8%&%# 3*)/=34%/# 4*# /%4%&'()%# 4:%# >:-1(3.+C3:%'(3.+#
regime of orecretes in the course of supergene processes during the most recent parts of the Earth history. The current research is
focused on the topmost metalliferous chemical residues and near-surface phosphate-bearing encrustations which act as a “sink” to
.#8(/%#&.),%#*?#%+%'%)41#()#.//(4(*)#4*#;.1%#'%4.+1"#$:%#*&%3&%4%1#.&%#1=;/(9(/%/#()4*#*D(3&%4%1#@*D(/%#>+=1#:-/&.4%AB#3.&;*3&%4%1#
@3.&;*).4%AB#1(+(3.3&%4%1#@1(+(3.AB#:.+3&%4%1#@:.+*,%)(/%1Q#0+B#RB#SB#.)/#T&AB#1=+3&%4%1#@1=+?.4%#>+=1#ONL#'()%&.+1U.+='()(='#>:*1>:.4%#
1=+?.4%#'()%&.+1AB#>:*13&%4%1#@>:*1>:.4%1AB#.&1%)*3&%4%1#@.&1%).4%1AB#.)/#9.)./*3&%4%1#@9.)./.4%1A"#L%CB#E*CB#.)/#*D.+.4%C;%.&(),#
*&%3&%4%1B# *?# +%11# 8(/%1>&%./# *33=&&%)3%# 4:.)# 4:%# .?*&%C'%)4(*)%/# 3:%'(3.+# &%1(/=%1B# 8%&%# ).'%/# .33*&/(),+-"# $:%# *&%3&%4%1#
3*)4.()#N;B#0=B#V)B#W)B#S%B#E)B#X(B#0*B#P"B#JMMB#.)/#O,B#.1#Y=.+(2%&B#%.3:#*?#8:(3:#(1#.//%/#4*#4:%#>&()3(>.+#/%)*'().4*&#@%","B#
1(+(3.3&%4%C@0=AA"#$:%#/%9%+*>'%)4#*?#*&%3&%4%1#(1#3*)4&*++%/#;-#4:%(&#>.&%)4#'.4%&(.+B#4:%#+.)/?*&'1B#.)/#4:%#3+('.4%"#$:%#4:&%%#
>&()3(>.+#?.34*&1#&%)/%&#4:%#*&%3&%4%1#=)/%&#14=/-#.#2&14C:.)/#'*&>:*C3+('.4(3.+#'.&Z%&#?*&#,%*'*&>:*+*,(141#.)/#3+('.4*+*,(141B#
.+(Z%B#.1#(++=14&.4%/#()#.#[*8#1:%%4"#0+('.4*+*,(141#'(,:4#+%.&)#8:.4#8.1#,*(),#*)#()#4:%#&%3%)4#>.14#;=4#.+1*#,%4#.#4**+#4*#>&%/(34#
what we might expect in the near future if the morphoclimatic zones shift across the globe.
@6A#<&%3&%4%1C@L%CE*A#.)/#.&1%)*3&%4%1#*)+-#/%9%+*>%/#*)#>.&%)4#'.4%&(.+#14&*),+-#%)&(3:%/#()#4:%#'.&Z%&#%+%'%)41#O1B#L%#
and Mo. Orecretes and carbocretes that occur in some sites as relic forms (see 3) may develop mineral deposits of their own near-
1=&?.3%B#%","B#;.=D(4%1B#?%&&(3&%4%1#*&#=&.)(?%&*=1#3.+3&%4%1"
@!A#W)#>**&+-C&%+(%?%/#.&%.1B#+*8C+.)/1B#>+.4%.=1B#.)/#:(,:+-C%&*/%/#'*=)4.()#;%+41#*?#N&%3.';&(.)#4:&*=,:#E%1*H*(3#.,%B#4:%#
full range of orecretes from oxicretes through orecretes may be expected. In rift and graben structures as well as modern mountain
;%+41#*?#0%)*H*(3#.,%B#:.+3&%4%1B#9.)./*3&%4%1B#.)/#>:*13&%4%1#.&%#+%11#8(/%1>&%./B#1()3%#4:%#&.4(*#*?#=>+(?4#91"#3:%'(3.+#8%.4:%&(),#
has a detrimental effect on these effervescence to be preserved when the morphoclimatic zone changed either by altitude or in time.
O'*),#4:%#*&%3&%4%1#3*)1(/%&.;+%#3:.),%1#()#4->%#.)/#Y=.)4(4-#'.-#;%#*;1%&9%/#.+*),#8(4:#+.4(4=/().+#3+('.4(3#H*).4(*)#?&*'#4:%#
>*+%#4:&*=,:#4:%#%Y=.4*&"#$:%1%#,+*;.+#:*&(H*)4.+#3:.),%1#.&%#%Y=(9.+%)4#4*#4:%#'()%&.+*,(3.+#9.&(.4(*)#%)3*=)4%&%/#.+*),#8(4:#
the vertical microclimatic zonation in mountainous regions with the (peri)glacial zone developing on top of the mountain chain.
7*8%9%&#.+*),#4:%1%#9%&4(3.+#4&.)1%341#()#:(,:+-C&%+(%?%/#.&%.1B#4:%#?=++#1>%34&='#*?#*&%3&%4%1#/*%1#&.&%+-#1:*8#=>#/=%#4*#.#'*&%#
.33%+%&.4%/#+.&,%C13.+%#=>+(?4#.)/#/*8)#8&.>>(),#&%+.4(9%#4*#[.4C+-(),#.&%.1"#X%9%&4:%+%11B#*&%3&%4%1#*??%&#.#;%44%&#()1(,:4#()4*#4:%#
weathering phenomena in mountainous areas than common weathering products such as clay minerals for their accommodation of
physico-chemically critical elements into their lattice.
@\A#$:%#+.4(4=/().+#3+('.4(3#H*).4(*)#*?#*&%3&%4%1#:.1#;%%)#/(13=11%/#?*&#4:%#'*14#&%3%)4#4('%#1+(3%1#*?#4:%#%.&4:#:(14*&-B#4:%#
Quaternary (!"2 Ma) and Neogene (!"20 Ma). The majority of orecretes investigated during this study formed during the Quater-
).&-B#.1#&%9%.+%/#;-#4:%#1:(?4#*?#'*&>:*3+('.4(3#H*)%1#.3&*11#4:%#,+*;%#.)/#;-#4:%#9%&4(3.+#H*)(),#()#'*/%&)#'*=)4.()#&.),%1"#
Using the oxygen isotopes of carbocretes to determine the paleotemperatures of orecretes along a transect perpendicular to various
'*&>:*3+('.4(3#H*)%1B#-(%+/%/#.#4&%)/#1('(+.&#4*#4:.4#*?#4:%#]=.4%&).&-#3+('.4%#3=&9%"#W&&%1>%34(9%#*?#4:%#>&%3(1%#.,%#*?#?*&'.4(*)B#
8:(3:#3.)#*)+-#;%#.3:(%9%/#?*&#1*'%#^CB#E)C#.)/#0C;%.&(),#*&%3&%4%1B#4:%1%#'%4.++(?%&*=1#/=&(3&=141#'.-#;%#.44&(;=4%/#4*#>%/*+*,(-
cal and hydrological processes whose physico-chemical regime may be constrained based on thermo-dynamical calculations. The
>:-1(3*C3:%'(3.+#&%,('%#(1#'.()+-#3*)4&*++%/#;-#4:%#3:%'(3.+#3*'>*1(4(*)#*?#4:%#'%4%*&(3#[=(/1#@>7#3:.),%1A#=)/%&#*D(/(H(),#
and near-ambient hydrous conditions.
(a) Oxicretes-(Fe-Mn-Cu -In) occur over the full pH range in the humid zone of moderate chemical weathering and likewise in
tropical humid zones with pervasive chemical weathering. They often mark the onset of supergene alteration and occupy the posi-
4(*)#*?#&%+(3#?*&'1#'.&Z(),B#()#>+.3%1B#.#3+('.4%B#8:(3:#)*#+*),%&#%D(141"
(b) Carbocretes-(Pb-Cu-Zn-Cd) formed within a pH-range similar to that of the oxicretes down to pH 4. Mountainous and per-
iglacial regions are the most favorable morphoclimatic zones due to the retarded decomposition of organic matter in their soil types.
$%'>%&.4=&%1#*?#3.&;*3&%4%1C@0=CV)CN;A#*;4.()%/#?&*'#<#(1*4*>%#14=/(%1#.+*),#4:%#XCL#4&%)/#24#4:%#+.4(4=/().+#'*&>:*3+('.4(3#
zonation across the globe. The temperature of formation controlled by the organic redox systems is higher in the humid tropical
and mid latitude zones than in more arid zones relative to the mean annual temperatures due to the elevated groundwater level and
increased rate of precipitation.
(c) Silicacretes-(Cu-Zn) form in a pH range that only partially overlaps with those of carbocretes and oxicretes (absent in the
strongly alkaline regime) and show up later in the succession of supergene alteration. Silicacretes favorably develop under “inter-
mediate” morphoclimatic conditions with a balanced ratio between precipitation and evaporation.
@/A#S*&#:.+3&%4%1C@0=CO,AB#/=%#4*#4:%(&#:(,:#1*+=;(+(4-B#+*8#>&%3(>(4.4(*)#>+=1#:(,:#%9.>*&.4(*)#&.4%1#.&%#/%3(1(9%#?*&#4:%(&#>&%1-
ervation. They are exclusive to the tropical semiarid and arid morphoclimatic zones in a low to neutral pH regime.
@%A# L=+3&%4%1C@S%C0=CN;CONLA# 1('(+.&# 4*# :.+3&%4%1# =1%/# 4*# >&%3(>(4.4%# ?&*'# .3(/(3# 1*+=4(*)1B# ()3+=/(),# 4:%# '.)C'./%# .3(/C
'()%C/&.().,%#U#OEK"#$:%-#.&%#()/(3.4(9%#*?#14&*),#%9.>*&.4(*)#()#'*&>:*3+('.4(3#H*)%1#8:%&%#4:%#3:%'(3.+#8%.4:%&(),#(1#&.4:%&#
moderate and wind speed is rather high. Temperature is not per se#.#3&(4%&(*)#?*&#4:%#>&%1%)3%#*&#.;1%)3%#*?#1=+?.4%1B#;=4#/&-)%11#
is critical for their precipitation. The boundaries between supergene and hypogene alteration is not sharp in this group of orecretes
where APS minerals (aluminium phosphate sulfate) bridge the gap between the supergene and hypogene alteration by their varied
solid solution series. Increasing amounts of REE within the APS s.s.s. (#"solid solution series) and substitution of phosphate for sul-
fate in APS s.s.s. takes place as supergene morphoclimatic processes become more dominant in the near-surface alteration process.
@?A#N:*13&%4%1#@O+CS%C0=CN;CJMMA#.&%#&.4:%&#:%4%&*,%)%*=1#8(4:#O+C%)&(3:%/#%)/#'%';%&1#>&%9.(+(),#()#.3(/(3#[=(/1#.)/#O+C
free members under neutral to alkaline conditions. In the morphoclimatic humid mid latitude and tropical wet-dry zones phoscretes
&%9%.+#.#&%+.4(9%#'.D('='#.1#.#?=)34(*)#*?#4:%#>:*1>:.4%#3-3+%#8(4:()#4:%#;(*1>:%&%U>%/*1>:%&%"
Metalliferous duricrusts (“orecretes”) – markers of weathering 125
@,A#d.)./*3&%4%1C@N;C0=CV)A#4.Z%#.)#()4%&'%/(.4%#>*1(4(*)#;%48%%)#1=+3&%4%1#.)/#:.+3&%4%1B#4*#>+.-#.#+%./(),#&*+%#()#4:%#1%-
Y=%)3%#*?#.&(/(4-#.1#?*++*81Q#1(+(3.3&%4%"$"sulcrete"%"vanadocrete"%"halcrete. They form exclusively under arid conditions as the rate
of chemical weathering is low. (Ultra)basic magmatic rocks or (meta)biolites in the hinterland are mandatory to provide the V for
the buildup of the orecrete.
e%-#8*&/1Q#/=&(3&=141B#,%*'*&>:*+*,-B#3+('.4%B#*&%#'()%&.+1B#1=>%&,%)%#.+4%&.4(*)B#0%)*H*(3"
1. Introduction climatic and related these morphodynamic processes to

particular zones on the globe (TRICART & CAILLEUX#6_5`B#
Supergene minerals range from oxygen-bearing miner- BÜDEL# 6_FFB# SUTHERLAND# 6__6B# THOMAS# 6__aB# TWIDALE
als originating from natural weathering in the gossan of 2002) (Fig.#!.B#;A"#W)#4:%#3=&&%)4#14=/-#4:%1%#>&*3%11%1#.&%#
>&%C%D(14(),# '()%&.+1# 4*# .&4(23(.+# 3:%'(3.+# 3*'>*=)/1# 3*)1(/%&%/# ?*&# 48*# /(??%&%)4# 4('%# 1+(3%1Q# @6A# ]=.4%&).&-#
3*.4(),#.)3(%)4#1'%+4%&C1+.,1B#,&*8(),#()#4.(+(),#>*)/1#*&# (Fig.#!.AB#@!A#X%*,%)%#@Fig. 2b).
covering the walls of adits and galleries as a result of post- So far only a few attempts have been made to unravel
mining oxidation (LLORCA & MONCHOUX#6__6B#ETTLER et the evolution of gossans embedded into the geomorpho-
.+"# !GG6B# BOUZARI & CLARK# !GG!B# MANASSE & MELLINI logical processes and thereby contribute to the landscape-
!GG!B#DILL#%4#.+"#!GG!B#YAKOVLEVA#%4#.+"#!GG\B#DILL#!GG`B# forming processes during the most recent parts of the
!GG_B#BELOGUB et al. 2008). Not all of them are generally geological past (CARLISLE#6_`\B#WILSON#6_`\B#GOUDIE &
agreed and accepted by geoscientists as minerals sensu PYE#6_`\B#ADAMS#%4#.+"#6__bB#BEAUVAIS & ROQUIN#6__bB#
stricto (NICKEL 1995). In the following sections priority is ANAND#%4#.+"#6__FB#PHILLIPS#%4#.+"#6__FB#MORDBERG#6___B#
given to those supergene minerals that developed in situ BOUZARI & CLARK#!GG!B#ARANCIBIA#%4#.+"#!GGbB#WARREN
by natural oxidation and weathering of bedrocks anoma- %4#.+"#!GGÀ"#$:%#>.>%&#(1#4*#/(13=11#4:%#('>.34#*?#3+('.4%B#
+*=1+-# %)&(3:%/# ()# ;.1%# '%4.+1# .)/# >:*1>:.4%B# ;%3.=1%# landform and parent material on the emplacement of these
they closely link geomorphological (land)forms in a re- duricrusts. Geographers as well as soil scientists who are
gion with the climate during a certain period of time and ?.'(+(.&# 8(4:# 3.+(3:%U# 3.+3&%4%1B# /*+3&%4%1B# ,->3&%4%1# *&#
they are also controlled by the mineralogical assemblage ?%&&(3&%4%1B#;=4#:.9%#+(44+%#Z)*8+%/,%#()#'()%&.+*,-#8(++#
*?#4:%(&#>.&%)4#'.4%&(.+"#$:%&%#.&%#.#?%8#Z%-14*)%#14=/(%1B# be given an insight into duricrusts abnormally enriched
&%[%34(),#4:%#./9.)3%1#()#1=>%&,%)%#.+4%&.4(*)#.)/#8%.4:- ()#%+%'%)41#1=3:#.1#N;B#0=B#V)B#X(B#P"B#L%B#.)/#O,#4:.4#
ering of metalliferous bedrocks. The papers edited by TI- typically respond more sensitively to climatic and mor-
TLEY#@!GG_A#.//&%11%1#4:%#/%%>%&U#&%/=3(),#H*)%B#=)/%&- >:*+*,(3.+# 3:.),%1# 4:.)# 4:%# .?*&%C'%)4(*)%/# 4->%1B# /=%#
neath what might be called metalliferous duricrusts and to the wider range of minerals accommodated in the ore-
the topic is looked at from an angle of an economic geolo- cretes and elements of different valence states involved
,(14# *)+-# .)/B# 4:=1B# (4# (1# )*4# 3*)1(/%&%/# :%&%# ?=&4:%&# *)"# in supergene alteration. Thereby the best match with the
WILLIAMS (1990) took a chemical approach with a lot of morphoclimatic and pedological zonations from high
thermo-dynamical calculations and integration of biologi- to low latitudes may be achieved (TRICART & CAILLEUX
cal and hydrological processes into supergene alteration. 6_F!B#^LKO#!GG5A"#L*'%#>:*1>:.4%C*)+-#/%>*1(41#8(4:#
The work of TAYLOR & EGGLETON (2001) is an update of a pronounced cap of phoscretes on top have been includ-
the classical paper by VALETON (1972) on bauxites. In their %/#()4*#4:%#>&%1%)4#()9%14(,.4(*)#4*#2++#()#4:%#,.>#3.=1%/#
&%,*+(4:# ,%*+*,-# 4:%-# .//&%11# 4:%# 8(/%# 2%+/# *?# '()%&.+# by the absence of metal deposits in this morphoclimatic
8%.4:%&(),#;=4#/*#)*4#1>%)/#4('%#*)#*D(/.4(*)#*?#1=+2/%1"# zone and as they often act as sink for a great many met-
This may be extended also to the numerous papers deal- .+1"#O+*),#.#&%?%&%)3%#4&.)1%34#?&*'#5Gc#X#4:&*=,:#\Gc#L"B#
(),#8(4:#3+.-#'()%&.+*,-#.)/#8%.4:%&(),B#*?#8:(3:#*)+-# some supergene carbonate-bearing mineral assemblages
a few may be cited here (SHEPPARD#6_FFB#TABOADA et al. were investigated for their paleotemperatures using O
6__GB# BRISTOW & EXLEY# 6__aB# HILLIER# 6__5B# PSYRILLOS isotope for calculations. While isotopes have been used
%4#.+"#6__`B#ALLEN et al. 2001). Neither study made an at- as a tool for calculating temperature (MELCHIORRE et al.
4%'>4#4*#.//&%11#1=+2/%#*D(/.4(*)#;-#()4%,&.4(),#3+('.4%# !GG6B# MELCHIORRE & ENDERS# !GG\AB# 4:%# '()%&.+*,(3.+#
.)/#,%*'*&>:*+*,-#*)#.#,+*;.+#;.1(1"#<)#.,,&%,.4%B#,%*- and climatological-geographical framework of samples
morphology is important during supergene alteration but has not been addressed on a global scale. To avoid gaps
climate is paramount. Geographers have termed the sci- between specialities as is the case often with modern col-
%)4(23#.>>&*.3:#4.Z%)#()#4:%#3=&&%)4#14=/-#4*#.//&%11#3+(- +%34(9%#8*&Z1#8:%)#,*(),#,+*;.+B#4:%#.=4:*&1#?*3=1%/#*)#
'.4%C()/=3%/B# +.)/13.>%C?*&'(),# >&*3%11%1# .1# '*&>:*C N;B#0=B#V)B#L;#.)/#NB#.#,&*=>#*?#1=>%&,%)%#'()%&.+(H.-
tions studied in detail as reference and supplemented their Orecretes are chemical residues, different in structure
investigations with a literature review (Table 1). and lateral extension whose thickness measures by the
Modeling of the physical-chemical regime in these decimeter, equivalent to the depth of soil-forming process-
1=>%&23(.+# *&%# 3*)3%)4&.4(*)1# (1# >&%1%)4%/# 1*# .1# 4*# ;%# es and the near-surface hydrological system. These mor-
used in combination with other data to constrain the phoclimatic markers form(ed) at the interface between
paleogeographic and paleoclimatological setting around atmosphere, lithosphere and hydrosphere. The chemi-
'()%&.+(H%/# 1(4%1# ()# 8%++C/%2)%/# '*&>:*3+('.4(3# H*)%1"# cal compounds in the metalliferous encrustations are
A strict color code system allows for a rapid recognition composed of oxygen-bearing anion complexes and(or)
*?#4:%#3+('.4%#H*)%1#()#4:%#9.&(*=1#('.,%1B#/(.,&.'1B#.)/# halogens that reacted with metals. Radioactive elements
tables. The (morpho)climatic subdivision used during uranium and thorium, alkaline earth and alkali elements
this study follows the Koeppen Climate Chart (PEEL et as sole components or in combination are excluded from
al. 2007). this study. They form duricrusts sensu stricto, e.g., cal-
Those readers who are particularly interested in the !"#$#%&'("'%)*#"+!,-.'("#'/#*(%,$%'(0'$1#,"'(20&'-%',$',%'$1#'
application of these orecretes to economic geology are case with aluminium and iron in the oxidic subtypes of
referred to the supplementary matter. orecretes which are transitional into laterite and bauxite.
Those parts of supergene alteration that developed un-
der Eh"!"0 are excluded from the study of orecretes sensu
!"#$%&'()*+*,-#.)/#0+.11(20.3(*) stricto as it is the case with paleogossans or second-type
oxidation zones (e.g. Tsumeb). They do not constitute
Different supergene metalliferous processes and a great hardpans visible to the naked eye and as such have no
variety of parent material led to a plethora of terms for relevance for morpho-climatic studies. Orecretes should
4:%#'%4.++(?%&*=1#/=&(3&=141B#*?4%)#,(9(),#/(??%&%)4#).'%1# be amenable to remote-sensing techniques dedicated to
for the same sort of near-surface ore mineral assemblag- $1#',/#0$,+!-$,(0'(3'*-"#0$'4-$#",-.%5
%1Q#f3:.>%.=#/%#?%&gB#fM(1%&)%&#7=4gB#f3.),.gB#f,*11.)g"# 61#' *(%$+7' ("' #0/,08' (3' $1#' 4#$-..,3#"()%' /)",!")%$%'
Collective terms such as “calamine” have been used for “-crete” is self-explanatory as being linguistically com-
'%4.++(?%&*=1# 3&=141B# 3*)4.()(),# '.()+-# V)"# $:%# 8*&/# pared with terms in other languages (English: crust,
gossan is often used for the topmost part of ore deposits French: croûte, German: Kruste, Spanish: costra/cor-
=)/%&,*(),#1=>%&,%)%#.+4%&.4(*)B#%)3*'>.11(),#'()%&.+1# teza).
In view of an ever-increasing number of interdiscipli-
>&%3(>(4.4%/#=)/%&#*D(/(H(),#.)/#&%/=3(),#3*)/(4(*)1B#4:%#
).&-#14=/(%1B#8%#.&%#()#)%%/#*?#3&%.4(),#3*''*)#,&*=)/1#
latter group of minerals formed at depth and is normal-
?*&#4:%1%#1=>%&23(.+#'%4.+#3*)3%)4&.4(*)1#1*#.1#4*#;%#=)-
ly only hit by drilling or cut into during deep trenching.
/%&14**/# ;-# &%./%&1# ?&*'# /(??%&%)4# 13(%)4(23# /(13(>+()%1"#
This hydrological level with dominantly reducing condi-
Therefore an easy-to-handle terminology of these mineral
tions and with stagnant groundwaters is excluded from
.11%';+.,%1# :.1# ;%%)# >=4# ?*&8.&/B# ?*++*8(),# 4%D4;**Z1#
this study (Fig. 1). In the lowermost hydraulic zone of the
*)#3:%'(3.+#&%1(/=%1#.)/#3+.11(23.4(*)#13:%'%1#./*>4%/#
,*11.)B#8:(3:#(1#%Y=(9.+%)4#4*#4:%#3+.11(3.+#3%'%)4.4(*)# in soil science (WILSON#6_`\B#GOUDIE & PYE#6_`\B#^LKO#
zone sensu EMMONS# @6_GGAB# SCHNEIDERHÖHN# @6_!aAB# .)/# 2005). It is a residual soil which developed in situ after
SMIRNOV# @6_55AB# &%/=3(),# 3*)/(4(*)1# (''%/(.4%+-# .4*># 1*'%#*?#4:%#1*+=;+%#3*)14(4=%)41#:.9%#;%%)#&%'*9%/#.)/U#
4:%#>&('.&-#1=+2/(3#*&%#>&*9*Z%/#1=>%&,%)%#*&#1%3*)/.&-# or redeposited. They may grade into aluminium-bearing
1=+2/%1B#1=3:#.1#3*9%++(4%B#3:.+3*3(4%B#.)/#O,#'()%&.+1#4*# types such as laterites and bauxites (ALLABY & ALLABY
precipitate and to be preserved (Fig. 1). 2003).
E%4.++(?%&*=1#/=&(3&=141#*&#*&%3&%4%1#.&%#/%2)%/#()#4:%# T-#.).+*,-#8(4:#4:%#3*''*)#4%&'()*+*,-#=1%/#/=&-
current study as follows (Fig.#6AQ#The duricrust are looked (),#()9%14(,.4(*)1#*?#/=&(3&=141#h#1%%#3.+3&%4%1B#,->3&%4%1B#
at from a wider angle and this term is used during the /*+3&%4%1B# ?%&&(3&%4%1# 4:%# /=&(3&=141# =)/%&# 3*)1(/%&.4(*)#
current study for deeply weathered residues that not only are denominated as orecretes. Those which solely con-
became hardened by a long-lasting exposure to air and tain oxygen-bearing anions are called oxicretes (Table
sunshine but have as main component a cement gluing 6A"# S*&# .# '*&%# /%4.(+%/# /%13&(>4(*)B# 4:%# %+%'%)41# 4->(-
together the previously loose material or forming a more 3.+# *?# 4:%# *&%3&%4%# *&# Y=.+(2%&1# '.-# ;%# %D>&%11%/# ()# .#
or less impermeable encrustation around the weathered self-explanatory way. Encrustations made up of tenorite
debris. The precipitated minerals may prevail over the de- and (or) cuprite are called cupriferous oxicrete or adopt-
bris or lack them so as to convert the near-surface weath- (),# 4:%# ,%)%&.++-# .,&%%/# WEOC14-+%# /%)*'().4(*)B# 4:%-#
ering product into a pure chemical residue. are called oxicrete-(Cu). The main constituents or anion-
Fig. 1. Cartoons to show the position of metalliferous duricrusts (orecretes) at the interface of different sphere and zones in the uppermost
part of the Earth Crust. aA#<&%3&%4%1#.1#/%2)%/#8(4:()#4:%#3=&&%)4#14=/-#()#&%+.4(*)#4*#4:%#.4'*1>:%&%B#+(4:*1>:%&%B#>%/*1>:%&%B#.)/#:-/&*-
sphere embedded into the common zonation of supergene ore mineralization including its reducing zone. b) Modern and fossil orecretes
()#&%+.4(*)#4*#'*/%&)#.)/#>.+%*.Y=(?%&1i#6"#W)#9.++%-1#.)/#;.1()1#2++%/#8(4:#1%/('%)41#48*#,%)%&.4(*)#*?#*&%3&%4%1#'.-#/%9%+*>#.4#/(??%&%)4#
/%>4:"#W)#4:(1#>.>%&#*)+-#4:%#4*>'*14#*)%#(1#4:%#*;j%34(9%#*?#()9%14(,.4(*)"#<D(/(H(),#.)/#&%/=3(),#>.&41#.&%#1>+(4#.>.&4#?&*'#%.3:#*4:%&i#!"#
<)#4*>*,&.>:(3#:(,:1#.)/#;.1%'%)4#=>+(?41#'*/%&)#.)/#>.+%*.Y=(?%&1#*9%&+.>#8(4:#%.3:#*4:%&#.)/#'*/%&)#*&%3&%4%1#.&%#f4%+%13*>%/g#()4*#
paleo-orecretes or fossil orecretes (relic orecretes).
complexes encountered in the various orecretes may eas- >+=1# .+='()(='C>:*1>:.4%C1=+?.4%1AB# >:*13&%4%1# @>:*1-
(+-# ;%# /%/=3%/# ?&*'# 4:%# >&%2DQ# 1(+(3.3&%4%# @1(+(3%*=1AB# >:.4%1AB# .&1%)*3&%4%# @.&1%).4%AB# .)/# 9.)./*3&%4%# @9.).-
:.+3&%4%# @:.+*,%)1B# 0+B# T&B# SB# .)/# RAB# 1=+3&%4%# @1=+?.4%1# date).
Table 1. N&('.&-#.)/#1%3*)/.&-#*&%#'()%&.+(H.4(*)#@f*&%3&%4%1gA#.1#.#?=)34(*)#*?#4:%#'*&>:*3+('.4(3#H*).4(*)#*)#4:%#,+*;%"#$:%#3*+*&#*?#4:%#+()%1#3*&&%1>*)/1#4*#4:%#3+.11(23.4(*)#.)/#3*+*&#3*/%1#=1%/#()#
Figs. 2a and 2b. Data of sites given in italics are from literature (see reference below)
Site-country:#4:%#).'%#*?#4:%#>&('.&-#/%>*1(4U#'()%&.+(H%/#1(4%#.)/#4:%#:*14#3*=)4&-#8:%&%#4:%#*&%3&%4%1#/%9%+*>%/
Supergene (secondary) mineralization:#4:%#*&%3&%4%1#.&%#+(14%/#3*&&%1>*)/(),#4*#4:%#4->(3.+#.)(*)#3*'>+%D#@*D(/%#>+=1#:-/&.4%1B#3.&;*).4%B#1(+(3.4%B#:.+*,%)(/%B#1=+?.4%#@>+=1#.+='()(='C>:*1>:.4%C1=+?.4%#
1"1"1AB#>:*1>:.4%B#.&1%).4%C9.)./.4%#1"1"1"A"#E(13%++.)%*=1#3*'>&(1%1#1%+%).4%1B#*D.+.4%B#'*+-;/.4%1#.)/#:='.4%#3*'>+%D%1"
Minerals given in italics refer to oxidic minerals which are transitional into the hypogene ore mineralization. Bold-faced letters denote oxidic minerals of hypogene origin intergrown with supergene oxidic
'()%&.+1"#E()%&.+1#=)/%&13*&%/#.&%#>&%1%)4#()#4:%#1=>%&,%)%#'()%&.+(H.4(*)B#*)#8.14%#/='>1#*&#8(4:()#('>*=)/'%)41#*?#4:%#'()(),#1(4%"
Morphoclimatic zones:#4:%#3+('.4%#&%?%&&%/#4*#(1#3:.&.34%&(14(3#?*&#4:%#>%&(*/#*?#4('%#=>#4*#!#E.#?&*'#)*8#@1*=&3%Q#TRICART & CAILLEUX#6_5À#.)/#?*&#3+('.4%1#;%48%%)#!#.)/#!G#E.#@1*=&3%Q#X%*,%)%C1*=&3%Q#
:44>QUU888"13*4%1%"3*'U+%,%)/":4'A"#K%9(.4(*)#?&*'#4:%#,+*;.+#&%?%&%)3%#'.>1#.&%#/=%#4*#&%,(*).+#/.4."
Mineral association: the orecretes are listed in decreasing order of abundance
Different color codes in this column denote relic mineral assemblages – below the horizontal boundary – which are indicative of precursor climates between 2 and 20 Ma.
Site Primary min- Secondary mineralization (Pb-Cu-Zn-In-Ni-Sb-W-Ag-Mo-REE-bearing orecretes) Morphocli- Morphocli- Association
Country eralization mate zone mate zone of orecretes
Element as- Oxicretes Carbocretes Silicacretes Halcretes Sulcretes Phoscretes Arsenocretes Orecretes- ( Quaternary ( Neogene (in decreasing
semblage / Vanadocretes (Se, Mo, Oxa- < 2 Ma) < 20 Ma) order of
ore type late) abundance)
Reference to oxide plus carbonate silicate halogenide sulfate (plus phosphate arsenate miscellane-
the primary hydrates (Cl-Br-J) APS minerals) ous
mineralization and/ vanadate
or country rocks
Uranium City U-Cu-Ni-Se Se-bearing malachite chalcomenite periglacial cool temper- orecrete
Canada vein-type tenorite schmiederite ate carbocrete-
Beck 1969, 1972 orecrete-(Se)
Lomex Cu porphyry- cuprite azurite chrysocolla gypsum mountaine- warm temper- carbocrete-
Canada type malachite plancheite anhydrite ous ate oxicrete
Scott et al. 2008; silicacrete
Singer et al. 2008
Morenci Cu cuprite azurite chrysocolla tsumebite turquoise dry conti- arid carbocrete
USA porphyry-type tenorite malachite brochantite nental oxicrete-
Moolick & Durek chalcanthite phoscretes
1966; Langton 1973; copiapite sulcrete
Marvin et al. 1987 silicacrete
Nuevo León, Pb-Zn vein goethite aurichalcite hemimorphite anglesite legrandite tropical arid arid oxicrete-
Mexico smithsonite mimetite carbocrete
orecrete-( As)
Panczner 1987 silicacrete
sulcrete
Aranzazú, Cu vein cuprite azurite atacamite tropical arid arid oxicrete-
Zacatecas, Mexico goethite malachite carbocrete
Panczner 1987 cerussite halcrete
Tajo Mine, Cu vein cuprite azurite chrysocolla tropical arid arid oxicrete-
Hidalgo del Parral, goethite malachite carbocrete
Chihuahua, Mexico silicacrete
Panczner 1987
or country rocks
Sonora-La Sb-As-Cu-Pb- stibiconite cerussite chrysocolla Cu-bearing gypsum apatite arseniosiderite tropical arid arid oxicrete-
Angostura Zn epithermal senarmontite malachite plancheite bromian alunite segnitite carbocrete
Mexico skarn bismutosti- hemimorphite chlorargyrite segnitite Sb- halcrete
biconite bearing sulcrete
cuprite carminite orecrete-(V-As)
mimetite silicacrete
conichalcite
beudantite
Camprubí et al. 2003 duhamelite
El Cobre Cu goethite azurite brochantite tropical humid tropical humid carbocrete-

Cuba veins and cuprite malachite chalcantite oxicrete
stratabound cryptomelane sulcrete
Schneider 1958;
mineralization manganite
Cazañas et al. 2003
(VHMS)
Agua Shuca Cerro Al-(As) lepidocrocite opaline-CT meta-alunogen crandallite dussertite tropical humid tropical humid sulcrete
Blanco epithermal cristobalite K- jarosite gorceixite phoscrete-
El Salvador amorphous Na-jarosite !"#$%&'($ silicacrete
matter woodhouseite orecrete
Dill et al. 2000, Dill svanbergite orecrete-(As)
2000 alunogen
aluminite
alunite
Malpelo Island, P variscite tropical humid tropical humid phoscretes
Colombia (4) phosphorite metavariscite
Palache et al. 1951 phosphosi-
derite
Cajamarca Province Al-(Cu) malachite tridymite jarosite. goyazite mountaine- tropical humid sulcrete
Peru epithermal cristobalite REE- !"#$%&'($) ous / tropical phoscrete-
opal CT woodhouseite- !"#$%&'($* arid silicacrete-
svanbergite goyazite s.s.s. carbocrete
gypsum
Dill et al. 1997a woodhouseite
svanbergite
svanbergite-
woodhouseite
s.s.s alunite
P-bearing
alunite
Cerro de Pasco Peru Pb-Cu-Zn-Ag- tenorite brochantite duftite mountaine- arid sulcrete
Bi replacement/ linarite ous / tropical oxicrete
Pedroni 1996; skarn deposit chalcanthite arid orecrete-(As)
Baumgarten et al.
2008
or country rocks
Casapalca Pb-Cu-Zn-Ag goethite malachite gypsum mountaine- arid oxicrete-
Peru subvolcanic azurite ous / tropical carbocrete
Rye and Sawkins veins-type arid
1974
Potosi Sb province Sb stibiconite despujolsite mountaine- arid oxicrete-
Bolivia veins - epither- senarmontite alunite ous sulcrete
Dill et al. 1995, 1997b mal deposits schafarzikite
Lipez-Millur-Cosuno Sb-Cu-Ba tenorite azurite plancheite chlorargyrite alunite mountaine- arid carbocrete-
Bolivia epithermal malachite ous oxicrete-
Dill et al. 1997b; Dill sulcrete
2003 silicacrete
halcrete
Jujuy Pb-Cu -Ag curpite malachite chrysocolla linarite tropical semiarid sulcrete
Argentina hydrothermal azurite anglesite arid carbocrete-
Sureda et al. 1986; impregnation smithsonite brochantite silicacrete-
Bahlburg 1990; sandstone- cerussite oxicrete
Oyarzun 1990 hosted
San Roque- Cu-Pb-Zn-In hematite cerussite brochantite tropical semiarid sulcrete
Patagonia hydrothermal dzhalindite antlerite arid oxicrete
Argentina vein-type to (Pb-bearing) carbocrete-(Pb)
Dill et al. 2013 stockwork
Mina La Luz Pb-Cu-Zn-(Au) cerussite hemimorphite linarite mottramite tropical semiarid orecrete-(V)
Argentina hydrothermal malachite –(As) arid sulcrete
this study vein-type azurite mottramite arid silicacrete
descloizite carbocrete-(Pb)
carbocrete-(Cu)
orecrete-(As)
Vazante Zn-(Bb-Ba) franklinite smithsonite hemimorphite tropical wet- arid carbocrete-
Brazil %"%*+,-./'&0)) willemite dry – humid silicacrete
Soares Monteiro et al. metamorpho- tropical
1999, 2007 genic
Arica Cu malachite halite gypsum tropical arid arid sulcrete
Chile volcanic- paratacamite thenardite halcrete
Bouzari & Clark 2002; hosted carbocrete
Maksaev et al. 2007;
Singer et al. 2008
Tarapaca Cu goethite chrysocolla atacamite brochantite pseudomala- tropical arid arid sulcrete
Chile porphyry-type tenorite plancheite antlerite chite halcrete
cuprite chalcedony chalcantite carbocrete-
Bouzari & Clark 2002; alunite-(Na) silicacrete-
Maksaev et al. 2007; phoscrete
Singer et al. 2008 oxicrete
or country rocks
Chuquicamata Chile Cu cuprite azurite chrysocolla paratacamite brochantite reichenbachite tropical arid arid halcrete
porphyry-type tenorite malachite plancheite halite gypsum pseudomala- sulcrete
atacamite antlerite chite carbocrete-
marshite jarosite silicacrete-
thenardite phoscrete
chalcanthite oxicrete
Maksaev et al. 2007 warm oxicrete
Cerro Guanaco Chile Cu-Au-Ag cuprite azurite atacamite brochantite olivenite tropical arid arid sulcrete
1'21*+,-./3('"%) tenorite iodian chlor- clinoclase halcrete
epithermal argyrite chenevixite carbocrete-
cuprojod- phoscrete
argyrite orecrete-(As)
oxicrete
this study warm oxicrete
Copiapo Cu cryptomelane malachite chrysocolla marshite brochantite turquoise tropical semiarid sulcrete
Chile porphyry –type todorokite rosasite shattuckite atacamite gypsum phospho- arid carbocrete
with goethite plancheite siderite halcrete
Fe-Cu-Au min- Ce oxide/ opal-CT strengite silicacrete
eralization hydroxide (?) pseudo- phoscrete
tenorite malachite orecrete-(As)
cuprite oxicrete
Marschik & Söllner warm oxicrete
2006
Combarbala Chile Al-(Cu) K-REE-bearing gorceixite Ca- tropical semiarid phoscrete
epithermal woodhouseite- Sr-bearing arid sulcrete
woodhouseite- !"#$%&'($))43*
Dill et al. 1995 hinsdalite- Sr-bearing
alunite Crandallite
K-bearing goyazite
svanbergite-
woodhouseite
s.s.s.
Salamanca Chile W cuprotungstite plancheite brochantite tropical semiarid silicacrete
veins hydrated chrysocolla arid sulcrete
Sillitoe et al. 1970 cuprotungstite warm oxicrete
Repparfjord Norway Cu goethite malachite mountaine- cool carbocrete
sandstone- ous / perigla- oxicrete
Pharaoh et al. 1983
hosted -meta- cial
morrphosed
or country rocks
Bidjovagge Norway Cu-Au green- goethite malachite periglacial cool carbocrete
stone-hosted oxicrete
Mathiesen 1969;
Cumming et al. 1993
Aitik Cu goethite malachite gypsum periglacial cool carbocrete
Sweden porphyry-type- oxicrete
Wanhainen et al. 2003 metamor-
phosed
Galmoy Lisheen Pb-Zn–Cu-As- goethite smithsonite chrysocolla gypsum olivenite wulfenite humid mid- warm oxicrete
Tynagh Ni -FeS smithsonite anglesite strashimirite latitude carbocrete
Ireland carbonate- Fe-bearing jarosite tyrolite silicacrete
Clifford et al. 1986; hosted (monheimite) copiapite beudandite tropical semi- sulcrete
Banks & Russell hydrozincite devilline annabergite arid orecrete-(As-
1992; Andrew 1993; cerussite Mo)
Hitzman 1995; malachite
Balassone et al. 2008 azurite
Freihung (NE Pb coronadite malachite chrysocolla linarite pyromorphite humid mid- tropical semi- carbocrete-
Bavaria) sandstone- cerussite Cu latitude arid oxicrete
Germany hosted cerussite hydrosilicate phoscrete
cerussite Cu- (unknown) sulcrete
Gudden 1975; Schmid bearing luddenite silicacrete
1981; Dill 1990; Dill et
al. 2007, 2008
Lichtenberg-Issigau- Cu-F tenorite malachite chrysocolla wroewolfeite pseudoma- humid mid- tropical semi- oxicrete
Siebenhitz (NE vein-type cuprite bismutite cerite brochantite lachite rhab- latitude arid carbocrete-
Bavaria) Germany goethite cerussite langite dophane-(Ce) phoscrete
cryptomelane chalcanthite rhabdophane- sulcrete
Dill 1985 mcconnellite devilline (Nd) bast- silicacrete
manganite naesite (?)
bismite
Berg (NE Bavaria) Ni-Fe goethite malachite Ni-bearing morenosite annabergite humid mid- tropical semi- oxicrete
Germany vein-type spertiniite hendricksite gypsum latitude arid carbocrete
pyrolusite antlerite orecrete-(As)
Dill 1985 arsenolite sulfur sulcrete
tenorite silicacrete
Schmölz-Erbendorf Zn-Pb-(Cu) malachite Cu-bearing chalcophanite pyromorphite humid mid- tropical semi- carbocrete
(NE Bavaria) vein-type aurichalcite hemimorphite natrojarosite latitude arid silicacrete
Germany rosasite chrysocolla brochantite sulcrete
cerussite langite phoscrete
Dill 1985 smithsonite linarite
anglesite
or country rocks
Auerbach (NE P-Fe goethite vivianite humid mid- tropical semi- oxicrete-
Bavaria) Germany pocket/ re- pyrolusite apatite latitude arid phoscrete
placement rockbridgeite
phospho-
siderite
ferroan vari-
Dill et al. 2009 scite
cacoxenite
wavellite
churchite-(Y)
crandallite
oxi-beraunite
strengite
Brandholz- Sb-Au-As bindheimite malachite pseudoboleite devilline wavellite mimetite humid mid- tropical semi- oxicrete-
Goldkronach vein-type schafarzikite botallackite gypsum scorodite latitude arid carbocrete-
Wolfersgrün (NE kermesite atacamite orecrete-(As)
Bavaria) Germany cervantite
senarmontite
Dill et al. 2008 stibiconite
Tirschenreuth (NE FeS lepidocrocite ferrialunite whitmoreite humid mid- tropical semi- oxicrete-
Bavaria) Germany graphite shales alunite- V-bearing latitude arid phoscrete
and –quartzite- jarosite s.s.s wavellite sulcrete
Dill & Bäumler 2007 hosted alunogen mag-
nesiocopiapite
coquimbite
Schwaz Cu-Hg-Ag romanechite malachite brochantite duftite mountaine- warm temper- oxicrete-
Austria carbonate- crednerite (?) azurite langite erythrite ous / humid ate carbocrete-
Arlt & Diamond 1998 hosted cuprite aurichalcite serpierite mimetite mid-latitude sulcrete
cerussite orecrete-(As)
Auronzo Pb-Zn- hydrozincite hemimorphite anglesite mountaine- warm temper- carbocrete-
Italy carbonate- cerussite ous / humid ate silicacrete
Schroll 2005 hosted smithsonite mid-latitude sulcrete
Maidanpek Serbia Cu tenorite malachite chrysocolla brochantite humid mid- warm temper- oxicrete-
porphyry-type cuprite azurite posnajkite latitude dry ate carbocrete-
Singer et al. 2008 continental sulcrete
silicacrete
Chalkidiki Peninsula Cu cuprite azurite chrysocolla anhydrite tropical semi- warm temper- oxicrete-
Greece porphyry-type goethite malachite arid ate carbocrete-
Marinos 1979; silicacrete
Kalogeropoulos et al. sulcrete
1989; Kroll et al. 2002;
Quadt von et al. 2005
or country rocks
Seriphos Island Cu-Fe goethite malachite brochantite pharmacosider- K-Cu humates/ tropical semi- warm temper- oxicrete-
Greece skarn-type azurite ite beudantite- oxalate (X) arid ate carbocrete-
(Sb) beu- orecrete-(As)
Dill et al. 2010a
dantite-(REE) sulcrete
arseniosiderite
conichalcite
Kalavassos Cyprus Cu-Fe-S tenorite malachite chrysocolla wroewolfeite tropical semi- warm temper- oxicrete-
VMS cuprite brochantite arid ate carbocrete-
Constantinou 1980; spertiniite gypsum sulcrete
Galley & Koski 1999, devilline silicacrete
Dill et al. 2007b
Bou Azzer Morocco Cu-Co-As heterogenite malachite chrysocolla retgersite erythrite anna- tropical semiarid oxicrete-
vein-type azurite Cu-bearing bergite phar- arid carbocrete-
fraipontite macosiderite silicacrete
arseniosiderite orecrete-(As)
beudantite orecrete-(V)
pharmacolite sulcrete
Essarraj et al. 2005 vanadinite
Ain Sefra, Algeria Cu sediment- malachite tropical semiarid carbocrete

Cox et al. 2003 hosted arid
El Kef Zn-Pb-Ba-P goethite smithsonite hermimorphite anglesite Sr-Mn phos- tropical semiarid carbocrete-
Tunisia carbonate- and hetaerolite otavite chalcedony corkite phate pyromor- arid silicacrete
shale-hosted (“hydrohete- cerussite zincian phite phospho- phoscrete
Dill et al. 2011 arolite”) hydrozincite hedyphane oxicrete-
chalcophanite goyazite sulcrete
zincite
Thies-Taiba Senegal P goethite apatite arid-tropical tropical humid phoscrete
phosphorite strengite semiarid oxicrete-
variscite
Flicoteaux 1982, Dill &
wavellite
Kantor 1997
crandallite
Nuba Mts. P-Cu-Zn goethite woudhouseite variscite tropical semi- tropical humid phoscrete
Sudan black shale turquoise arid-tropical sulcrete
faustite wet-dry oxicrete-
Dill et al. 1991 wavellite
crandallite-
woudhouseite
s.s.s. apatite
Kilembe/ Kasese Cu-Co goethite malachite chrysocolla brochantite torbernite tropical semi- tropical humid sulcrete phos-
Uganda sediment- cuprite chalcoalumite arid-tropical crete
Muwanga 1997 hosted-meta- wet-dry silicacrete
morphosed carbocrete
oxicrete
or country rocks
Kipushi Mine Shaba Zn-Pb-Cu-Fe goethite azurite anglesite kipushite adamite tropical humid tropical humid phoscrete
DR Congo (5) +,-./$+)5'(1) aurichalcite brochantite libethenite carbocrete
Ga, Ge, Mo, W, cerussite chalcanthite pseudomala- oxicrete
V carbonate- malachite chite sulcrete
Lhoest 1995, Heijlen hosted pyromorphite vanadinite orecrete-(V)
et al. 2008 reichenbachite orecret-(As)
tsumebite
vauquelinite
turquoise
Lumumbashi Cu-Co heterogenite malachite chrysocolla libethenite tropical humid tropical humid phoscrete
L‘Etoile du Congo stratiform and tenorite azurite pseudomala- silicacrete
Mine vein-type chite carbocrete
DR Congo cornetite oxicrete
Dewaele et al. 2006
Malawian deposits REE-(Zn-Pb- goethite rhabdophane tropical wet- tropical humid phoscrete
Cu) Mn-oxide/ (Ce-La) dry oxicrete
carbonatite- hydrates goyazite
Dill 2007 hosted
pegmatite-
hosted
carbonaceous
shales
Kalengwa Mine, Cu malachite tropical semi- tropical semi- carbocrete
Zambia sediment- azurite arid arid
Cox et al. 2003 hosted
(sandstone-
hosted)
Kabwe Mine (Broken Zn-Pb strata- psilomelane aurichalcite chrysocolla anglesite libethenite beudantite tropical semi- tropical semi- phoscrete
Hill Mine), bound and azurite linarite parahopeite mimetite arid arid carbocrete
Zambia replacement cerussite hopeite silicacrete
within carbon- rosasite phosphophyllite orecrete-(V)
Notebaart & Korowki descloizite
ate rocks smithsonite pyromorphite orecrete-(As)
1980; Kamona & mottramite
scholtzite
Friedrich 2007 vanadinite
tarbuttite
Joumbira Namibia Pb-Cu-Zn cuprite malachite tropical semiarid carbocrete
fault-controlled azurite arid oxicrete
Diehl 1990; Hahne et
carbonate-
al. 2001
hosted
Novo Redondo Cu chrysocolla tropical arid arid silicacrete
Angola sediment-
Cox et al. 2003 hosted
(sandstone-
hosted)
or country rocks
Tsumeb Namibia Pb-Cu-Zn tenorite malachite chrysocolla atacamite brochantite pyromorphite duftite tropical arid arid oxicrete-
carbonate- goethite hydrozincite hemimorphite anhydrite calcio-duftite carbocrete-
hosted azurite dioptas serpierite arseniosiderite silicacrete
smithsonite tsumebite aurichalcite halcrete
beudantite orecrete-(As)
seginite orecrete-(V)
scorodite phoscrete
Kamona et al. 1999; descloizite
Chetty & Frimmel vanadinite
2000
Matchless Namibia Cu-FeS cuprite malachite chrysocolla halite jarosite brushite tropical arid arid oxicrete-
volcanic-hosted huntite gypsum carbocrete-
blödite silicacrete
copiapite halcrete
Klemd et al. 1987; starkeyite sulcrete
Maiden 1993; Cook et melanterite phoscrete
al. 1994; Petzel 1996;
Dill et al. 2002
Khan Mine Namibia Cu goethite malachite chrysocolla atacamite brochantite tropical arid arid oxicrete-
veins tenorite carbocrete-
Ramdohr 1938 cuprite silicacrete
halcrete
sulcrete
Wadi Araba Jordan Cu –Mn-(Ba) tenorite malachite chrysocolla halite apatite tropical arid arid silicacrete
sandstone- spertiniite plancheite atacamite halcrete
Burgath et al. 1984 hosted Mn oxide- shattuckite paratacamite vanadinite oxicrete-
hydroxide paratacamite cuprian carbocrete-
crednerite F-bearing orecrete-(V)
Almalyk-Ungurlikan Cu cuprite malachite. chrysocolla anglesite turquoise mimetite Dry continen- arid oxicrete-
Uzebisktan porphyry - tenorite azurite gypsum tal (mountain- phoscrete
quartz veins cerussite eous) silicacrete
Dill 1999, Singer et descloizite carbocrete-
al. 2008 sulcrete
orecrete-(V)
orecrete-(As)
Kounrad Kazakhstan Cu malachite chrysocolla jarosite Dry conti- arid carbocrete
porphyry-type azurite alunite nental silicacrete
Dill 1999; Singer et
sulcrete
al. 2008
Saindak, Pakistan Cu goethite azurite jarosite tropical arid arid carbocrete
porphyry-type cuprite cerussite oxicrete
Singer et al. 2008 delafossite malachite sulcrete
or country rocks
Yazd Pb-Zn-Cu quenselite smithsonite fraipontite paratacamite gypsum turquoise tropical semiarid carbocrete-
Iran –FeS veins goethite cerussite Cd-bearing arid – arid / oxicrete-
Huckriede et al. 1962; and carbonate- smithsonite Zn greenalite descloizite mountaine- phoscrete
Zarasvandi et al. hosted Cd-bearing chrysocolla ous silicacrete
2005; Singer et al. (otavite) hemimorphite sulcrete
2008 hydrozincite halcrete
azurite orecrete-(V)
malachite
Aynak, Afghanistan chrysocolla brochantite tropical semi- tropical semi- silicacrete
chalcanthite arid-arid/ arid-arid/ sulcrete
Orris & Bliss 2002
mountaine- mountaine-
ous ous
Lachah Meydouk Cu-(Pb) tenorite malachite brochantite turquoise tropical semiarid carbocrete-
Iran porphyry-type cuprite azurite turquoise arid oxicrete-
http://www.ngdir. ferroan phoscrete
ir/GeoportalInfo/ rhabdophane- sulcrete
SubjectInfoDetail. (Ce)
asp?PID=61
Al Khod Cu-Fe-S goethite gypsum tropical arid arid oxicrete-
Oman black shales natrojarosite sulcrete
pickeringite
Dill et al. 2007c apjohnite
spangolite
glaucocerinite
Mongolian deposits Fe-Cu goethite malachite (brochantite) (turquoise) dry continen- dry conti- oxicrete-
black shales azurite tal (mountain- nental carbocrete-
Dill et al. 2006a,b coal eous) (warm tem- sulcrete
sandstone- perate to arid) phoscretes
hosted
Bawdwin Pb-Cu-Zn-Ag tenorite rosasite brochantite annabergite tropical humid tropical humid carbocrete-
Birma (Myanmar) VMS/ Kuroko- zincian cerussite anglesite erythrite oxicrete-
type sensu lato smithsonite cuprocopiapite sulcrete
antlerite orecrete-(As)
Brinkmann & Hinze plumbojarosite
1981; Müller & Weiser Cu- and Al-
1981 bearing
linarite
Kao Boh Ngam Pb-Zn hydrozinkite hemimorphite tropical humid tropical humid carbocrete-
Thailand carbonate- smithsonite silicacrete
Goossens 1978; hosted (MVT)
Diehl & Kern 1981;
Premmanee &
Jarnyaharn 1997
or country rocks
Bo Noi and Pa Pb-Zn-Ba goethite cerussite hemimorphite tropical humid tropical humid carbocrete-
Daeng carbonate- smithsonite Zn- silicacrete
Thailand hosted (MVT) hydrozinkite hydrosilicate
Reynolds et al. 2003 (hendricksite)
Phu Joe Area Sb-Hg cervantite lewisite tropical humid tropical humid oxicrete-
Sankhlaburi vein-type senarmontite romeite silicacrete
Thailand
Department of Mineral
Resources 1999
Ma Ta mae Thae Doi Sb –(W) stibiconite tropical humid tropical humid oxicrete-
Ngom and Pha Hao. vein-type goethite
Thailand bindheimite
monimolite
romeite
Dill et al. 2008 valentinite
hydroromeite
schafarzikite
hydrated
scheelite
ferritungstite
hydrated
wolframite
Haii Nai Thailand Sb stibiconite tropical humid tropical humid oxicrete-
vein-type goethite
bindheimite
monimolite
Dill et al. 2008 romeite
valentinite
hydroromeite
Kuching Malaysia Sb-Au senarmontite. tropical humid tropical humid oxicrete-
Dill & Horn 1996 epithermal- stibiconite
skarn
Desa Toraget- Al-(Au) alunogen alunite- tropical humid tropical humid phoscrete
Sulawesi Indonesia epithermal aluminite woodhouseite sulcrete
alunite Pb- s.s.s.
Kavalieris et al. 1992; bearing alunite-
Dill et al. 1995c woodhouseite
s.s.s.
Narogong-Java P hematite wavellite tropical humid tropical humid oxicrete-
Indonesia phosphorite goethite phoscrete
Koesoemadinatae
1985; Dill & Kantor
1997
or country rocks
Cho Dien Vietnam Zn-Pb pyrolusite smithsonite hemimorphite beudantite tropical humid tropical humid carbocrete-
carbonate- cerussite to tropical silicacrete
Kusnir 1964; Kamitani hosted aurichalcite mid-latitude oxicrete
et al. 2007 malachite orecrete-(As)
Tennant Creek Au-Cu-Bi cuprite azurite chrysocolla phosphohedy- tropical semi- tropical semi- oxicrete-
(Northern Territory) sandstone- goethite phane arid arid phoscrete
Australia hosted plumbogum- carbocrete
Davidson & Large mite silicacrete
1998 variscite
pyromorphite
Malbunka Copper Cu cuprite malachite chrysocolla atacamite tropical arid tropical arid silicacrete
Mine (Northern sandstone- azurite oxicrete-
Territory) Australia shale-hosted carbocrete
(12) halcrete
McLouglin 2009
Anabama Hill Cu goethite malachite chrysocolla turquoise tropical semi- tropical semi- carbocrete
(South Australia), porphyry-type arid arid oxicrete
Australia phoscrete
Singer et al. 2008 silicacrete
Heazelwood Hill, Pb-Cu-Zn-Ba brochantite humid mid- warm temper- sulcrete

Australia greenstone- latitude ate carbocrete
Huston & Kamprad hosted
2000; Corbett 2001
Mount Lyell Cu-Au-(Ba) tenorite malachite brochantite humid mid- warm temper- sulcrete
Australia VMS-epither- latitude ate carbocrete
Huston & Kamprad mal
2000; Corbett 2001 disseminated
Table 2. Chemical composition of minerals formed by per descensum processes and referred to in the text and tables.
Mineral Chemical composition Mineral Chemical composition
adamite Zn2(AsO4)(OH) cuprotungstite Cu3(WO4)2(OH)2
aluminite Al2(SO4)(OH)4·7(H2O) descloizite @N;BV)A0=@d<4)(OH)
alunite KAl3(SO4)2(OH)6 despujolsite Ca3Mn (SO4)2(OH)6·3(H2O)
alunogen Al2(SO4)3·17(H2O) devilline CaCu4(SO4)2(OH)6·3(H2O)
anglesite Pb(SO4) dioptase CuSiO2(OH)2
anhydrite CaSO4 duftite PbCu(AsO4)(OH)
annabergit Ni3(AsO4)2·8(H2O) duhamelite Pb2Cu4T(@d<4)4(OH)3·8(H2O)
antlerite Cu3(SO4)(OH)4 dussertite T.S%3(AsO4)2(OH)5
apatite Ca5@SB0+B<7A@N<4)3 dzhalindite In(OH)3
apjohnite MnAl2(SO4)4·22(H2O) erythrite Co3(AsO4)2·8(H2O)
arseniosiderite Ca2Fe3(AsO4)3O3·3(H2O) faustite @V)B0=AO+6(PO4)4(OH)8·4(H2O)
arsenolite As2O3 feroxyhyte Fe3+O(OH)
asbolane Ni0.3Co0.1Ca 0.1Mn2+1.5O1.5(OH)2·0.6(H2O) ferrihydrite Fe3+2O3·0.5(H2O)
atacamite Cu2Cl(OH)3 [*&%)3(4%C@0%A# @0%B#k.AO+3(PO4)2(OH)6
aurichalcite @V)B0=A5(CO3)2(OH)6 fraipontite @V)BO+A3@L(BO+A2O5(OH)4
azurite Cu3(CO3)2(OH)2 franklinite @V)BS%BE)AS%2O4
bastnaesite @0%Bk.A@0<3)F glaucocerinite @V)B0=A5Al3(SO4)1.5(OH)16·9(H2O)
bayldonite @0=BV)A3Pb(AsO3OH)2(OH)2 goethite l FeO(OH)
beudantite PbFe3+3(AsO4)(SO4)(OH)6 gorceixite T.O+3(PO4)2(OH)5·(H2O)
bindheimite Pb2Sb2O6@<B<7A goyazite SrAl3(PO4)2(OH)5·(H2O)
bismite T(2O3 greenalite Fe2.3Fe0.5Si2.2O5(OH)3.3
bismutite T(2(CO3)O2 gypsum CaSO4·2(H2O)
bismutostibiconite T(@L;BS%A2O7 halite NaCl
blödite Na2Mg(SO4)2·4(H2O) halotrichite FeAl2(SO4)4·22(H2O)
botallackite Cu2Cl(OH)3 hemihedrite Pb10Zn(CrO4)6(SiO4)2F2
brochantite Cu4(SO4)(OH)6 hemimorphite Zn4Si2O7(OH)2·(H2O)
bromargyrite O,T& hendricksite e@V)BE,BE)A3Si3AlO10(OH)2
brushite CaHPO4·2(H2O) hetaerolite ZnMn2O4
cacoxenite (Fe3+BO+A25(PO4)17O6(OH)12·75(H2O) heterogenite CoOOH
carminite PbFe2(AsO4)2(OH)2 hinsdalite @N;BL&AO+3(PO4)(SO4)(OH)6
cerite @k.B0%B0.A9@E,BS%A@L(<4)6[SiO3(OH)](OH)3 hopeite Zn3(PO4)2·4(H2O)
cerussite PbCO3 huntite CaMg3(CO3)4
cervantite Sb2O4 hydrozincite Zn5(CO3)2(OH)6
chalcanthite CuSO4·5(H2O) iranite Pb10Cu(CrO4)6(SiO4)2F1.5(OH)0.5
chalcedony SiO2 jarosite KFe3(SO4)2(OH)6
chalcoalumite CuAl4(SO4)(OH)12·3(H2O) kemmlitzite @L&B0%AO+3(AsO4)(SO4)(OH)6
chalcomenite Cu(SeO3)·2(H2O) kermesite Sb2S2O
chalcophanite @V)BS%2+BE)2+)Mn4+3O7·3(H2O) kipushite @0=BV)A5Zn(PO4)2(OH)6·(H2O)
chenevixite Cu2Fe2(AsO4)2(OH)4·(H2O) langite Cu4(SO4)(OH)6·2(H2O)
chlorargyrite AgCl leadhillite Pb4(SO4)(CO3)2(OH)2
chrysocolla Cu1.75Al0.25H1.75(Si2O5)(OH)4·0.25(H2O) legrandite Zn2(AsO4)(OH)(H2O)
chrysoprase Ni-bearing silicate (willemseite) lepidocrocite m FeO(OH)
churchite-(Y) YPO4·2(H2O) lewisite @0.BS%BX.A2@L;B$(A2O7
clinoclase Cu3(AsO4)(OH)3 libethenite Cu2(PO4)(OH)
conichalcite CaCu(AsO4)(OH) linarite PbCu(SO4)(OH)2
copiapite Fe5(SO4)6(OH)2·20(H2O) luddenite Pb2Cu2Si5O14·14(H2O)
3*Y=(';(4% Fe2(SO4)3·9(H2O) malachite Cu2(CO3)(OH)2
cornetite Cu3(PO4)(OH)3 manganite MnO(OH)
cornwallite Cu5(AsO4)2(OH)4 marshite CuI
coronadite Pb(Mn4+Mn2+)8O16 mcconnellite CuCrO2
crandallite CaAl3(PO4)2(OH)5·(H2O) melanterite Fe2+(SO4)·7(H2O)
crednerite CuMnO2 mimetite Pb5(AsO4)3Cl
cryptomelane K(Mn4+Mn2+)8O16 mitridatite Ca2Fe3+3(PO4)3O2·3(H2O)
cuprite Cu2O monimolite @N;B0.A2Sb2O7
cuprocopiapite CuFe4(SO4)6(OH)2·20(H2O) morenosite NiSO4·7(H2O)
Table 2 (continued).
Mineral Chemical composition Mineral Chemical composition
mottramite N;@V)B0=A@d<4)(OH) scorodite Fe(AsO4)·2(H2O)
nadorite PbSbO2Cl segnitite PbFe3H(AsO4)2(OH)6
olivenite Cu2AsO4(OH) senarmontite Sb2O3
opal SiO2·n(H2O) serpierite 0.@0=BV)A4(SO4)2(OH)6·3(H2O)
otavite CdCO3 shattuckite Cu5(SiO3)4(OH)2
oxi-beraunite @S%BE)AS%5(PO4)4O(OH)4·6(H2O) smithsonite ZnCO3
parahopeite Zn3(PO4)2·4(H2O) spangolite Cu6Al(SO4)(OH)12Cl·3(H2O)
paratacamite @0=BV)A2(OH)3Cl spertiniite Cu(OH)2
pharmacolite CaHAsO4·2(H2O) starkeyite MgSO4·4(H2O)
pharmacosiderite KFe4(AsO4)3(OH)4·6-7(H2O) stibiconite Sb3O6(OH)
philipsbornite PbAl3(AsO4)2(OH)5·(H2O) strashimirite Cu8(AsO4)4(OH)4·5(H2O)
phoenicochroite Pb2CrO5 strengite FePO4·2(H2O)
phosphohedyphane Ca2Pb3(PO4)3Cl svanbergite SrAl3(PO4)(SO4)(OH)6
phosphophyllite Zn2@S%BE)A@N<4)2·4(H2O) tarbuttite Zn2(PO4)(OH)
phosphosiderite Fe3(PO4)·2(H2O) tenorite CuO
plancheite Cu8Si8O22(OH)4·(H2O) thenardite Na2(SO4)
plumbojarosite PbFe6(SO4)4(OH)12 thorikosite Pb3@L;BO1A<3(OH)Cl2
posnjakite Cu4(SO4)(OH)6·(H2O) todorokite Na0.2Ca0.05K0.02Mn4+4Mn3+2 O12·3(H2O)
pseudoboleite Pb5Cu4Cl10(OH)8·2(H2O) torbernite Cu(UO2)2(PO4)2·12(H2O)
pseudomalachite Cu5(PO4)2(OH)4 tsumebite Pb2Cu(PO4)(SO4)(OH)
psilomelane T.@72O)Mn3+5O10 tungstite WO3·(H2O)
pyrolusite MnO2 4=&Y=*(1%# CuAl6(PO4)4(OH)8·4(H2O)
pyromorphite Pb5(PO4)3Cl tyrolite CaCu5(AsO4)2(CO3)(OH)4·6(H2O)
Y=.&4HB#3&(14*;.+(4%B#4&(/-'(4% SiO2 valentinite Sb2O3
Y=%)1%+(4%# PbMnO2(OH) vanadinite Pb5(VO4)3Cl
reichenbachite Cu5(PO4)2(OH)4 variscite AlPO4·2(H2O)
retgersite NiSO4·6(H2O) 9.=Y=%+()(4% Pb2Cu(CrO4)(PO4)(OH)
rhabdophane @0%Bk.AN<4·(H2O) vivianite Fe3(PO4)2·8(H2O)
rockbridgeite (Fe2+BE)AS%3+4(PO4)3(OH)5 wavellite Al3(PO4)2@<7BSA3·5(H2O)
romanèchite @T.B72O)2(Mn4+BE)3+)5O10 whitmoreite Fe2+Fe3+2(PO4)2(OH)2·4(H2O)
romeite @0.BS%BE)BX.A2@L;B$(A2O6@<B<7BSA willemite Zn2SiO4
rosasite @0=BV)A2(CO3)(OH)2 woodhouseite CaAl3(PO4)(SO4)(OH)6
santanaite Pb9Pb2CrO16 8**/&=?24% @V)BE)2+)2Mn4+5O12·4(H2O)
schafarzikite FeSb2O4 wroewolfeite Cu4(SO4)(OH)6·2(H2O)
scheelite CaWO4 wulfenite PbMoO4
schmiederite Pb2Cu2(SeO3)(SeO4)(OH)4 zincite ZnO
scholzite CaZn2(PO4)2·2(H2O)
0.&;*3&%4%1#.&%#.;=)/.)4#()#3.&;*).4%#'()%&.+1B#%","B# <&%3&%4%1C@L%AB# C@E*AB# .)/# @*D.+.4%A# :.9%# )*4# ;%%)#

malachite. Pedogenic or hydraulic uraniferous duricrusts ,(9%)#1>%3(.+#).'%1#*?#4:%(&#*8)B#*8(),#4*#4:%#&.&(4-#*?#
or uraniferous calcretes have uranyl vanadates in a ground orecretes containing SeO3!nhB#L%<4!nhB#E*<4!nh#B#.)/#02O4!nh
mass of calcareous minerals (MANN & DEUTSCHER#6_F`B# (oxalate) in nature.
BRIOT#6_`\B#CARLISLE#6_F`B#6_`\B#HAMBLETON-JONES et al.
6_àB#HARTLEB#6_``B#NASH & MCLAREN#!GG\B#BOWELL et
.+"#!GG`B#DILL#6_``B#!G66A"#$*#.9*(/#3*)?=1(*)#.)/#.;(/%# 3. Methodology
;-#4:%#).'(),#()4&*/=3%/#.;*9%B#4:%#4%&'#3.+3&%4%1#(1#)*4#
used in the scope of supergene mineralizing processes out- The samples were taken either from surface encrustations
1(/%#4:%#2%+/#*?#?*11(+#?=%+1"#^&.)(?%&*=1#3.+3&%4%1B#8:(3:# on top of the mineralized bedrocks which were stained in
are largely treated in the literature and of widespread oc- 9(9(/+-#,&%%)B#;+=%#.)/#;&*8)#3*+*&1B#*&#.+*),#?&.34=&%1#
3=&&%)3%#()#4:%#/%1%&41#*?#X.'(;(.B#^LOB#O=14&.+(.B#.)/# and solution cavities down to about 1 m below ground.
*)#4:%#O&.;(.)#N%)()1=+.B#.&%#)*4#/%.+4#8(4:#()#4:(1#>.>%&# The selection of samples during the current study aimed
for reasons of size and since they follow in their process- at covering almost all morphoclimatic zones from pole
response models common pedogenic calcretes. 4*#4:%#%Y=.4*&"#L*'%#f;+.3Z#:*+%1g#8:(3:#3*=+/#)*4#:.9%#
142
H. G. Dill et al.
Fig. 2. Morphoclimatic zonation and geomorphological-geodynamic setting. a) The position of the orecretes (metalliferous duricrusts) referred to in the text in relation to the
morphoclimatic zonation of the globe during the period of time"!"!#E.#U#]=.4%&).&-#@1*=&3%#*?#/.4.Q#TRICART & CAILLEUX#6_F!A#h#1%%#.+1*#$.;+%#6#@3*+=')#66A"#T+=%#/*41#&%?%&#
to data from literature (see Table 1) which were selected for reasons of climatic coverage.
Fig. 2 (continued). b) The position of the orecretes (metalliferous duricrusts) referred to in the text in relation to the morphoclimatic zonation of the globe during the period of
time"!"!G#E.#U#X%*,%)%#@1*=&3%#*?#/.4.Q#'*/(2%/#?&*'#:44>QUU888"13*4%1%"3*'U+%,%)/":4'A#h#1%%#.+1*#$.;+%#6#@3*+=')#6!A
144
H. G. Dill et al.
Fig. 2 (continued). c) The position of the orecretes (metalliferous duricrusts) referred to in the text in relation to the geodynamic and resultant geomorphological zonation of
4:%#,+*;%#@1*=&3%#*?#/.4.Q#SUMMERFIELD 1991).
Fig. 2 (continued). d) The position of the orecretes (metalliferous duricrusts) referred to in the text in relation to the intensity of weathering on the globe and the resultant clay
'()%&.+1#.)/#4&(9.+%)4#*D(/%1#@1*=&3%#*?#/.4.Q#SUMMERFIELD 1991).
been covered by samples were mentioned in the text and 4. Geographic and geological settings
4:%#4.;+%B#.)/#3*9%&%/#;-#.#&%9(%8#*?#+(4%&.4=&%"
Apart from the routine mineral-optical analyses with The global geomorphological setting resulted from cli-
4:%# '(3&*13*>%B# .++# 1.'>+%1# 8%&%# ()9%14(,.4%/# ;-# IJK"# matic processes during the late Cenozoic (Fig.#!.B#;A"#$:(1#
XRD patterns were recorded using a Philips X'Pert '.-#;%#/%/=3%/#?&*'#.#Y=(3Z#+**Z#.4#4:%#'*&>:*3+('.4(3#
PW3710&-2 & diffractometer (Cu-K' radiation gener- zonation on display in the general map elaborated by TRI-
.4%/#.4#aG#Zd#.)/#aG#'OAB#%Y=(>>%/#8(4:#.#6c#/(9%&,%)3%# CART & CAILLEUX (1958) and BÜDEL (1977) who also gave
1+(4B#.#1%3*)/.&-#'*)*3:&*'.4*&B#.#>*()4#/%4%34*&#.)/#.# a brief account on the temperature and precipitation of
sample changer (sample diameter 28 mm). The supergene each zone. The landscape responds to variable climatic
minerals encountered in the various orecretes are given in processes by developing a characteristic assemblage
Table 1 and their chemical composition in Table 2. of major and minor landforms (DILL#%4#.+"#!GG5B#!GGb.B#
The scanning electron microscope FEI QUANTA 600 TURKINGTON & PARADISE#!GG5B#!"#$% 2006).
SMo#PK7#8.1#=1%/#?*&#4:%#'()%&.+#(/%)4(23.4(*)#.)/#('- 0+('.4%# (1# *)%# 1(/%# *?# 4:%# %Y=.4(*)# ()# 1:.>(),# 4:%#
age analysis for morphological studies. The SEM QUAN- landscape and accountable for the different types of orec-
TA 600 FEG was linked with a EDS System (GEMINI) retes (Table 3). The geological setting is the other side of
*>%&.4%/# =)/%&# 4:&%%# /(??%&%)4# >&%11=&%# &%,('%1Q# 7(,:# 4:%#%Y=.4(*)"#$:%&%#.&%#,%*+*,(3.+#14&=34=&%1#4:.4#:.9%#.#
9.3=='# @3.# 6G#MCb#';.&AB# @!A# k*8d.3# @.>>&*D"# 6# 4*# stronger effect than climate when it comes to the forma-
6G#';.&AB#@\A#MLME#@.>>&*D"#6G#4*#\G#';.&A"#K=%#4*#4:%# tion of landform associations. Therefore a brief overview
=1%#*?#+*8C9.3#3*)/(4(*)1B#4:%1%#'()=4%#:.)/C>(3Z%/#>.&- of the major units underlying these morphoclimatic zones
ticles need not to be sputtered prior to measurement. needs to be given below (Fig.#!3A"#O//(4(*).++-B#4:%#()4%)-
W)# 1*'%# 3.1%1# *?# =)3%&4.()4-B# %+%34&*)# '(3&*>&*;%# sity of weathering and the common weathering products
analyses (EMPA) were carried out using a CAMECA that developed on the various geological structures are il-
LI6GG# %Y=(>>%/# 8(4:# 29%# 8.9%+%),4:C/(1>%&1(9%# 1>%3- lustrated (Fig. 2d).
trometers and a Princeton Gamma Tech energy-dispersive The Archaean rocks represent the oldest rock series
1-14%'#@MKLA"#<D(/%B#>:*1>:.4%B#.)/#1(+(3.4%#>:.1%1#8%&%# *)#M.&4:B#8:(3:#?*&'%/#&*=,:+-#;%48%%)#\`GG#.)/#!5GG#
analyzed at an acceleration voltage of 20 kV and a sample Ma and are the nuclei of much larger continents such
3=&&%)4#@*)#;&.11A#*?#!G#)O"#$:%#'()%&.+1#.+;(4%B#3:&*'(4%B# .1# 4:%# o=-.).# 1:(%+/B# 4:%# o.;*)# .)/# L*=4:# W)/(.)# 3&.-
Z.%&1=4(4%B#.+'.)/()%B#.>.4(4%B#'.,)%4(4%B#>%)4+.)/(4%B#;(- 4*)#*&#4:%#T.+4(3#1:(%+/#@WILDE#%4#.+"#!GG6B#WYCHE et al.
*4(4%B#&=4(+%B#&:*/*)(4%B#.)/#,.+%).#.1#8%++#.1#>=&%#'%4.+1# 2004). They form the vast lowlands and plateaus covered
were used as standards. by a varied group of supergene clay and oxidic minerals
Powdered samples were analyzed for their chemi- (Fig.#!3B#!/A"#$:%#N&*4%&*H*(3#4%&&.()1#.;=)/.)4#()#;.)/%/#
cal composition using a PANalytical Axios and a iron formation deposits surround these cratons (CANFIELD
PW2400XRF spectrometer. Samples are prepared by 2005). During the Neoproterozoic the supercontinent Ro-
'(D(),#8(4:#.#[=D#'.4%&(.+#.)/#'%+4(),#()4*#,+.11#;%./1"# /()(.#;%,.)#?.++(),#.>.&4B#1>+(44(),#=>#.+*),#,&.;%)1#()4*#
The beads are analyzed by wavelength dispersive x-ray /(??%&%)4# ?&.,'%)41B# %","B# O'.H*)(.B# T.+4(3.B# k.=&%)4(.B#
[=*&%13%)3%#1>%34&*'%4&-#@PKCIJSA"#$*#/%4%&'()%#+*11# and Siberia. These areas forming the cores of some of the
*)#(,)(4(*)#@k<WAB#6GGG#',#*?#1.'>+%#'.4%&(.+#.&%#:%.4%/# >&%1%)4#%D(14(),#3*)4()%)41#.&%#13.44%&%/#.&*=)/#4:%#%Y=.-
to 1030 °C for 10 min. After mixing the residue with 5.0 g
+(4:(='#'%4.;*&.4%#.)/#!5#',#+(4:(='#;&*'(/%B#(4#(1#?=1%/#
at 1200 °C for 20 min. The calibrations are validated by Table 3. Temperature and precipitation in the various morpho-
.).+-1(1# *?# ()4%&).4(*).++-# 3%&4(2%/# &%?%&%)3%# '.4%&(.+1"# 3+('.4(3#H*)%1#@'*/(2%/#?&*'#SUMMERFIELD 1991).
(Monitor(#1.'>+%1#.)/#6\G#3%&4(2%/#&%?%&%)3%#'.4%&(.+1# Morphoclimate Zone Temperature Precipitation
(CRM) are used for the correction procedures. (mean annual-°C) (cm)
CO2 of carbonate samples was liberated for the isotope Mountaineous variable variable
analyses through reaction with 100 % phosphoric acid Periglacial-(glacial) < 0°C #n# # # G#4*#6GG
at 73 °C in the online Carbo-Kiel carbonate preparation Humid mid-latitude #n# G#4*#!Gc0 #n# # aG#4*#6`G
line. Carbon and oxygen isotope analyses of CO2 were Dry continental #n# G#4*#6Gc0 #n# # 6G#4*#aG
measured with a MAT 251 IR-MS. The isotope values
Tropical arid #n6G#4*#\Gc0 #n# # # G#4*#\G#
are reported in the common delta-notation relative to V-
Tropical semiarid #n6G#4*#\Gc0 #n# # \G#4*#bG#
NKT#14.)/.&/"#$:%#14.)/.&/#/%9(.4(*)#8.1#.;*=4#)UhnG"Gb#
per mil for carbon and)UhnG"6#>%&#'(+#?*&#*D-,%)#(1*4*>%# Tropical wet-dry #n!G#4*#\Gc0 #n# # bG#h#65G
'%.1=&%'%)41B#;.1%/#*)#&%>+(3.4%#.).+-1%1#*?#.#14.)/.&/" Tropical humid #n!G#4*#\Gc0# > 150
4*&#8(4:#4&*>(3.+#3+('.4(3#3*)/(4(*)1B#.1#8%++#.1#.4#:(,:%&# tents (Table 1). In the succeeding sections typical super-

latitudes covered by periglacial landforms. At higher lati- gene mineral assemblages from various morpho-climatic
tudes only a low rate of weathering is observed (Fig. 2d). zones were described so as to help recognize them in the
The Paleozoic Caledonian and Variscan fold belts were 2%+/#.)/#()#?*++*8C=>#+.;*&.4*&-#8*&Z#.)/#'.Z%#=1%#*?#
mountain ranges that may be visible in some places on these mineral assemblages as marker for morpho-climatic
4:%#'*&>:*3+('.4(3#'.>B#.1#%D%'>+(2%/#;-#4:%#0.+%/*)- processes. An independent tool to determine the (paleo)
(/%1#()#L3.)/().9(.B#;=4#4:%#'.j*&(4-#*?#4:%'#.&%#>.&4(.++-# formation temperature lies within the isotope analysis of
eroded to their core zone (Fig. 2c). The weathering rate in carbocretes that were dealt with in section 5.2
these ancient geodynamic units was controlled by the cli-
matic conditions (Fig.#!.B#/A"#O++#4:%#'*&%#1*B#4:%#O+>(/(3# 5.1.1 Supergene Se mineralization in siliceous
or modern fold belts are recognized in the morphoclimatic sedimentary rocks
'.>B# '.Z(),# =># 4:%# f'*=)4.()*=1# H*)%g# *?# 4:%(&# *8)B#
8:(3:#(1#8%++#/%9%+*>%/B#%","B#.+*),#4:%#O)/%1#4:.4#3.'%# In northern Canada supergene orecretes have been de-
into existence due to the subduction of the Nacza plate rived from Cu-Co-Pb-Ni selenides hosted by metamor-
beneath the South American plate (GREGORY-WODZICKI >:*1%/#1%/('%)4.&-#Y=.&4HC.+;(4%C'=13*9(4%#&*3Z1"#O>.&4#
2000). In the mountainous regions which are character- ?&*'# %)3&=14.4(*)1# *?# '(3&*3&-14.++()%# ,&%%)# '.+.3:(4%B#
ized by highly variable weathering with little accumula- blue chalcomenite is the major Se-bearing oxidic miner-
tion of weathering products the orecretes become a signif- als developing from Se-bearing tenorite (Fig. 3a). Its or-
icant or the only tool to discriminate the type and intensity thorhombic-disphenoidal crystals are well preserved and
of weathering (Fig. 2d). Volcanic rocks ascended along *)+-#()#1*'%#>.&41#.&%#3*9%&%/#8(4:#.#2+.'%)4*=1#3*;8%;#
intercontinental grabens and genetically lined up within *?#-*=),%&#13:'(%/%&(4%"#W)#.#?%8#1>%3('%)1B#.>.&4#?&*'#
4:%'B#1=3:#.1#.+*),#4:%#M.14CO?&(3.)#J(?4B#>%&4.()#4*#4:%# 4:%# 2;&*=1# .,,&%,.4%1# .+1*# '*)*3+()(3C>&(1'.4(3# 3&-1-
same morphoclimatic zone (Fig. 2c). Intercontinental or tal aggregates of schmiederite formed on chalcomenite
()4&.3&.4*)(3# ;.1()1B# 1*'%# &%+.4(9%+-# 1:.++*8# .)/# 3(&3=- (Fig. 3b).
+.&# ()# 1:.>%B# ?*&'%/# 8(4:()# 14.;+%# 3*)4()%)4.+# ()4%&(*&1B#
such as the Michigan-Illinois basins in the Middle West 5.1.2 Supergene Cu mineralization in siliceous
*?#4:%#^LOB#4:%#E*13*8#;.1()#*)#4:%#J=11(.)#>+.4?*&'B# magmatic rocks
and the Congo basin in Africa. Some of the large basins
.&%#4:%#L.:.&.#;.1()#2++%/#8(4:#3*)4()%)4.+#$&(.11(3B#R=&.1- This type of supergene Cu mineralization originated from
1(3B# .)/# 0&%4.3%*=1# 1%/('%)41# .)/# 4:%# E%1*H*(3# <&/*1# 0=# 1=+2/%1# .)/# >-&(4%"# $:%# 3.&;*3&%4%1C@0=A# ?*++*8-
T.1()#@MACGREGOR et al. 1998). Despite the differences (),#*D(3&%4%1C@0=A#3*)1(14#'.()+-#*?#.H=&(4%B#4:.4#(1#8%++#
in the age of formation and the lithology of the basin (/%)4(2%/#;-#(41#/%%>#;+=%#3*+*&B#'.+.3:(4%B#3:&-1*3*++.B#
2++B# 4:%-# 3+*1%+-# &%1%';+%# 4:%# 9.14# N&%3.';&(.)# 3&.4*)1# and plancheite (Fig. 3c). Plates of azurite are pseudomor-
considering their position in the morphoclimatic and geo- >:*1%/#;-#3:&-1*3*++.#.)/#=)/%&+.()#;-#3=>&(4%B#8:(3:#()#
morphological maps (Fig. 2c). These large depocenters of vugs developed bundles of acicular crystals sprays. In the
sedimentary rocks occur from tropical through temperate /&-# 3*)4()%)4.+# >.&4# *?# 4:%# ^LOB# 4:%# 8(/%1>&%./# *33=&-
morphoclimatic zones and are representative of the low- &%)3%#*?#4:%#0=C;%.&(),#>:*1>:.4%#4=&Y=*(1%#&%)/%&1#4:(1#
+.)/1B#>%)%>+.()1B#.)/#>+.4%.=1#8(4:#8%.4:%&(),#>&*/=341# supergene Cu mineralization different from other areas de-
strongly dependent on the climatic zonation (Fig.#!.B#/A" 13&(;%/#?&*'#)*&4:%&)#O'%&(3."#W)#4:%#.&(/#H*)%#()#0:(+%B#
the supergene mineralization is marked by the green and
;+=%#*D(/(3#'()%&.+1B#'.+.3:(4%B#>.&.4.3.'(4%B#3:&-1*3*+-
5. Results +.B#>+.)3:%(4%B#4=&Y=*(1%#.)/#&*1.1(4%#8:(3:#.&%#.33*'>.-
nied by halite and sulfates such as thenardite and gypsum
4"5# #6*7#3*#/(10*8%&#*&%0&%3%1#()#39%#2%+/#.)/#39%# ()#&:-4:'(3.++-#;.)/%/B#1=>%&,%)%#0=#*&%#@Fig.#\/B#\%B#\?B#
laboratory \,B#\(B#a.B#a;B#Table 1). Atacamite occurs in well-devel-
The outward appearance of supergene mineral oped crystal aggregates also in the tropical semiarid zones
assemblages on different bedrocks of Africa (Table6A"#O>.&4# ?&*'# 0=# 1(+(3.4%1B# 0=# :.+*,%-
)(/%1#.)/#0=#>:*1>:.4%#/%9%+*>%/#*)#4%)*&(4%B#4:%-#&.&%+-#
L%3*)/.&-#*&#1=>%&,%)%#0=B#V)B#N;B#L;B#NB#O1B#L%B#.)/#d# contain marshite (Fig. 4a). Cuprotungstite and brochantite
mineral assemblages is controlled by the parent minerali- rarely developed during supergene alteration in semi-arid
H.4(*)#.)/#;-#4:%#3:%'(3.+#3*'>*1(4(*)#*?#4:%#:*14#&*3Z1B# zones (Fig.#a3A"#<)#4:%#:(,:#'*=)4.()#>+.4%.=1#()#4:%#T*-
8:(3:# :.9%B# ()# >+.3%1B# %+%9.4%/# 1(+(3.# *&# 3.&;*).4%# 3*)- +(9(.)# O)/%1B# 1=>%&,%)%# .H=&(4%B# '.+.3:(4%B# >+.)3:%(4%B#
and tenorite developed (Fig.#a/B# %A"# 0.&;*3&%4%1C@0=A#

formed the latest mineral association on Cu-bearing inter-
mediate to felsic magmatic rocks. Their supergene min-
eral assemblage is rather monotonous with oxicretes-(Cu)
1=33%%/%/# ;-# 3.&;*3&%4%1C@0=AB# .)/# 1(+(3.3&%4%1C@0=A# *?#
chrysocolla (Table 1) (Fig. 4f).
5.1.3 Supergene Cu mineralization in basic magmatic

rocks
L%9%&.+# 0=CT(CX(CO1C;%.&(),# 9%()1# ()# :='(/C'(/C+.4(-
tude regions in Germany contain a variegated spectrum
*?# *D(/%1B# 1=+?.4%1B# .)/# >:*1>:.4%1# 8(4:# 1=;*&/().4%# .&-
senates evolved along fractures or developed orecretes-
(Cu) and -(Ni) in basic magmatic rocks (Fig.#5.B#5;B#53A"#
M9%)#(?#)*#>&('.&-#JMM#'()%&.+1#8%&%#(/%)4(2%/#1%3*)/-
ary rhabdophane-(Ce) and rhabdophane-(Nd) developed
well-formed crystals aggregates in these veins. The Co-
Ni-As-Cu mineralization in semiarid Morocco are excep-
tional for their element association and the lithological
control of their ore mineralization. Apart from the com-
'*)# 3.&;*3&%4%1C@0=AB# (4# (1# :%4%&*,%)(4%B# .&1%).4%1B# .)/#
minor amounts of vanadates which originated from the
/%3*'>*1(4(*)# *?# 0*CX(# .&1%)(/%1# .)/# 0=# 1=+2/%1# *?#
the parent mineralization (Table 1). In addition to some
*D(/%1B# 1=3:# .1# 4%)*&(4%B# 3=>&(4%B# 1>%&4()((4%B# .)/# 1*'%#
malachite Cu sulfates are rather widespread in the ba-
sic magmatic rocks of the semiarid zone of the Eastern
Mediterranean Sea (Table 1) (Fig.#5/A"#W)#1*=4:%&)#O?&(3.B#
3=>&(4%B# 3:&-1*3*++.B# '.+.3:(4%B# .)/# :%'.4(4%# *&(,().4%/#
?&*'#4:%#>&('.&-#0=#.)/#S%#1=+2/%1"
5.1.4 Supergene Cu mineralization in siliceous

sedimentary rocks
Supergene Cu mineralization in siliceous sedimentary
&*3Z1#(1#9%&-#'=3:#/(??%&%)4#?&*'#%Y=(9.+%)4#'()%&.+(H.-
4(*)#()#'.,'.4(3#&*3Z1"#W)#4:%#>%&(,+.3(.+#H*)%#()#X*&8.-B#
a primary chalcopyrite-pyrite mineralization gave rise to
b Fig. 3. Macro- and microtextures of orecretes-(Cu-Se) in siliceous sedimentary and felsic magmatic rocks. a) Orthorhombic-disphenoidal
3&-14.+1#*?#3:.+3*'%)(4%#@LMECMKLA"#^&.)(='#0(4-B#L.1Z.43:%8.)B#0.)./.i#b) Monoclinic-prismatic crystal aggregates of schmiederite
&%>+.3(),# 3:.+3*'%)(4%# 3*9%&(),# L%C;%.&(),# 4%)*&(4%# =)/%&)%.4:# @LMECMKLA"# ^&.)(='# 0(4-B# L.1Z.43:%8.)B# 0.)./.i# c)# L(+(3(2%/# .)/#
9=,,-#3*>>%&#*&%#3*.4%/#;-#3:&-1*3*++.#.)/#>+.)3:%(4%#&%>+.3%/#;-#.H=&(4%#@.HA#.)/#'.+.3:(4%#@'.+A"#k*&)%DB#T&(4(1:#0*+=';(.B#0.)./.i#
d)#<&%3&%4%C@0=A#3*'>*1%/#*?#3=>&(4%B#()#>+.3%1B#/%9%+*>(),#3=;(3#:.;(41#@3=A"#$:%#*&%3&%4%1#.&%#3*.4%/#;-#3*)(3:.+3(4%#.)/#+(44+%#'.+.-
3:(4%#@'.+C3*)A"#k(14.#T+.)3.#)%.&#7%&*(3.#0.&;*&3.B#XP#E%D(3*i#e) Chrysocolla (chr) alternating with thin bands of atacamite (ata) and
>1%=/*'.+.3:(4%#@>1%A#&%>+.3%/#;-#,->1='#@LMECMKLA#0:=Y=(3.'.4.B#0:(+%i#f)#L4*3Z8*&ZC+(Z%#1=>%&,%)%#'()%&.+(H.4(*)#*?#.4.3.'(4%B#
&*1.1(4%#.)/#>+.)3:%(4%#()#4:%#4*>#*?#>*&>:-&-#3*>>%&C4->%#/%>*1(41"#0*>(.>*B#0:(+%"#g) Globular “hedgehog” of green atacamite (ata) on
3=>&(4%#@3=>A"#0*>(.>*B#0:(+%i#h)#^)3*)?*&'(4-C&%+.4%/#)*)C1=+2/(3#0=#*&%#8(4:#;+=(1:C,&%%)#1=+3&%4%1C@0=A#*?#;&*3:.)4(4%#.)/#4%)*&(4%"#
T%+*8#4:%#7.=+.,%#=)3*)?*&'(4-#@/*44%/#+()%A#4:%#^>>%&#<8%)#L.)/14*)%#14%%>+-#/(>1#4*8.&/1#4:%#+%?4"#$:%#1.)/14*)%#(1#*9%&+.()#;-#4:%#
'.&()%#1.)/14*)%1#.)/#1:.+%1#*?#4:%#N(*)%%&#o&*=>#.4#E4"#k-%++B#O=14&.+(."
Fig. 3 (continued). i) Cartoons to show the crystal morphology and color of the most important orecrete-forming minerals so as to ease
(/%)4(23.4(*)#*?#4:%'#8(4:#4:%#:.)/#+%)1#*&#4:%#=).&'%/#%-%#()#4:%#2%+/
malachite as the only supergene Cu minerals (Fig. 5e). In 5.1.8 Supergene Pb-Zn mineralization in calcareous
4:%# 4&*>(3.+# :='(/# H*)%# *?# 0%)4&.+#O?&(3.B# *)# 1(+(3%*=1# sedimentary rocks
1%/('%)4.&-# &*3Z1# .>>+%C,&%%)# >1%=/*'.+.3:(4%B# /%%># L=+2/(3# N;CV)CT.CO,C@X(C0*A# '()%&.+(H.4(*)# 4:.4# /%-
;+=%# 3*&)%4(4%B# .)/# 1*'%# >%3=+(.&# 0=# >:*1>:.4%1# /%9%+- veloped carbonate rocks and were subjected to humid-
oped (Table#6B#Fig.#5?B#b.A"#^)/%&#4&*>(3.+#.&(/#3*)/(4(*)1# mid-latitude weathering conditions mainly brought about
*)#4:%#O&.;(.)#N%)()1=+.B#>&('.&-#3*>>%&#'()%&.+(H.4(*)# cerussite and smithsonite with little Fe and Pb sulfates
gave rise to silicacretes-(Cu) and carbocretes-(Cu). Ata- (Table#6B#Fig. 7b). The residual mineralization in Ireland
3.'(4%#(1#>&%1%)4B#.1#8%++#.1#3=>&(.)#9.)./()(4%#.'*),#4:%# *)#4*>#*?#4:%#1=+2/(3#'()%&.+(H.4(*)#(''%/(.4%+-#=)/%&-
most recent oxidic minerals (Table# 6B# Fig. 6b). The Cu- neath the glacial till deposits is either unconsolidated or
bearing solutions often percolated down into the underly- semi-consolidated. The oxidic minerals were deposited in
ing rocks guided by unconformities or fractures and lead .#Z.&14(3#&%+(%?#=)/%&)%.4:#4(++#/%>*1(41"#W)#k(1:%%)B#*8(),#
to bluish-green sulcretes-(Cu) of brochantite and tenorite 4*# 4:%# >&%1%)3%# *?# >&('.&-# X(CO1# 1=+2/%1# %?[*&%13%)3%#
()#1%/('%)4.&-#1%Y=%)3%1#3*'>*1%/#*?#1.)/14*)%1#.)/#.&- of annabergite may be spotted in the cored drill sections
gillaceous sediments (Fig. 3h). (Fig.#F3A"#N;CV)#'()%&.+(H.4(*)#()#W4.+-B#$=)(1(.B#$:.(+.)/B#
and Vietnam are abundant in orecretes-(Zn-Pb) contain-
(),#:-/&*H()3(4%B#3%&=11(4%B#1'(4:1*)(4%#.)/#:%'('*&>:(4%#
5.1.5 Supergene Cu mineralization in calcareous (Fig.#F/B#F%B#F?A"
sedimentary rocks
The carbonate-hosted Cu-Hg-Ag mineralization convert- 5.1.9 Supergene Sb-(Pb-Zn) mineralization in
ed in the course of supergene alteration into globular ag- siliceous magmatic rocks
gregates of azurite (Fig. 6c) or supergene Cu sulfates and
arsenates associated with tenorite (Table# 6B# Fig. 6d). In $:%#*&%3&%4%1#()#4:%#.&(/#H*)%1#*?#)*&4:8%14%&)B#E%D(3*B#
have originated from supergene alteration of various Sb-
calcareous roof rocks of granodioritic intrusions primary
As-Cu-Pb-Zn mineralization. They cover all groups of
.&1%)(/%1#.)/#1=+2/%1#.+4%&%/#()4*#1=>%&,%)%#.&1%)*3&%4%1B#
*&%3&%4%1#?&*'#*D(3&%4%1#*?#L;#4:&*=,:#0=CB#V)CB#.)/#N;#
0=#3.&;*).4%1#.)/#0=Ce#:='.4%U#*D.+.4%1#/=&(),#4:%#%.&+-#
.&1%)*3&%4%1# .)/# 9.)./*3&%4%1B# ()3+=/(),# ;&*'(/%1# .)/#
T&*)H%#O,%#.&*=)/#\\!5#4*#!`_GT0#@DILL et al. 2010a).
3:+*&(/%1#*?#0=#.)/#O,B#8:(3:#,.9%#&(1%#4*#:.+3&%4%1#@Ta-
ble 1).
5.1.6 Supergene Pb-Zn mineralization in siliceous
magmatic rocks 5.1.10 Supergene Sb mineralization in siliceous and
The subvolcanic Ag-Pb-Zn-Cu mineralizations in the An- calcareous sedimentary rocks
des have malachite and azurite as the major supergene
Supergene Sb mineralization has been discovered in si-
alteration minerals in their orecretes (Fig.#b%AB# 8:(+%# ()#
liceous and calcareous sedimentary rocks from mid-lat-
the tropical humid zones Pb-Zn-Cu deposits developed (4=/%#4:&*=,:#4&*>(3.+#:='(/#H*)%1#()#T*+(9(.B#o%&'.)-B#
carbocretes-(Pb-Zn) and sulcretes-(Cu-Pb-Al) with sub- $:.(+.)/B#.)/#E.+.-1(."#E*)*4*)*=1#14(;)(4%#'()%&.+(H.-
ordinate amounts of tenorite (Fig.#b?B#F.A"#W)#4:%#4&*>(3.+# 4(*)#:.1#3%&9.)4(4%B#1%).&'*)4(4%B#.)/#14(;(3*)(4%B#8:%&%.1#
1%'(.&(/#4*#8%4C/&-#H*)%1#()#N.4.,*)(.B#&%3%)4+-#()/(='# gold-bearing stibnite parent material also bears bindheim-
:.1# ;%%)# .//%/# 4*# 4:%# .11*3(.4(*)# *?# >&('.&-# %+%'%)41B# (4%B# Z%&'%1(4%# 1=>>+%'%)4%/# 8(4:# 1*'%# 1=+?.4%1# .)/# .&-
leading to dzhalindite in the orecretes that are dominated senates in the orecrete-(Sb) (Table 1). In humid tropical
by sulcretes and orecretes-(V) (Table 1) (DILL et al. 2013). zones stibnite has been replaced in its uppermost part
under supergene conditions by siliceous and oxidic orec-
5.1.7 Supergene Pb-Zn mineralization in siliceous &%4%1C@L;A#8(4:B#%","B#&*'%(4%#.)/#3%&9.)4(4%#@Fig.#`.B#`;A"
sedimentary rocks
Sandstone-hosted Pb-Cu-Ag mineralization in semi-arid 5.1.11 Supergene P-S mineralization in magmatic
rocks
H*)%1#()#L*=4:#O'%&(3.#(1#*?4%)#.11*3(.4%/#8(4:#0=CB#V)C#
.)/#N;#3.&;*).4%1B#3:&-1*3*++.#.)/#.#8(/%#&.),%#*?#1=+?.4%# W)#M+#L.+9./*&B#N%&=#.)/#L=+.8%1(B#W)/*)%1(.#'=3:#*?#4:%#
@+().&(4%B#.),+%1(4%B#;&*3:.)4(4%A#()#4:%#1=>%&,%)%#4*>14&.- hypogene alunite mineralization is converted near-surface
tum (Table 1). The Pb mineralizations under study in the ()#.#,&%.4#9.&(%4-#*?#ONL#'()%&.+1B#1=3:#.1#j.&*1(4%B#X.C
humid-mid-latitude zone are bound to siliciclastic rocks. j.&*1(4%B# 8**/:*=1%(4%B# 19.);%&,(4%B# .)/# >:*1>:.4%1# *?#
Their supergene base-metal mineralization is made up of 4:%#3&.)/.++(4%C,*&3%(D(4%C[*&%)3(4%#1"1"1"#8(4:#1*'%#/=1-
E)#*D(/%1B#>:*1>:.4%1B#1(+(3.4%1B#.)/#1=+?.4%1#@Table 1). sertite (Fig.#`3B#`/A"
Table 4. Temperatures of formation of carbocretes-(Cu) (malachite) and carbocretes-(Pb) (cerussite) as a function of climate zones. Cal-
culation of temperatures see text. The last column yields the temperature difference between the temperature calculated based upon the
isotope data and the mean temperature as part of the climatological data array published by SUMMERFIELD (1991).
Country Mineral Morphoclimate Zone Temperature Precipitation :#18O ‰ Temperatur Temperature
(mean annual) difference
°C mm vs. PDB °C °C
Iran malachite mountaineous variable variable – 1.3 13 ?
Serbia malachite humid mid-latitude 0 to 20 °C 400 to 1800 – 4.6 28 8
Serbia malachite humid mid-latitude 0 to 20 °C 400 to 1800 – 4.1 26 6
Morocco malachite tropical semiarid 10 to 30 °C 300 to 600 – 3.9 34 4
R*&/.) malachite tropical arid 10 to 30 °C 0 to 300 – 3.1 30 0
Namibia malachite tropical arid 10 to 30 °C 0 to 300 – 6.1 44 14
Thailand cerussite tropical humid 20 to 30 °C > 1500 nh#6!"_ 45 15
T(&'.#E-.)'.& cerussite tropical humid 20 to 30 °C > 1500 nh#6a"_ 51 21
T(&'.#E-.)'.& cerussite tropical humid 20 to 30 °C > 1500 nh#6a"G 45 15
T(&'.#E-.)'.& cerussite tropical humid 20 to 30 °C > 1500 nh#6a"b 49 19
Congo DR malachite tropical humid 20 to 30 °C > 1500 – 7.8 53 23
5.1.12 Supergene P-S mineralization in sedimentary NORTHROP & CLAYTON#@6_bbA#?*&#/*+*'(4%B#;-#O’NEIL et

rocks al. (1969) for calcite and by GILG et al. (2008) for smith-
sonite. The temperature of formation of carbonates in car-
$:%#O=%&;.3:# (&*)14*)%1B# o%&'.)-# %9*+9%/# *)# R=&.11(3#
bocretes was constrained by calculations using the oxy-
Z.&14(2%/# >+.4?*&'# 3.&;*).4%1# 8(4:# S%# >:*1>:.4%1# >&%9-
,%)# (1*4*>%# ?&.34(*).4(*)# %Y=(+(;&(.# ;%48%%)# 3.&;*).4%#
.+%)4+-# 2++(),# 9=,1# .)/# ?&.34=&%1# @Table 1). The Eocene
minerals and water published for azurite and malachite by
>:*1>:*&(4%1# ()# L%)%,.+B# ()4%&3.+.4%/# .'*),# 3+.-14*)%1B#
MELCHIORRE & ENDERS (2003) and for cerussite by MEL-
sandstones and calcareous sediments saw their apatite to
CHIORRE et al. (2001).
be replaced by a group of variegated aluminium-phos-
phate-sulfate minerals (FLICOTEAUX 1982). The most tre- W)#4:%#3=&&%)4#14=/-B#4:%#+*8%14#4%'>%&.4=&%#:.1#;%%)#
'%)/*=1#&%/%>*1(4(*)#4**Z#>+.3%#()#4:%#X=;.#E41"B#L=/.)B# recorded for malachite which developed under tropical
8:%&%#1%&(3(4%C3:+*&(4%#13:(141B#,&.>:(4%#13:(141#.)/#3:%&41# semiarid to arid climatic conditions in a mountainous re-
were altered during the Quaternary supergene alteration ,(*)#()#W&.)#8(4:#6\#c0B#?*++*8(),#4:%#,+*;.+#/(14&(;=4(*)#
4*#1%3*)/.&-#.>.4(4%B#3&.)/.++(4%B#8.9%++(4%B#9.&(13(4%B#.)/# of morphoclimatic zones published by TRICART & CAIL-
H()3(.)#4=&Y=*(1%#@Table#6B#Fig. 8e). LEUX (1972) (Table#aB#Fig. 2a). The highest temperature of
as much as 53 °C was obtained for carbocretes-(Cu) with
malachite that formed under tropical humid climatic con-
5.2 Oxygen isotopes and the temperatures of
ditions in Central Africa (Table 4). There is a trend of the
formation of carbocretes
temperature of formation to increase towards the tropical
Isotope fractionation has been used for long to determine humid zone. The rate of precipitation and annual mean
the temperature of formation of different carbonate min- temperature has also been reported for the various climate
%&.+1"#W1*4*>%#?&.34(*).4(*)#%Y=(+(;&(.#;%48%%)#3.&;*).4%# zones to allow for a comparison with the temperatures of
minerals and water have among others been published by oxidation in each of the orecretes.
b Fig. 4. Macro- and microtextures of orecretes-(Cu) in siliceous magmatic rocks. a)#E.11(9%#;+=(1:#4=&Y=*(1%#@4=&A#>.&4(.++-#3*9%&%/#8(4:#

'.+.3:(4%#@'.+A"#0*>(.>*B#0:(+%"#b) Cuprite (cup) crystals interwoven with each other and grading at the edge into chalcotrichite (cha)
@LMECMKLA"#0*>(.>*B#0:(+%"#c)#0=>&*4=),14(4%#@3=8A#.)/#.):%/&.+#;&*3:.)4(4%#@;&*A#@LMECMKLA"#k+.'=3*#L.+.'.)3.B#0*Y=(';*#J%-
,(*)B#0:(+%"#d)#M&=>4(9%#;&%33(.#'()%&.+(H%/#8(4:#.H=&(4%#@.HAB#'.+.3:(4%#@'.+A#.)/#1=;*&/().4%#.'*=)41#*?#>+.)3:%(4%#@>+.A#/%9%+*>(),#*)#
.+=)(4%#@.+A#k(>%HB#T*+(9(."#e)#OH=&(4%#'()%&.+(H.4(*)#3%'%)4(),#4:%#1(+(3(2%/#?&.,'%)41#*?#4:%#;&%33(.#()#4:%#*&%3&%4%C@0=AB#k(>%HB#T*+(9(."#
f)#OH=&(4%#.)/#'.+.3:(4%#3*9%&(),#211=&%#>+.)%1#()#.#;&%33(.4%/#+.4(4%#>*&>:-&-"#X%.&#d.4:(B#)*&4:%&)#o&%%3%"
6. Discussion of the origin of orecretes cretes can be deduced from various studies (WHITESAND
6_5\B#GRAY & MURPHY#!GG!B#BRITISH GEOLOGICAL SURVEY
6.1 The origin of orecretes as a result of @ToLA#!GG_B#SCHULER et al. 2011) (Fig. 9).
morphoclimatic processes and parent material
O# [*8# 1:%%4# ()# Fig. 9 illustrates the complex interrela-

6.2 Climate and the formation of orecretes
tionship between the various parameters that are of con-
trol on the formation of orecretes. The “family tree” of 6.2.1 Temperature of oxidation versus palaeoclimatic
orecrete formation highlightens the leading role that the temperature
physico-chemical regime plays in the development of
these chemical residues with its tie lines to climate and N&%3(>(4.4(*)B# %9.>*&.4(*)# .)/# 4%'>%&.4=&%# .&%# 4:%# 9.&(-
>.&%)4# '.4%&(.+B# ;*4:# *?# 8:(3:# .&%# +()Z%/# ;-# 4:%# ?*&'.- .;+%1#()#4:%#3+('.4%#H*).4(*)#?&*'#4:%#>*+%#4*#4:%#%Y=.4*&#
tion of the landscape. The orecretes listed in Table 1 have (Fig.#_B# 6GA"# $:%-# ,*9%&)# 4:%# >:-1(3.+C3:%'(3.+# &%,('%#
;%%)# /(13=11%/B# ()# &%+.4(*)# 4*# 4:%# '*&>:*3+('.4(3# H*).- that can best be approximated by Eh-pH cross-plots and
4(*)#?&*'#4:%#>*+%#4*#4:%#%Y=.4*&#.1#'*&>:*3+('.4(3#'.&Z- 4:%#14.;(+(4-#2%+/1#*?#4:%#'()%&.+1#()9*+9%/#()#4:%#;=(+/C=>#
ers (Fig.#6GB#Table 3). of the orecretes (Figs.#_B#66B#6!B#6\B#6aB#65A"
Figure 10a is based on the data listed in Table 1 with Casting pressure aside as a variable in these near-am-
each of these sites shown in one of the maps of Fig. 2. ;(%)4# 3*)/(4(*)1B# +%.9%1# 4:%# ?*&'.4(*)# *?# *&%3&%4%1# *)+-#
The mountainous regions have to be kept as a separate related to the ratio of precipitation vs. evaporation and the
entity. The zonation starts off from different climatic 3:%'(3.+#3*'>*1(4(*)#*?#4:%#'%4%*&(3#[=(/1"#$8*#/(??%&-
zones and eventually ends up in the glacial or cool zone ent types of temperatures have to be distinguished from
on top of Cenozoic mountain belts (Fig.#!3B#/A"#0+('.4(3# each other (Table 4). It is the existing temperatures which
changes translate into the physical-chemical regime under changes along with the latitude and the height in moun-
which the orecretes formed. The physical and chemical tainous areas and the temperature of formation or oxida-
processes responsible for the formation of orecretes are tion (Table#aA"#L=+?.4%C;%.&(),#[=(/1#>+.-#4:%#'*14#('>*&-
correlative with different climatic and geomorphologi- 4.)4#>.&4#/=&(),#/%3*'>*1(4(*)#*?#1=+2/%1#1=3:#.1#>-&(4%B#
cal processes shaping the landscape and impacting on the marcasite or sphalerite (RIMSTITD# %4# .+"# 6__aA"# T.34%&(.#
hydrology (morphoclimatic changes). To some extent the such as Thiobacillus ferrooxidans provoke an increase
>&('.&-#&*3ZC?*&'(),#'()%&.+1#:.9%#.)#()[=%)3%#*)#4:%# of the sulfate concentration (NÄVEKE# 6_`bB# GEHRING et
pH conditions through the buffering effect. Calcareous .+"#6__aB#KONHAUSER#6__`B#KASAMA & MURAKAMI#!GG6B#
rock-forming minerals for example may buffer the acidity FERRIS# %4# .+"# !GGaB# JAMES & FERRIS 2004). The microor-
during sulphide oxidation. On the other hand the redox ganisms are aerobic and acidophile. They grow by means
&%,('%#'.-#;%#()[=%)3%/#;-#4:%#>&%1%)3%#*&#.;1%)3%#*?# of ferrous iron or chemical reduced forms of sulfur. The
1=+2/(3#'()%&.+1#@Fig. 9). carbon involved in the process has been derived from
O1# 4*# 4:%# ?*&'.4(*)# *?# 4:%# +.)/13.>%B# &%?%&%)3%# (1# atmospheric carbon (NORRIS#!GGFB#RAWLINGS & JOHNSON
given in the following sections to some comprehensive 2007). Fungal weathering and iron crystalline formation
studies (SUMMERFIELD# 6__6B# BREMER# 6__\B# !GG!B# HAR- was studied by FELDMANN et al. (1997). These biologi-
RIS# 6__aB# THOMAS# 6__aB# 6__5B# !GGaB# LAVEE# %4# .+"# 6__`B# 3.++-#'%/(.4%/#&%/*D#>&*3%11%1#@4&.)1?*&'.4(*)#1=+2/%#p#
GLENNIE# !GG5B# HOLDEN 2008). As to the parent rocks of sulfate) also caused a local temperature increase. From
*&%3&%4%1B# 4:%# &%./%&# (1# &%?%&&%/# 4*# 3*''*)# 3+.11(23.- the periglacial to the tropical humid zone the temperature
tion schemes of mineralizing processes in comprehensive and the precipitation both increase (Fig. 10b). The pro-
studies (HUTCHINSON# 6_`\B# SAWKINS# 6__GB# EVANS# 6__\B# duction of litter and the depth of the weathering mantle
ROBB# !GGaB# LAZNICKA# !GGbB# DILL 2010b). The interrela- increase along with that and so does the bacterial activity
tionship between substrate and soil-forming processes in the formation of orecretes (Fig.#!/B#Table 4). There is
4:.4#>+.-#.+1*#.#1(,)(23.)4#>.&4#()#4:%#,%)%&.4(*)#*?#*&%- a slight increase relative to the paleotemperature in the
b Fig. 5. Macro- and microtextures of orecretes-(Cu) in basic magmatic rocks and in siliceous sedimentary rocks. a) Earthy malachite lining
.#,*%4:(4%C;%.&(),#211=&%#()#;+.3Z#1:.+%1#*?#k.4%#K%9*)(.)#.,%"#T%&,B#o%&'.)-"#b) Earthy annabergite bleached and converted into Ni
1=+?.4%#@'*&%)*1(4%A#*)#1(/%&(4%"#T%&,B#o%&'.)-"#c)#O3(3=+.&#3&-14.+1#*?#.)).;%&,(4%#@LMECMKLA"#T%&,B#o%&'.)-"#d) Plates of spertiniite
@LMECMKLA"#e.+.9.11*1B#o&%%3%"#e)#E%4.1%/('%)41#3=4#;-#1:%.&#H*)%1#%D>*1%/#()#.#4&%)3:"#L:%.&#9%()1#3*)4.()#'.+.3:(4%B#8:%&%.1#4:%#
?&.34=&%1#&=))(),#>%&>%)/(3=+.&+-#4*#4:%1%#1:%.&#H*)%1#.&%#3*.4%/#8(4:#&=14#;&*8)#,*%4:(4%"#J%>>.&?j*&/B#X*&8.-"#f) Lamellae of siliceous
.)/#>:*1>:.4%C;%.&(),#*&%3&%4%1C@0=A#*)#'%4.>%+(4%#@=>>%&#+%?4#3*&)%&A"#0:&Q#3:&-1*3*++.B#3*Q#3*&)%4(4%B#>'Q#>1%=/*'.+.3:(4%#@4:()#1%34(*)B#
Nic (-)). Lubumbashi DR Congo.
humid mid-latitude zone and a conspicuously strong in- spertiniite is typical of the late-stage supergene alteration
crease when passing into the tropical humid zone (Table (Table#6B#Fig. 1b).
aB#Fig. 10b). Oxicretes-(Fe)-(Mn): Manganese is chemically related to
Temperatures of formation of carbocretes-(Cu-Zn-Pb) (&*)"# K=%# 4*# 4:%# &%/*DC&%+.4%/# 9.&(.4(*)B# *D(/(3# S%# .)/#
obtained from isotope studies along a N-S trend gener- E)#'()%&.+1#:.9%#14.;(+(4-#2%+/1#)*4#9%&-#'=3:#/(??%&%)4#
.++-# 24# 4:%# 4%'>%&.4=&%# /.4.# >=;+(1:%/# ;-# SUMMERFIELD ?&*'#%.3:#*4:%&#8(4:#&%,.&/#4*#4:%(&#1:.>%B#@Fig.#663B#/A"#
(1991). The array of the temperature of formation of car- Oxidic manganese minerals precipitated from meteoric
bocretes is a good match to the climatic zonation of the waters of a higher alkalinity than those of iron (Fig.#663B#
]=.4%&).&-"#W)#3*)3+=1(*)B#4:%#3.&;*3&%4%1#.)/#4:%#*4:%&# /A"# O1# '%4%*&(3# 8.4%&1# ()2+4&.4%/# ()4*# >&('.&-# 1=+2/(3#
orecretes formed during the most recent parts of the Earth mineral assemblages during the initial stages of weather-
history under more or less identical climatic conditions (),B#4:%#&%1=+4.)4#3:.),%1#*?#4:%#,%*3:%'(3.+#3*)/(4(*)1#
as today. An elevated rate of precipitation such as in the led to a lowering of the pH value from"%"pH 7 to slightly
humid climatical zones increased the temperature of for- acidic. Oxicretes forming very early during supergene al-
'.4(*)# /=&(),# *D(/.4(*)# *?# 1=+2/%1# .)/# 3.=1%/# .# '*&%# teration behave like azonal duricrusts whose formation
1(,)(23.)4#/(??%&%)3%#;%48%%)#4:%#3.+3=+.4%/#4%'>%&.4=&%# is driven mainly by the local palaeodrainage system and
and the annual mean temperature (temperature of reaction ('>.34%/#;-#4:%#3*'>*1(4(*)#*?#4:%#>&('.&-#1=+2/(3#*&%#
or oxidation) (Table#aB#Fig. 9). (''%/(.4%+-#=)/%&)%.4:B#&.4:%&#4:.)#.1#.#H*).+#/=&(3&=14#
which is strongly impacted by the atmospheric conditions
6.2.2 Physico-chemical regime of oxicretes sensu DIXON (1994). There are some orecretes-(Fe) linked
8(4:#>.&4(3=+.&#'*&>:*3+('.4(3#H*)%1B#1=3:#.1#4:%#/%1%&4#
Oxicretes-(Sb)-(Bi)-(W): Oxicretes-(Sb) occur at Eh" %"0 varnish under arid climatic conditions (GOUDIE & PYE
over a very wide pH range (BROOKINS 1987) (Fig.#66.B Ta- 1983). These Fe encrustations are a widespread phenom-
ble 4). Yellow to brown oxicretes-(Sb) may be expected enon all across the desert at various altitudes above the
under almost all climatic conditions (Fig. 10a). The stabil- ,&*=)/8.4%&# +%9%+# *&# &.(1%/# >.+%*+.Z%# 4%&&.3%1B# '.&Z(),#
(4-#2%+/#?*&#L;@<7A3 denotes an area which is transitional strandlines of early lake stages (ABU GHAZLEH & KEMPE
()4*#:->*,%)%#L;#'()%&.+(H.4(*)#.)/B#:%)3%B#)*4#3*)1(/- 2009).
ered further on during the current discussion of metallif- Orecretes-(Fe) coupled or uncoupled with orecretes-
erous duricrusts (Fig. 11a). These orecretes are of limited (Mn) are decisive tools for the hydrological and redox re-
use as morphoclimatic markers. ,('%1"#$:%#14.;(+(4-#2%+/1#()#Fig. 11c and 11d are calculat-
Oxicretes-(Cu): Orecretes-(Cu) with only tenorite oc- ed for the least-hydrated mineral phases of each element.
cur within an alkaline hydrous regimes (Fig.#66;B# Table Hematite may be replaced by goethite under more humid
5). Cuprite which formed prior to tenorite in all samples conditions. The sort of Fe or Mn minerals that develop in
under study is slightly more tolerant to more acidic pore 4:%#&%/=3(),#2%+/#*?#%.3:#M:C>7#/(.,&.'B#/%>%)/1#=>*)#
1*+=4(*)1# .)/B# 4:%&%?*&%B# (1# >&%1%&9%/# .+1*# =)/%&# .3(/(3# 4:%#.)(*)1B#%","B#70<3"#0*)3+=1(9%+-B#>%&(,+.3(.+B#4%'>%&-
conditions down to pH" #"5 (Fig. 11a). Near-surface en- ate and tropical climates are the most favorable loci for the
3&=14.4(*)1#'.-#.+1*#3*)4.()#0=#1=+2/%1#;%1(/%1#0=#*D- oxicretes (Fig. 10a). Due to the variable cover of the Mn
ides in their basal parts and thereby provide a redox mark- .)/#S%#14.;(+(4-#2%+/1#()#4:%#*D(/(H(),#>.&4#*?#4:%#M:C>7#
er at a rather elevated Eh level (Fig. 11a). Its application /(.,&.'B#4:%-#3.)#;%#.>>+(%/#.1#&%/*D#()/(3.4*&1#?*&#/(?-
.1#.#'*&>:*3+('.4(3#'.&Z%&#(1#3*)2)%/#4*#4:%#:='(/#.)/# ferent hydrological and pedological parts of the duricrusts
temperate climate zones. The presence of orecretes-(Cu) (KRASILNIKOV# %4# .+"# !GG_B# DILL# %4# .+"# !G6G;A"# E*&%*9%&B#
in other morphoclimatic zones may be interpreted as a rel- the presence of K in cryptomelane offers favorable condi-
ic mineral indicative of more humid climate and an inten- tions to date this paleo-redox zone in orecretes (VASCON-
1(9%#[=1:(),#*=4#*?#.)(*)#3*'>+%D%1#4*#&%.34#8(4:#0=2+. CELOS#%4#.+"#6__aB#VASCONCELOS#6___B#QUANG#%4#.+"#!GG\B#
T*4:#3=>&(4%#.)/#4%)*&(4%#/%9%+*>%/#9%&-#%.&+-B#8:%&%.1# ARANCIBIA#%4#.+"#!GGbB#DILL et al. 2010b).
b Fig. 6. Macro- and microtextures of orecretes-(Cu) and orecretes-(Pb-Zn) in siliceous and calcareous sedimentary rocks as well as felsic
magmatic rocks. a)#<&%3&%4%C@0=A#@>:*13&%4%A#8(4:#3.9(4(%1#.)/#9=,1#2++%/#8(4:#;+=%#3*&)%4(4%#.)/#,&%%)#>1%=/*'.+.3:(4%"#k=;=';.1:(B#
DR Congo. b) Thin coatings of faint green chrysocolla and atacamite highlight the presence of stratabound Cu mineralization in cross-
;%//%/#3*),+*'%&.4(3#1.)/14*)%1#*?#'(//+%#0.';&(.)#.,%"#P./(#K.).B#R*&/.)"#c) Dolomite hosting tetrahedrite-tennantite s.s.s. is replaced
along fractures by malachites. From the selvage of these fractures azurite penetrates the matrix in form of globular aggregates (thin sec-
tion- Nic)A"#L3:8.HB#O=14&(."#d)#<&%3&%4%C@0=CN;A#'./%#=>#*?#;&*3:.)4(4%#@;&*AB#+().&(4%#@+()A#.)/#4%)*&(4%"#0*+Y=(j(&3.#/(14&(34#)%.&#0%&&*#
/%#N.13*B#N%&="#e) Orecrete-(Cu) with botryoidal textures of azurite (az) and subordinate amounts of malachite (mal) in a matrix of goethite
@,*%A"#0.1.>.+3.B#N%&="#f)#0%&=11(4%#&:*';1#8(4:()#*&%3&%4%C@N;A#8(4:#Y=.&4H#/%;&(1#8.1:%/#()4*#4:%(&#()4%&14(3%1#.)/#3.9(4(%1#3.=1%/#;-#
/(.,%)%4(3#>&*3%11%1#@4:()#1%34(*)B#X(3#@)AAB#T.8/8()B#E-.)'.&"
6.2.3 Physico-chemical regime of carbocretes solution) but is much more stable than smithsonite and
the copper carbonates (see below) in the oxidized zone
Carbocretes-(Zn-Cd): Together with Zn-bearing silica- (LEVERETT et al. 2005). Fine-grained cerussite replac-
3&%4%1B# 3.&;*3&%4%1C@V)A# '.Z%# =># 4:%# +(*)*s share of the (),# ,.+%).# ()C1(4=# .)/# '.3&*3&-14.++()%# 3%&=11(4%# 2++(),#
)*)C1=+2/%#V)C*&%1#.+1*#Z)*8)#.1#fk.>(1#0.+.'().&(=1gB# open fractures and cavities were discussed by SZCZERBA
f0.+.'()%gB# fo.+'%(gB# *&# fo.+'.)g# ()# 4:%# +(4%&.4=&%"# &'()*+$*",- (2009). Microscopic observations of speci-
These orecretes can form under a wide range of climatic mens and thermodynamic considerations lead to the con-
conditions (Table 1). From the physico-chemically point clusion that galena can be replaced by lead carbonate
*?#9(%8B#4:%#*&%3&%4%1#1:*=+/#;%#&%14&(34%/#4*#4:%#%D4&%'%# /(&%34+-B# )*4# )%3%11.&(+-# 4:&*=,:# .)# ()4%&'%/(.4%# 1=+?.4%#
alkaline part of the pH range (Fig. 10a). Increasing the ac- >:.1%#()#4:%#>&%1%)3%#*?#(&*)#1=+2/%1#=)/%&,*(),#*D(/.-
tivity of Zn and(or) raising the partial pressure of CO2 4(*)#.)/#3*)/=3(9%#4*#.)#.3(/(23.4(*)#*?#4:%#'%4%*&(3#1*-
%D>.)/1# 4:%# 14.;(+(4-# 2%+/# *?# 1'(4:1*)(4%# @Fig.#6!.B# ;A"# lutions. The authors considered the reaction on the gal-
Decreasing PCO2 may lead through hydrozincite to zincite 9.)(3#3*=>+(),#*?#4:%1%#48*#1=+2/%1#.1#4:%#'*14#/%3(1(9%#
(see also silicacretes-(Zn)) (MCPHAIL et al. 2003). In fer- process. There are a few cerussite-only mineralizations
roan smithsonite (“monheimite”) part of the Zn content (DILL#%4#.+"#!GG`.B#PIRAJNO et al. 2010). A different mode
has been substituted for by bivalent Fe (BAK & NIEC#6_F`B# of formation has to be invoked than simple weathering.
BAK & ZABINSKI#6_`6A"#W4#(1#14(++#.)#*>%)#Y=%14(*)#8:%4:%&# The mineralizing processes have been described as dia-
this ferroan smithsonite can be used as a redox marker in ,%)%4(3#*&#%>(,%)%4(3U#[=(/#'(D(),#8(4:#.#14&*),#('>.34#
the supergene environment similar to the Fe-Mn system of evapotranspiration. This is especially true for cerussite
(Fig.#66;B#3A"#$:%#S%0<3 component encountered within that developed under arid climatic conditions in a sabkha
ferroan smithsonite is like siderite only stable under re- or playa regime (Table 1).
ducing conditions in a rather narrow pH range (neutral Carbocretes-(Cu): The overall CO2 content in the atmos-
to slightly acidic) (Fig. 12d). At near-ambient conditions phere together with the CO2 created by the organic litter
(25 °C) the activity of dissolved species have to be at log ()#4:%#4*>1*(+#.&%#1=?23(%)4#4*#3&%.4%#4:%1%#=;(Y=(4*=1#0=#
aFe"#"hn\#.)/#+*,#aHCO3"#"hn\#4*#-(%+/#.#1'.++#8()/*8#8(4:()# 3.&;*).4%1B# ,(9(),# 4:%# 3.&;*3&%4%1C@0=A# 4:%(&# ,&%%)# .)/#
8:(3:# 4:%# 14.;(+(4-# 2%+/1# *?# S%0<3 and ZnCO3 overlap blue staining (Fig.#\3B#a?B#5.B#5%B#b%B#6!%B#?A"#$:%#14.;(+(4-#
(Fig.#6!;B#/A"#W)#).4=&%B#.#1(,)(23.)4#*9%&+.>#*?#;*4:#14.;(+- 2%+/#*?#'.+.3:(4%#()3&%.1%1#*)#()3&%.1(),#NCO2 and on in-
(4-#2%+/1#'.-#*)+-#;%#.3:(%9%/#.4#%+%9.4%/#4%'>%&.4=&%1# creasing Cu activities in the meteoric solutions (Fig.#6!%B#
($"100 °C). Therefore (monheimite(-bearing orecretes are ?A"#W4#:.1#4*#;%#)*4%/B#4:.4#4:%#Y=.)4(4-#*?#3.&;*3&%4%1C@0=A#
supposed to be preserved under low-temperature hypo- in many arid morphoclimatic zones diminishes in favor of
gene or late diagenetic conditions in a reducing hydraulic silicacretes-(Cu) or halcretes-(Cu) (Fig. 10a). The trans-
regime. They are not part of the carbocretes-(Zn) sensu formation of malachite into azurite at approx. 195 °C by
stricto#.)/#/*#)*4#Y=.+(?-#.1#.#1('>+%#&%/*D#()/(3.4*&#()# release of water has no relevance for the environments un-
the supergene environment underneath the carbocretes- der consideration in the current study (FROST et al. 2002).
(Zn) – see Irish Pb-Zn deposits (Table 1). The scenario of S(%+/# *;1%&9.4(*)1# .)/# %D>%&('%)41# *)# %Y=(+(;&.4(*)# *?#
(41#?*&'.4(*)#(1#Y=(4%#1('(+.&#4*#8:.4#:.1#;%%)#/%13&(;%/# azurite and malachite showed that these Cu-bearing so-
from Thailand as (hydrothermal karst(B#8:%&%#?%&&*.)#3.+- lutions had carbonate concentrations corresponding to a
cite is common under slightly reducing conditions (DILL partial pressure of CO2 of at least 10nhn!"\ atm. In order to
%4#.+"#!GG5;B#!GG`;A" '.()4.()#.#0=C3*)3%)4&.4(*)#1=?23(%)4#4*#>&%3(>(4.4%#.H=&-
Carbocretes-(Pb): 0.&;*3&%4%1B#;%.&(), cerussite develop (4%B#4:%#1*+=4(*)1#.+1*#'=14#:.9%#:./#.)#*D(/.4(*)#>*4%)-
in environments similar to those recorded for smithsonite. 4(.+#:(,:#%)*=,:#4*#*D(/(H%#1=+2/%#4*#1=+?.4%#@MENSCHEL &
^)+(Z%# 1'(4:1*)(4%B# 3%&=11(4%# 3.))*4# .33*''*/.4%# ()4*# USDOWSKI 1975). WOODS & GARRELS (1986) revealed that
its structure bivalent Fe for crystallographic reasons. malachite responds rapidly to changes of the log PCO2 and
Lead carbonate occurs down to a pH of approximately 3*)9%&41# .;*9%# 3."# h6"5# ()4*# .H=&(4%"# T%+*8# +*,aCu #" hna#
3 (Fig. 12c). Cerussite is more soluble (certainly in acid or increasing alkalinity malachite is replaced by tenorite
b Fig. 7. Macro- and microtextures of orecretes-(Pb-Zn) in felsic magmatic rocks and calcareous sedimentary rocks. a) Galena showing a
3*'>+%D#()4%&,&*84:#*?#/(??%&%)4#3&-14.+#'*&>:*+*,(%1#[*.4(),#()#.#'.1:#*?#&*1.1(4%#.)/#3=>&*3*>(.>(4%#@LMECMKLA"#T.8/8()B#E-.)-
mar. b)#L'(4:1*)(4%#@\"5#84"#q#S%A#8(4:#>+.4%1#*?#:-/&*H()3(4%"#o.+'*-B#W&%+.)/"#c) Core section with effervescence of annabergite in Ni
.&1%)(/%C;%.&(),#.&,(++(4%1"#k(1:%%)B#W&%+.)/"#d)#M*3%)%#N;CV)C;%.&(),#+('%14*)%#;&%33(.#()4%&1%34%/#;-#211=&%1"#$:%#*>%)#3.9(4(%1#.&%#+()%/#
8(4:#3*++*'*&>:*=1#*&%3&%4%1C@V)A#'.()+-#3*'>*1%/#*?#1'(4:1*)(4%"#L%Z.&).CM+#e%?#&%,(*)B#$=)(1(."#e) Nest of interwoven aggregates of
:%)/&(3Z1(4%#@LMECMKLA"#N.%#K.),B#$:.(+.)/"#f) Orecrete-(Zn) abundant in smithsonite developing in solution cavities of Givetian lime-
14*)%1"#0:*#K(%)B#d(%4).'"
Fig. 9. S+*8#1:%%4#4*#(++=14&.4%#4:%#('>.34#*?#9.&(*=1#>.&.'%4%&1#()#4:%#2%+/1#*?#3+('.4%B#,%*'*&>:*+*,-#.)/#>.&%)4#'.4%&(.+#*)#4:%#?*&'.-
tion of orecretes. In rounded brackets the section is given where it is referred to in the text.
(Fig.#6!%B#?A"#WOODS & GARRELS (1986) analyzed several 6.2.4 Physico-chemical regime of silicacretes
samples from groundwater and surface water. Their data
points of the chemical composition mostly plot into the Silicacretes-(Cu): Copper-bearing silicacretes encom-
14.;(+(4-# 2%+/# *?# '.+.3:(4%"#OH=&(4%# )%%/1# %+%9.4%/# NCO2 pass a wide range of minerals which sometimes escape
to develop on silicate-hosted Cu deposits being exposed .# >&*>%&# '()%&.+*,(3.+# /%2)(4(*)# @VAN OOSTERWYCK-
to dry climatic conditions (Table 1). As it is the case with GASTUCHE & GRÉGOIRE 1971). They range in composition
*D(3&%4%1C@0=AB#4:%&%#.&%#.+1*#()(4(.+#14.,%1#*?#3.&;*3&%4%1C ?&*'#3:.+3%/*)-B#4:&*=,:#3=>&(?%&*=1#Y=.&4H#.)/#*>.+()%B#
@0=A#()#'%4.++(?%&*=1#/=&(3&=141#4:.4#&%[%34#.#3+('.4%#&%- siliceous to pure chrysocolla- and plancheite-bearing en-
,('%#Y=(4%#/(??%&%)4#?&*'#4:%#>&%1%)4#*)%B#?*&3(),#4:%'#4*# 3&=14.4(*)1"# $:%&%?*&%B# 8%# =1%# 4:%# ).'%1# 3:&-1*3*++.B#
be called paleo-carbocretes or a relic mineral association plancheite and Cu-bearing opaline sensu lato. The chem-
(Fig. 1b). ical system of supergene Cu mineralization has been ad-
b Fig. 8. Macro- and microtextures of orecretes-(Sb) in siliceous and calcareous sedimentary rocks and of phoscretes and sulcretes in mag-
matic and sedimentary rocks. a)#L*+=4(*)#3.9(4(%1#+()%/#8(4:#;*4&-*(/.+#3%&9.)4(4%#@LMECMKLA"#N:=#R*%B#$:.(+.)/"#b) Close-up view of
Fig. 8a showing 1st generation globular cervantite and stellate aggregates of a 2nd#,%)%&.4(*)#*?#3%&9.)4(4%#@LMECMKLA"#N:=#R*%B#$:.(+.)/"#
c)#E.11(9%#'(3&*3&-14.++()%#'%4.C.+=)*,%)#@LMECMKLA"#O,=.#L:=3.B#M+#L.+9./*&"#d)#N1%=/*3=;(3#3&-14.+1#*?#T.C#.)/#NC;%.&(),#.+=)(4%#
@LMECMKLA"#O,=.#L:=3.B#M+#L.+9./*&"#e)#S%&&(.+=)(4%#>1%=/*'*&>:*1(),#S%#1=+2/%1#()#1:.+%1#@LMECMKLA"#$(&13:%)&%=4:B#o%&'.)-"
dressed by CRANE et al. (2001) and is mostly cited herein >7# 66# 1*+(/# >:.1%1# 1=3:# .1# Y=.&4H# *&# (41# 2)%C,&.()%/#
for discussion of the depositional environment. Azurite '*/(23.4(*)# 3:.+3%/*)-# '.-# %D(14# @Fig. 13a). ZHANG
which is known to occur predominantly under more arid @6__aA#*=4+()%/#4:%#14.;(+(4-#2%+/#*?#3:&-1*3*++.#4*#1>.)#
climatic conditions is often associated with cupriferous the pH range from pH 4 to pH 13 ([Cu]"#"10nhnb#E"B#rLs"
silica and eventually converted into chrysocolla as the #" 10nhnb M and [Si]" #" 10nhnb and 10nhn` M) in the oxidizing
H4SiOa@.YA# increased in the pore solution. The concentra- part of the Eh-pH diagram. Dioptase is stable below pH
tion of dissolved species of silica increases in meteoric 6 depending upon the availability of dissolved Cu in the
[=(/1# 8:(+%# 4:%# >7# 9.+=%1# *?# 4:%# [=(/1# &(1%1"# O4# !5#c0# solution (KISELEVA et al. 1993). It is easily determined
and using the dissolved species as logaSiO2 #" hn\B# ;%+*8# and certainly cannot be grouped among those Cu-bearing
Fig. 10. Orecretes as a function of climate and geomorphology (“morphoclimatic marker”). a) Orecretes vs. morphoclimatic changes c
based on data of the current study. The y-axis gives the relative abundance of each type of orecrete in volume percentage. The x-axis is to
show the morphoclimatic changes. The coloration refers to the shading used in Table 5. b) Variation in the weathering mantle depth and
composition in relation to climatic and biotic variables STRAKHOV (1967) in SUMMERFIELD (1991). c) Orecretes vs. processes shaping the
landscape in response to precipitation and temperature. Processes have been taken from comprehensive papers by TRICART & CAILLEUX
@6_F!AB#BÜDEL#@6_FFAB#SUMMERFIELD#@6__6AB#THOMAS#@6__aB#!GG6AB#GALLOWAY & HOBDAY#@6__bAB#BREMER#@!GG!AB#TWIDALE#@!GG!AB#GLENNIE
(2005) and TAYLOR & EGGLETON (2009). d) Orecretes vs. pedology and hydrology in response to precipitation and temperature (SCHEFFER &
SCHACHTSCHABEL#6_FbA"#T&*8)#?&.'%#/%)*4%1#.#14&*),#per ascensumB#&%/#.#14&*),#per descensum component during migration of meteoric
[=(/1"#0+.11(23.4(*)#13:%'%#.33*&/(),#4*#FOOD AND AGRICULTURE ORGANIZATION OF THE UNITED NATIONS (2008).
Fig. 11.#M:C>7#/(.,&.'1#*?#*D(3&%4%1C@S%AB#C@E)AB#C@0=A#.)/#C@L;A"#L:./%/#.&%.#/%)*4%1#14.;(+(4-#2%+/1#*?#*&%3&%4%1"#O11='%/#3*)3%)4&.-
4(*)1#*?#/(11*+9%/#1>%3(%1#.&%#,(9%)#;%+*8#()#'*+U+"#a) Eh-pH diagram to show the oxicrete-(Sb) mineralization at 25 °C using the dissolved
species as logaSb"#"hnbB#+*,aS #"hn\"#N:-1(3.+C3:%'(3.+#;.1(1#BROOKINS#@6_`FAi#b) Eh-pH diagram to show the oxicrete-(Cu) mineralization at
25 °C using the dissolved species as logaCu"#"hnbB#+*,aHCO3 #"hn\B#+*,aSO4"#"hn\i#c) Eh-pH diagram to show the oxicrete-(Fe) mineralization at
25 °C using the dissolved species as logaFe"#"hnbi#d) Eh-pH diagram to show the oxicrete-(Mn) mineralization at 25 °C using the dissolved
species as logaMn"#"hnb"
Fig. 12.#M:C>7#/(.,&.'1#*?#3.&;*3&%4%1C@V)AB#C@N;AB#C@0=A#.)/#S%#3.&;*).4%#>+*44%/#4*#/%13&(;%#4:%#>:-1(3.+C3:%'(3.+#&%,('%#*?#?%&&*.)# c
1'(4:1*)(4%"#L:./%/#.&%.#/%)*4%1#14.;(+(4-#2%+/1#*?#*&%3&%4%1"#O11='%/#3*)3%)4&.4(*)1#*?#/(11*+9%/#1>%3(%1#.&%#,(9%)#;%+*8#()#'*+U+"#a) Eh-
pH diagram to show the carbocrete-(Zn) mineralization at 25 °C using the dissolved species as logaZn"#"hn`B#+*,aHCO3"#"hn\B#+*,aHSO4"#"hn\i#b)
Eh-pH diagram to show the carbocrete-(Zn) mineralization at 25 °C using the dissolved species as logaZn"#"hnaB#+*,aHCO3"#"hn\B#+*,aHSO4"#"hn\i#
c) Eh-pH diagram to show the carbocrete-(Pb) mineralization at 25 °C using the dissolved species as logaPb"#"hn`B#+*,aHCO3"#"hn\B#+*,aHSO4"#"
hn\i#d) Eh-pH diagram to show the carbonate-bearing (Fe) mineralization at 25 °C using the dissolved species as logaFe"#"hn\B#+*,aHCO3"#"hn\i#
e) Eh-pH diagram to show the carbocrete-(Cu) mineralization at 25 °C using the dissolved species as logaCu"#"hnaB#+*,aHCO3"#"hn\B#+*,aSO4 #"
hn\i#f) Eh-pH diagram to show the carbocrete-(Cu) mineralization at 25 °C using the dissolved species as logaCu"#"hn\B#+*,aHCO3"#"hn!B#+*,aSO4"
#"hn\"
Fig. 13.#M:C>7#/(.,&.'1#*?#1(+(3.3&%4%1B#:.+3&%4%#.)/#1=+3&%4%1"#L:.-
/%/#.&%.#/%)*4%1#14.;(+(4-#2%+/1#*?#*&%3&%4%1"#a) Eh-pH diagram to
show the precipitation of silicacretes at 25 °C using the dissolved
species as logaSiO2"#"hn\i#b) Eh-pH diagram to show the argillaceous
part of silicacrete-(Zn) mineralization at 25 °C using the dissolved
species as logaFe"#"hnbB#+*,.E,UV)"#"hn!i#c) Eh-pH diagram to show the
halcrete-(Cu) mineralization at 25 °C using the dissolved species
as logaCu"#"hnaB#+*,aCl"#"h6i#d) Eh-pH diagram to show the sulcrete-
@ONLA#'()%&.+(H.4(*)#.4#!5#c0#'*/(2%/#?&*'#KEITH#%4#.+"#@6_FaAi#e)
Eh-pH diagram to show the sulcrete-(Fe) mineralization at 25 °C
'*/(2%/#?&*'#LAL (2005).
silicates forming modern silicacretes-(Cu). Its presence surface conditions over the entire pH spectrum (GARRELS
indicates the presence of (paleo) silicacretes and relic & CHRIST 1965).
?*&'1B#%","B#$1='%;B#X.'(;(."#E(3&*;(.+#()9*+9%'%)4#()#
the formation of copper silicate and oxide mineralization 6.2.6 Physico-chemical regime of sulcretes
has been discussed by NELSON et al. (2007) but cannot
be claimed to have a broader impact on silicacretes else- Sulcrete-(Cu-Pb): Anglesite is an intermediate product
where judging by the present studies. 4:.4# ?*&'%/# /=&(),# 1=>%&,%)%# .+4%&.4(*)# *?# ,.+%)."# T=4#
Silicacretes-(Zn): Silicacretes bearing Zn have to be 9%&-#&.>(/+-B#4:%#>&*3%11#*?#3*)9%&1(*)#*?#,.+%).#()4*#*D-
splitted up into two different groups. Group I consists of (/(3# N;C;%.&(),# '()%&.+1# %)/1# =># ()# 3%&=11(4%# .)/B# 4:=1B#
:%'('*&>:(4%B# .# 1*&*1(+(3.4%"# o&*=># WW# (1# *?4%)# 3*)1(/- anglesite does not form a major constituent of sulcretes-
ered to be composed of zincian phyllosilicates like sau- (Pb). Anglesite is stable between pH 6 and pH 2 (ABDUL-
3*)(4%# *&# H()3(.)# 1.>*)(4%B# 4&(*34.:%/&.+# 1'%34(4%1B# .)/# SAMAD et al. 1982). Dependent upon the log aSO4B#.4#:(,:-
?&.(>*)4(4%B#.#'%';%&#*?#4:%#1%&>%)4()%#,&*=>"#W)#4:%#M+# er alkalinity anglesite turns into linarite (pH"%"bB#+*,aSO4
e%?#.&%.B#$=)(1(.B#.)#()C/%>4:#14=/-#*?#>:-++*1(+(3.4%1#&%- %" hn5A"#O4# .# >7# ;%48%%)# \# .)/# 5B# +%./:(++(4%B# .# '()%&.+#
vealed that the zincian smectite-group mineral was not a bridging the gap between carbocretes and sulcretes forms
pure zincian phyllosilicate but in fact a smectite-(illite)- instead of the afore-mentioned linarite. When the pH is
mixed layer with disseminated Zn-Fe spinel. Smectite +*8%&%/#/=&(),#3:%'(3.+#8%.4:%&(),B#0=#*D(/%1#.)/#0=#
group minerals are only stable at a rather high alkalin- 1=+2/%1# ;%3*'%# 4:%&'*/-).'(3.++-# =)14.;+%# .)/# '.+.-
ity where the amount of silica to generate smectite-group chite or azurite develop dependent on the CO2 partial pres-
>:-++*1(+(3.4%1# ()14%./# *?B# %","B# Z.*+()(4%# (1# ,=.&.)4%%/"# sure (Fig.#6!%B#?A"#T&*3:.)4(4%#8:*1%#14.;(+(4-#2%+/#(1#)*4#
Trioctahedral smectite group minerals come into exist- very much different from that of the Cu carbonates does
ence at 25 °C as the amount of bivalent cations such as not appear in Eh-pH diagrams until the sulfur concentra-
Mg2+ and Zn2+ prevails over Fe2+ (Fig. 13b). Smectite- tion is as high as 10nh6 M. (ZHANG 1994). A constant sup-
bearing silicacretes-(Zn) develop in the transition zone >+-#*?#1=+?=&#3.)#;%#.33*'>+(1:%/#()#4:%#).4=&.+#.Y=%*=1#
from humid to drier climatic zones (Fig. 10). In an almost 1*+=4(*)1# =)/%&# :->%&.&(/# 3+('.4(3# 3*)/(4(*)1"#O4# !5#c0B#
Fe-free environment with elevated contents of Mg and or brochantite is thermodynamically stable over posnjakite
Zn the trioctahedral smectites develop between pH 7 and 8:(3:# ?*&'%/# 2&14"#P&*%8*+?%(4%# (1# 3*)9%&4%/# ()4*# >*1-
8. Above this pH level the zincian serpentine analogues njakite and brochantite (DABINETT et al. 2008). Therefore
3*'%#()4*#;%(),"#$:%#1-14%'#:.1#;%%)#1('>+(2%/#.1B#%","B# sulcretes-(Cu) used to evolve under a high- sulphidation
the dissolved Na concentration has not been considered regime (TRIANTAFYLLIDIS & SKARPELIS 2006).
:%&%"# 0.+3=+.4%/# .34(9(4-C.34(9(4-# /(.,&.'1# .4# !5#c0B# =1- Sulcrete-(APS): E.)-#1=+3&%4%1C@ONLAB#/*'().4%/#;-#.+-
ing extrapolated log K values by MCPHAIL#%4#.+"#@!GGbAB# unite sulfate-enriched APS minerals have proved to be of
indicate that hemimorphite is stable at slightly acidic to hypogene origin (Table# 6A"# T-# 3*)4&.14B# 1=+3&%4%1C@ONLA#
.+Z.+()%#>7#9.+=%1#.4#Y=.&4H#1.4=&.4(*)#.)/#/(11*+9%/#H()3# dominated by phosphate-enriched APS are undoubtedly
concentrations of 10nhn5 M. of supergene origin. There are several papers shedding
some light on the physical-chemical regime during which
these minerals develop (PYSIAK & GLINKA#6_`6B#STOFFRE-
6.2.5 Physico-chemical regime of halcretes
GEN & ALPERS# 6_`FB# STOFFREGEN# 6__\B# DILL# !GG6B# DILL
Halcretes-(Cu-Ag): Atacamite and paratacamite are stable %4#.+"#6__6B#6__5;B#6__53B#6__F.B#!GGGB#MORDBERG et al.
()#.#9%&-#&%14&(34%/#14.;(+(4-#2%+/#@ROSE 1976). Atacamite !GG6B#RUDOLPH#%4#.+"#!GG\B#GABOREAU#%4#.+"#!GG5B#!GGFA"#
forms under conditions of exceedingly low concentra- Alunite- and jarosite-dominated sulcretes-(APS) pre-
tions of H2S.Y and HSt (MOSSMAN & HEFFERMAN 1978). cipitate under rather low pH" !"5 (Fig.#6\/A"# R.&*1(4%# *3-
W4#&%Y=(&%1#1.+()%#8.4%&#8(4:#.)#.;)*&'.++-#:(,:#3:+*&()%# cupies a position in the Eh-pH diagram pinpointing the
concentration to precipitate and dissolves rapidly so that most acidic and most oxidizing conditions in the Fe-S-
strong evaporation is mandatory for its preservation in the <#1-14%'"#o&./(),#()4*#4:%#>:*13&%4%1C@ONLAB#8:(3:#.&%#
geological record. Such conditions are only achieved un- 4&%.4%/#:%&%#*)+-#?*&#&%.1*)1#*?#>&%1%)4.4(*)B#%D>.)/1#4:%#
der tropical arid to semiarid climatic conditions or under 14.;(+(4-# 2%+/# 4*8.&/1# '*&%# .+Z.+()%# 3*)/(4(*)1"# P**/-
a peculiar hydrographic regime operative at the western houseite may come close to pH"#"7. Sulcretes-(APS) need
[.)Z1# *?# 4:%# 1*=4:%&)#O)/%1# @Fig.#6\3B# Table 1). Chlo- >.&%)4#&*3Z1#.;+%#4*#>&*9(/%#O+B#S%B#L#.)/#e"#$:%#1*=&3%#
&*.&,-&(4%B# j*/.&,-&(4%# .)/# '.&1:(4%# .&%# '()%&.+1# 4->(3.+# *?#1=+?=&#(1#1=>>+(%/#'.()+-#;-#9.&(*=1#'*/(23.4(*)1#*?#
of arid to semiarid climatic zones (BOYLE 1997). Chlo- S%C/(1=+2/%# 4:.4# /%3*'>*1%/# ()# 4:%# 3*=&1%# *?# 8%.4:%&-
roargyrite is stable in seawater and chloride-rich near- ing. Aluminium and alkali elements have been originated
?&*'# >:-++*1(+(3.4%1B# 1=3:# .1# (++(4%B# .)/# (&*)# '.-# :.9%# E%+.)4%&(4%B#3*>(.>(4%B#.)/#:.+*4&(3:(4%#.&%#:(,:+-#1*+-
been derived from oxicretes-(Fe) as illustrated by the fol- uble in water. Therefore this variegated group of sulfate
lowing reactions or may be traced back to the very begin- minerals can only survive under extremely arid condi-
)(),#*?#1=>%&,%)%#.+4%&.4(*)#*?#S%#/(1=+2/%1" tions and their presence may change on a day-by-day ba-
sis (JERZ & RIMSTIDT#!GG\B#PETERSON#%4#.+"#!GG5B#XU et al.
illite)>-&(4%#p#j.&*1(4%)kaolinite
2009). Ferrous sulfates occur in the oxidizing territory of
2 K0.5 Al2.5 Si3.5 O10(OH)2)3 FeS2)10 H2O")11.25 O2#p# .Y=%*=1#1-14%'1#;%+*8#>7#5B#8:(+%#?%&&(3#1=+?.4%1#3*'%#
KFe3(SO4)2(OH)6)2.5Al2Si2O5(OH)4)2 SiO2)4HSO4nh)4 up at a pH"!"2 and much higher redox potential (Fig. 13d).
H+
illite)>-&(4%#p#.+=)(4%)kaolinite 6.2.7 Physico-chemical regime of phoscretes
2 K0.5 Al2.5 Si3.5 O10(OH)2)FeS2)3 H2O")3.75 O2# p# Phoscretes-(Pb-Al):# O3(/(3# '%4%*&(3# [=(/1# >%&3*+.4(),#
KAl3(SO4)2(OH)6 )Al2Si2O5(OH)4)5 SiO2)0.5 Fe2O3 through rocks enriched in apatite are held accountable for
eC1'%34(4%#p#.+=)(4% much of the phosphate and part of the calcium released
to form either APS minerals (see previous section on sul-
3 KAl7Si11O30(OH)6)4 K+)24 H+)14 SO4!nh)66 H2<#p#F# cretes) or Cu- and Pb-bearing phosphates. The destruction
KAl3(SO4)2(OH)6)33 H4SiO4@.YA of alkaline feldspars in the course of weathering leads to
,*%4:(4%#p#j.&*1(4% 4:%#&%+%.1%#*?#.+='()(='B#.+Z.+()%#%.&4:#.)/#.+Z.+()%#%+%-
ments which are necessary for the build-up of more com-
6 FeO(OH))2K+)2H+)4 HSO4nh#p#!#eS%3(SO4)2(OH)6
plex phosphate minerals (NRIAGU & MOORE 1984). Pyro-
The afore-mentioned processes affected mainly the K+ morphite coexists with Pb carbonate at pH"%"6.5 (DILL et
budget during supergene alteration and led to a drop of the al. 2010b). Lead phosphate replaces smithsonite as pH
pH (Fig. 13d). Similar to cryptomelane present in some drops slightly below pH 6.5. The HPO4 !nh concentration
*D(3&%4%1C@E)AB#1=+3&%4%1C@ONLA#%)&(3:%/#()#.+=)(4%#:.9%# necessary to form this Pb phosphate is provided as apa-
an inherent clock which allows for dating of the super- tite decomposes on decreasing pH. The pH relation as-
,%)%# :-/&*+*,(3.+# .)/# >%/*+*,(3.+# >&*3%11%1B# =1(),# 4:%# sists in constraining the physical-chemical regime during
eCO&# *&# O&CO&C4%3:)(Y=%# @BRANNATH & SMYKATZ-KLOSS 8:(3:#1%3*)/.&-#.>.4(4%#()#.>(3&%4%1#3.)#;%#>&%1%&9%/B#.#
6__!B#VASCONCELOS#%4#.+"#6__aB#RUFFET#%4#.+"#6__bB#HAUPT- fact also applicable to brushite. The solubility products of
MANN & LIPPOLT#!GGGB#MOTE#%4#.+"#!GG6B#ARANCIBIA et al. >-&*'*&>:(4%1# .&%# %D4&%'%+-# +*8B# 6GnhF6"bB# 6GnhFb"`B# 6GnhF`"6
!GGbA"# T.1%/# *)# .,%# /.4(),# *?# .+=)(4%# @1=+3&%4%1C@ONLAA# and 10nhnà"a# ?*&# [=*&*CB# :-/&*D-+CB# ;&*'*CB# .)/# 3:+*&*#
.)/# 8./# @*D(3&%4%1C@E)AAB# )='%&*=1# .=4:*&1# 3+.('# 4:%# pyromorphites (CHEN et al. 1997). Apatite consumes the
presence of semiarid conditions during the interval from same amount of H+ as is liberated in the pyromorphite
29 to 9 Ma (latest Oligocene through Miocene) which >&%3(>(4.4(*)B#3*)1%Y=%)4+-B#4:%&%#1:*=+/#)*4#;%#.#&%'.&Z-
+%/#4*#1=>%&,%)%#*D(/.4(*)#>&*2+%1#@ALPERS & BRIMHALL able change in the pH of the solution (MAVROPOULOS et al.
6_``B#QUANG#%4#.+"#!GG5B#ARANCIBIA et al. 2006). Age dat- 2002). The chemical changes are more or less “pH con-
ing of alunite from Peruvian K alunite deposits led to the servative” shown in the reaction below (Table 5).
same age (DILL et al. 1997). Ca10 (PO4)6 (OH)2 (s))x Pb2+#p#N;10 (PO4)6 (OH)2 (s))x
Sulcrete-(Fe):#M?[*&%13%)4#1.+4#3&=141B#'.()+-#'%+.)4%&(4%B# Ca2+
:.+*4&(3:(4%B#3*>(.>(4%B#.)/#3+*41#*?#:.+(4%#/%9%+*>%/#=)/%&#
A further drop below approx. pH 4 will open up the
4:%#>&%1%)4C/.-#3+('.4%#.4#E.43:+%11B#X.'(;(.#@Table 1).
2%+/#8:%&%#4:%#.+='()*=1#N;#>:*1>:.4%1#*?#4:%#>+=';*,-
They are uncommon to geogene supergene processes but
ummite-group are stable (see also Cu-Al-P relation).
used to form by man-made activities in post-mining min- Phoscretes-(Cu-Al): Copper-bearing phoscretes are stable
eralization. The formation of halotrichite from the most *9%&#.#8(/%#>7#1>&%./#()#4:%#*D(/(H%/#>.&41#*?#.Y=%*=1#
3*''*)# S%# /(1=+2/%# >-&(4%# .1# %D>*1%/# 4*# .4'*1>:%&(3# 1-14%'1"# $:%(&# 14.;(+(4-# 2%+/# ,%41# &%/=3%/# *)# /%3&%.1-
3*)/(4(*)1#(1#1:*8)#;%+*8Q ing pH below 5 (Fig. 14a). Cornetite precipitated from
FeS2 )3.5 O2 )H2<#p#S%2+)2 SO4!nh)2H+ 1+(,:4+-# .3(/(3# 4*# )%=4&.+# '%4%*&(3# [=(/1# @CRANE et al.
2001) (Fig. 11b). Pseudomalachite formed from meteor-
Fe2+)0.25 O2 )H+#p#G"5#72O)Fe3+
ic solutions at a lower pH than cornetite and libethenite
Fe2+@.YA#)4 SO4!nh@.YA#)2Al3+@.YA#)22 H2<#p#S%O+2(SO4)4 22 developed at the lowest level in the pH range at a given
H2O(s) log.7!N<anh (Fig.#6a;B# uCOA"# $:%# 1(/%C;-C1(/%# *?# .++# 0=#
Fig. 14.#M:C>7#/(.,&.'1#*?#>:*13&%4%1"#L:./%/#.&%.#/%)*4%1#14.;(+(4-#2%+/1#*?#*&%3&%4%1"#a) Eh-pH diagram to show the phoscretes-(Cu)

at 25 °C using the dissolved species as logaCu"#"hn\B#+*,aHPO42"#"hn\i#b) H2PO4!nh-pH diagram to show the variation of Cu phosphates in
>:*13&%4%1C@0=A#.4#!5#c0#@'*/(2%/#?&*'#CRANE#%4#.+"#!GG6A"#$:%#4&.)1%34#OCOv#/%)*4%1#4:%#>:*1>:.4%#.34(9(4-#1:*8)#()#S(,"#66.i#c) Eh-pH
diagram to show the phoscretes-(Cu) at 25 °C using the dissolved species as logaCu"#"hn\B#+*,aHPO42"#"hnaB#+*,aAl"#"hnai#d) Eh-pH diagram to
show the phoscretes-(Fe) at 25 °C using the dissolved species as logaFe"#"hn\B#+*,aHPO42"#"hn\"
phosphates in phoscretes-(Cu) of the Congolese deposits (1) Al(OH)3)H3PO4)CuSO4#p#4=&Y=*(1%)H2SO4)H2O

documents that phoscretes developed over a very wide
(2) alunite)H3PO4)CuSO4)e#p#4=&Y=*(1%)K2SO4)H+
>7# &.),%B# 8(4:# '()%&.+(H(),# [=(/1# ,%44(),# '*&%# .3(/(3#
through time (cornetite" %%" libethenite) in the course of T-#.).+*,-#8(4:#&%.34(*)#@6AB#4=&Y=*(1%#:.1#;%%)#/%-
4:%(&#?*&'.4(*)"#$:%#%9*+=4(*)#*?#4=&Y=*(1%#.)/#?.=14(4%B# rived from crandallite as the pH decreased (DILL et al.
>.&4#*?#4:%#0=CO+CV)#>:*1>:.4%#1"1"1"B#14.&41#?&*'#/(??%&%)4# 6__6A"# T%+*8# >7# aB# N<4-anion complexes are available
>.&%)4# '.4%&(.+B# %(4:%&# ?&*'# 3=>&(?%&*=1# ;+.3Z# 1:.+%1# *&# to react with Cu2+ at moderately oxidizing conditions
:(,:C1=+>:(/.4(*)#%)9(&*)'%)41B#/%9%+*>(),#()#'.,'.4(3# (Fig.#6a3A"#$=&Y=*(1%# *33=&1# 8(4:()# 4:%# 9*+3.)(3# *&# 1=;-
*&#1%/('%)4.&-#'%4.++(?%&*=1#1-14%'1Q volcanic rock as long as a high acidity persists.
Phoscretes-(Fe-Al): W&*)C@WWAC>:*1>:.4%B# &%>&%1%)4%/# ;-# to more acidic conditions dependent upon the HPO4!nh
9(9(.)(4%B# ?*&'%/# =)/%&# '*/%&.4%+-# *D(/(H(),# 4*# &%/=3- activity (NRIAGU 1976). Rockbridgeite and whitmoreite
ing conditions at a pH"%"5"#<)#()3&%.1(),#M:B#;(9.+%)4#S%# .&%# &%>&%1%)4.4(9%# *?# .# ,&*=># *?# S%# >:*1>:.4%1B# .33*'-
4=&)1# ()4*# 4&(9.+%)4# S%"#O1# .# 3*)1%Y=%)3%# *?# 4:.4# *D(/.- '*/.4(),# S%# .)/# 1*'%# E)# ()4*# 4:%(&# +.44(3%B# .)/# ;%(),#
4(*)B#14&%),(4%#*&#(41#>*+-'*&>:#>:*1>:*1(/%&(4%#%9*+9%/# present at the interface Fe(II)-Fe(III) (Table 1). They oc-
at pH"!"5. The couple ferric-ferrous iron phosphate known 3=&# ()# 3*)3&%4(*)1# 4*,%4:%&# 8(4:# )*)4&*)(4%B# 4*/*&*Z(4%B#
to be present at the base of phoscretes is a redox marker and barite. Their paragenesis records the evolving pore-
for poorly aerated conditions in paleosols (swamps) (Ta- water chemistry as these concretions were uplifted into
ble 1) (Fig. 11d). Variscite and wavellite may supposedly the fresh-ground-water zone along with an increase in Eh
?*&'#=)/%&#1('(+.&#3*)/(4(*)1#.1#14&%),(4%B#=)/%&#)%=4&.+# and pH (ROGERS & BROWN#6_F_B#MEDRANO & PIPER#6__FB#
Fig. 15.#M:C>7#/(.,&.'1#*?#.&1%)*3&%4%1#.)/#9.)./*3&%4%1"#L:./%/#.&%.#/%)*4%1#14.;(+(4-#2%+/1#*?#*&%3&%4%1"#a) Eh-pH diagram to show the

arsenocretes-(Pb-Cu) at 25 °C using the dissolved species as logaCl"#"hn\B#+*,aCu"#"hna#()#4:%#>&%1%)3%#*?#,(;;1(4%#@'*/(2%/#?&*'#LEVERETT
%4#.+"#!GG5Ai#b) Eh-pH diagram to show the arsenocrete-(Fe) at 25 °C using the dissolved species as logaFe"#"hn\B#+*,aAsO4"#"hnai#c) Eh-pH
diagram to show the vanadocretes-(Pb-Cu-Zn) at 25 °C using the dissolved species as logaV"#"hn\i#d) Eh-pH diagram to show the orecretes-
(Se) at 25 °C using the dissolved species as logaSe"#"hnb"
CHUKANOV 2005). The afore-mentioned phosphate marks 6.2.9 Physico-chemical regime of orecretes-
the passage from the hypogene to the supergene alteration (Se-Mo-oxalate)
()#.#1=+?=&C/%23(%)4B#)%.&C1=&?.3%#H*)%#@DILL et al. 2009).
Phoscretes-(REEAQ# W)# 4:%# >:*13&%4%1# =)/%&# 14=/-B three The compartment “miscellaneous” refers to orecretes that
:-/&.4%/# >:*1>:.4%1# 3.&&-(),# .1# '.j*&# 3*'>*)%)41# 0%B# are rather uncommon in comparison with the orecretes
X/B#.)/#@*&A#k.#8%&%#*;1%&9%/"#J:.;/*>:.)%#.)/#[*&%)- '%)4(*)%/#>&%9(*=1+-"#$:%-#3*)4.()#L%B#E*B#.)/#*D.+.4%#
3(4%C/*'().4%/#ONL#1"1"1"B#.&%#/(.,)*14(3#*?#48*#/(14()34# (Table 1). The mean values of selenium and molybdenum
14.;(+(4-# 2%+/1B# ;*4:# *?# 8:(3:# .&%# ,*9%&)%/# ;-# 3:.),%1# in the Earth’s crust are low relative to those elements
of pH. Field evidence and laboratory trials revealed that playing a leading role in providing anions to build up
rhabdophane-(Ce-Nd-La) comes into being at rather low 9.&(*=1#*&%3&%4%1"#$:=1#L%C#.)/#E*C;%.&(),#*&%3&%4%1B#4:%#
temperatures relative to monazite (AKERS et al. 1993). It +.44%&# 3*)4.()(),# 8=+?%)(4%B# 3*'%# ()4*# ;%(),# *)+-# 8:%)#
(1# 14.;+%# =)/%&# )%=4&.+# .)/# .+Z.+()%# 3*)/(4(*)1B# 8:%&%.1# the parent rocks are strongly enriched in Se or Mo – for
[*&%)3(4%# ?*&'%/# ()# >+.3%# *?# &:.;/*>:.)%# .1# 4:%# '%4%- deposits see DILL (2009c). According to the calculations
*&(3#[=(/1#4=&)#'*&%#.3(/(3B#&%1%';+(),#()#(41#?*&'.4(*)# of BROOKINS# @6_`ÀB# L%<3!nh and SeO4!nh complexes are
*4:%&#ONL#'()%&.+1#;%.&(),B#%","B#T.2+B#0.2+ or Sr2+ (DILL stable over a wide pH range except below pH 2 and hence
2001). The third REE-bearing mineral of relevance in can react with Cu to form the minerals mentioned in Ta-
>:*13&%4%1#(1#3:=&3:(4%C@wAB#8:(3:#?*&'%/#+.4%#=)/%&#*D(- ble 1. Molybdenum behaves in a different way with mo-
/(H(),#3*)/(4(*)1#()#E)CS%#+('*)(4%1B#%","B#.4#O=%&;.3:B# lybdates only being stable at a pH"%"10. Oxalate-humate
Germany. Churchite has been synthesized by HUKUO & ;%.&(),# %)3&=14.4(*)1# :.9%# *)+-# &%3%)4+-# ;%%)# (/%)4(2%/#
HIKICHI# @6_F_A# 8(4:()# .# >7# &.),%# *?# G"5nhn\# .)/# .4# 4%'- .4#L%&(?*1B#o&%%3%#@DILL et al. 2010a). Se- and Mo-bearing
peratures"$"!G#c0"#P(4:#4:(1#()#'()/B#3:=&3:(4%C@wA#(1#3.14# orecretes are rare constituents of orecretes sensu stricto
.1#4:%#7JMM#.).+*,=%#4*# [*&%)3(4%B#8:(3:# 4.Z%1#=>#4:%# of geogene nature. Oxalate-bearing encrustations are very
LREE instead in an acidic weathering regime. Phosphates young encrustations that developed in typical post-mining
enriched in LREE use to be formed at shallow depth in the mineralization and may be considered as metastable rela-
8%.4:%&(),#>&*2+%B#7JMMC1%)1(4(9%#.).+*,=%1#>&%3(>(4.4- tive to the other orecretes or protocretes of carbocretes.
ed below (LOTTERMOSER 1990). There are other rather uncommon orecretes containing
:%.9-#'%4.+1#1=3:#.1#4:%#3:&*'.4%1B#8:(3:#:.9%#)*4#;%%)#
discussed in this paper on morphoclimatic issues. Several
6.2.8 Physico-chemical regime of arseno- and
hexavalent Cr minerals exist which may guide the explo-
vanadocretes
&.4(*)#,%*+*,(14#4*#0&C%)&(3:%/#&*3Z1Q#(&.)(4%B#9.=Y=%+()-
Arsenocretes-(Fe-Pb-Cu-Zn):# O&1%).4%1B# 8:(3:# .&%# ?.&# (4%B#>:*%)(3*3:&*(4%B#1.)4.).(4%#.)/#:%'(:%/&(4%"#$:%#'*14#
+%11# 3*''*)# ()# ).4=&%# 4:.)# >:*1>:.4%1B# .&%# 3.>.;+%# *?# &%)*8)#*?#4:(1#,&*=>#(1#3&*3*(4%#?&*'#K=)/.1B#O=14&.+(.#
substituting at least for part of the (PO4)\nh anion complex- .)/#?&*'#,*+/C;%.&(),#Y=.&4H#9%()1#()#4:%#1*=4:%&)#N.&.#
%1B#1*#4:.4#()#1*'%#3.1%1#>:*13&%4%1#.)/#.&1%)*3&%4%1#'.-# L4.4%B#T&.H(+#@ANGELICA et al. 1997). They are a good tool
*33=&#4*,%4:%&B#1=3:#.1#()#1*'%#Z.*+()#/%>*1(41#()#0%)4&.+# to locate Cr-bearing ore deposits but have no relevance
Europe (phoscretes" %%%" arsenocretes). Arsenocretes are for geomorphological or climatological issues.
composed of a wide range of base metal and iron arse- ^&.)(?%&*=1# *&%3&%4%1# Y=.+(?-# ?*&# .)# ()4%,&.4(*)# ()4*#
).4%1B# ;%(),# 9%&-# '=3:# /(??%&%)4# ()# 4:%(&# 14.;(+(4-# 2%+/1# the current study. They can behave as morphoclimatic
(Fig. 15). Mimetite and scorodite are stable over the entire marker as well as an ore guide (DILL et al. 2010d). Their
pH range at a rather high Eh value (Fig.#65.B#;A"#$:%(&#14.- 1>%3(.+# &./(*C>:-1(3.+# .)/# 3:%'(3.+# ;%:.9(*&B# :*8%9%&B#
;(+(4-#2%+/1#.&%#,*9%&)%/#'.()+-#;-#4:%#>&%1%)3%#*?#3:+*- )%%/1#.)#()C/%>4:#4&%.4'%)4B#4:.4#8*=+/#,*#?.&#;%-*)/#4:%#
rine and the activities of metals involved in the alteration scope of this presentation and therefore the reader is re-
>&*3%11"#T-#.).+*,-#8(4:#>:*1>:.4%C#.)/#1=+?.4%C;%.&(),# ferred to the study of DILL et al. (2010d).
ONL#'()%&.+1B#8:(3:#&%[%34#4:%#f.3(/(3#%)/#'%';%&1g#*?#
>:*13&%4%1#.)/#1=+3&%4%1B#&%1>%34(9%+-B#>:(+(>1;*&)(4%#.)/#
kemmlitzite are held to be the marker minerals in arseno- 6.3 Landforms and the formation of orecretes
3&%4%1#/(.,)*14(3#?*&#14&*),+-#.3(/(3#>*&%#[=(/1"#0*)1(/%&-
6.3.1 Geomorphology
ing the lack of philipsbornite in nature and the presence
of kemmlitzite in a few kaolin deposits in Germany very Shaping the landforms is a complex process involving
+*8#>7#9.+=%1B#.1#*;1%&9%/B#%","B#()#'()%#8.14%#/='>1B# >%/*+*,-B# ,%*'*&>:*+*,-# .)/# :-/&*+*,-# *)# /(??%&%)4#
supposedly do not play a decisive role in creating these scales (Fig. 9) (DALRYMPLE# %4# .+"# 6_b`B# GOUDIE & PYE
.&1%)(3C;%.&(),#'%4%*&(3#[=(/1#@HAK et al. 1969). 6_`\B#COUSSOT & MEUNIER#6__bB#COLLINSON#6__bB#GOUDIE
& VILES#6___B#BOUCHARD & JOLICOEUR#!GGGB#CHEN et al. nied (Fig. 9). Yet it is not the chemical composition of the
!GGGB#MEADOWS#!GG6B#THOMAS#!GG6B#TWIDALE 2002). parent material but its geodynamic position that left its
$:%# Y=%14(*)# 8:%4:%&# 4:%# >&%1%)4# +.)/?*&'1# *)# 4:%# imprint on the evolution of the various orecretes (Figs.#!3B#
globe are in balance with the present climate or whether /B#_A"#P:%)#(4#3*'%1#4*#4:%#/%9%+*>'%)4#*?#*&%3&%4%1B#4:%#
they represent relics is widely discussed in geomorphol- ancient high-altitude core zones within modern fold belts
ogy (OLEJNIK & KEDZIORA# 6__6B# RINALDO# %4# .+"# 6__aB# behave like the deeply eroded cratons in the hinterland of
HAVEL#!GGGB#CENTENO et al. 2010). Where mountain for- modern mountain belts (Fig. 2c). In Fig.#6G3B an x-y plot
mation is still going on and spreading of the crustal plates =1(),#4%'>%&.4=&%#.)/#>&%3(>(4.4(*)#.1#.D%1B#4:%#>&%9.(+-
3.=1%1#/*8)8&.>(),#*?#>.&4#*?#4:%#3&=14B#4:%#?*&'.4(*)#*?# ing processes shaping the landscape are shown in relation
4:%#+.)/13.>%#(1#3%&4.()+-#)*4#*)+-#/&(9%)#;-#4:%#3+('.4%B# to the relative abundance of orecretes which are illustrat-
but more strongly by tectonic processes. This is also true ed in pie-chart diagrams. The selection of land-forming
for the orecretes in the region (Fig. 2c). This fact places processes is based on comprehensive geomorphological
even more weight behind the stability diagrams calculated and geological studies (TRICART & CAILLEUX#6_F!B#BÜDEL
for the various orecretes based on chemical compounds 6_FFB#SUMMERFIELD#6__6B#THOMAS#6__aB#!GG6B#GALLOWAY
(Figs.#66B#6!B#6\B#6aB#65A"#O#'*/%+#4*#1:*8#4:%#/(14&(;=4(*)# & HOBDAY# 6__bB# BREMER# !GG!B# TWIDALE# !GG!B# GLENNIE
of orecretes in response to planation and incision has to !GG5B# TAYLOR & EGGLETON 2009). Frost and wind ac-
take into consideration this fact. On a regional geomor- 4(*)1B# 1*+([=34(*)# .)/# '.11# '*9%'%)41# *)# 14%%>+-# /(>-
>:*+*,(3.+#13.+%B#*&%3&%4%1#'.-#;%#3*&&%+.4%/#8(4:#.&%.1# ping slopes and much of water concentrated in snow and
of different degrees of dissection from the mountainous ice neither give a variegated nor an abundant spectrum of
areas of modern fold belts through vast lowlands (Fig. 2c). orecretes in the (peri)-glacial zone (Fig. 10c). The humid-
'(/C+.4(4=/%#H*)%#4.Z%1#.#4&.)1(4(*).+#>*1(4(*)B#8(/%)(),#
Highly dissected areas differ from less intensively dissect-
the orecrete spectrum known from the peri-glacial zone
%/#.&%.1#;-#Y=.+(4-#.)/#Y=.)4(4-#*?#4:%#*&%3&%4%1#@Fig. 2c).
but also dissecting orecretes formed under more elevat-
Halcretes and vanadocretes which need strong evapora-
ed temperatures and a higher rate of precipitation which
tion are normally absent from the mountainous areas and
may have to be named relic forms. Glacial erosion and
widespread in the large inland basins (playa). Furthermore
scouring during the glacial periods have removed such
4:%-# .+1*# /(??%&# ?&*'# %.3:# *4:%&# ;-# Y=.)4(4-"# N:*13&%4%1#
relic forms but in some cases ice sheets also may have
found favorable conditions to develop in thick regolith >&*4%34%/#4:%'#.)/#4:=1#3*)4&(;=4%/#4*#4:%(&#>&%1%&9.4(*)B#
(Fig.#!3B#!/B#6G.A"#L('(+.&#4*#*4:%&#3:%'(3.+#&%1(/=%1#=>+(?4# %","B#()#W&%+.)/#@BALASSONE et al. 2008). Omitting the polar
and erosion in highly dissected landscapes are detrimen- /%1%&41B#;.1%/#*)#4:%#&.()?.++B#4:&%%#/(??%&%)4#3.4%,*&(%1#*?#
4.+#?*&#4:%#3:%'(3.+#&%1(/=%1#4*#/%9%+*>#.#'.4=&%#>&*2+%"# /%1%&4#'.-#;%#/%2)%/"#W4#(1#4:%#1%'(C.&(/#/%1%&4B#,&./(),#
O)#%D3+=1(*)#?&*'#4:.4#&=+%#.&%#4:%#:(,:C.+4(4=/%#>+.()1B# into the dry continental steppe in the continental interi-
1=3:#.1#4:%#fO+4(>+.)*g#()#4:%#T*+(9(.)B#0:(+%.)#.)/#O&- *&B# 8(4:# &.()?.++# ;%48%%)# !GG# .)/# 5GG#''B# 4:%# .&(/# /%-
,%)4()%#O)/%1#.1#8%++#.1#()#4:%#0%)4&.+#O1(.)#W)4%&(*&B#%","# sert with 25 to 200 mm rainfall and the hyper-arid desert
Afghanistan (Fig.#!3A"#N%)%>+.()%/#.&%.1#.)/#9.14#/%1%&41B# with more than 12 consecutive rain-free months (GLENNIE
.+4:*=,:#/(??%&%)4#8(4:#&%,.&/#4*#4:%#4->%#*?#*&%3&%4%1B#*?- 2005). The hyper-arid zone may be excluded from the fa-
?%&#4:%#'*14#?.9*&.;+%#3*)/(4(*)1#.1#4:%-#>&*9(/%#4:%#Y=(- vorable sites to form orecretes due to the strong aeolian
%13%)3%#4*#;=(+/#=>#.#'.4=&%#8%.4:%&(),#>&*2+%" .33='=+.4(*)B# %","B# ()# 4:%# J=;xO+Ce:.+(B# L.=/(# O&.;(.#
Uplift and tectonics which contribute to the shaping and Oman and for the lack of water to give rise to any
of the landscape are not per se# /%4%&(*&.4(),# 4:%# Y=.+(4-# of the processes described in Figs.#66B#6!B#6\B#6a#.)/#65"#
of orecretes. It depends upon the relation in time between Semi-arid and arid climatic zones provide a good mix of
encrustation and the kinematic processes whether the :(,:#4%'>%&.4=&%U#%9.>*&.4(*)#.)/#,%*'*&>:*+*,(3.+#Y=(-
thickness of orecretes may diminish or increase. If the %13%)3%#4*#3&%.4%#.#'.4=&%#8%.4:%&(),#>&*2+%#@Fig. 10c).
9%&4(3.+#=>+(?4#Z%%>1#>.3%#8(4:#*&%3&%4%#?*&'.4(*)#=)/%&B# Peneplanation provides favorable sites to form orecretes
%","B#4&*>(3.+#8%4C/&-#*&#1%'(C.&(/#3+('.4(3#3*)/(4(*)1B#4:%# ()# 4%&'1# *?# Y=.)4(4-# .)/# Y=.+(4-"# N%/('%)4.4(*)# 8(4:# .+-
thickness of orecretes may be increased resulting in the luvial fan deposition heralds the destruction of these loci
?*&'.4(*)# *?# .# 14.(&3.1%C+(Z%# 1%&(%1# *?# >+.()1"# $%34*)(31B# favorable for the concentration of the orecretes.
erosion and formation of chemical residues is in a state
*?# %Y=(+(;&(='"# o(9%)# 4:%# 1.'%# &.4%# *?# =>+(?4# =)/%&# +%11# 6.3.2 Hydrology
?.9*&.;+%#3+('.4(3#3*)/(4(*)1B#%","#=)/%&#:='(/#'(/C+.4(-
tude conditions causes the thickness of orecretes to shrink Irrespective of the type and sinuosity of the drainage sys-
or causes their complete erosion. 4%'B# 4:%# &%+.4(9%# >*1(4(*)# *?# 4:%# *&%3&%4%# 4*# 4:%# 4:.+8%,#
P(4:#4:(1#()#'()/B#.)#()/(&%34#()[=%)3%#*?#4:%#>.&%)4# has a major impact on the proximity of orecrete to the
material on the formation of the orecretes cannot be de- >&('.&-#*&%U#1*=&3%#&*3Z#@Fig. 1b). Oxicretes are typical
of morphoclimatic zones characterized by heavy rain- generation of orecretes may develop at different depth.
?.++1#.33*'>.)(%/#;-#.#14&*),#[=1:(),#*=4#*?#.)(*)#3*'- Oxidizing and reducing parts are split apart from each
plexes to create orecretes others than oxicretes (Table#6B# other. On topographic highs and basement uplifts mod-
3). The hydraulic regime responsible for a perennial or %&)#.)/#>.+%*.Y=(?%&1#*9%&+.>#8(4:#%.3:#*4:%&#.)/#'*/%&)#
.4#+%.14#>%&(*/(3.++-#.34(9%#[=9(.+#&%,('%#(1#3&=3(.+#4*#4:%# orecretes are “telescoped” into paleo-orecretes.
formation of the landscape prone to oxicretes (Fig. 2c).
Oxicretes may come into existence in humid mid-latitude 6.3.3 Pedology
climatic zones and likewise in tropical humid zones with
pervasive chemical weathering (Fig.#!/A"#T-#3*)4&.14B#/&-# Pedology and hydrology are closely related with each
morphoclimatic zones are less favorable loci for oxicretes *4:%&"# W)# 4:%# 3=&&%)4# 14=/-B# 1*(+C?*&'(),# >&*3%11%1# 8(++#
to develop. ;%# 4&%.4%/# ()# 4:%# 8.-# /*)%# ;-# >%/*+*,(141B# .1# %D%'>+(-
Considering the pH-range during which carbocretes 2%/#;-#4:%#fo+*;.+#.)/#).4(*).+#1*(+1#.)/#4%&&.()#/(,(4.+#
.)/#*D(3&%4%1#%9*+9%B#(4#(1#)*4#1=&>&(1(),#4*#1%%#4:%#/(14&(- /.4.;.1%1g#@SO<#6__5B#STAHR#%4#.+"#!GGÀ"#N%/*+*,-#:.1B#
bution curve of carbocretes running almost parallel to that :*8%9%&B#;%%)#3*)2)%/#4*#4:*1%#>%/*+*,(3.+#?%.4=&%1#1=3:#
of the oxicretes (Table# 5B# Fig. 10a). Sources of ordinary .1#*&,.)(3#3.&;*)#3*)4%)4B#:-/&.=+(3#>&*>%&4(%1#.)/#1*(+C
chemical residues only containing Ca as the main con- parent material which are relevant when it comes to a cor-
14(4=%)4B#4:%(&#'%3:.)(1'1#*?#>&%3(>(4.4(*)#.)/#4:%#%)9(- relation of soil formation and geomorphology in view of
ronmental conditions were discussed by a great variety the orecretes under study (SCHAETZL & ANDERSON 2005).
of authors among others by WRIGHT & TUCKER (1991). Fig. 16a displays the organic carbon content in soil evolv-
The vadose carbocretes are supposed to have formed by ing from different bedrocks of different buffer capacity
processes such as evaporation at the capillary fringe as as a function of the climate given by the Koeppen-Geiger
.#4*>14&.4='B#8:(+%#4:%#>:&%.4(3#h#,&*=)/8.4%&C&%+.4%/## h# climates (BATJES# !GGÀ"# $:%# 3*/(),# TP:# (1# &%>&%1%)4.-
3.&;*3&%4%1#/%9%+*>%/#()#[=9(.+#/&.().,%#1-14%'1B#()#*4:- 4(9%#*?#4:%#:*4#.&(/#3+('.4%#*&#/%1%&4#8(4:#.+'*14#)*#Y=.+(-
%&#8*&/1B#8:%)#[=9(.+#.34(9(4-#:.1#*33=&&%/#?*++*8(),#.# 4.4(9%+-#1(,)(23.)4#()[=%)3%#*)#4:%#1*(+#?*&'.4(*)"#0*/%#
period of pre-existing duricrust formation and the vadose O?#'(&&*&1#4:%#%Y=.4*&(.+B#?=++-#:='(/#3+('.4%#8:%&%B#)*4#
carbocretes got dissected. It is the reverse case illustrated only the total organic carbon shows elevated contents but
in Fig.#6;B# 8:%&%# 4:%# *+/%&# /=&(3&=14# ?*&'%/# =)/%&)%.4:# siliceous and basic rocks conspicuously split apart. The
4:%#'*&%#&%3%)4#*)%"#W)#:='(/#H*)%1#8(4:#14&*),#[=9(.+# >%/*+*,(3.+#H*)%#'%)4(*)%/#2&14#(1#.;=)/.)4#()#:.+3&%4%1B#
.34(9(4-#4:(1#13%).&(*#*33=&&%/"#K*8)#3=44(),#*?#4:%#[=- 9.)./*3&%4%1#.)/#1=+3&%4%1B#8:(+%#4:%#1%3*)/#(1#%)&(3:%/#
vial drainage was associated with a lowering of the water in carbocretes and oxicretes.
table and sparked a stacked pattern of carbocretes. Moun- W)#>%/*+*,(3.+#4%&'1B#4:%#*D(3&%4%1#=)/%&#14=/-#8%&%#
tainous and periglacial regions are favorable locations to 3+.11(2%/#.1#14.,)(3#.)/#:%+/#4*#;%#&%>&%1%)4.4(9%#*?#:--
?*&'# 3.&;*3&%4%1B# 1()3%# 4:%# .4'*1>:%&(3# 3.&;*)# >&%1%)4# /&(3#*&#,+%-#1*(+1#4:.4#?*&'%/#=)/%&#3*)/(4(*)1#*?#[**/-
all across the globe is added up with an increased pres- (),B#*&#>*)/(),#+*),#%)*=,:#4*#/%9%+*>#.).%&*;(3#3*)/(-
ervation potential of these morphoclimatic zones for or- tions in the upper part (greenish tint). This rock color is
,.)(3#+(44%&B#/=%#4*#4:%#&%4.&/%/#/%3*'>*1(4(*)#*?#*&,.)(3# related to the massive part and must not be confounded
matter in their soils. Carbocretes can develop in a wide for the green color of Cu carbonates or sulfates. They
&.),%#*?#'*&>:*3+('.4(3#H*)%1"#$:%-#:.9%#;%%)#&%3*&/%/B# ?*&'# ()# 8%4+.)/1# @18.'>1B# '.&1:%1B# ;*,1AB# 8:*1%# 1*(+#
%","B#?&*'#3.+3&%4%1#.)/#3.1%C:.&/%)%/#3*),+*'%&.4%1#()# types are saturated with moisture either permanently or
4:%#3*)4()%)4.+#L(8.+(Z#o&*=>#()#)*&4:%&)#W)/(.B#.)#.&%.# 1%.1*).++-"# $:%# /%>*1(4(*).+# %)9(&*)'%)41# *?# *D(3&%4%1B#
which saw a tropical climate during this period of time usually are placed within the phreatic zone with buff grey
like in the present-day Kalahari Desert (KHADKIKAR et al. colors. Their color turns into brownish or even reddish
!GGGB#NASH & MCLAREN#!GG\B#MCQUEEN#!GGbB#TANDON tints when being exposed to an increased oxygen partial
& NARAYAN 2006). pressure or shifted into the vadose zone which is accom-
It is the oxicretes and carbocretes that are related to >.)(%/#;-#.)#()3&%.1%#()#4:%#9.+%)3%#14.4%#*?#0=#@W#p#WWAB#
the active channel systems of the drainage systems. Hal- S%#@WW#p#WWWAB#E)#@WW#p#WdA"#BRANNATH & SMYKATZ-KLOSS
cretes and vanadocretes take up the opposite end of the (1992) tried to translate these changes in the valence state
.++=9(.+C[=9(.+# /&.().,%# 1-14%'# ()# 4:.4# 4:%-# *33=>-# 4:%# into the degree of humidity.
topstratum of the abandoned parts (Fig.#6.B#;A"#W)#'*/%&)# Silicacretes have a rather ambivalent position with
.)/# ?*11(+# :-/&*+*,(3.+# 1-14%'1# @>.+%*.Y=(?%&1A# *D(/(H- respect to this zonation. The pH ranges typical of metal-
ing and reducing zones of orecretes take different levels liferous silicacretes only partially overlap with those of
(Fig.#6;A"#W)#9.++%-1#.)/#;.1()1#2++%/#8(4:#1%/('%)41#48*# 3.&;*3&%4%1#.)/#*D(3&%4%1B#1=,,%14(),#4:.4#1(+(3.3&%4%1#,*#
a different way as to the depositional environment and minimum. This agrees well with the occurrence of mod-
may come later in the succession of supergene alteration ern terrestrial phoscretes at the southern tip of the Indian
(Table 5) – this does not apply for dioptase which is a subcontinent (DAHANAYAKE & SUBASINGHE#6_`_A"#T*4:#%+-
relic form in the sampling sites under study. Ordinary %'%)41# N# .)/# 0# >+.-# .)# %11%)4(.+# &*+%# ()# 4:%# ;(*1>:%&%U
;+*3Z-# 1(+(3.3&%4%B# 4&.)1(4(*).+# ?&*'# 1(+3&=14# 4*# ?%&&(3&=14# >%/*1>:%&%B#Z)*8)#.1#4:%#>:*1>:.4%C#.)/#3.&;*)#3-3+%1B#
.&%# &%3*&/%/# ?&*'# P(13*)1()B# ^LOB# 4*# :.9%# ?*&'%/# .1# &%1>%34(9%+-"#V*).+#*&%3&%4%#?*&'.4(*)#&%[%341#4:%#.9.(+-
late as the mid-Miocene and need to be described as relic ability of both elements in the pedosphere under different
forms (DURY & KNOX 1971). Field occurrence of metal- climatic conditions with Al-bearing phoscretes predomi-
+(?%&*=1# 1(+(3.3&%4%1# 9.&(%1# 1(,)(23.)4+-"#$:%-# .&%# .;1%)4# nating in the tropical wet-dry zones (SCHULZE et al. 2001).
in the cold humid morphoclimatic zones and experience d.)./*3&%4%1#.)/#.&1%)*3&%4%1#/*#)*4#1(,)(23.)4+-#/(?-
a relative increase under warm dry climatic conditions. In ?%&#?&*'#%.3:#*4:%&#()#4%&'1#*?#4:%#>7#*?#'()%&.+(H(),#[=-
/&-#3*)4()%)4.+#&%,(*)1B#4:%#3:%'(3.+#8%.4:%&(),#(1#'*/- ids (Fig.#6b;B#3B#Table 5). Their role as a climatic marker
%&.4%# 4*# +*8B# [=9(.+# .34(9(4-# :(,:# /=&(),# 4:%# 8%4# 1%.1*)# (1B#:*8%9%&B#1(,)(23.)4+-#/(??%&%)4"#O&1%)*3&%4%1#.&%#('-
and strong winds. This may also be applied to the tropical pacted more by certain types of parent materials rich in
semiarid and wet-dry morphoclimatic zones (Fig.#6G.B#;A"# O1B# 8:%&%.1# 9.)./*3&%4%1# 4.Z%# .)# ()4%&'%/(.4%# >*1(4(*)#
Ore-bearing silicacretes favorably develop under “inter- ;%48%%)#1=+3&%4%1#.)/#:.+3&%4%1B#4*#>+.-#.#+%./(),#&*+%#()#
mediate” morphoclimatic conditions with a balanced ratio 4:%#1%Y=%)3%#*?#.&(/(4-#4:.4#'.-#;%#>=4#()#*&/%&#*?#()3&%.1-
between precipitation and evaporation-see also the wide (),#.&(/(4-#.1#?*++*81Q#1(+(3.3&%4%"+"sulcrete"!"vanadocrete"
range of pH values (Table 5). Silicacretes are scarcely !"halcrete (Fig.#6G.B#;A"#$:%-#?*&'#%D3+=1(9%+-#=)/%&#.&(/#
formed under extreme climatic conditions as they are typ- conditions when the rate of chemical weathering is low.
(3.+#*?#4:%#>*+.&#*&#%Y=.4*&(.+#&%,(*)1#@Fig. 10). Precipi- W)#>%/*+*,(3.+#4%&'1B#48*#1%>.&.4%#,&*=>1#:.9%#4*#;%#
tation of silicacretes is mainly driven by changes in the distinguished from each other. Group one is directly cor-
[=(/#3*'>*1(4(*)#.)/#3*)1%Y=%)4+-#/*%1#)*4#&%)/%&#4:%1%# related with the total organic carbon content and marked
orecretes a good marker for climatic changes. ;-#*D(3&%4%1B#3.&;*3&%4%1#.)/#1*'%#>:*13&%4%1#@Figs.#6GB#
Fig. 17b shows an opposite trend to that shown in 17a). The second group of soils with little or almost
Fig.#6F.#&%[%34(),#4:%#9.&(.4(*)#*?#1*/(='#8:(3:#(1#3*)- )*# *&,.)(3# 3.&;*)# /%9%+*>%/# .)# (''.4=&%# 1*(+# >&*2+%#
4.()%/#()#:.+(4%#*?#*D(1*+1B#&(3:#()#4:(1#1.+4#'()%&.+#;=4#+*8# (Fig. 17b). This group of soils stands for the halcretes and
()#4*4.+#*&,.)(3#3.&;*)"#K=%#4*#4:%#:(,:#1*+=;(+(4-#*?#X.0+B# 1=+3&%4%1B#8:(+%#1(+(3.3&%4%1#4.Z%#.)#()4%&'%/(.4%#>*1(4(*)#
low precipitation and high evaporation rates are decisive between the two pedological zones. In both zones basic
for the preservation of these halcretes-(Cu) and -(Ag). ;%/&*3Z1# @=+4&.'.23# &*3Z1B# '%4.3.&;*).4%1B# 3.+3.&%*=1#
They are restricted to the tropical semiarid and arid mor- rocks) have a strong say in terms of the buffering capac-
phoclimatic zones. Halcretes may successfully be used (4-#.)/B#4:%&%;-B#/%'*)14&.4%#4:.4#()#.#>%/*+*,(3.+#&%,('%#
as a climatic marker (Fig.#6GA"# L('(+.&# 4*# :.+3&%4%1B# 1=+- on solid bedrocks the parent material still is a decisive
3&%4%1# =1%/# 4*# >&%3(>(4.4%# ?&*'# .3(/(3# 1*+=4(*)1B# ()3+=/- factor on the formation of orecretes. The impact of these
(),#4:%#'.)C'./%#.3(/C'()%C/&.().,%#U#OEK#@Table 5). bedrocks of high buffering capacity diminishes the more
These orecretes are indicative of strong evaporation in hydrological phenomena such as reworking are involved
morphoclimatic zones where the chemical weathering is and unconsolidated sediments make up the basal parts of
rather moderate and wind speed is rather high as it is the the solum (Fig. 1b).
3.1%# ()# N.4.,*)(.B# O&,%)4().B# .)/# $.1'.)(.B# O=14&.+(.B# Hydrology and pedology are two sides of the same
;*4:#*?#8:(3:#+(%#8(4:()#4:%#3(&3='.&34(3#'.&(4('%#H*)%B# 3*()1#()#4:%#14=/-#*?#*&%3&%4%1B#4:%-#'.-#;%#,&*=)/8.4%&C
also known as the “Roaring Fourties”. The latter humid &%+.4%/# *&# >%/*,%)(3"# O++# 1*(+# 4->%1B# 1=;/(9(/%/# ()# 4:(1#
temperate zone is different from the overall zones where study according to the Food and Agriculture Organization
1=+3&%4%1#/%9%+*>%/#()#[.4C+-(),#3*)4()%)4.+#()4%&(*&#'*&- of the United Nations (2008) that are affected by a strong
phoclimatic zones which are characterized by low rates per descensum or per ascensum# '(,&.4(*)# *?# [=(/1# .&%#
of precipitation (Fig.#!.B# 3A"#$%'>%&.4=&%# (1# )*4# per se a susceptible to the formation of orecretes (Fig. 10d).
3&(4%&(*)#?*&#4:%#>&%1%)3%#*&#.;1%)3%#*?#1=+?.4%1B#;=4#/&-- 0.+3(1*+1B# /=&(1*+1B# 1*(+1# 8(4:# 1%3*)/.&-# 1.+41B# .)/#
ness is critical for their precipitation. &%,*1*+1#1:*8#.#14&*),#>%&#.13%)1='#'(,&.4(*)#*?#[=(/1#
N:*13&%4%1# .)/# 3.&;*3&%4%1# ;%(),# =;(Y=(4*=1# .3&*11# in semiarid and arid climatic conditions. Red and yellow
the globe show an antithetic trend in their distribution soils-highly weathered argic soils (e.g. alisols)in tropical
patterns (Fig. 10a). In the morphoclimatic humid-mid- 8%4#.)/#/&-#3+('.4%#H*)%1#1:*8#;*4:#/(&%34(*)1#*?#[=(/#
latitude and tropical wet-dry zones phoscretes reveal a '*9%'%)41B#8:(+%#?%&&.+1*+1#.)/#>+()4:*1*+1#:.9%#.#14&*),#
&%+.4(9%# '.D('='B# 8:%&%.1# 3.&;*3&%4%1# &=)# 4:&*=,:# .# /*8)8.&/#3*'>*)%)4#()#4:%(&#[=(/#'*9%'%)4#@Fig. 10d).
Fig. 16.# L*(+# >&*>%&4(%1B# ;%/&*3Z# .)/#

climate. The climate is given by the
Koeppen-Geiger climates (based on
/.4.# ?&*'# 4:%# PWLM# /.4.;.1%i# BATJES
2008) Af" #" %Y=.4*&(.+B# ?=++-# :='(/i#
Am" #" %Y=.4*&(.+B# '*)1**).+i# O8" #"
%Y=.4*&(.+B#8()4%&#/&-i#TL:"#":*4#.&(/B#
14%>>%i# TP:" #" :*4# .&(/B# /%1%&4i# 0?;" #"
8.&'# 4%'>%&.4%B# ?=++-# :='(/B# 8.&'#
summer. The Koeppen-Geiger climates
are cited from KOTTEK et al. (2006). The
9%&4(3.+# ;.&1# ,(9%# 4:%# _5#q# 3*)2/%)3%#
interval of the organic carbon content
*?#1*(+1#?&*'#,&.)(4%B#;.1.+4#.)/#+('%1-
tone. a) Organic carbon in soils on top
of different bedrocks of different buffer
capacity as function of the climate. b)
Exchangeable Na in soils on top of dif-
ferent bedrocks of different buffer ca-
pacity as function of the climate (SCHU-
LER et al. 2011).
These soils are more susceptible to encrustations like ore- 6.4 Parent material and the formation of orecretes
cretes than their counterparts from the polar and boreal
H*)%# .1# 8%++# .1# :='(/# '(/C+.4(4=/%# H*)%"# 0:%&)*1%'1B# W)#4:%#>&%9(*=1#1%34(*)1#*)#>%/*+*,-#.)/#:-/&*+*,-B#4:%#
Z.14.)*1%'1B#.)/#>:.%*1%'1#()#4:%#9.14#14%>>%1#.)/#>&.(- ()[=%)3%# *?# 4:%# ;%/&*3Z# *)# 4:%# ?*&'.4(*)# *?# *&%3&%4%1#
ries of the continental interior have a moderate potential could not entirely be cast aside. The parent material has to
to form orecretes (Fig. 10d). be looked at from two different angles as far as the evolu-
tion of orecretes is concerned (Fig. 9). Rock-forming min- bocretes blanketing calcareous or ultrabasic magmatic
erals constitute the wide range of host rocks – see section rocks are chemical residues concentrating heavy metals
5"6"#$:%-#:.9%#.#1(,)(23.)4#('>.34#*)#4:%#()*&,.)(3#;=??- in a strongly buffering regime provoked by the bedrocks.
ering systems and the pH range (Fig.#_B#6bB#Table 5) and Halcretes show the least impact by the parent material
play a decisive role for the type of orecrete (Fig.#_A"#T-# among all chemical residues under study.
3*)4&.14B#4:%#1=+2/(3#.)/#*D(/(3#'()%&.+1#()#4:%#1=;14&.4%# APS minerals investigated during the present and pre-
take an ambivalent position in that they play a minor role 9(*=1#14=/(%1#>&*9%/#4:%(&#.';(9.+%)4#*&(,()B#;=4#)%(4:%&#
as to which type of orecrete may come up but a major role eC#)*&#X.#.+=)(4%#%D.'()%/#?&*'#0:(+%B#N%&=B#T*+(9(.#.)/#
.1#Y=.+(2%&#?*&#4:%#*&%3&%4%#(41%+?#@Fig. 9). Argentina fall into the category “supergene” (DILL 2003).
Oxicretes were encountered on top of all types of de- <)#.#8*&+/8(/%#13.+%B#>=&%#.+=)(4%#()#1=+3&%4%C@ONLA#*?#
>*1(41# .)/# 4:%# Y=.+(2%&1# T(B# L;B# .)/# P# .&%# %D3+=1(9%+-# undoubtedly supergene origin seems to be very rare and
controlled by the underlying primary deposits abundant weathering processes postulated based on dating of pure
in these elements (Figs.#_A"# <D(3&%4%1C@L;AB# .+;%(4# %-%C .+=)(4%# .&%# :%+/# Y=%14(*).;+%# @Table 1). The situation is
3.43:%&1#/=%#4*#4:%(&#9(9(/#-%++*8#3*+*&B#:.9%#&.&%+-#;%%)# Y=(4%#/(??%&%)4#?*&#/(.,%)%4(3#.)/#%>(,%)%4(3#.+=)(4%#8:(3:#
addressed and mainly mentioned along with studies fo- precipitated from intrastratal or basinal brine movements
cused on primary Sb mineralization (COUTO# %4#.+"#6__GB# (DILL 2001). The growth of minerals in sulcretes is fos-
MUNOZ#%4#.+"#6__!B#ORTEGA#%4#.+"#6__bB#DILL#6_`53B#6__`B# 4%&%/#;-#4:%#=;(Y=(4-#*?#>-&(4%"#$:%#;*=)/.&(%1#;%48%%)#
BELLOT# %4# .+"# !GG\B# DILL# %4# .+"# 6__5.B# 6__F;B# !GG`;A"# supergene and hypogene alteration are not sharp in this
O'*),#4:%#8(/%#&.),%#*?#*D(/(3#L;#'()%&.+1B#*)+-#14(;(3- group of orecretes (BRIMHALL#6_`FB#BRIMHALL & CRERAR
*)(4%#.)/#(41#.?2+(.4%1B#%","B#;(1'=4*14(;(3*)(4%B#;()/:%('- 1987). Increasing amounts of REE within the APS s.s.s.
ite and cervantite may be considered as truly supergene. .)/# .# 1(,)(23.)4# 1=;14(4=4(*)# *?# >:*1>:.4%# ?*&# 1=+?.4%#
E.)-#*3:&%1#*?#T(#.)/#P#?*++*8#1=(4#4*#L;#()#4:%(&#/(1-
takes place as morphoclimatic processes become more
tribution.
dominant in the alteration process and preexisting hypo-
<D(3&%4%1# ;%.&(),# E)# '()%&.+1# .&%# 3*)2)%/# 4*# '%-
gene alteration is gradually obliterated.
teoric waters of a higher alkalinity than those of Fe
In the supergene alteration zone of black shales or
(Fig.#663B#/A"#$:(1#(1#*)%#*?#4:%#'.j*&#&%.1*)1#8:-#4:%1%#
@'%4.A>:*1>:*&(4%1B#>:*13&%4%1#.&%#*?4%)#.;=)/.)4"
%+%'%)41B#1*#3+*1%+-#&%+.4%/#8(4:#%.3:#*4:%&#()#:->*,%)%#
Although basic or ultrabasic source rocks in the hin-
/%>*1(41B#=1%/#4*#1>+(4#.>.&4#=)/%&#1=>%&,%)%#3*)/(4(*)1"#
terland are necessary to provide the vanadium for the
Thus oxicretes-(Mn) prefer calcareous bedrocks or used
;=(+/=>#*?#4:%#9.)./*3&%4%1B#4:%&%#(1#1%+/*'#.#/(&%34#&%+.-
to develop on top of carbonate-hosted ore deposits (Ta-
tion between the vanadates under study and a parent rock
ble 1). This was also proved by a region wide survey on
Fe- and Mn orecretes on different bedrocks in Southern or vanadiferous protore underneath the orecrete. Another
Germany (DILL 1985b). source for vanadium has to be looked for among the car-
O'*),#4:%#3.&;*3&%4%1C@V)AB#1'(4:1*)(4%#.)/#:-/&*- bonaceous sedimentary rocks (DILL et al. 2009b).
zincite may be expected only in the supergene part of E*&%#4:.)#.)-#*4:%&#*&%3&%4%B#.&1%)*3&%4%1#.&%#.#'(&-
3.&;*).4%C:*14%/#1>:.+%&(4%#'()%&.+(H.4(*)B#8:(+%#*4.9(4%C ror image of the parent mineral assemblages which either
1'(4:1*)(4%#1"1"1"#.&%#*)+-#>&%1%)4#()#3.&;*3&%4%1C@V)AB#(?# contain pure arsenides or have arsenic substituting at least
sphalerite is enriched in Cd or even greenockite is pre- ?*&#>.&4#*?#4:%#1=+?=&#*&#.)4('*)-#()B#%","B#4:%#?.:+*&%#1"1"1#
1%)4#()#1=?23(%)4#.'*=)41#()#4:%#>.&%)4#*&%#'()%&.+1B#%","B# (Table 1).
L%Z.&).#.)/#w.H/#()#$=)(1(.#.)/#W&.)B#&%1>%34(9%+-"#$:%# T-# .)/# +.&,%B# 4:%# >.&%)4# '.4%&(.+# &%>&%1%)4%/# ;-# 4:%#
smithsonite-otavite s.s.s. is exclusively controlled by the >&('.&-# '()%&.+# .11*3(.4(*)U# >.&.,%)%1(1# @*&%C?*&'(),#
parent material (Fig.#6!.B#;A" '()%&.+1AB# .)/# 4:%# +(4:*+*,(3.+U>%4&*+*,(3# 1-14%'# @&*3ZC
The carbocretes are present from the periglacial forming minerals) have a different impact on the devel-
through the tropical humid morphoclimatic zones. En- opment of orecretes. The rock-forming minerals govern
:.)3%/#*D(/.4(*)#*?#>-&(4%B#%","B#()#;+.3Z#1:.+%1#>&%9%)41# 4:%#4->%#*?#*&%3&%4%B#8:(+%#4:%#1=+2/%#'()%&.+1#3*)4&(;=4%#
%)4(&%+-# >&%3(>(4.4(*)# *?# 3.&;*3&%4%1B# *8(),# 4*# .# 1:.&># 4*# ;=(+/C=># *?# 4:%(&# Y=.+(2%&1# @Fig.#_A"# J%+(3# 1=+2/%1# ()#
drop in pH (Fig.#6!.B# ;B# 3A"# $:%# ;=??%&(),# %??%34# *?# 3.+- the orecretes may sustain a residual redox system and
careous bedrocks has to be considered during formation lower the Eh in the transition zone towards the depth
of carbocretes as it is the case with the partial pressure (Fig. 1a). In contrast to the bacterially mediated redox
of carbon dioxide. Azurite which needs elevated PCO2 to >&*3%11%1B#4:(1#&%/*D#1-14%'#(1#/&(9%)#;-#()*&,.)(3#>&*-
develop is only encountered in carbocretes-(Cu) on car- cesses at the brink from the phreatic into the vadose
bonate-hosted base metal mineralization (Table 1). Car- hydraulic zones.
Table 5. Overview of the pH range (black) common to the various types of orecretes. Areas shaded in gray mark pH ranges during which
orecretes rarely occur. The coloration of orecretes is to correlate with the color code used in Fig. 10.
7. Summary and Conclusions 7.2 Second order lithosphere-atmosphere-

hydrosphere
T-# /%2)(4(*)B# *&%3&%4%1# .//%/# =># 8(4:# 1*'%# Y=.+(2%&1#
?*&#.#'*&%#>&%3(1%#/%13&(>4(*)#*?#3:%'(3.+#3*'>*1(4(*)B# The current investigations reveal a zonal arrangement of
.&%# ,%*,%)%# '%4.++(?%&*=1# :.&/>.)1B# %)3&=14.4(*)1# *&# *&%3&%4%1"# W)# >**&+-C&%+(%?%/# .&%.1B# +*8C+.)/1B# >+.4%.=1B#
duricrusts near- or at the earth’s surface. highly-eroded mountain belts of Precambrian through
T%(),#%'>+.3%/#.4#4:%#()4%&?.3%1#;%48%%)#>%/*1>:%&%B# E%1*H*(3#.,%B#4:%#?=++#&.),%#*?#*&%3&%4%1#?&*'#*D(3&%4%1#
.4'*1>:%&%B#:-/&*1>:%&%B#.)/#+(4:*1>:%&%#4:%-#?*&'#3+(- through to special orecretes may be expected (Fig. 10).
'.4%#'.&Z%&1B#.>>+(3.;+%#4*#4:%#'*14#&%3%)4#>.&41#*?#4:%# $:%1%#'*/%&)#*&%3&%4%1B#*)#4*>#*?#.#,&%.4#9.&(%4-#*?#&*3Z#
Earth*1# :(14*&-B# 8:(+%# /=&(3&=141# *?# %Y=(9.+%)4# '()%&.+# 4->%1B# =1=.++-# /%9%+*># '%1.1# *&# 13.&>1B# >.&4(3=+.&+-# ()-
.11*3(.4(*)1B#%","B#3:&-1*3*++."%%"/(*>4.1%B#3.)#.+1*#3*)- cluding silicacretes and oxicretes-(Fe) and -(Mn) which
tribute to elucidate the paleoclimate (Fig. 1a). Moreover are associated with talus and colluvium. In rift valley and
they are an integral part of the inventory of landforms '*/%&)# '*=)4.()# ;%+41# *?# >&%/*'().)4+-# 0%)*H*(3# .,%B#
and thus a target of geomorphological investigations. :.+3&%4%1B# 9.)./*3&%4%1B# .)/# >:*13&%4%1# /*# &.&%+-# 1:*8#
They form under near-ambient conditions in a prevalently up as they have poor preservation potential. The survival
oxidizing regime and precipitate(d) from mineralizing *?# 1*'%# *?# 4:%1%# %?[*&%13%)3%1# (1# ,*9%&)%/# ;-# 4:%# 48*#
[=(/1# 3*9%&(),# 4:%# ?=++# >7# &.),%# @Table 5) and may in- counteracting processes uplifting (tectonic) and unroof-
corporate a wide range of elements (Table 2) (DILL et al. ing (erosion). Increasing uplift led to increasingly high
!G6G/A"#$:%-#'.-#;%#1=;j%34%/#4*#.#4&(>.&4(4%#1=;/(9(1(*)B# &%+(%?B# :()/%&(),# 3:%#'(3.+# 8%.4:%&(),# .)/# /('()(1:%/#
&%[%34(),#.#,&./=.+#/(13*))%34(*)#;%48%%)#1=;14&.4%#.)/# the chance for these orecretes to be preserved. Retarded
orecrete and a preponderance of climate over lithology. uplift and erosion during mountain building favor their
Orecretes are a mirror image of the chemical composition formation and preservation. This reaction-response model
*?#4:%#'%4%*&(3#[=(/1#.)/#.#-.&/14(3Z#*?#4:%#('>.34#*?#3+(- (1# 9.+(/# *)+-# (?# 4:%# >:-1(3.+# >&*3%11%1# .&%# ()# /(1%Y=(+(;-
mate and mineralogy on the formation of the landscape. rium with the chemical processes. If uplift takes place in
The morphoclimate zones were considered for two time a climate zone with lesser intensity of orecrete formation
slices. One global time slice is representative of the Qua- 4:.)#()#4:%#H*)%#*?#?*&'.4(*)B#*&%3&%4%1#.&%#)%,.4(9%+-#.?-
4%&).&-B# 4:%# *4:%&# *?# 4:%# X%*,%)%# @TRICART & CAILLEUX fected (Fig.#6FA"#W?#>:-1(3.+#>&*3%11%1#.&%#()#%Y=(+(;&(='#
6_5`B# 6_F!A"# S*&# .# '*&%# /%4.(+%/# 4&%.4'%)4B# 4:%# 3+('.4%# 8(4:#4:%#3:%'(3.+#>&*3%11%1B#()#*4:%&#8*&/1B#(?#=>+(?4#.)/#
was constrained using the study from KOTTEK et al. (2006) 3:%'(3.+#.+4%&.4(*)#Z%%>#>.3%#8(4:#%.3:#*4:%&B#%D3+=/(),#
as it makes use of the common Koeppen Climate Zona- :(,:+-# 1*+=;+%# %?[*&%13%)3%1B# 4:%# 4:(3Z)%11# *?# 3*''*)#
tion. The global and the regional climatic zonation are a orecretes may increase. There is a horizontal zonation
good match of the distribution of orecretes (Fig.#!.B# ;A"# ?&*'#4:%#>*+%#4:&*=,:#4:%#%Y=.4*&#()#4%&'1#*?#Y=.+(4-#.)/#
The distribution of orecretes through time only suffered Y=.)4(4-#*?#*&%3&%4%1"#O#9%&4(3.+#H*).4(*)B#;=4#()3*'>+%4%#
'()*&#3:.),%1#B#8:%)#/%>*1(41#+*3.4%/#)%.&#4:%#;*=)/.&-# as to the spectrum of orecretes when compared with the
of a morphoclimatic zone came to rest in different one in less-reliefed terrains may be drawn for the mountainous
the course of some climate changes throughout the late &%,(*)1B#8:%&%#4:%#>%&(,+.3(.+U#,+.3(.+#H*)%#=1%/#4*#;%#%)-
Cenozoic (Table 1). Many of the orecretes formed during countered at the highest altitude (Fig. 10a).
the most recent parts of the Earth*1#:(14*&-B#/=&(),#4:%#+.4%#
Pleistocene and the Holocene.
7.3 Third order atmosphere-hydrosphere-
pedosphere
7.1 First order lithosphere-atmosphere
N&%3(>(4.4(*)#.)/#%9.>*&.4(*)U4%'>%&.4=&%#.&%#'*14#/%3(-
The formation of orecretes is morphoclimatically-driven sive for the presence or absence of orecretes in the top-
(Fig.#6G.B# ;B# 3A# .)/# >.&%)4C'.4%&(.+C&%+.4%/# 4*# /(??%&%)4# most part of the stratigraphic record (Fig.#6GB# Table 3).
degrees (Fig.#_A"# <&%3&%4%1C@L%CE*A# .)/# .&1%)*3&%4%1B# Orecretes owing to their wide range of elements involved
scarcely distributed across the globe relative to their in their evolution have an edge over common calcretes
3*=)4%&>.&41B# .&%# >.&%)4# '.4%&(.+C1%)1(4(9%# .>.&4# ?&*'# or silicacretes sensu stricto because they are much more
their role as a marker for the physical-chemical regime of 3.1%C1%)1(4(9%# .)/# .++*8# ?*&# .# 2)%C4=)(),# *?# /=&(3&=14#
their depositional environment (Fig.#!B# Table 1). Carbo- formation and the description of the physico-chemical
3&%4%1B# 1=+3&%4%1B# :.+3&%4%1B# >:*13&%4%1# .)/# 9.)./*3&%4%1# regime and (paleo)climate much better than their more
are typical markers for the climate. 8(/%1>&%./#;=4#+%11#/(9%&1(2%/#3*=)4%&>.&41"
Fig. 17. Synoptical overview of the intensity of orecrete formation as a function of the morphoclimatic zones. For details see also Fig. 10.
Carbocretes and phoscretes are characterized by two +%.14#&%[%34#.)#%.&+-#14.,%#/=&(),#4:%#%)4(&%#?*&'.4(*)#*?#

'.j*&# 3*'>*)%)41# *?# 4:%# .4'*1>:%&%# .)/# >%/*1>:%&%B# orecretes. There is no sharp boundary between oxicretes
respectively (pedogenic orecretes). They are very wide- and duricrusts with prevailing oxides and hydrates of Fe
spread across the globe and controlled by the phosphate .)/#O+"#<D(3&%4%1#.1#4:%-#8%&%#/%2)%/#()#4:%#3=&&%)4#14=/-#
cycle within the pedosphere (Fig.#6G.B#/A"#o&*=)/8.4%&C may gradually convert into bauxite as the aluminium con-
derived calcretes may gradually turn into pedological 4%)41#()3&%.1%#*&#()4*#?%&&(3&%4%1B#&%1>%34(9%+-B#.1#4:%#(&*)#
3.+3&%4%1B# %D>&%11%/# .'*),# *4:%&1# ;-# /(??%&%)4# 4%D4=&%1# contents increase. In the course of these alteration conti-
;=4#)*4#;-#3*'>*1(4(*)"#L*#/*#4:%#*&%3&%4%1B#8:%&%#1(+(- nental oxidic Al and Fe ore deposits may develop from
3.3&%4%1# 4.Z%# .# 4&.)1(4(*).+# >*1(4(*)"# $:%# 1=+3&%4%1B# 9.- simple weathering residues. See as far as duricrusts and
nadocretes and halcretes are the main contenders of the chemical residues are concerned also the comprehensive
f:-/&.=+(3# *&%3&%4%1g# 4:.4# ?*&'# .# 1%Y=%)3%# &%[%34(),# papers by GOUDIE & PYE#@6_`\AB#?*&#+.4%&(4%#.)/#;.=D(4%#
increasing evaporation or aridity in the morphoclimatic by TAYLOR & EGGLETON (2009) and for mineral deposits
zonation in poorly-reliefed terrains. Oxicretes play an ex- DILL# @!G6G;A"# $:%&%?*&%B# f+('*)(4(3g# *D(3&%4%1# '.-# ;%#
3%>4(*).+#>.&4B#/%'*)14&.4(),#14&*),#+%.3:(),#.)/#.44%14- found at the beginning and the end of successions of pedo-
(),#4*#.,(),#*?#4:%#*&%3&%4%1"#$:%&%?*&%B#()#.#3*)4()=*=1# ,%)(3#.)/#:-/&.=+(3#*&%3&%4%1"#0.&;*3&%4%1#.&%B#()#>+.3%1B#
>&*2+%# *&# 4:%# 14&.4(,&.>:(3# &%3*&/B# 4:%-# '.-# .4# +%.14# ()# :.++'.&Z1#*?#.#&%+(3#'()%&.+#.11%';+.,%B#4**"#T-#3*)4&.14B#
parts be representative of relic forms when the supergene halcretes have not been observed as such and held to be
.+4%&.4(*)#8.1#Y=(4%#/(??%&%)4#?&*'#4:%#'*/%&)#*)%#*&#.4# orecretes in an initial stage.
The individual orecretes may be characterized as fol- Phoscretes (Al-Fe-Cu-Pb-REE) are a heterogeneous
lows with respect to their physico-chemical regime in the group with their Al-enriched end members being wide-
9.&(*=1#'*&>:*3+('.4(3#H*)%1Q 1>&%./#()#.3(/(3#[=(/#&%,('%1#8:(+%#4:%(&#O+C?&%%#'%';%&1#
<D(3&%4%1C@S%CE)C0=CL;CT(CPCW)A#*33=&#*9%&#4:%#?=++# prevail under neutral to alkaline conditions. They prefera-
pH range in the humid zone of moderate chemical weath- ;+-#/%9%+*>#()#'*&>:*3+('.4(3#H*)%1#8(4:#14&*),+-#[=34=-
ering and likewise in tropical humid zones with pervasive ating intensities of chemical and mechanical weathering.
chemical weathering. Vanadocretes-(Pb-Cu-Zn) take an intermediate posi-
Carbocretes-(Pb-Cu-Zn-Cd) have a pH-range run- 4(*)#;%48%%)#1=+3&%4%1#.)/#:.+3&%4%1B#1*#.1#4*#>+.-#.#+%./-
ning almost parallel to that of the oxicretes down to pH 4 (),#&*+%#()#4:%#1%Y=%)3%#*?#.&(/(4-#.1#?*++*81Q#L(+(3.3&%4%"+"
and as such often occur as relic forms. Mountainous and sulcrete"!"vanadocrete"!"halcrete. They form exclusively
periglacial regions are favorable morphoclimatic zones under arid conditions as the rate of chemical weathering is
due to the retarded decomposition of organic matter in low. These orecretes need no pervasive chemical weather-
their soils. They are also very widespread in zones nor- ing and disappear under conditions of strongly chemical
'.++-#/*'().4%/#;-#'%3:.)(3.+#8%.4:%&(),#()4%&2),%&(),# weathering.
8(4:#.++=9(.+#.)/#[=9(.+#>+.3%&#/%>*1(41"#$%'>%&.4=&%1#*?# The synoptical overview reveals in which morphocli-
carbocretes-(Cu-Zn-Pb) obtained from O isotope studies '.4(3#H*)%#*&%3&%4%1#/%9%+*>%/#;%14"#$:%#2&14C*&/%&#'.D-
.+*),#4:%#XCL#4&%)/#24#4:%#+.4(4=/().+#'*&>:*3+('.4(3#H*- ('='#+(%1#8(4:()#4:%#4&*>(3.+#8%4C/&-#H*)%B#%1>%3(.++-#.4#
nation across the globe. The temperature of reaction grad- its border regions (Fig. 17). A second-order relative maxi-
ually deviates from the annual mean temperature in the mum in the humid mid-latitudes is do some extent caused
3*=&1%# *?# *D(/.4(*)# *?# 1=+2/%1# 4*8.&/1# 4:%# %Y=.4*&# .)/# by relic forms.
more humid depositional environments and runs through
a maximum in the humid tropical zones (Table 4). Acknowledgements
Silicacretes-(Cu-Zn) form in a pH range that only par-
tially overlaps with those of carbocretes and oxicretes (not Chemical analyses were carried out in the laboratory of
in the strongly alkaline part). They show up later in the ToJ#;-#S"#KORTE. The preparation of samples and SEM
succession of supergene alteration. Silicacretes favorably analyses were performed by D. KLOSA. D. WECK has car-
/%9%+*>#=)/%&#f()4%&'%/(.4%g#'*&>:*3+('.4(3#3*)/(4(*)1B# &(%/# *=4# 4:%# IJK# .).+-1%1# @ToJA"# L*'%# *?# 4:%# >:*4*-
where chemical weathering is moderate and mechanical graphs of the mineral specimens have been taken by Mr.
weathering wanes. HAKE and S. PIETRZOK# @ToJA"# K=&(),# 4:(1# +*),C+.14(),C
K=%# 4*# 4:%# :(,:# 1*+=;(+(4-# *?# :.+3&%4%1C@0=CO,AB# +*8# study there were numerous colleagues and persons inside
precipitation and high evaporation rates are decisive for .)/# *=41(/%# *?# ToJB# ()9*+9%/# /=&(),# 1.'>+(),B# 1.'>+%#
their preservation. They are exclusive to the tropical semi- provision and preparation without which a study like that
arid and arid morphoclimatic zones in a low to neutral pH could not have been realized. H. G. D. would like to ex-
regime. Weathering is very moderate within these mor- press his thanks to R. BARRITZ and U. SCHULER#@ToJA#?*&#
>:*3+('.4(3#H*)%1#.)/#3*)2)%/#4*#4:%#4*>'*14#>.&4#*?#4:%# discussion. We express our gratitude to an anonymous
;%/&*3ZB#8:%&%#4:%1%#'()%&.+#.11%';+.,%1#%(4:%&#3*.4#*&# reviewer and R. KLEMD#@o%*H%)4&='#X*&/;.-%&)B#e&=1-
penetrate the underlying rocks along cracks. 4%)/-).'(ZB#o%*3:%'(%#=)/#k.,%&14y44%)Z=)/%A#8:*#&%-
Sulcrete-(Fe-Cu-Pb-APS) similar to halcretes used to 9(%8%/# 4:%# >.>%&# ?*&# 4:%# zX%=%1# R.:&;=3:# E()%&.+*,(%#
>&%3(>(4.4%#?&*'#.3(/(3#1*+=4(*)1B#()3+=/(),#4:%#'.)C'./%# Abhandlungen and to the Editor-in-Chief H.-G. STOSCH
.3(/C'()%C/&.().,%#U#OEK"#$:%#;*=)/.&(%1#;%48%%)#1=- @W)14(4=4# ?{&# O),%8.)/4%# o%*8(11%)13:.?4%)B# E()%&.+*-
pergene and hypogene alteration is not sharp members of gie und Petrologie) for his editorial handling of our paper.
this group of orecretes where APS minerals (aluminium
phosphate sulfate) bridge the gap between the two types
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4(*)B#P.,%)(),%)#@8(4:#/.4.1%4A" BROOKINSB# K"# o"# @6_`FAQ# M:C>7# /(.,&.'1# ?*&# ,%*3:%'(14&-"# h#
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BECKB#k"#L"#@6_b_AQ#^&.)(='#/%>*1(41#*?#4:%#O4:.;.13.#&%,(*)B#L.1- M"#@%/"AB#o%*+*,-#*?#4:%#E()%&.+#K%>*1(41#*?#O=14&.+(.#.)/#N.>=.#
Z.43:%8.)"#h#L.1Z.43:%8.)#K%>.&4'%)4#*?#E()%&.+#J%1*=&3%1B# X%8#o=()%."#$:%#O=14&.+(.)#W)14(4=4%#.)/#E%4.++=&,-B#E%+;*=&)%#
J%>*&4B#6!bB#6aG#>>" Monograph 14Q#6b!5nh6b!_"
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T%.9%&+*/,%#K(14&(34"#h#W)Q#EVANSB#M"#k"#@%/"AB#^&.)(='#K%>*1(41# NALS,#"#@!GG\AQ#O,%1#*?#%>(4:%&'.+#/%>*1(41#()#E%D(3*"#J%,(*)-
*?#0.)./."#0.)./(.)#W)14(4=4%#*?#E()(),#.)/#E%4.++=&,-B#L>%3(.+# .+#1(,)(23.)3%#.)/#+()Z1#8(4:#4:%#%9*+=4(*)#*?#$%&4(.&-#9*+3.)(1'"#
Volume 33Q#`5nhn_a" – Econ. Geol. 98Q#6G!_nh6G\F"
CANFIELDB#K"#M"#@!GG5AQ#$:%#%.&+-#:(14*&-#*?#.4'*1>:%&(3#*D-,%)"#h# CUMMING, G. L., KRSTIC, D., BJØRLYKKE, A. & AASEN, H. @6__\AQ#

Annual Review of Earth and Planetary Sciences 33Q#6hn\b" S=&4:%&# .).+-1%1# *?# &./(*,%)(3# '()%&.+1# ?&*'# 4:%# T(/j*9.,,%#
CARLISLEB#K"#@6_FÀQ#$:%#/(14&(;=4(*)#*?#3.+3&%4%1#.)/#,->3&%4%1#()# ,*+/C3*>>%&#/%>*1(4B#S())'.&ZB#X*&4:%&)#X*&8.-"#h#E()%&"#.)/#
the southwestern United States and their uranium favorability. Petrol. 49Q#b\nhFG"
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bGnhFb"
d7EL#/%>*1(4#@0=;.A"#%9(/%)3%#?&*'#[=(/#()3+=1(*)1#.)/#1=+?=&# DEPARTMENT OF MINERAL RESOURCES# @6___AQ# o%*+*,(3.+# E.># *?#
(1*4*>%1"#h#R"#*?#o%*3:%'"#MD>+*&.4(*)#;<=>;?Q#`5nhn_G" $:.(+.)/# 6"!B5GGBGGG"# h# K%>.&4'%)4# *?# E()%&.+# J%1*=&3%1B#
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Coruña 35Q#__nh6G`" ()#4:%#8%14%&)#>.&4#*?#4:%#k=2+(.)#?*+/C.)/C4:&=14#;%+4B#e.4.),.#
CHEN, J., BLUME, H.-P. & BEYER, L.# @!GGGAQ# P%.4:%&(),# *?# &*3Z1# @K%'*3&.4(3#J%>=;+(3#*?#0*),*A"#h#R"#*?#O?&(3.)#M.&4:#L3(%)3%1#
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tion of heavy metal remediation using mineral apatite. – Water 4:%&'.+#.+4%&.4(*)#*?#4:%#T&.)/;%&,#.+Z.+()%#3*'>+%DB#X.'(;(."#
Air Soil Pollution 98Q#5FhF`" h#o%*+"#L=&9"#*?#X.'(;(.B#E%'*(&#10Q#6hn55"
CHETTY, D. & FRIMMEL, H. E.#@!GGGAQ#$:%#&*+%#*?#%9.>*&(4%1#()#4:%# DIEHLB#N"#|#KERNB#7"#@6_`6AQ#o%*+*,-B#E()%&.+*,-#.)/#,%*3:%'(1-
,%)%1(1#*?#;.1%#'%4.+#1=+2/%#'()%&.+(H.4(*)#()#4:%#X*&4:%&)#N+.4- try of carbonate-hosted lead-zinc deposits in Kanchanaburi Prov-
?*&'# *?# 4:%# N.)CO?&(3.)# K.'.&.# T%+4B# X.'(;(."# o%*3:%'(3.+# ()3%B#P%14%&)#$:.(+.)/"#h#M3*)"#o%*+"#76Q#!6!`nhn!6ab"
.)/#[=(/#()3+=1(*)#%9(/%)3%#?&*'#3.&;*).4%#8.++#&*3Z#.+4%&.4(*)"# DILLB#7"#o"#@6_`5.AQ#K(%#d%&%&H=),#.'#P%14&.)/#/%&#T:'(13:%)#
– Miner. Deposit. 35Q#\banhn\Fb" Masse. – Metallogenese in einer ensialischen Orogenzone. –
o%*+"#R.:&;"#K#73Q#\nhnab6"
CHUKANOVB#X"#d"#@!GG5AQ#E()%&.+1#*?#4:%#e%&3:#(&*)C*&%#;.1()#()#
DILLB#7"#o"#@6_`5;AQ#$%&&%14&(.+#?%&&*'.),.)%1%#*&%#3*)3%)4&.4(*)1#
Eastern Crimea. – Mineralogical Almanac. Ocean Pictures Ltd.
?&*'#E(/CM=&*>%.)#T.1%'%)4#T+*3Z1#.)/#4:%(&#('>+(3.4(*)#3*)-
8Q#6h6G_" cerning the environment of formation during Late Cenozoic (N
CLIFFORD, J. A., RYAN, P. & KUCHA, H. @6_`bAQ#O#&%9(%8#*?#4:%#,%*- T.9.&(.#U#S"#J"#o%&'.)-A"#h#L%/('%)4"#o%*+"#45Q#FFhn_b"
+*,(3.+# 1%44(),# *?# 4:%# $-).,:# *&%# ;*/-B# 0*"# o.+8.-"# h# W)Q#AN- DILLB#7"#o"#@6_`53AQ#O)4('*)(?%&*=1#E()%&.+(H.4(*)#?&*'#4:%#E(/C
DREW, C. J., CROWE, R. W. A., FINLAY, S., PENNELL, W. M. & PYNE, M=&*>%.)# L.D*4:=&(),(.)# V*)%i# E()%&.+*,-B# o%*+*,-B# o%*-
R"#S"#@%/1"AB#o%*+*,-#.)/#o%)%1(1#*?#E()%&.+#K%>*1(41#()#W&%+.)/B# 3:%'(14&-# .)/# %)1(.+(3# <&(,()"# h# W)4%&).4"# R"# *?# M.&4:# L3(%)3%1#
W&(1:#O11*3(.4(*)#?*&#M3*)"#o%*+"#a6_nhna\_" 74Q#aaFhnabb"
COLLINSONB#R"#K"#@6__bAQ#O++=9(.+#1%/('%)41"#h#W)Q#READINGB#7"#o"# DILLB#7"#o"#@6_`ÀQ#K(.,%)%4(3#.)/#%>(,%)%4(3#^"B#T.B#.)/#;.1%#'%4-
@%/"AB#L%/('%)4.&-#M)9(&*)'%)41Q#N&*3%11%1B#S.3(%1#.)/#L4&.4(,- .+# '()%&.+(H.4(*)# ()# 4:%# .&%).3%*=1# ^>>%&# $&(.11(3# fT=&,1.)/-
&.>:-B#T+.3Z8%++B#<D?*&/B#>>"#\Fhn`!" stein” (Southern Germany). With special reference to mineraliza-
CONSTANTINOUB# o"# @6_`GAQ# E%4.++*,%)%1(1# .11*3(.4%/# 8(4:# 4:%# tion in duricrusts. – Miner. and Petrol. 89Q#_\nh6G5"
$&**/*1#<>:(*+(4%"#h#W)Q#PANAYIOTOU"#O"#@%/"AB#<>:(*+(4%1"#N&*3"B# DILLB#7"#o"#@6__GAQ#K(%#L3:8%&'()%&.+CS{:&=),#()#/%&#$&(.1#H8(1-
W)4%&).4"#*>:(*+(4%#1-'>*1(='B#X(3*1(.B#0->&=1B#0->&=1"#E()(1- 3:%)#P%(/%)#=)/#N&%11.4:#'(4#;%1*)/%&%&#T%&{3Z1(3:4(,=),#/%&#
try of Agriculture and Natural Resources Geological Survey De- T=)4'%4.++'()%&.+(1.4(*)%)"#h#M&+.),%&#o%*+"#O;:"#118Q#b6hF\"
>.&4'%)4B#>"#bb\nhnbFa" DILLB#7"#o"#@6__ÀQ#M9*+=4(*)#*?#L;#'()%&.+(1.4(*)#()#'*/%&)#?*+/#
COOK, N. J., KLEMD, R. & OKRUSCH, M. @6__aAQ#L=+2/%#'()%&.+*,-B# belts. Comparison of the Sb mineralisation in the Central Andes
'%4.'*&>:(1'#.)/#/%?*&'.4(*)#()#4:%#E.43:+%11#'.11(9%#1=+2/%# @T*+(9(.A#.)/#4:%#P%14%&)#0.&>.4:(.)1#@L+*9.Z(.A"#h#E()%&"#K%-
/%>*1(4B#X.'(;(."#h#E()%&"#K%>*1(4"#29Q#6h65" posit. 33Q#\5_nhn\F`"
DILLB# 7"# o"# @6___AQ# N*+-'%4.++(3# *&%# /%>*1(41# ()# 4:%# e.H.Z:14.)C
CORBETTB# e"# K"# @!GG6AQ# X%8# '.>>(),# .)/# ()4%&>&%4.4(*)# *?# 4:%#
e-&,-H14.)#;*&/%&#&%,(*)"#h#V"#?{&#.),%8.)/4%#o%*+"#aaQ#!!nhn\G"
E*=)4# k-%++# E()(),# K(14&(34B# $.1'.)(."# O# +.&,%# :-;&(/# 0=C
DILLB# 7"# o"# @!GG6AQ# $:%# ,%*+*,-# *?# .+='()(='# >:*1>:.4%1# .)/#
Au System with an exhalative Pb-Zn top. – Econ. Geol. 96Q# sulfates of the alunite supergoup. A review. – Earth Science Re-
6G`_nh666!" views 53Q#!5nhn_\"
COUSSOT, P. & MEUNIER, M.#@6__bAQ#J%3*,)(4(*)B#3+.11(23.4(*)#.)/# DILLB# 7"# o"# @!GG\AQ#O# 3*'>.&.4(9%# 14=/-# *?#ONL# '()%&.+1# *?# 4:%#
'%3:.)(3.+#/%13&(>4(*)#*?#/%;&(1#[*81"#h#M.&4:CL3(%)3%#J%9(%81# N.3(23#&('#?*+/#;%+41CP(4:#1>%3(.+#&%?%&%)3%#4*#L*=4:#O'%&(3.)#
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COUTO, H., ROGER, G., MOELO, Y. & BRIL, H.#@6__GAQ#k%#/(14&(34## \G6hn\!G"
.)4('*()%C*&#K=&(3*CT%(&.*#@N*&4=,.+A"#~9*+=4(*)#>.&.,~)~4(Y=%# DILLB#7"#o"#@!GGFAQ#O#&%9(%8#*?#'()%&.+#&%1*=&3%1#()#E.+.8("#P(4:#
%4#,~*3:('(Y=%i#('>+(3.4(*)1#'~4.++*,~)(Y=%1"#h#E()%&"#K%>*1(4"# special reference to aluminium variation in mineral deposits. –
25Q#b_nhn`6" R"#*?#O?&(3.)#M.&4:#L3(%)3%1#47Q#65\nh6F\"
CRANE, M. J., SHARPE, J. L. & WILLIAMS, P. A.#@!GG6AQ#S*&'.4(*)# DILLB# 7"# o"# @!GGÀQ# o%*,%)%# .)/# .)4:&*>*,%)(3# 3*)4&*+1# *)# 4:%#
of Chrysocolla and Secondary Copper Phosphates in the Highly '()%&.+*,-# .)/# ,%*3:%'(14&-# *?# '*/%&)# .++=9(.+C@[=9(.+A# ,*+/#
Weathered Supergene Zones of some Australian Deposits. – Re- >+.3%&#/%>*1(41#()#'.)C'./%#+.)/13.>%1#()#S&.)3%B#L8(4H%&+.)/#
cords of the Australian Museum 53Q#a_nhn5b" .)/#o%&'.)-"#h#R"#*?#o%*3:%'"#MD>+*&.4(*)#99Q#!_nhnbG"
DILLB#7"#o"#@!GG_AQ#N-&*'%4.++=&,(3.+#&%+(31#*?#N;C0=CS%#/%>*1(41# transect from the taiga to the desert in Central Mongolia-Evo-

in south-eastern Germany. An exploration tool and a record of lution of landforms in the mid-latitude continental interior as a
'()(),#:(14*&-"#h#R"#*?#o%*3:%'"#MD>+*&.4(*)#100Q#\Fhn5G" ?=)34(*)#*?#3+('.4%#.)/#9%,%4.4(*)"#h#R"#?*&#O1(.)#M.&4:#L3(%)3%1#
DILLB#7"#o"#@!G6GAQ#$:%#f3:%11;*.&/g#3+.11(23.4(*)#13:%'%#*?#'()- 27Q#!a6hn!ba"
eral deposits. Mineralogy and geology from aluminium to zirco- DILL, H. G., KHISHIGSUREN, S., MAJIGSUREN, Y., MYAGMARSUREN, S.,
nium. – Earth Science Reviews 100Q#6hna!G" BULGAMAA, J. & HONGOR, O.#@!GGb;AQ#O#&%9(%8#*?#4:%#)*)C'%4.+-
DILLB#7"#o"#@!G66AQ#O#3*'>.&.4(9%#14=/-#*?#=&.)(='#h#4:*&(='#.3- lic industrial minerals of Mongolia. The impact of geological and
cumulation at the western edge of the Arabian Peninsula and geographical factors on their formation and use. – Internat. Geol.
'()%&.+# /%>*1(41# 8*&+/8(/%"# h# O&.;(.)# R"# *?# o%*13(%)3%1# 4Q# Review 48Q#6!_nh6F\"
6!\nh6ab" DILL, H. G., KUS, J., ABED, A. M., SACHSENHOFER, R. F. & ABUL
DILL, H. G. & BÄUMLER, W.#@!GGFAQ#O+=)(4CR.&*1(4CE(13:Z&(14.++;(+- KHAIR H.#@!GG_3AQ#K(.,%)%4(3#.)/#%>(,%)%4(3#.+4%&.4(*)#*?#0&%4.-
dungen in Metakieselschiefern bei Tirschenreuth in der Oberp- ceous to Paleogene organic-rich sedimentary successions typical
?.+H"#h#o%*+"#T+y44%&#X*&/*14CT.-%&)#57Q#66_nh6!!" *?#4:%#8%14%&)#'.&,()#*?#4:%#O&.;(.)#N+.4%B#)*&4:8%14%&)#R*&/.)"#
DILL, H. G. & HORN, E. E.# @6__bAQ# $:%# *&(,()# *?# .# :->*,%)%# – GeoArabia 14Q#6G6h6aG"
sarabauite-calcite mineralization at the Lucky Hill Au-Sb mine DILL, H. G., LUDWIG, R.-R., KATHEWERA, A. & MWENELUPEMBE, J.
L.&.8.ZB#E.+.-1(."#h#R"#*?#L*=4:%.14#O1(.)#M.&4:#L3(%)3%1#14Q# @!GG5.AQ# O# +(4:*?.3(%1# 4%&&.()# '*/%+# ?*&# 4:%# T+.)4-&%# J%,(*)"#
!_nhn\5" Implications for the interpretation of palaeosavanna depositional
DILL, H. G. & KANTOR, W.# @6__FAQ# K%>*1(4(*).+# %)9(&*)'%)4B# systems and for environmental geology and economic geology
3:%'(3.+# ?.3(%1# .)/# .# 4%)4.4(9%# 3+.11(23.4(*)# *?# 1*'%# 1%+%34%/# ()#1*=4:%&)#E.+.8("#h#R"#*?#O?&(3.)#M.&4:#L3(%)3%1#41Q#\a6hn\_\"
>:*1>:.4%#.33='=+.4(*)1"#h#o%*+"#R.:&;"#K#105Q#\nhna\" DILL, H. G., MELCHER, F. & BOTZ, R.#@!GG`;AQ#E%1*C#4*#%>(4:%&'.+#
DILL, H. G., BOSSE H.-R. & KASSBOHM J.#@!GGGAQ#E()%&.+*,(3.+#.)/# W-bearing Sb vein-type deposits in calcareous rocks in western
chemical studies of volcanic-related argillaceous industrial min- Thailand. with special reference to their metallogenetic position
erals of the Central American Cordillera (western El Salvador).
in SE Asia. – Ore Geol. Review 34Q#!a!nhn!b!
– Econ. Geol. 95Q#56Fhn5\`"
DILL, H. G., MELCHER, F., KAUFHOLT, S., TECHMER, A., WEBER, B.
DILL, H. G., BOSSE, H.-R., HENNING, K-H., FRICKE, A. & AHREND, H.
& BÄUMLER, W.# @!G6G.AQ# N*14CE(*3%)%# .)/# ;&*)H%C.,%# 1=>%&-
@6__F.AQ#E()%&.+*,(3.+#.)/#3:%'(3.+#9.&(.4(*)1#()#:->*,%)%#.)/#
,%)%# 0=CN;# .&1%).4%C:='.4%U# *D.+.4%C3.&;*).4%# '()%&.+(H.4(*)#
supergene kaolin deposits in a mobile fold belt. – The Central
.4#E%,.#k(9./(#h#L%&(?*1B#o&%%3%"#h#0.)./(.)#E()%&.+*,(14#48Q#
Andes of northwestern Peru. – Miner. Deposit. 32Q#6a_nh6b\"
6b\nh6`6"
DILL, H. G., BOTZ, R., LUPPOLD, F. W. & HENJES-KUNST, F.#@!GG5;AQ#
DILL, H. G., PERTOLD, Z. & RIERA KILIBARDA, C.#@6__F;AQ#L%/('%)4C
Hypogene and supergene alteration of the Late Palaeozoic Rat-
hosted and volcanic-hosted Sb vein mineralization in the Potosi
;=&(# k('%14*)%# /=&(),# 4:%# E%1*H*(3# .)/# 0%)*H*(3# @$:.(+.)/B#
&%,(*)#@0%)4&.+#T*+(9(.A"#h#M3*)"#o%*+"#92Q#b!\nhnb\!"
Surat Thani Province). Implications for the concentration of
DILL, H. G., PÖLLMANN, H., BOSECKER, K., HAHN, L. & MWIYA,
'()%&.+# 3*''*/(4(%1# .)/# :-/&*3.&;*)1"# h# W)4%&).4"# R"# *?# M.&4:#
Sciences 94Q#!anhnab" S.# @!GG!AQ# L=>%&,%)%# '()%&.+(H.4(*)# ()# '()(),# &%1(/=%1# *?# 4:%#
DILLB#7"#o"B#BUSCHB#e"#|#BLUMB#X"#@6__6AQ#0:%'(14&-#.)/#*&(,()# Matchless cupreous pyrite deposit (Namibia) – A clue to the ori-
*?#9%()+(Z%#>:*1>:.4%#'()%&.+(H.4(*)B#X=;.#E41"#@L=/.)A"#h#<&%# ,()#*?#'*/%&)#.)/#?*11(+#/=&(3&=141#()#1%'(.&(/#3+('.4%1"#h#R"#*?#
o%*+*,-#J%9(%8B#bQ#_nhn!a" Geochem. Exploration 75Q#a\nhFG"
DILL, H. G., FRICKE, A., HENNING, K.-H. & THEUNE, C. H.#@6__5;AQ# DILL, H. G., SACHSENHOFER, R. F., GRECULA, P., SASVÁRI, T., PALINKAŠ,
An aluminium-phosphate mineralization from the hypogene La 56')64'.$7$829"3:;$;<)7"34'(64'(<7!"3:=)5"10);4'(64'=7$,>)(0)4'
Vanguardia kaolin deposit (Chile). – Clay Minerals 30Q#!a_nhn!5b" W., GARUTI, G., ZACCARINI, F., ARBOUILLE, D. & SCHULZ, H.-M.
DILL, H. G., FRICKE, A., HENNING, K.-H.& GEBERT, H.#@6__53AQ#O)# @!GG`.AQ# S*11(+# ?=%+1B# *&%# h# .)/# ()/=14&(.+# '()%&.+1"# h# W)Q# MC-
APS mineralization in the kaolin deposit Desa Toraget from CANNB#$"#@%/"AB#o%*+*,-#*?#0%)4&.+#M=&*>%B#o%*+"#L*3"#*?#k*)-
)*&4:%&)#L=+.8%1(#U#W)/*)%1(."#h#R"#*?#L*=4:%.14#O1(.)#M.&4:#L3(- /*)B#L>%3"#N=;+"B#k*)/*)B#6\a6h6aa_"
ences 11Q#!`_nhn!_\" DILL, H. G., WEBER, B. & FÜSSL, M.#@!GGF.AQ#E()%&.+*,(13:%#=)/#
DILL, H. G., FUESSL, M. & BOTZ, R. @!GGF;AQ#E()%&.+*,-#.)/#@%3*- sedimentpetrographische Untersuchungen an Pb-Cu-Fe-füh-
nomic) geology of zeolite-carbonate mineralization in basic ig- renden Trias-Vererzungen zwischen Grafenwöhr und Freihung
)%*=1# &*3Z1# *?# 4:%#$&**/*1# 0*'>+%DB# 0->&=1"# h# X"# R;"# E()%&"# @<;%&>?.+HA"#h#o%*+"#T+y44%&#X*&/*14CT.-%&)#57Q#6G5nh66`"
Abh. 183Q#!56hn!b`" DILL, H. G., WEBER, B. & GERDES, A. (!G6G%AQ# 0*)14&.()(),# 4:%#
DILL, H. G., GARRIDO, M. M., MELCHER, F., GOMEZ, M. C., WEBER, physical-chemical conditions of Pleistocene cavernous weather-
B., LUNA, L. & BAHR, A.#@!G6\AQ#L=+2/(3#.)/#)*)C1=+2/(3#()/(='# ing in Late Paleozoic granites. – Geomorphology 121Q#!`\nhn!_G"
mineralization of the epithermal Au-Cu-Zu-Pb-Ag deposit San DILL, H. G., WEBER, B. & KAUFHOLD, S.# @!GG_.AQ# $:%# *&(,()# *?#
J*Y=%#@N&*9()3(.#J(*#X%,&*B#LM#O&,%)4().A#h#8(4:#1>%3(.+#&%?%&- siderite-goethite-phosphate mineralization in the karst-related
%)3%#4*#f()/='#8()/*8g#()#V()3#1=+2/%"#h#<&%#o%*+*,-#J%9(%8# ?.=+4;*=)/# (&*)# *&%# /%>*1(4#O=%&;.3:B# o%&'.)-B# .# 3+=%# 4*# 4:%#
51Q#6G\h6!`" 4('(),#*?#:->*,%)%#.)/#1=>%&,%)%#S%CO+#>:*1>:.4%1#()#XM#T.-
DILL, H. G., GERDES, A. & WEBER, B.#@!G6G/AQ#O,%#.)/#'()%&.+*,-# 9.&(."#h#X"#R;"#E()%&"#O;:"#186Q#!`\nhn\GF"
of supergene uranium minerals – tools to unravel geomorpho- DILL, H. G., WEBER, B., GERDES, A. & MELCHER, F.# @!GG_;AQ#$:%#
+*,(3.+#.)/#>.+.%*:-/&*+*,(3.+#>&*3%11%1#()#,&.)(4(3#4%&&.()1#@T*- S%CE)#>:*1>:.4%#.>+(4%#fL(+;%&,&=;%g#)%.&#P.(/:.=1B#o%&'.)-"#
:%'(.)#E.11(?B#LM#o%&'.)-A"#h#o%*'*&>:*+*,-#117Q#aanhnb5" Epithermal phosphate mineralization in the Hagendorf-Pleystein
DILL, H. G., HANSEN, B., KECK, E. & WEBER, B.#@!G6G3AQ#0&->4*- pegmatite province. – Miner. Mag. 72Q#66a\nh66b`"
melane a tool to determine the age and the physical-chemical DILL, H. G., WEHNER, H., KUS, J., BOTZ, R., BERNER, Z., STÜBEN, D.
regime of a Plio-Pleistocene weathering zone in a granitic terrain & AL-SAYIGH, A. @!GGF3AQ#$:%#M*3%)%#J=1.-+#S*&'.4(*)B#<'.)B#
@7.,%)/*&?B#LM#o%&'.)-A"#h#o%*'*&>:*+*,-#121Q#\FGnhn\FF" carbonaceous rocks in calcareous shelf sediments. environment
DILL, H. G., KHISHIGSUREN, S., MAJIGSUREN, Y. O., MYAGMARSUREN, *?# /%>*1(4(*)B# .+4%&.4(*)# .)/# :-/&*3.&;*)# >*4%)4(.+"# h# W)4%&).4"#
S. & BULGAMAA, J.#@!GGb.AQ#o%*'*&>:*+*,(3.+#14=/(%1#.+*),#.# R"#*?#0*.+#o%*+*,-#72Q#`_nh6!\"
DILL, H. G., WEISER, T., BERNHARDT, I. R. & RIERA KILIBARDA, C. GALLOWAY, W. E. & HOBDAY, D. K.# @6__bAQ# $%&&(,%)*=1# 3+.14(3#
@6__5.AQ#$:%#3*'>*1(4%#,*+/C.)4('*)-#9%()#/%>*1(4#.4#e:.&'.# depositional systems-Application to fossil fuel and groundwater
@T*+(9(.A"#h#M3*)"#o%*+"#90Q#56hnbb" &%1*=&3%1"#h#L>&(),%&B#T%&+()B#a`_#>>"
DILL, H. G., WEISS, W., BOTZ, R. & DOHRMANN, R.#@!G66AQ#N.+%*)- GARRELS, R. M. & CHRIST, J. C.# @6_b5AQ# L*+=4(*)1B# '()%&.+1B# .)/#
4*+*,(3.+B#'()%&.+*,(3.+#.)/#3:%'(3.+#14=/(%1#*?#1-),%)%4(3#.)/# %Y=(+(;&(."#h#L.)#S&.)3(13*"#S&%%'.)#0**>%&B#a5G#>>"
%>(,%)%4(3# N;CV)CT.CN# '()%&.+(H.4(*)1# .4# 4:%# 14&.4*4->%# *?# 4:%# GEHRING, A. U., LANGER, M. R. & GEHRING, C. A.#@6__aAQ#S%&&(?%&-
eUN#;*=)/.&-#@M+#e%?#.&%.B#$=)(1(.A"#h#W)4%&).4"#R"#*?#M.&4:#L3(- ous bacterial encrustations in lateritic duricrusts from southern
ences 100Q#`G5nhnàb" Mali (West Africa). – Geoderma 61Q#!6\nhn!!!"
DIXON, J. C.#@6__aAQ#K=&(3&=141"#h#W)Q#ABRAHAMSB#O"#K"#|#PARSONSB# GILG, H. A., BONI, M., HOCHLEITNER, R. & STRUCK, U.#@!GGÀQ#L4.;+%#
O"#R"#@%/1"AB#o%*'*&>:*+*,-#*?#K%1%&4#M)9(&*)'%)41"#0:.>'.)# isotope geochemistry of carbonate minerals in supergene oxida-
.)/#7.++B#k*)/*)B#>>"#`!nh6G5" tion zones of Zn–Pb deposits. – Ore Geol. Reviews 33Q#66Fh6\\"
DURY, G. H. & KNOX, J. C.#@6_F6AQ#K=&(3&=141#.)/#/%%>C8%.4:%&(),# GLENNIEB#e"#P"#@!GG5AQ#$:%#/%1%&4#*?#L*=4:%.14#O&.;(."#h#o%*O&.-
>&*2+%1#()#1*=4:8%14%&)#P(13*)1()"#h#L3(%)3%#174Q#!_6hn!_!" ;(.#L>%3"#d*+"B#E.).'.B#!6\#>>"
EMMONS, S. F.#@6_GGAQ#$:%#1%3*)/.&-#%)&(3:'%)4#*?#*&%#/%>*1(41"#h# GOOSSENSB#N"#R"#@6_FÀQ#$:%#'%4.++*,%)(3#>&*9()3%1#*?#T=&'."#$:%(&#
Amer. Inst. of Mining Engineers Transactions 30Q#6FFhn!6F" /%2)(4(*)1B#,%*+*,(3#&%+.4(*)1:(>1B#.)/#4:%(&#%D4%)1(*)#()4*#0:(-
ESSARRAJ, S., BOIRON, M. C., CATHELINEAU, M., BANKS, D. A. & BEN- ).B#W)/(.B#.)/#$:.(+.)/"#h#W)Q#N&*3%%/(),1#*?#4:%#$:(&/#J%,(*).+#
HARREF, M.#@!GG5AQ#N%)%4&.4(*)#*?#1=&?.3%C%9.>*&.4%/#;&()%1#()4*#
Conference on Geology and Mineral Resources of Southeast
4:%# N&*4%&*H*(3# ;.1%'%)4# .)/# /%>*1(4(*)# *?# 0*# .)/#O,# .4# T*=#
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Earth Sciences 41Q#!5nhn\_"
ETTLER,V., LEGENDRE, O., BODÉNAN, F. & TOURAY, J.-C.#@!GG6AQ#N&(- phology-Precipitates and residua in the near-surface environ-
mary phases and natural weathering of old lead–zinc pyrometal- '%)4"#h#O3./%'(3#N&%11B#k*)/*)B#a\_#>>"
+=&,(3.+#1+.,#?&*'#N&;&.'B#0H%3:#J%>=;+(3"#h#0.)./(.)#E()%&- GOUDIEB#O"# L"# |#VILESB# 7"#O"# @6___AQ#$:%# ?&%Y=%)3-# .)/# '.,)(-
alogist 39Q#`F\nhn```" tude concept in relation to rock weathering. – Z. Geomorph.
EVANSB#O"# E"# @6__\AQ# <&%# ,%*+*,-# .)/# ()/=14&(.+# E()%&.+1# h#O)# N. F. Suppl. 115Q#6F5nh6`_"
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SO<#@6__5AQ#o+*;.+#.)/#).4(*).+#1*(+1#.)/#4%&&.()#/(,(4.+#/.4.;.1%1# 4&(;=4(*)"#h#6F4:#P0LLB#T.),Z*ZB#$:.(+.)/"
(SOTER) – Procedures Manual. World Soil Resources Reports GREGORY-WODZICKIB# e"# E"# @!GGGAQ# ^>+(?4# :(14*&-# *?# 4:%# 0%)4&.+#
Fa#J%9"#6AQ#SO<B#^)(4%/#X.4(*)1" .)/#X*&4:%&)#O)/%1"#O#&%9(%8"#h#o%*+"#L*3"#*?#O'%&"#T=++"#112Q#
FELDMANN, M., NEHER, J., JUNG, W. & GRAF, F. @6__FAQ# S=),.+# 1091–1105.
Y=.&4H#8%.4:%&(),#.)/#(&*)#3&-14.++()%#?*&'.4(*)#()#.)#O+>()%#%)- GUDDENB# 7"# @6_F5AQ# V=&# T+%(?{:&=),# ()# $&(.1CL%/('%)4%)# /%&#
vironment. – Eclog. Geol. Helvetiae 90Q#5a6hn55b" )&/+(3:%)#<;%&>?.+H"#h#o%*+*,(3.#T.9.&(3.#74Q#\\nhn55"
FERRIS, F. G., HALLBECK, L., KENNEDY, C. B. & PEDERSEN, K.#@!GGaAQ# HAHNE, K., VIETOR, T., TRUMBULL, R. & KAUFMANN, H.#@!GG6AQ#J%-
Geochemistry of acidic Rio Tinto headwaters and role of bacteria mote sensing studies of dike distribution in the Cretaceous Hen-
in solid phase metal partitioning. – Chem. Geol. 212Q#!_6hn\GG" 4(%1#T.-h<=4j*#K(Z%#18.&'B#XP#X.'(;(."#h#W)4%&).4(*).+#K(Z%#
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%,.+#*33(/%)4.+B#%4.>%1#%4#,=(/%1#/%#+x.+4%&.4(*)"#h#L3(%)3%#o%*+"# !GG6B#>"#6"
Memoire 67Q#6hn!a_" HAK, J., JOHAN, Z., KVACEK, M. & LIEBSCHER, W. @6_b_AQ#e%''+(4H-
FOOD AND AGRICULTURE ORGANIZATION OF THE UNITED NATIONS (4%#.#)%8#'()%&.+#*?#4:%#8**/:*=1%(4%#,&*=>"#h#X"#R;"#E()%&"#E:"#
@!GGÀQ#P*&+/#J%?%&%)3%#T.1%#?*&#L*(+#J%1*=&3%1#!GGb"#h#6st Up- 1969Q#!G6hn!6!"
/.4%#!GGF#o%&'.)#%/(4(*)B#ToJi#6aa#>>" HAMBLETON-JONES, B. B., HEARD, R. G. & TOEN, P. D.#@6_àAQ#MD>+*-
FRÍAS, D., NOUSIR, S., BARRIO, I., MONTES, M., LÓPEZ, T., CENTENO, &.4(*)#?*&#1=&23(.+#=&.)(='#/%>*1(41"#h#W)Q#TOENB#N"#K"#@%/"AB#L=&2-
M. A. & ODRIOZOLA, J. A.#@!GGFAQ#L-)4:%1(1#.)/#3:.&.34%&(H.4(*)# 3(.+#^&.)(='#K%>*1(41"#WOMOC$%3/*3C\!!B#d(%)).B#>"#b6hnba"
of cryptomelane- and birnessite-type oxides. – Precursor effect HARRISB#L"#O"#@6__aAQ#0+('.4(3#H*).+(4-#*?#>%&(,+.3(.+#+.)/?*&'1#()#
Materials Characterization 58Q#FFbnhF`6" mountain areas. – Arctic 47Q#6ành6_!"
FROST, R. L., DING, Z., KLOPROGGE, J. T. & MARTENS, W. N.#@!GG!AQ# HARTLEBB#R"#P"#<"#@6_`ÀQ#$:%#k.),%&#7%()&(3:#^&.)(='#K%>*1(4"#
Thermal stability of azurite and malachite in relation to the for-
Southwest Namibia. – Ore Geol. Reviews 3Q#!FFhn!`F"
mation of mediaeval glass and glazes. – Thermochimica Acta
HAUPTMANN, S., LIPPOLT, H. J. @!GGGAQ# 40O&U39Ar dating of central
390Q#6\\nh6aa"
European K-Mn oxides – a chronological framework of super-
GABOREAU, S., BEAUFORT, D., VIELLARD, PH., PATRIER, P. & BRUNE-
gene alteration processes during the Neogene. – Chem. Geol.
TON, P.#@!GG5AQ#O+='()(='#>:*1>:.4%C1=+?.4%#'()%&.+1#.11*3(.4%/#
with Proterozoic unconformity-type uranium deposits in the East 170Q#\Fhn`G"
O++(,.4*&#J(9%&#^&.)(='#S(%+/B#X*&4:%&)#$%&&(4*&(%1B#O=14&.+(."#h# HAVEL, J. J.#@!GGGAQ#M3*+*,-#*?#4:%#?*&%141#*?#1*=4:#8%14%&)#O=14&.+-
Canadian Mineralogist 43Q#`6\nhn`!F" (.#()#&%+.4(*)#4*#3+('.4%#.)/#+.)/?*&'1"#h#N:K#4:%1(1B#E=&/*3:#
GABOREAU, S., CUNEY, M., QUIRT, D., BEAUFORT, D., PATRIER, P. & ^)(9%&1(4-B#\``#>>"
MATHIEU, R.# @!GGFAQ# L(,)(23.)3%# *?# .+='()(='# >:*1>:.4%C1=+- HILLIERB#L"#@6__5AQ#M&*1(*)B#1%/('%)4.4(*)#.)/#1%/('%)4.&-#*&(,()#
fate minerals associated with U unconformity-type deposits. The *?#3+.-1"#h#W)Q#VELDEB#T"#@%/"AB#<&(,()#.)/#'()%&.+*,-#*?#3+.-1"#
O4:.;.13.#;.1()B#0.)./."#h#O'%&(3.)#E()%&.+*,(14#92Q#!bFhn!`G" X%8#w*&ZB#L>&(),%&Cd%&+.,B#>"#6b!nhn!6_"
GALLEY, A. G. & KOSKI, R. A.# @6___AQ# L%44(),# .)/# 3:.&.34%&(1- HITZMANB#E"#P"#@6__5AQ#E()%&.+(H.4(*)#()#4:%#W&(1:#V)CN;C@T.CO,A#
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0"#$"#T.&&(%#.)/#K"#E"#7.))(),4*)B#d*+3.)(3C.11*3(.4%/#'.11(9%# & SEARS, S.#@%/1"AB#W&(1:#0.&;*).4%C:*14%/#V)CN;#K%>*1(41"#L*3"#
1=+2/%#/%>*1(41i#>&*3%11%1#.)/#%D.'>+%1#()#'*/%&)#.)/#.)3(%)4# *?#M3*)*'(3#o%*+*,(141B#o=(/%;**Z#L%&(%1#!6Q#!5nhnb6"
1%44(),1"#h#L*3*&&*B#XEB#^)(4%/#L4.4%1B#L*3(%4-#*?#M3*)*'(3#o%- HOLDENB#R"#@!GGÀQ#O)#W)4&*/=34(*)#4*#N:-1(3.+#o%*,&.>:-#.)/#4:%#
ologists 8B#>"#!!6hn!ab" M)9(&*)'%)4"#h#N&%)4(3%#7.++B#Fb_#>>"
HUCKRIEDE, R., KÜRSTEN, M. & VENZLAFF, H. (6_b!AQ#V=&#o%*+*,(%# KROLL, T., MÜLLER, D., SEIFERT, T., HERZIG, P. M. & SCHNEIDER, A.
/%1#o%;(%4%1#H8(13:%)#e%&'.)#=)/#L.,.)/#@W&.)A"#h#T%(:"#H='# @!GG!AQ# N%4&*+*,-# .)/# ,%*3:%'(14&-# *?# 4:%# 1:*1:*)(4%C:*14%/#
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HUKUO, K. & HIKICHI Y.#@6_F_AQ#L-)4:%1%1#*?#&.&%#%.&4:#*&4:*>:*1- Deposit. 37Q#6\Fh6aa"
phates (RPO4·nH2<B#J"#"k.CCCw;B#)"#"Gnhn!A"#h#T=++"#X.,*-.#W)14"# KUŠNIRB#W"#@6_baAQ#J%1=+4.41#/%1#4&.9.=D#/%#&%3:%&3:%#%4#/%#>&*1>%3-
of Technol. 31Q#6F5nh6`!#@()#R.>.)%1%A" 4(*)#/.)1#+.#&~,(*)#/%#0:*#K(%)"#h#^)>=;+"#J%>*&4#K(&%34*&#o%)-
HUSTON, D. L. & KAMPRAD, J.#@!GGGAQ#$:%#8%14%&)#$:.&1(1#/%>*1(4# %&.+#o%*+*,-#d(%4).'#7.)*(B#!55#>>"
h#Og:(,:#1=+>:(/.4(*)g#0=CO=#/%>*1(4#()#4:%#E4#k-%++#2%+/B#*?# LALB#J"#@!GG5AQ#M)3-3+*>%/(.#*?#1*(+#13(%)3%1"#h#!nd#%/(4(*)B#$.-+*&#
possible Ordovician age. – AGSO Research Newsletter 32Q#!nhnb" .)/#S&.)3(1#W)3B#6bGG#>>"
HUTCHINSONB#0"#L"#@6_`\AQ#M3*)*'(3#/%>*1(41#.)/#4:%(&#4%34*)(3#1%4- LANGTONB# R"# E"# @6_F\AQ# <&%# ,%)%1(1# ()# 4:%# E*&%)3(CE%43.+?# /(1-
4(),"#h#E.3'(++.)B#k*)/*)#365 pp. trict. – American Inst. of Mining Engineers Transactions 254Q#
ILANI, S. & STRULL, A.#@6_`ÀQ#^&.)(='#'()%&.+(H.4(*)#()#4:%#R=/%.)# !aFhn!5F"
K%1%&4#.)/#()#4:%#)*&4:%&)#X%,%9B#W1&.%+"#h#<&%#o%*+"#J%9(%81#4Q# LAVEEB# 7"B# IMESONB#O"# 0"# & SARAHB# N"# @6__ÀQ#$:%# ('>.34# *?# 3+(-
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JAMES, R. E. & FERRIS, F. G.#@!GGaAQ#M9(/%)3%#?*&#'(3&*;(.+#'%/(- iterranean-arid transect. – Land Degradation and Developm. 9Q#
ated iron oxidation at a neutrophilic groundwater spring. – Chem. aGFhna!!"
Geol. 212Q#\G6hn\66" LAZNICKAB#N"#@!GG5AQ#o(.)4#'%4.++(3#/%>*1(41"#S=4=&%#1*=&3%1#*?#()-
JERZ, J. K. & RIMSTIDT, J. D.#@!GG\AQ#M?[*&%13%)4#(&*)#1=+?.4%#'()- /=14&(.+#'%4.+1"#h#L>&(),%&B#T%&+()B#7%(/%+;%&,B#F\!#>>"
%&.+1"#N.&.,%)%1(1B#&%+.4(9%#14.;(+(4-B#.)/#%)9(&*)'%)4.+#('>.34"# LEVERETT, P., MCKINNON, A. R. & WILLIAMS, P. A.#@!GG5AQ#L=>%&-
– American Mineralogist 88Q#6_6_nh6_\!" ,%)%#,%*3:%'(14&-#*?#4:%#%)/%.9*&#*&%#;*/-B#0*;.&B#XLPB#.)/#
KALOGEROPOULOS, S. I., KILIAS, S. P., BITZIOS, D. C., NICOLAOU, M. &%+.4(*)1:(>1# 4*# *4:%&# /%>*1(41# ()# 4:%# 0*;.&# T.1()"# h# J%,*+(4:#
& BOTH, R. A. @6_`_AQ#o%)%1(1#*?#4:%#<+-'>(.1#3.&;*).4%C:*14%/# !GG5#h#$%)#w%.&1#*?#0J0#kMEMB#>"#6_6h6_a"
N;CV)#@O=B#O,A#1=+2/%#*&%#/%>*1(4B#%.14%&)#0:.+Z(/(Z(#N%)()1=+.B# LLORCA, S. & MONCHOUX, P. @6__6AQ# L=>%&,%)%# 3*;.+4# '()%&.+1#
northern Greece. – Econ. Geol. 84Q#6!6Gnh6!\a" from New Caledonia. – Canadian Mineralogist 29Q#6a_nh6b6"
KAMITANI, M., OKUMURA, K., TERAOKA, Y., MIYANO, S. & WATANABE, LOSERTB#R"#@6_FaAQ#$:%#?*&'.4(*)#*?#14&.4(?*&'#3*>>%&#/%>*1(41#()#
Y. @!GGFAQ#E()%&.+#J%1*=&3%1#E.>#*?#M.14#O1(."#h#o%*+"#L=&9%-# relation to alteration of volcanic series (on north Chilean exam-
*?#R.>.)" >+%1A"#h#J%H>&.9-#%1Z*+*9%)1Z~#OZ./"#d/"#J*3)(Z#84Q#6hFF"
KAMONA, A. F., LÉVÊQUE, J., FRIEDRICH, G. & HAACK, U.# @6___AQ# LOTTERMOSERB# T"# o"# @6__GAQ# J.&%C%.&4:# %+%'%)4# '()%&.+(1.4(*)#
k%./#(1*4*>%1#*?#4:%#3.&;*).4%C:*14%/#e.;8%B#$1='%;B#.)/#e(- 8(4:()#4:%#E4"#P%+/#3.&;*).4(4%#+.4%&(4%B#P%14%&)#O=14&.+(."#h#k(-
>=1:(#N;CV)C0=#1=+2/%#/%>*1(41#()#&%+.4(*)#4*#N.)#O?&(3.)#*&*- thos 24Q#656h6bF"
,%)%1(1# ()# 4:%# K.'.&.)Ck=2+(.)# S*+/# T%+4# *?# 0%)4&.+#O?&(3."# h#
MACGREGOR, D. S. & MOODY, R. T. J.#@6__ÀQ#E%1*H*(3#.)/#0%)*-
Miner. Deposit. 34Q#!F\nhn!`\"
H*(3#>%4&*+%='#1-14%'1#*?#X*&4:#O?&(3."#h#W)Q#MACGREGOR, D. S.,
KASAMA, T. & MURAKAMI, T.# @!GG6AQ# $:%# %??%34# *?# '(3&**&,.)-
MOODY, R. T. J. & CLARK-LOWES, D. D.#@%/"AB#N%4&*+%='#o%*+*,-#
isms on Fe precipitation rates at neutral pH. – Chem. Geol. 180Q#
*?#X*&4:#O?&(3.B#k*)/*)B#o%*+"#L*3"#L>%3"#N=;+"#132Q#!G6hn!6b"
117–128.
MAKSAEV, V., TOWNLEY, B., PALACIOS, C. & CAMUS, F.#@!GGFAQ#E%-
KEITH, W. J., CALK, L. & ASHLEY, R. P.#@6_F_AQ#0&-14.+1#*?#3*%D-
4.++(3#*&%#/%>*1(41"#h#W)Q#MORENO, T. & GIBBONS, W.#@%/1"AB#$:%#
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4(*)#E()%&.+*,-#N%4&*+*,-"#h#^L#o%*+"#L*3"B#N&*?%11(*).+#N.>%&#
MANASSE, A. & MELLINI, M.#@!GG!AQ#0:%'(3.+#.)/#4%D4=&.+#3:.&.3-
66!aC0B#>>"#06h05"
KHADKIKAR, A. S., CHAMYAL, L. S. & RAMESH, R.#@!GGGAQ#$:%#3:.&- terization of medieval slags from the Massa Marittima smelting
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GALIEVA, M. R.#@6__\AQ#$:%&'*/-).'(3#>&*>%&4(%1#*?#3*>>%&#1(+(-
& SLATER, R. A.#@%/1"AB#E()%&.+#/%>*1(41#*?#M=&*>%B#!B#L*=4:%.14#
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25Q#b!6hnb\G" MARSCHIK, R. & SÖLLNER, F.#@!GGbAQ#M.&+-#0&%4.3%*=1#^hN;#H(&3*)#
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.)/#'%4.'*&>:*1%/#'.11(9%#1=+2/%#/%>*1(4"#h#M3*)"#o%*+"#82Q# Miner. Deposit. 41Q#F`5nhn`G6"
5`Fhn5__" MARVIN, R. F., NAESER, C. W., BIKERMAN, M., MEHNERT, H. H. &
KOESOEMADINATAEB#J"#N"#@6_`5AQ#W)4&*/=34(*)#*?#4:%#,%*+*,-#*?#8%14# RATTE, J. C.# @6_`FAQ# W1*4*>(3# .,%1# *?# >*14CN.+%*3%)%# (,)%*=1#
R.9."#h#^)>=;+"#J%>*&4#*?#4:%#o%*+*,(3.+#L=&9%-#*?#W)/*)%1(.B# &*3Z1#8(4:()#.)/#;*&/%&(),#4:%#0+(?4*)#6#I#!#Y=./&.),+%B#O&(H*-
T.)/=),B#!`#>>" ).CX%8#E%D(3*"#h#X%8#E%D(3*#T=&%.=#*?#E()%1#.)/#E()%&.+#
KONHAUSER,# e"# <"# @6__ÀQ# K(9%&1(4-# *?# ;.34%&(.+# (&*)# '()%&.+(H.- J%1*=&3%1B#T=++"#118Q#5nhnb\"
tion. – Earth Science Reviews 43Q#_6h6!6" MATHIESENB#0"#<"#@6_b_AQ#O)#*33=&&%)3%#*?#=)=1=.+#'()%&.+1#.4#T(/-
KOTTEK, M., GRIESER, J., BECK, C., RUDOLF, B. & RUBEL, F.#@!GGbAQ# jovagge. – Northern Norway. Norges Geologiske Undersøkelse
P*&+/#'.>#*?#e>>%)Co%(,%&#0+('.4%#0+.11(23.4(*)#=>/.4%/"#h# 266Q#`bnh6Ga"
Met. Z. 15Q#!5_nhn!b\" MAVROPOULOS, E., ROSSI, A., COSTA, A., PEREZ, C., MOREIRA, J. &
KRASILNIKOV, P., MARTI, I., ARNOLD, R. & SHOBA, S. A.# @!GG_AQ# SALDANHA, M.# @!GG!AQ# L4=/(%1# *)# 4:%# '%3:.)(1'1# *?# +%./# ('-
7.)/;**Z# *?# L*(+#$%&'()*+*,-B# 0*&&%+.4(*)# .)/# 0+.11(23.4(*)"# mobilization by hydroxyapatite. – Environm. Science Technol.
h#M.&4:13.)B#aaG#>>" 36Q#6b!5nh6b!_"
MCPHAIL, D. C., SUMMERHAYES, E., WELCH, S. & BRUGGER, J.#@!GG\AQ# NÄVEKEB# J"# @6_`bAQ# T.34%&(.+# +%.3:(),# *?# *&%1# .)/# *4:%&# '.4%&(-
$:%# o%*3:%'(14&-# *?# V()3# ()# 4:%# J%,*+(4:"# h# W)Q# ROACHB# W"# 0"# .+1"#h#W)14(4=4#?{&#E(Z&*;(*+*,(%B#$%3:)(13:%#^)(9%&1(4y4#T&.=)-
@%/"AB#O/9.)3%1#()#J%,*+(4:"#0J0#?*&#k.)/13.>%#M)9(&*)'%)41# 13:8%(,B# *)+()%Q# 888"1>.3%1:(>C%.&4:"/%UJMEUX.%9%Z%":4'#
.)/#E()%&.+#MD>+*&.4(*)B#>>"#!`Fhn!_6" (eingesehen 18.06.2010)
MCPHAIL, D. C., SUMMERHAYES, E., JAYARATNE, V. & CHRISTY, A. NELSON, M., KYSER, K., CLARK, A. & OATES, C.#@!GGFAQ#0.&;*)#(1*-
@!GGbAQ#7%'('*&>:(4%#1*+=;(+(4-#.)/#14.;(+(4-#*?#+*8C$#H()3#'()- tope evidence for microbial involvement in exotic copper silicate
%&.+1"#h#o%*3:('"#0*1'*3:('"#O34.B#9"#L=>>+"#1B#Oa6anhOa6b" '()%&.+(H.4(*)B# 7=()Y=()4(>.# .)/# E().# L=&B# X*&4:%&)# 0:(+%"# h#
MCQUEEN, K. G.# @!GGbAQ# 0.+3&%4%# ,%*3:%'(14&-# ()# 4:%# 0*;.&C Econ. Geol. 102Q#6\66h6\!G"
0(&(+.';*)%#&%,(*)B#X%8#L*=4:#P.+%1"#h#0J0#kMEM#<>%)#S(+%# NICKEL, E. H.#@6__5AQ#K%2)(4(*)#*?#.#'()%&.+"#h#E()%&"#E.,"#59Q#
Report 200. 767–768.
MEADOWSB# E"# M"# @!GG6AQ# $:%# &*+%# *?# ]=.4%&).&-# %)9(&*)'%)4.+# NORRISB#N"#J"#@!GGFAQ#O3(/*>:(+%#/(9%&1(4-#()#'()%&.+#1=+2/%#*D(/.-
3:.),%#()#4:%#%9*+=4(*)#*?#+.)/13.>%1Q#3.1%#14=/(%1#?&*'#1*=4:%&)# 4(*)"#h#W)Q#RAWLINGSB#K"#M"#|#JOHNSONB#K"#T"#@%/1"AB#T(*'()(),B#
Africa. – Catena 42Q#\_nhn5F" L>&(),%&B#T%&+()B#7%(/%+;%&,B#6__nhn!6b"
MEDRANO, M. D. & PIPER, D. Z.#@6__FAQ#S%C0.C>:*1>:.4%B#S%C1(+(- NORTHROPB#K"#O"#|#CLAYTONB#J"#X"#@6_bbAQ#<D-,%)C(1*4*>%#?&.3-
3.4%B#.)/#E)C*D(/%#'()%&.+1#()#3*)3&%4(*)1#?&*'#4:%#E*)4%&%-# 4(*).4(*)1# ()# 1-14%'1# 3*)4.()(),# /*+*'(4%"# h# R"# *?# o%*+*,-# 74Q#
Formation. – Chem. Geol. 138Q#_nhn!\" 6Fanh6_b"
MELCHIORRE, E. B. & ENDERS, M. S.# @!GG\AQ# L4.;+%# (1*4*>%# ,%*- NOTEBAARTB# 0"# P"# |# KOROWKIB# L"# N"# @6_`GAQ# S.'*=1# '()%&.+# +*-
chemistry of copper carbonates at the Northwest Extension de- 3.+(4(%1Q# $:%# T&*Z%)# 7(++# '()%# @V.';(.A"# h# E()%&"# J%3*&/# 11Q#
>*1(4B# E*&%)3(# /(14&(34B#O&(H*)."# ('>+(3.4(*)1# ?*&# 3*)/(4(*)1# *?# \\_nhn\a`"
supergene oxidation and related mineralization. – Econ. Geol. NRIAGU, J. O. & MOORE, P. B.#@6_àAQ#N:*1>:.4%#'()%&.+1"#h#L>&(),-
98Q#bGFhnb!6" %&B#T%&+()B#7%(/%+;%&,B#X%8#w*&ZB#$*Z-*B#aa!#>>"
MELCHIORRE, E. B., WILLIAMS, P. A. & BEVINS, R. E.#@!GG6AQ#O#+*8# NRIAGUB#R"#<"#@6_FbAQ#N:*1>:.4%C3+.-#'()%&.+#&%+.4(*)1#()#1*(+1#.)/#
4%'>%&.4=&%#*D-,%)#(1*4*>%#4:%&'*'%4%&#?*&#3%&=11(4%B#8(4:#.>- 1%/('%)41"#h#0.)./(.)#R"#*?#M.&4:#L3(%)3%1#13Q#F6FhF\b"
>+(3.4(*)1# .4# T&*Z%)# 7(++B# )%8# L*=4:# P.+%1B#O=14&.+(."# h# o%*- O’NEIL, J. R., CLAYTON, R. N. & MAYEDA, T. K.# @6_b_AQ# <D-,%)#
chim. Cosmochim. Acta 65Q#!5!Fhn!5\\" (1*4*>%#?&.34(*).4(*)#()#/(9.+%)4#'%4.+#3.&;*).4%1"#h#R"#*?#0:%'"#
MENSCHEL, G. & USDOWSKI, E.# @6_F5AQ# MD>%&('%)4%++%# ^)4%&1=- Physics 51Q#55aFhn555`"
3:=),%)# {;%&# /(%# L4.;(+(4y4# 9*)# 0=Ce.&;*).4# H=&# e+y&=),# /%&# OLEJNIK,#R"#|#KEDZIORA,#O"#@6__6AQ#O#'*/%+#?*&#:%.4#.)/#8.4%&#;.+-
Genese von Azurit im Cornberger Sandstein. – Contributions to ance estimation and its application to land use and climate varia-
Miner. and Petrol. 49Q#6a6h6aF" tion. – Earth Surf. Proc. and Landf. 16Q#bG6hnb6F"
ORTEGA, L., OYARZUN, R. & GALLEGO, M.#@6__bAQ#$:%#E.&-#J*1.#
!"#$%B#N"#@!GGbAQ#o&.)(4%#+.)/13.>%1#*?#4:%#8*&+/"#h#<D?*&/#^)(-
k.4%# 7%&3-)(.)# L;CO=# /%>*1(4B# 8%14%&)# L>.()"# o%*+*,-# .)/#
9%&1(4-#N&%11B#X%8#w*&ZB#\à#>>"
geochemistry of mineralizing processes. – Miner. Deposit. 31Q#
MOOLICK, R. T. & DUREK, J. J.#@6_bbAQ#$:%#E*&%)3(#/(14&(34"#h#W)Q#TI-
6F!nh6`F"
TLEY, S. R. & HICKS, C. L.#@%/1"AB#o%*+*,-#*?#4:%#>*&>:-&-#3*>>%&#
OYARZUNB# R"# @6__GAQ# $:%# '%4.++(?%&*=1# *&%# /%>*1(41# *?# 0:(+%# .)/#
/%>*1(41B#1*=4:8%14%&)#X*&4:#O'%&(3."#h#^)(9%&1(4-#*?#O&(H*).#
O&,%)4()%# .)/# 4:%(&# ,%*+*,(3.+# ?&.'%8*&Z"# h# W)Q# FONTBOTE, L.,
N&%11B#$=31*)B#>"#!!6hn!\6"
AMSTUTZ, G. C., CARDOZO, M., CEDILLO, E. & FRUTOS, J. (%/1"AB#
MORDBERGB#k"#M"#@6___AQ#o%*3:%'(3.+#%9*+=4(*)#*?#.#K%9*)(.)#/(.-
L4&.4.;*=)/#*&%#/%>*1(41#()#4:%#O)/%1"#L>&(),%&B#T%&+()B#`65#>>"
1>*&%h3&.)/.++(4%h19.);%&,(4%C;%.&(),# 8%.4:%&(),# >&*2+%# ()# 4:%#
PEDRONIB#o"# @6__bAQ#k%#/(14&(34#'()(%&#/%#0%&&*#/%#N.13*#h#O)/%#
E(//+%#$('.)B#J=11(."#h#R"#*?#o%*3:%'"#MD>+*&"#66Q#\5\nhn\b6" N~&=9(%)%"#h#J(9(14.#E()%&.+*,(3.#W4.+(.).#4Q#\b\nhn\F6"
MORDBERG, L. E., STANLEY, C. J. & GERMANN, K.#@!GG6AQ#E()%&.+*- PEEL, M. C., FINLAYSON, B. L. & MCMAHON, T. A.#@!GGFAQ#^>/.4%/#
gy and geochemistry of trace elements in bauxites. the Devonian 8*&+/# '.># *?# 4:%# e>>%)ho%(,%&# 3+('.4%# 3+.11(23.4(*)"# h# 7--
L3:=,*&1Z#/%>*1(4B#J=11(."#h#E()%&"#E.,"#65Q#`6h6G6" drol. Earth System Sciences 11Q#6b\\nh6baa"
MOSSMAN, D. J. & HEFFERMAN, K. J.#@6_FÀQ#<)#4:%#>*11(;+%#>&('.- PETERSON, R. C. & GRANT, A. H.#@!GG5AQ#K%:-/&.4(*)#.)/#3&-14.+-
ry precipitation of atacamite and other metal chlorides in certain lization reactions of secondary sulfate minerals found in mine
stratabound deposits. – Chem. Geol. 21Q#656h65_" waste. in situ powder-diffraction experiments. – Canadian Min-
MOTE, T. I., BECKER, T. A., RENNE, P. & BRIMHALL, G. H. @!GG6AQ# eralogist 43Q#66F6h66`6"
0:&*)*+*,-# *?# %D*4(3# '()%&.+(H.4(*)# .4# M+# L.+9./*&B# 0:(+%B# ;-# PETZEL, V. F. W.#@6__bAQ#$:%#%3*)*'(3#>*4%)4(.+#*?#4:%#E.43:+%11#
40
O&U39Ar dating of copper wad and supergene alunite. – Econ. '()(),# .&%."# h# E()(),# k(3%)3%# EabUaU\"# ^)>=;+(1:%/# &%>*&4B#
Geol. 96Q#\56hn\bb" P()/:*%ZB65#>>"
MÜLLER, P. & WEISER, T.#@6_`6AQ#L4=/(%1#*?#4:%#>%4&*+*,-#.)/#*&%# PHARAOH, T., RAMSAY, D. M. & JANSEN, Ø.#@6_`\AQ#L4&.4(,&.>:-#.)/#
'()%&.+*,-#()#4:%#.&%.#*?#4:%#T.8/()#*&%#/(14&(34B#X*&4:%&)#L:.)# structure of the northern part of the Repparfjord- Komagfjord
L4.4%B#T=&'."#h#o%*+"#R.:&;"#K#43Q#5\nhnba" P()/*8B#S())'.&ZB#X*&4:%&)#X*&8.-"#h#X*&,%1#o%*+*,(1Z%#^)-
MUNOZ, M., COURJAULT-RADÉ, P. & TOLLON, F.#@6__!AQ#$:%#'.11(9%# dersøkelse 377Q#6hna5"
stibnite veins of the French Palaeozoic basement. a metalloge- PHILLIPS, J. D., LAMPE, M., KING, R. T., CEDILLO, M., BEACHLEY, R. &
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171–177. Coastal Plain. – Z. Geomorph. N. F. 41Q#bFhF_"
MUWANGAB#O"#@6__FAQ#M)9(&*)'%)4.+#('>.341#*?#0*>>%&#'()(),#.4# PIRAJNO, F., BURLOW, R. & HUSTON, D.# @!G6GAQ# $:%# E.,%++.)# N;#
e(+%';%B# ^,.)/."#O# ,%*3:%'(3.+# ()9%14(,.4(*)# *?# :%.9-# '%4.+# /%>*1(4B# P%14%&)#O=14&.+(.i# .# )%8# 3.4%,*&-# 8(4:()# 4:%# 3+.11# *?#
>*++=4(*)#*?#/&.().,%#8.4%&1B#14&%.'#1%/('%)41#.)/#1*(+1#()#4:%# 1=>%&,%)%#)*)C1=+2/%#'()%&.+#1-14%'1"#h#<&%#o%*+*,-#J%9(%81#
Kilembe valley in relation to mine waste disposal. – Unpublished 37Q#6G6h66\"
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Internat. 111Q#\nhn!!" $:.(+.)/B#6_nhn!aB#O=,=14#6__FB>"#Fa`nhF5`"
PSYRILLOS, A., MANNING, D. A. C. & BURLEY, S. D.# @6__ÀQ# o%*- SCHINDLER, M., HAWTHORNE, F. C. & BAUR, W. H.#@!GGGAQ#O#3&-14.+C
chemical constraints on kaolinisation in the St. Austell gran- chemical approach to the composition and occurrence of vana-
(4%B# 0*&)8.++B# M),+.)/"# h# R"# *?# 4:%# o%*+"# L*3"# *?# k*)/*)# 155Q# dium minerals. – Canadian Mineralogist 38Q#6aa\nh6a5b"
`!_nhnàG" SCHMID, H.#@6_`6AQ#V=&#T+%(?{:&=),#()#/%&#'(44+%&%)#$&(.1#/%&#<;%&>-
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A-39Ar age of hypogene and supergene mineralization in the j(),B#0:().B#6`nhn!6#O=,=14#!GG5B#6F5nh6F`"
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Peru. – Econ. Geol. 98Q#6b`\nh6b_b"
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4:%# L:=),=&.# S*&'.4(*)B# 1*=4:8%14%&)# M4:(*>(."# h# O'%&(3.)# o%&.(1B# T&.H(+"# E.11# ;.+.)3%# .)/# 14.;+%# (1*4*>%# 3:.&.34%&(14(31#
Mineralogist 64Q#6b_nh6F6" of the hydrothermal alterations. – Gondwana Res. 11Q#\b!nhn\`6"
ROSE, A. W.#@6_FbAQ#$:%#%??%34#*?#3=>&*=1#3:+*&(/%#3*'>+%D%1#()# SOARES MONTEIRO, L. V., BETTENCOURT, J. S., SPIRO, B., GRACA, R. &
DE OLIVEIRA, T. F.#@6___AQ#$:%#d.H.)4%#H()3#'()%B#E().1#o%&.(1B#
the origin of red-bed copper and related deposits. – Econ. Geol.
71Q#6G\bnh6Ga`" T&.H(+i#3*)14&.()41#()#8(++%'(4(3#'()%&.+(H.4(*)#.)/#[=(/#%9*+=-
RUDOLPH, W. W., MASON, R. & SCHMIDT, P.#@!GG\AQ#L-)4:%4(3#.+=- tion. – Exploration and Mining Geol. 8Q#!6hna!"
STAHR, K., KANDELER, E., HERRMANN, L. & STRECK, T. @!GGÀQ#
nites of the potassium-oxinium solid solution series and some
T*/%)Z=)/%#=)/#L4.)/*&4+%:&%#h#o&=)/8(11%)#T.3:%+*&"#h#M=-
*4:%&#'%';%&1#*?#4:%#,&*=>"#1-)4:%1(1B#4:%&'.+#.)/#IC&.-#3:.&-
,%)#^+'%&#d%&+.,B#L4=44,.&4"
.34%&(H.4(*)"#h#M=&"#R"#E()"#15Q#_6\nhn_!a"
STOFFREGEN, R. E. & ALPERS, C. N.#@6_`FAQ#P**/:*=1%(4%#.)/#19.)-
RUFFET, G., INNOCENT, C., MICHARD, A., FÉRAUD, G., BEAUVAIS,
bergite in hydrothermal ore deposits. products of apatite destruc-
A., NAHON, D. & HAMELIN, B.# @6__bAQ# O# ,%*3:&*)*+*,(3.+# tion during advanced argillic alteration. – Canadian Mineralogist
40
O&U39Ar and 87J;U81Sr study of K-Mn oxides from the weather- 25Q#!G6hn!66"
(),#1%Y=%)3%#*?#OH=+B#T&.H(+"#h#o%*3:('"#0*1'*3:('"#O34.#60Q# STOFFREGENB# J"# M"# @6__\AQ# L4.;(+(4-# &%+.4(*)1# *?# j.&*1(4%# .)/# ).-
!!6_nhn!!\!" 4&*.+=)(4%# .4# 6GGnhn!5G#c0"# h# o%*3:('"# 0*1'*3:('"# O34.# 58Q#
RYE, R. O. & SAWKINS, F. J.#@6_FaAQ#S+=(/#W)3+=1(*)#.)/#14.;+%#(1*- _G\nhn_6b"
4*>%#14=/(%1#*)#4:%#0.1.>.+3.#O,CN;CV)C0=#K%>*1(4B#0%)4&.+#O)- SUMMERFIELD, M. A.#@6__6AQ#o+*;.+#,%*'*&>:*+*,-"#h#R*:)#P(+%-#
/%1B#N%&="#h#M3*)"#o%*+"#69Q#6`6hn!G5" .)/#L*)1#W)3"#X%8#w*&ZB#5\F#>>"
SAWKINS, F. J.#@6__GAQ#E%4.+#/%>*1(41#()#&%+.4(*)#4*#>+.4%#4%34*)(31"#h# SUREDA, R. J., GALLISKI, M. A., ARGANARAZ, P. & DAROCA, J.#@6_`bAQ#
L>&(),%&B#T%&+()B#7%(/%+;%&,B#X%8#w*&ZB#$*Z-*B#ab6#>>" O1>%34*1# '%4.++*,%)~4(3*1# /%# X*&*%14%# O&,%)4()*# @N&*9()3(.#
SCHAETZL, R. J. & ANDERSON, S.#@!GG5AQ#L*(+1Q#,%)%1(1#.)/#,%*'*&- L.+4.#-#R=j=-A"#h#0.>&*3*&)(*#1Q#\_nhn_5"
>:*+*,-"#h#0.';&(/,%#^)(9%&1(4-#N&%11B#0.';&(/,%B#F_6#>>" (-,-27.)4'!6'&'()*+$*",-4'-6#@!GG_AQ#J%'.&Z1#*)#4:%#*&(,()#*?#
SCHEFFER, F. & SCHACHTSCHABEL, P. (6_FbAQ# k%:&;=3:# /%&# T*/%)- 3%&=11(4%#()#4:%#^>>%&#L(+%1(.)#V)CN;#/%>*1(41B#N*+.)/"#h#E()%&-
Z=)/%"#h#M)Z%#d%&+.,B#L4=44,.&4B#\_a#>>" alogia 40Q#5anhnba"
TABOADA, T., ROMERO, R. & GARCÍA-PAZ, C.# @6__GAQ# P%.4:%&(),# analytical electron microscopy. – American Mineralogist 79Q#
%9*+=4(*)#*?#.#;(*4(4%#,&.)(4%#@M+#N()/*B#o.+(3(.B#XP#L>.()A"#h# `Gnhn_G"
Chem. Geol. 84Q#6\Gnh6\!" WANHAINEN, C., BROMAN, C. & MARTINSSON, O. @!GG\AQ#$:%#O(4(Z#
TANDON, S. K. & NARAYAN, D.#@!GGbAQ#0.+3&%4%#3*),+*'%&.4%B#3.1%# Cu–Au–Ag deposit in northern Sweden. a product of high salin-
hardened conglomerate and cornstone- a comparative account of (4-#[=(/1"#h#E()%&"#K%>*1(4"#38Q#F65nhF!b"
pedogenic and non-pedogenic carbonate from the continental Si- WARDENB#O"# R"# @6_`5AQ# J%.>>&.(1.+# *?# ,%*+*,(3.+# 1%44(),# .)/# >*-
8.+(Z#o&*=>B#N=)j.;B#W)/(."#h#L%/('%)4*+*,-#28Q#\b!nhn\bF" 4%)4(.+#*?#e(+%';%#3*>>%&#'()%B#^,.)/."#h#$&.)1.34(*)1#*?#4:%#
TAYLOR, G. & EGGLETON, R. A.#@!GG_AQ#J%,*+(4:#,%*+*,-#.)/#,%*- W)14(4=4(*)#*?#E()(),#.)/#E%4.++=&,-B#T#94Q#_anh6G5"
'*&>:*+*,-"#h#R*:)#P(+%-#|#L*)1B#\F5#>>" WARREN, I., ARCHIBALD, D. A. & SIMMONS, S. F. @!GGÀQ#o%*3:&*-
THOMASB# E"# S"# @6__aAQ# o%*'*&>:*+*,-# ()# 4:%# $&*>(31"# h# P(+%-B# )*+*,-# *?# %>(4:%&'.+# O=CO,# '()%&.+(H.4(*)B# '.,'.4(3C:-/&*-
Chichester 460 pp. 4:%&'.+# .+4%&.4(*)B# .)/# 1=>%&,%)%# 8%.4:%&(),# ()# 4:%# M+# N%})#
THOMASB#E"#S"#@6__5AQ#E*/%+1#?*&#+.)/?*&'#/%9%+*>'%)4#*)#>.1- K(14&(34B#X*&4:%&)#0:(+%"#h#M3*)"#o%*+"#103Q#`56hn`ba"
sive margins. Some implications for relief development in glaci- WHITESANDB#M"#N"#@6_5\AQ#L*'%#&%+.4(*)1:(>1#;%48%%)#4:%#3+.11(23.-
ated areas. – Geomorphology 12Q#\nh65" 4(*)#*?#&*3Z1#;-#,%*+*,(141#.)/#4:%#3+.1#1(23.4(*)#*?#1*(+1#;-#1*(+#
THOMASB#E"#S"#@!GGaAQ#k.)/13.>%#1%)1(4(9(4-#4*#&.>(/#%)9(&*)'%)- scientists. – Soil Science Soc. Proc. 17Q#6\`nh6a!"
tal change – a Quaternary perspective with examples from tropi- WILDE, S. A., VALLEY, J. W., PECK, W. H. & GRAHAM, C. M.#@!GG6AQ#
cal areas. – Catena 55Q#6GFh6!a" Evidence from detrital zircons for the existence of continen-
THOMASB#E"#S"#!GG6AQ#k.)/13.>%#1%)1(4(9(4-#()#4('%#.)/#1>.3%#h#.)# tal crust and oceans on the Earth 4.4 Gyr ago. – Nature 409Q#
introduction. – Catena 42Q#`\nhn_`" 6F5nh6F`"
TITLEY#@%/"A#@!GG_AQ#L=>%&,%)%#M)9(&*)'%)41B#N&*3%11%1B#.)/#N&*/- WILLIAMSB#N"#O"#@6__GAQ#<D(/%#H*)%#,%*3:%'(14&-"#h#M++(1#7*&8.&/B#
ucts – SEG Spec. Publ. 14. X%8#w*&ZB#k*)/*)B#$*&*)4*B#L-/)%-B#$*Z-*B#L(),.>*&%B#!`b#>>"
WILSONB#J"#0"#k"#@6_`\AQ#J%1(/=.+#/%>*1(41"#L=&?.3%#&%+.4%/#8%.4:-
TRIANTAFYLLIDIS, S. & SKARPELIS, N.#@!GGbAQ#E()%&.+#?*&'.4(*)#()#
%&(),# >&*3%11%1# .)/# '.4%&(.+1"# h# o%*+"# L*3"# L>%3"# N=;+"# 66B#
.)#.3(/#>(4#+.Z%#?&*'#.#:(,:C1=+>:(/.4(*)#*&%#/%>*1(4"#e(&Z(B#XM#
T+.3Z8%++#k*)/*)B#!5`#>>"
o&%%3%"#h#R"#*?#o%*3:%'"#MD>+*&.4(*)#88Q#b`nhF6"
WOODS T. L. & GARRELSB# J"# E"# @6_`bAQ# ^1%# *?# *D(/(H%/# 3*>>%&#
TRICART, J. & CAILLEUX, A.#@6_5ÀQ#0*=&1#/%#o%*'*&>:*+*,(%#W"#h#
minerals as environmental indicators. – Applied Geochem. 1Q#
o%*'*&>:*+*,(%#L4&=34=&.+%"#0"#K"#^"B#N.&(1B#!5!#>>"
181–187.
TRICART, J. & CAILLEUX, A.#@6_F!AQ#W)4&*/=34(*)#4*#3+('.4(3#,%*'*&-
WRIGHT, V. P. & TUCKER, M. E.#6__6AQ#0.+3&%4%1Q#.)#()4&*/=34(*)"#
>:*+*,-"#h#k*),'.)B#k*)/*)B#!_5#>>"
h#W)Q#WRIGHTB#d"#N"#|#TUCKERB#E"#M"#@%/1"AB#0.+3&%4%1"#W)4%&).4"#
TURKINGTON, A. V. & PARADISE, T. R.# @!GG5AQ# L.)/14*)%# 8%.4:%&- O11*3"#*?#L%/('%)4*+*,(141#J%>&()4#L%&(%1#d*+"#!B#T+.3Z8%++#L3(-
ing. a century of research and innovation. – Geomorphology 67Q# %)4(23#N=;+(3.4(*)1B#<D?*&/B#6hn!!"
!!_nhn!5\" WYCHE, S., NELSON, D. R. & RIGANTI, A.# @!GGaAQ# a\5Gnhn\6\G# E.#
TWIDALE, C. R. (!GG!AQ# $:%# 48*C14.,%# 3*)3%>4# *?# +.)/?*&'# .)/# detrital zircons in the Southern Cross Granite–Greenstone Ter-
+.)/13.>%# /%9%+*>'%)4# ()9*+9(),# %43:(),"# *&(,()B# /%9%+*>'%)4# &.)%B#P%14%&)#O=14&.+(."#('>+(3.4(*)1#?*&#4:%#%.&+-#%9*+=4(*)#*?#
and implications of an idea. – Earth Science Reviews 57Q#\FhFa" 4:%#w(+,.&)#0&.4*)"#h#O=14&.+(.)#R"#*?#M.&4:#L3(%)3%1#51Q#\6hna5"
^LKO#@!GG5AQ#^)(4%/#L4.4%1#K%>.&4'%)4#*?#O,&(3=+4=&%#.)/#X.4=- XU, W., TOSCA, N. J., MCLENNAN, S. M. & PARISE, J. B. @!GG_AQ#
ral Resources. – Washington. Humidity-induced phase transitions of ferric sulfate minerals
VALETONB#W"#@6_F!AQ#T.=D(4%1"#h#M+1%9(%&B#O'14%&/.'B#!!b#>>" studied by in situ and ex situ X-ray diffraction. – American Min-
VAN OOSTERWYCK-GASTUCHE, M. C. & GRÉGOIRE, C.#@6_F6AQ#M+%3- %&.+*,(14B#94Q#6b!_nh6b\F"
4&*)# '(3&*13*>-# .)/# /(??&.34(*)# (/%)4(23.4(*)# *?# 1*'%# 3*>>%&# YAKOVLEVA, V. A., BELOGUB, E. V., NOVOSELOV, K. A.#@!GG\AQ#L=>%&-
1(+(3.4%1"#h#E()%&"#L*3"#*?#R.>.)#L>%3"#N.>%&#1Q#6_bnhn!G5" gene iron sulpho-selenides from the Zapadno-Ozernoe copper-
VASCONCELOSB# N"# E"# @6___AQ# eCO&# 40O&U39Ar geochronology of H()3#'.11(9%#1=+2/%#/%>*1(4B#L*=4:#^&.+1B#J=11(."#.#)%8#1*+(/C1*-
weathering processes. – Annual Review of Earth and Planetary lution series between pyrite FeS2 and dzharkenite FeSe2. – Miner.
Sciences 27Q#6`\nhn!!_" Mag. 67Q#\55nhn\b6"
VASCONCELOS, P. M., RENNE, P. R., BRIMHALL, G. H. & BECKER, T. A. ZARASVANDI, A., LIAGHAT, S. & ZENTILLI, M.#@!GG5AQ#o%*+*,-#*?#4:%#
@6__aAQ# K(&%34# /.4(),# *?# 8%.4:%&(),# >:%)*'%).# ;-# \_O&CaGO&# K.&&%:CV%&&%1:Z# .)/#O+(CO;./# >*&>:-&-# 3*>>%&# /%>*1(41B# 0%)-
and K-Ar analysis of supergene K-Mn oxides. – Geochim. Cos- tral Iran. – Internat. Geol. Review 47Q#b!Gnhnbab"
mochim. Acta 58Q#6b\5nh6bb5" ZHANGB# k"# @6__aAQ# M+%34&*3:%'(3.+# %Y=(+(;&(='# /(.,&.'1# ?*&#
VASCONSELOS, P. M., WENK H. R. & ECHER, C.#@6__aAQ#W)C1(4=#14=/-# 1=+2/(H.4(*)#*?#*D(/%#3*>>%&#'()%&.+1"#h#E()%&.+1#M),()%%&(),#
of the thermal behavior of cryptomelane by high-voltage and 7Q#_!Fhn_\!"
E.)=13&(>4#&%3%(9%/Q#<34*;%&#6bB#!G6!i#.33%>4%/Q#R.)=.&-#\GB#!G6\"
J%1>*)1(;+%#%/(4*&Q#7"Co"#L4*13:
Authors’ addresses:
HARALD G. DILL (corresp. author),#S%/%&.+#W)14(4=4%#?*&#o%*13(%)3%1#.)/#X.4=&.+#J%1*=&3%1B#N"#<"#T*D#56G6b\B#\Gb\6#7.))*9%&B#
o%&'.)-"#MC'.(+Q#/(++;,&"/%B#8%;1(4%Q#888":,%*/(++"/%
BERTHOLD WEBER, T{&,%&'%(14%&Ce)*&&#L4&"#`B#_!b\F#P%(/%)#("/"<N?"B#o%&'.)-"
REINER BOTZ,#^)(9%&1(4-#e(%+B#o%*+*,(3.+CN.+%*)4*+*,(3.+#K%>.&4'%)4B#<+1:.=1%)14&.%#aGCbGB#!a66`#e(%+B#o%&'.)-"
Supplementary material related to economic .&%#3:.&.34%&(H%/#;-#3.9(4(%1#.)/#>*3Z%41#14(++#;%(),#2++%/#

geology and ore deposits 8(4:#Z.*+()#()#.)#.34(9%#,%*4:%&'.+#2%+/#@DILL et al. 2000).
The Cenozoic volcanic and volcaniclastic rocks that host
4:%1%#/%>*1(41#()# 4:%#O:=.3:.>.)# ,%*4:%&'.+#2%+/#?*&'#
1. Supergene mineral assemblages across the >.&4# *?# 4:%# .++*3:4*)*=1# 1=(4%# *?# 4:%# 0.&(;;%.)# N+.4%B#
globe which was pushed eastward accompanied by an intensive
intra-arc rifting and an extensive arc volcanism. Much of
1.1 North America 4:%#.+=)(4%#'()%&.+(H.4(*)#(1#*?#:->*,%)%#*&(,()B#8:(3:#(1#
3*)9%&4%/#)%.&C1=&?.3%#()#.#,&%.4#9.&(%4-#*?#ONL#'()%&.+1B#
Uranium City-Beaverlodge, CanadaQ#W)#4:%#T%.9%&+*/,%# 1=3:#.1# j.&*1(4%B# X.Cj.&*1(4%B#8**/:*=1%(4%B#19.);%&,(4%B#
K(14&(34B# .# >&('.&-# ^C0=CX(CL%# '()%&.+(H.4(*)# *33=&1# .)/# >:*1>:.4%1# *?# 4:%# 3&.)/.++(4%C,*&3%(D(4%C[*&%)3(4%#
(BECK# 6_b_B# 6_F!A"#$:%# 1=>%&,%)%# *&%3&%4%1# =)/%&# 3*)- s.s.s. with some dussertite (DILL 2000).
sideration have been derived from Cu-Co-Pb-Ni sele-
)(/%1# 3+.=14:.+(4%B# 4-&&%+(4%B# ;%&H%+(.)(4%B# Z+*3Z'.))(4%B#
.)/# ='.),(4%# :*14%/# ;-# '%4.1%/('%)4.&-# Y=.&4HC.+;(4%C 1.3 South America
muscovite rocks.
Cajamarca Province, PeruQ#$:%#'()%&.+(H.4(*)#()#4:%#0.-
Lornex Mine-British Columbia, CanadaQ# W)# T&(4(1:# 0*- jamarca Province is not very much different from what
lumbia calc-alkaline porphyry Cu-Mo-(Au) deposit :.1#;%%)#&%3*&/%/#?&*'#4:%#M+#L.+9./*&#:(,:C1=+2/.4(*)C
formed in a volcanic arc setting (SCOTT#%4#.+"#!GG`B#SINGER 4->%#/%>*1(41B#1*# 4:.4#.)#()C/%>4:#4&%.4'%)4#)%%/#)*4# ;%#
%4# .+"# !GGÀ"# N&('.&-# '()%&.+(H.4(*)# 3*)1(141# *?# ;*&)(4%B# performed (Table 1). Epithermal deposits in an now ex-
3:.+3*>-&(4%B# '*+-;/%)(4%B# .)/# >-&(4%"#$:%# 0.&;*3&%4%1C 4()34# ,%*4:%&'.+# 2%+/# *?# :->*,%)%C:-/&*4:%&'.+# .)/#
@0=A#?*++*8(),#*D(3&%4%1C@0=A#'.()+-#3*)1(14#*?#.H=&(4%B# hypogene-steam-heated types were converted into a su-
8%++#(/%)4(2%/#;-#(41#/%%>#;+=%#3*+*&B#'.+.3:(4%B#3:&-1*- pergene APS mineralization (DILL et al. 1997a) (Table 1).
3*++.B#.)/#>+.)3:%(4%" $:%-#/%9%+*>%/#()#.#1%&(%1#*?#1(+(3(3+.14(3B#9*+3.)(3+.14(3#
Morenci-Arizona, USAQ#W)#4:%#E*&%)3(CK(14&(34B#0=CE*C .)/#9*+3.)(3#&*3Z1#*?#.#'.,'.4(3#.&3B#4:.4#%9*+9%/#/=&(),#
Au porphyry similar to the afore-mentioned type from 4:%#$%&4(.&-B#4:%#2).+#14.,%1#*?#4:%#O)/%.)#*&*,%)-"
T&(4(1:# 0*+=';(.# /%9%+*>%/# @MOOLICK & DUREK# 6_bbB#
Cerro de Pasco, PeruQ# $:%# +.&,%# 0%&&*# /%# N.13*# ;.1%C
LANGTON#6_F\B#MARVIN et al. 1987) (Table 1).
metal deposit in central Peru consists of a large pyrite-
Sonora District, MexicoQ#$:%# *&%3&%4%1# ?&*'# )*&4:8%14- Y=.&4H# ;*/-# &%>+.3(),# '.()+-# k*8%&# E%1*H*(3# N=3.&#
ern Mexico have originated from supergene alteration of 3.&;*).4%#&*3Z1#8(4:#V)CN;#*&%1#;%.&(),B#S%C&(3:#1>:.+-
various epithermal Sb-As-Cu-Pb-Zn mineralization. This erite and a second mineralization stage superimposed on
mineralization is genetically related to an igneous activity 4:%#2&14"#W4#3*)1(141#*?#0=CO,CO=CV)CN;CT(C0=#3.&;*).4%C
lasting from the Oligocene through the Miocene (Cam- replacement ore bodies (PEDRONI#6__bB#BAUMGARTEN et al.
prubí et al. 2003). 2008).
Casapalca, PeruQ# $:%# 1=;9*+3.)(3# O,CN;CV)C0=# 9%()C

1.2 Central America 4->%#/%>*1(41#0.1.>.+3.B#N%&=B#:.1#'.+.3:(4%#.)/#.H=&(4%#
as the major supergene alteration minerals in the orecrete
El Cobre, CubaQ# 0*>>%&# 9%()1# 8(4:# 1*'%# E)# '()%&.+1# (RYE & SAWKINS 1974).
were mined at El Cobre near Santiago de Cuba (SCHNEI-
DER# 6_5À"#$:%# M+# 0*;&%#d7EL# /%>*1(4B# +(%1# ()# 4:%# ()- Potosi province, BoliviaQ#O# +.&,%# )=';%&# *?# 1'.++C13.+%#
4%&'%/(.4%# 9*+3.)*# 1%/('%)4.&-# 1%Y=%)3%# *?# 4:%# L(%&&.# mining operations target on the Sb occurrences in Pale-
Maestra intraoceanic island arc. It comprises (a) strati- ozoic clastic rocks as well as in Tertiary acidic igneous
?*&'# *&%# ;*/(%1# 8(4:# ;.&-4%# .)/# .):-/&(4%B# @;A# 14&.4.- &*3Z1# ()# 4:%# N*4*1(# &%,(*)B# T*+(9(.# @DILL# %4# .+"# 6__5B#
;*=)/#*&%#;*/(%1#?*&'%/#;-#1(+(3(23.4(*)#.)/#1=+2/.4(*)# 1997b). They exhibit a fairly monotonous primary min-
*?# +('%14*)%1# *&# 1=+?.4%# ;%/1B# @3A# 14*3Z8*&Z# H*)%1# 8(4:# %&.+#.11%';+.,%#8(4:#14(;)(4%#.1#4:%#'.j*&#3*)14(4=%)4"#T-#
.):-/&(4%B# Y=.&4HB# .)/# >-&(4%# .)/# @/A# Y=.&4H# 9%()1# 8(4:# contrast with many Sb mining districts elsewhere in the
1=+2/%# *&%1"# N-&(4%B# 3:.+3*>-&(4%B# .)/# 1>:.+%&(4%# .&%# 4:%# world both sediment- and volcanic-hosted Sb deposits oc-
'*14#.;=)/.)4#1=+2/%1#@CAZAÑAS et al. 2003). cur side-by-side within the study area.
Agua Shuca and Cerro Blanco deposits, El SalvadorQ#$:%# Lipez-Millur-Cosuno region, BoliviaQ#L*=4:#*?#N*4*1(#()#
48*#%>(4:%&'.+#/%>*1(41B#O,=.#L:=3.#.)/#0%&&*#T+.)3*B# 4:%#&%,(*)#*?#k(>%HB#L;#.)/#0=#'()%&.+(H.4(*)#*?#%>(4:%&-
Fig. 1s. Orecretes as a function of mineral deposit and parent rock (“ore guide”). The y-axis gives the relative abundance of each
!"#$%&'%&($)($!$%*+%,&-./$%#$()$+!01$2%03%4($)($!$5%,52%/*+$(0-&1*)0-%)60+1$5%705$8%&+%80!0%&'%!6$%).(($+!%5!.8"9%73%:0(*0!*&+%&'%
mineral deposits along a schematic cross section from the ocean to the continent redrawn from DILL (2010).
mal origin was recorded by DILL et al. (1997b) and DILL Cerro Guanaco, ChileQ# O4# 0%&&*# o=.).3*# %>(4:%&'.+#
@!GG\A"#$:%#0*1=*#.)/#E(++=&(#9*+3.)(3#%/(23%1#3*)1(14# :(,:C1=+2/.4(*)C4->%#0=CO=CO,#'()%&.+(H.4(*)#()#0&%4.-
of a spectrum of volcanic and pyroclastic rocks of dacitic ceous through Paleogene felsic to intermediate volcanic
3*'>*1(4(*)B#8:(3:#%9*+9%/#/=&(),#4:%#E(*3%)%#.)/#N+(*- rocks brought about orecretes-(Cu-Ag) with a variegated
3%)%"#T%1(/%1#:->*,%)%#.+=)(4%B#1=>%&,%)%#.H=&(4%B#'.+.- mineral assemblage (Table 1).
3:(4%B#>+.)3:%(4%B#.)/#4%)*&(4%#/%9%+*>%/#()#4:%#=>>%&'*14#
Copiapó region, ChileQ# W)# 4:%# .&(/# &%,(*)# *?# 0*>(.>}B#
part of the deposit. Carbocretes-(Cu) form the latest min-
3*+*&?=+# 14*3Z8*&ZC+(Z%# *&%3&%4%1C@0=A# 8(4:# .4.3.'(4%B#
eral association. &*1.1(4%B#.)/#>+.)3:%(4%#/%9%+*>%/#*)#>*&>:-&-C4->%#0=C
Au ore in plutonic and subvolcanic rocks of intermediate
Jujuy region, ArgentinaQ#L.)/14*)%C:*14%/#N;C0=CO,#/%-
chemical composition and early Cretaceous age (MARS-
posit formed as a result of hydrothermal impregnation in
CHIK & SÖLLNER# !GGbA"# X%.&# L.)# J.'*)C0*>(.>}B# *&%-
4:%#R=-=-#/(14&(34#()#O&,%)4()%"#L:.+%1#.)/#1.)/14*)%1#*?#
cretes-(Cu-Fe) with Cu silicates and halogenides devel-
Ordovician through Tertiary age contain faultbound and
oped on different parent iron-copper-deposits (Table 1).
stratiform mineralization with pyrite and marcasite ac-
3*'>.)(%/#;-#O,C0=CL;#1=+2/%1#.)/#.&1%)(/%1#@SUREDA Salamanca, Coquimbo region, ChileQ#$:(1#'()%&.+(H.4(*)#
%4#.+"#6_`bB#BAHLBURGB#6__GB#OYARZUN 1990). is not only the most southern mineralization under con-
1(/%&.4(*)#()#4:%#3=&&%)4#14=/-B#;=4#.+1*#/(??%&%)4#8(4:#&%-
Patagonia, ArgentinaQ# W)# 4:%# 4&*>(3.+# 1%'(.&(/# H*)%# *?# spect to the elements associated with Cu. Wolframite and
N.4.,*)(.#1%9%&.+#9%()C4->%#/%>*1(41#;%.&(),#[=*&(4%B#N;C chalcopyrite gave rise to cuprotungstite and brochantite
0=CV)#1=+2/%1#.)/#O=#.&%#=)/%&#%D>+*&.4(*)#*&#3=&&%)4+-# during supergene alteration. SILLITOE et al. (1970) also re-
mined. Only recently indium has been added to the asso- corded cuproscheelite from this study area.
ciation of elements of economic interest and mineralogi-
cally proven by the discovery of dzhalindite (Table 1) in a Combarbalá, ChileQ#K(*&(4(3#.)/#.)/%1(4(3#&*3Z1#*?#0&%-
>&*1>%34#)%.&#L.)#J*Y=%#@DILL et al. 2013). 4.3%*=1# 4*# N.+%*3%)%# .,%# ()# 4:%# &%,(*)# *?# W++.>%+U0:(+%#
1=??%&%/# 14&*),# :-/&*4:%&'.+U# %>(4:%&'.+# Z.*+()(1.4(*)#
Vazante, BrazilQ# $:%# d.H.)4%# V)# /%>*1(4# (1# +*3.4%/# ?.&# )%.&#0*';.&;.+"#W4#(1#.33*'>.)(%/#;-#1(+(3(23.4(*)#.)/#
.>.&4# ?&*'# 4:%#O)/%.)# /%>*1(41# *)# 4:%# T&.H(+(.)# 3&.4*)# advanced argillic alteration. The resultant alteration zones
and consists dominantly of an unusual willemitic ore that contain alunite s.s. s. and aluminium-phosphate-sulfate
falls outside the scope of this investigation for its hypo- (APS) minerals of the woodhouseite-group with subordi-
,%)%# *&(,()"# L'.++# 1=+2/%# ;*/(%1# 8%&%# 4%34*)(3.++-# ('- ).4%#.'*=)41#*?#,*&3%(D(4%B#[*&%)3(4%B#.)/#,*-.H(4%#@DILL
et al. 1995) (Table 1).
;&(3.4%/#8(4:#4:%#8(++%'(4(3#*&%B#8(4:()#4:%#d.H.)4%#1:%.&#
zone during the Neo-Proterozoic (SOARES MONTEIRO et al.
6___B#!GGFA"#$:%#)*)C1=+2/(3#V)#*&%#*&(,().4%/#?&*'#4:%# 1.4 Northern and western Europe
>&%3(>(4.4(*)#*?#'%4.+#?&*'#1=+?=&C>**&#[=(/1#=)/%&#*D(-
dized conditions in the Vazante shear zone. Repparfjord, NorwayQ# $:%# 1.)/14*)%C:*14%/# 0=# /%>*1(4#
.4# J%>>.&?j*&/B# X*&8.-B# 8.1# ()4%&>&%4%/# ;-# PHARAOH et
Arica, ChileQ#W)#4:%#.&(/#H*)%#)%.&#O&(3.B#14&.4(?*&'#3*>- .+"#@6_`\A#.1#.#1-)1%/('%)4.&-B#/(.,%)%4(3B#.)/#%>(,%)%4(3#
per deposits developed in relation to alteration of volcanic chalcopyrite-pyrite mineralization emplaced into Precam-
series (Table 1). brian red bed metasediments.
Cerro Colorado-Tarapaca region, ChileQ# N*&>:-&-# 3*>- Bidjovagge, NorwayQ#$:(1#(1#.+1*#4&=%#?*&#4:%#0=CO=#/%-

per deposit form the parent material for the supergene al- >*1(4#.4#T(/j*9.,,%#()#4:%#N&*4%&*H*(3#e.=4*Z%()*#,&%%)-
teration in the Tarapaca region (BOUZARI & CLARK#!GG!B# stone belt (MATHIESEN#6_b_B#CUMMING et al. 1993).
MAKSAEV#%4#.+"#!GGFB#SINGER et al. 2008) (Table 1). Aitik, SwedenQ#$:%#N.+%*>&*4%&*H*(3#O(4(Z#0=CO=CO,#/%-
posit in northern Sweden is interpreted to be a porphyry
Chuquicamata, ChileQ#$:%#0:=Y=(3.'.4.#>*&>:-&-#3*>-
h# 4->%# /%>*1(41# 8(4:# .?2+(.4(*)# 4*# 4:%# S%C*D(/%h0=hO=#
per deposits may be treated as the textbook porphyry in
deposits but its true nature is to a large extent blurred by
the region and has been looked at from different angles
metamorphism (WANHAINEN et al. 2003).
(MAKSAEV# %4# .+"# !GGFA"# 0=# :-/&*1(+(3.4%1B# >:*1>:.4%1B#
:.+*,%)(/%1B# .)/# 3.&;*).4%1# /*'().4%# 4:%# *&%3&%4%1B# +*- Galmoy-Lisheen, IrelandQ# $:%# 14&.4.;*=)/# .)/# :*&14C
3.++-B#1:*8(),#=>#.1#&:-4:'(3.++-#;.)/%/B#1=>%&,%)%#0=# ;*=)/# 1=+2/(3# W&(1:C4->%# N;CV)CT.CO,C@X(C0*A# /%>*1-
ore. (41# X.9.)B# k(1:%%)B# L(+9%&'()%1B# $-).,:B# .)/# o.+'*-#
developed in Lower Carboniferous carbonate rocks. In pyrite gave rise to a couple of Fe phosphates and mainly
.# 1:.++*8# 4&*>(3.+# 1%.# >&('.&-# 1=+2/%1# @1>:.+%&(4%B# ,.- ferrialunite as their host rocks underwent chemical weath-
+%).B#>-&(4%B#'.&3.1(4%A#1-)/(.,%)%4(3.++-#3*)3%)4&.4%/#()# ering (Table 1).
.#'=//-#1=;14&.4%#()#.#)%.&C1:*&%#%)9(&*)'%)4"#L=+2/%1#
&%>+.3%/# 3.&;*).4%# '()%&.+1B# *33=&# .1# 1%/('%)4.&-# +.-- Schwaz, AustriaQ#$:%#3.&;*).4%C:*14%/#0=C7,CO,#/%>*1-
%&1B# /(11%'().4(*)1B# ;&%33(.U?&.34=&%# ()2++B# .)/# '.11(9%# it at Schwaz is well-known for its complex tetrahedrite-
1=+2/%1"#$:(1#'()%&.+(H.4(*)#3*)4()=%/#/=&(),#7%&3-)(.)# tennantite s.s.s. –“schwatzite” (ARLT & DIAMOND 1998).
?.=+4(),#8:%)#1=+2/%1#;%3.'%#&%'*;(+(H%/#()4*#9%()#'()- Auronzo, Italy: The carbonate-hosted Pb-Zn ore minerali-
eral associations (ANDREWB#6__\B#HITZMAN#6__5B#BALAS- H.4(*)#*33=&1#()#.#'*=)4.()*=1#U#:='(/#'(/C+.4(4=/%#'*&-
SONE et al. 2008). At Tynagh a polymetallic Pb-Zn-Ag de-
phoclimatic setting similar to that of the Schwaz deposit
>*1(4B#8:(3:#8.1#)*4#()9%14(,.4%/#/=&(),#4:(1#14=/-#;-#4:%# ()#O=14&(."# 0*''*)+-# 3+.11(2%/# .1# Ed$C/%>*1(4B# 4:%1%#
.=4:*&1B#'=1%='CY=.+(4-#.H=&(4%B#'.+.3:(4%B#.)/#3%&=11(4%# N;CV)#/%>*1(41#*?#4:%#O+>()%#E*=)4.()#J.),%B#8:(3:#.&%#
were found together with Cu arsenates (CLIFFORD et al. stratabound to Triassic carbonate units are also named
6_`bB#BANKS & RUSSELL 1992) APT-deposits (Alpine-type) to highlight their peculiar
character (SCHROLL 2005).
1.5 Central Europe
1.6 Southern Europe
Freihung, NE-Bavaria-GermanyQ The Freihung non-
1=+2/(3#N;#/%>*1(4#(1#?.3(%1#;*=)/#4*#4:%#'.&,().+#3.+3.&- Maidanpek, SerbiaQ#$:%# E.(/.)>%ZCK(14&(34# (1# *>%&.4%/#
eous-siliciclastic beds of the Middle-Upper Triassic beds for its porphyry-copper-type deposits (SINGER et al. 2008)
(GUDDEN#6_F5B#SCHMID#6_`6B#DILL#6__GB#DILL#%4#.+"#!GGFB# (Table 1).
2008). Cerussite formed to a great extent in a sabkha-like
environment and has to be kept separate from the overall Chalkidiki Peninsula, GreeceQ#$:%# 0:.+Z(/(Z(# N%)()1=+.#
supergene base-metal mineralization made up of Mn ox- (1#8%++#%)/*8%/#8(4:#0=#>*&>:-&(%1#.4#LZ*=&(%1B#;&%33(.#
(/%1B#>:*1>:.4%1B#1(+(3.4%1B#.)/#1=+?.4%1#@Table 1). H*)%1#()#>*&>:-&(4(3#+.4(4%1#)%.&#d.4:(B#.)/#N;CV)@O=B#O,A#
1=+2/%#*&%#.4#<+-'>(.1B#E./%'#k.Z*1B#.)/#E.9&%1#N%-
Lichtenberg-Issigau-Siebenhitz-Berg, NE-Bavaria-Ger- 4&%1B# 8:(3:# /%9%+*>%/# ()# 3.+3(4(3C&:*/*3:&*1(4(3#'.&;+%1#
manyQ# L%9%&.+# 0=CT(CX(CO1C;%.&(),# [=*&(4%# 9%()1# 8%&%# during a Tertiary metallogenetic igneous event (MARINOS
mined in the past (DILL 1985). 6_F_B# KALOGEROPOULOS# %4# .+"# 6_`_B# KROLL# %4# .+"# !GG!B#
QUADT von et al. 2005) (Table 1).
Erbendorf-Schmölz, NE-Bavaria-GermanyQ# $:%1%# *&%#
veins are structurally similar to the afore-mentioned vein Serifos, GreeceQ#W)#4:%#8.Z%#*?#4:%#%'>+.3%'%)4#*?#.#+.4%#
/%>*1(41B#;=4#.4#.#9.&(.)3%#8(4:#&%1>%34#4*#.;=)/.)3%#*?#N;# Miocene skarn-type Fe mineralization at Mega Livadi on
and Zn minerals (DILL 1985). 4:%# W1+%# *?# L%&(?*1B# o&%%3%B# .&1%)(3.+#3*>>%&# '()%&.+(H.-
tion of hydrothermal origin formed in calcareous roof
Auerbach, NE-Bavaria-GermanyQ#$:%#O=%&;.3:#1(/%&(4%C rocks of a granodioritic intrusion. This hypogene mineral
goethite ironstone deposit evolved during the Cenoma- .11%';+.,%#8(4:#>-&(4%B#O1C%)&(3:%/#?.:+*&%B#.)/#.&1%)*-
)(.)# ()# .# [=9(.+C+.3=14&()%# /%>*1(4(*).+# %)9(&*)'%)4# *)# pyrite suffered strong alteration during the Pliocene and
4:%# R=&.11(3# Z.&14(2%/# 3.&;*).4%# >+.4?*&'"# K=&(),# 4:%# Quaternary by descending meteoric waters (DILL et al.
1=>%&,%)%#.+4%&.4(*)B#>.&4#*?#4:%#>:*1>:*&=1#3*)4.()%/#()# 2010a).
the iron ore was released and then gave rise to Fe phos-
>:.4%1#>&%9.+%)4+-#2++(),#9=,1#.)/#?&.34=&%#4&=)3.4(),#.)/# Kalavassos, CyprusQ# X='%&*=1# >.>%&1# :.9%# ;%%)# >=;-
bounding the ore body (Table 1) (DILL et al. 2009). +(1:%/#*)#4:%#>%4&*+*,-B#,%*/-).'(3#%9*+=4(*)#*?#4:%#?.-
mous Cu-FeS2C;%.&(),# 9*+3.)(3C'.11(9%# 1=+2/%# @dELA#
Brandholz-Goldkronach-Wolfersgrün, NE-Bavaria-Ger- deposits of the Troodos Ophiolite which were taken as a
manyQ#$:%1%#9%()C4->%#O=CL;CO1#/%>*1(41#'.-#;%#.44&(;- reference-type of its own called “Cyprus-type” (CONSTAN-
uted to the group of mesothermal Au-Sb veins. Thrust- TINOU#6_`GB#GALLEY & KOSKI#6___B#DILL et al. 2007b).
bound vein mineralization in the Saxothuringian Zone not
*)+-#3*)4.()1#14(;)(4%B#.&1%)*>-&(4%B#.)/#L;#1=+?*1.+41B#;=4#
also native antimony (DILL et al. 2008). 1.7 Northern and Central Africa
Tirschenreuth-Großklenau, NE-Bavaria-Germany: Si- Bou Azzer, MoroccoQ#$:%# :-/&*4:%&'.+# 0*CX(CO1# 9%()1#

liceous black shales of early Paleozoic age abundant in .4# T*=# OHH%&B# E*&*33*B# .&%# %D3%>4(*).+B# ?*&# 4:%(&# %+%-
ment association and the lithological control of their ore Lubumbashi, DR CongoQ#$:%#fL4.&#*?#4:%#0*),*#E()%gB#
mineralization (ESSARRAJ et al. 2005). Veins containing DR Congo ( kxM4*(+%#/=#0*),*#E()%AB#(1#.)#.;.)/*)%/#
1Z=44%&=/(4%B# &.''%+1;%&,(4%B# )(3Z%+(4%B# ,%&1/*&?24%B# .)/# 3*>>%&# '()%# 8(4:()# 4:%# 0=C0*# ;%+4B# 8:(3:# (1# 3:.&.34%&-
chalcopyrite are bound to a fault system intersecting Pre- ized by a series of sediment-hosted deposits extending
cambrian rocks and serpentinite (Table 1). from the DR Congo into Zambia. Stratiform as well as
vein-type deposits have been observed in this copper belt
El Kef region, TunisiaQ#$:%#M+#e%?#.&%.#(1#%D3%>4(*).+#()# (DEWAELE et al. 2006). Mineralization has been a very
'.)-# 8.-1"# $:%# Kj%;%+# L%Z.&).# N;CV)CT.CN# /%>*1(4# (1# +*),C+.14(),# .)/# >*+->:.1%# >&*3%11# ()# 4:(1# &%,(*)B# 8(4:#
+*3.4%/#.4#4:%#*?23(.+#14&.4*4->%#*?#4:%#eUN#;*=)/.&-#.)/# 4:%# *)1%4# *?# 1=+2/%# '()%&.+(H.4(*)# .+&%./-# /=&(),# %.&+-#
encompasses syn(dia)genetic shale- and carbonate-hosted diagenesis of the Precambrian sedimentary series.
Zn-P and epigenetic ore mineralizations (DILL et al. 2011).
d%()+%41B# +%)1%1B# .)/# 3.9(4(%1# .&%# 2++%/# 8(4:# 1=+2/(3# .)/#
)*)C1=+2/(3#'()%&.+#.11%';+.,%1B#4:%#+.44%&#,(9(),#&(1%#4*# 1.8 Southern Africa
*&%3&%4%1C@V)CN;A"# $:%# Kj%;%+# L%Z.&).# N;CV)CT.CN# /%-
Malawian deposits: Malawi is rich in carbonatite-host-
posits take an intermediate position between base-metal
ed REE and pegmatite-hosted rare metal deposits (DILL
deposits with orecretes developing in their topmost parts
2007). These mineral deposits sporadically contain Zn-
.)/#4:%#>:*1>:*&(4%#1%.'1#?=&4:%&#1*=4:B#4:.4#1.8#4:%#?*&-
.)/#N;#1=+2/%1"#L=+2/(3#/%>*1(41#.&%#&.&%#.3&*11#4:%#3*=)-
mation of phoscretes in their topmost parts during chemi-
4&-#.)/#)*4.;+%#S%C#.)/#0=#1=+2/%#.33='=+.4(*)#3.)#*)+-#
cal weathering.
be recorded from the Katengeza kyanite-graphite-mica
,)%(11#()#4:%#N&%3.';&(.)#T.1%'%)4#0*'>+%D"
Thies-Taiba, SenegalQ#$:%#M*3%)%#>:*1>:*&(4%1#'()%/#.4#
$.(;.B#L%)%,.+B#.&%#()4%&3.+.4%/#.'*),#3+.-14*)%1B#1.)/- Joumbira, NamibiaQ# X%.&# 4:%# L.+%'# o&.)(4%B# /*+*'(4(3#
stones and calcareous sediments and representative of the marbles and schists are mineralized in a stockwork-like
phosphate-end member (FLICOTEAUX#6_`!B#DILL & KAN- 8.-# 8(4:# 0=CB# N;CB# .)/# V)# 1=+2/%1B# 4:.4# 1=;1%Y=%)4+-#
TOR#6__FA"#$:%#'*14#4&%'%)/*=1#&%/%>*1(4(*)B#.+;%(4#+%11# 8%&%# 3*)9%&4%/# ()4*# '.+.3:(4%B# .H=&(4%B# .)/# 0=# *D(/%1"#
14&*),#4:.)#()#$:(%1B#4**Z#>+.3%#/=&(),#=>>%&#M*3%)%#4*# This mineral assemblage is lined up together with a cou-
%.&+-# <+(,*3%)%# =)/%&# 1=;.%&(.+# 3*)/(4(*)1B# 8:%)# .>.- ple of mineral deposits along the NW-SE striking Water-
tite was replaced by a group of variegated aluminium- ;%&,#S.=+4B#4:.4#()4%&1%341#4:%#K.'.&.#'%4.1%/('%)41#.)/#
phosphate-sulfate minerals sensu STOFFREGEN & ALPERS Panafrican granites (DIEHL#6__GB#HAHNE et al. 2001).
(1987).
Tsumeb, NamibiaQ# $:%# 0=C&(3:# f$1='%;C4->%g# /%>*1(41#
Nuba Mountains, SudanQ# $:%# ,%*+*,(3.+# 1%44(),# *?# 4:%# are hosted by Neo-Proterozoic platform carbonates of the
9%()+(Z%# =&.)(?%&*=1# >:*1>:.4%# '()%&.+# .11%';+.,%B# ()# <4.9(#o&*=>B#X.'(;(."#$:%1%#/%>*1(41#?*&'%/#;-#4:%#&%-
4:%# X=;.# E41"B# L=/.)B# (1# )*4# 9%&-# '=3:# /(??%&%)4# ?&*'# .34(*)#*?#:*4#[=(/1#>.11(),#.#9.&(%4-#*?#.Y=(?%&#1-14%'1B#
the afore-mentioned phosphate-only deposits in Sen- where they became saline and enriched in metals. Eventu-
egal (DILL#%4#.+"#6__6A"#W)#4:%#L=/.)%1%#14=/-#1(4%1B#1:%.&# .++-B#4:%#'%4.+1#8%&%#>&%3(>(4.4%/#()#Z.&14#>(>%1#.)/#;&%3-
H*)%1# 4&.)1%34# 1%&(3(4%C3:+*&(4%# 13:(141B# ,&.>:(4%# 13:(141# cia horizons (KAMONA# %4# .+"# 6___B# CHETTY & FRIMMEL
and cherts of probable Upper Precambrian age which are 2000).
enriched in base metals and in phosphate.
Khan Mine – Swakopmund District, NamibiaQ# $:(1# .)-
Kilembe-Kasese, UgandaQ# $:%# 1%/('%)4C:*14%/# '%4.- cient copper mine south of Arandis was closed in 1918
morphosed Kilembe Cu-Co deposit lies within the Pre- (RAMDOHR 1938). The mineralized structure zone has as
3.';&(.)# T=,.)/.C$*&*# 1-14%'B# 8:(3:# 3*)1(141# *?# similar association of orecretes as the afore-mentioned
Y=.&4H(4%1B#3*),+*'%&.4%1B#4:*+%((4(3#>(++*8#+.9.1B#'%4.>%- deposit but without phosphates and arsenates.
+(4%1B#.)/#13:(141#@MUWANGA#6__FA"#W41#>&('.&-#1=+2/%#*&%# Matchless Mine, NambiaQ#$:%#'()%&.+#.11%';+.,%#8:(3:#
'()%&.+1# .&%# >-&(4%B# 3:.+3*>-&(4%B# .)/# >-&&:*4(4%# >&%1%)4# was mined in the now exhausted Matchless mine is asso-
()#4:%#&.4(*#*?#6!QFQ6"#S=&4:%&'*&%B#+()).%(4%B#1>:.+%&(4%B# ciated with the amphibolitic Matchless Member (KLEMD
1(%,%)(4%B#>%)4+.)/(4%B#.)/#'*+-;/%)(4%#8%&%#&%3*&/%/#;-# %4#.+"#6_`FB#PETZEL#6__bA"#$:%#'()%#1%Y=%)3%#3*)1(141#*?#
MUWANGA (1997). Ore minerals were mainly concentrated ;(*4(4%C1%&(3(4%#13:(14B#.)/#.'>:(;*+(4%#13:(14#4:.4#3*)4.()#
()#14&.4(?*&'#+.-%&1B#.)/#4*#.#+%11%&#/%,&%%#()#211=&%1"#0*- +%)1%1# *?# '.,)%4(4%C;%.&(),# Y=.&4H(4%"# $:%# /%>*1(4# 3*)-
balt ranges from 0.12 to 4.4 % in individual pyrite grains sists of a footwall zone of stratabound pyrite mineraliza-
(WARDEN 1985). tion and three chalcopyrite-bearing copper ore shoots. The
/%>*1(4#:.1#;%%)#()4%&>&%4%/#4*#;%#*?#T%11:(C4->%#@MAIDEN 1.10 Southeast Asia and Australia

6__\B#COOK#%4#.+"#6__aA"#$:%#'.j*&#1=+2/%#'()%&.+1#%)-
3*=)4%&%/#()#4:%#*&%#;*/-#.&%#>-&(4%B#3:.+3*>-&(4%B#>-&&:*- Mongolian deposits: A wide range of deposits were con-
4(4%B#'.&3.1(4%B#1>:.+%&(4%B#.)/#,.+%)."#L=>%&,%)%#'()%&.+1# 1(/%&%/# 4:&*=,:*=4# .# 2%+/# 3.'>.(,)# ()# E*),*+(.# @DILL
*&(,().4(),# ?&*'# 4:%1%# 1=+2/%1# .&%# 3=>&(4%B# 3:&-1*3*++.B# %4#.+"#!GGb;A"#$:%-#.&%#:*14%/#;-#3.&;*).3%*=1B#.&,(++.-
'.+.3:(4%B#.)/#:%'.4(4%#.)/#'()%&.+1#()#4:%#4.(+(),1#('- 3%*=1B# .)/# .&%).3%*=1# :*14# &*3Z1# 8(4:# +(44+%# S%# .)/# 0=#
>*=)/'%)4#.1#.#&%1=+4#*?#;%)%23.4(*)#*?#4:%#*&%#.)/#4:%# .33*''*/.4%/#()#4:%#+.44(3%#*?#1=+2/%1#@Table 1) (DILL et
current climatic conditions (DILL et al. 2002). .+"#!GGb.B#;A"
Bawdwin, Birma (Myanmar): In a monographic study on

1.9 Middle East (Western Asia) 4:%#,%*+*,-B#>%4&*+*,-#.)/#*&%#'()%&.+*,-#*?#4:%#T.8/8()#
Pb-Zn deposits BRINKMANN & HINZE (1981) and MÜLLER
Wadi Araba, JordanQ#$:%#>&('.&-#3*>>%&#'()%&.+(H.4(*)# & WEISER (1981) discussed the origin of this ore deposit.
()# 4:%# P./(#O&.;.B# R*&/.)B# 8.1# 14=/(%/# ;-# BURGATH et O33*&/(),# 4*# 4:%1%# .=4:*&1B# 4:%# N;CV)# '()%&.+(H.4(*)# (1#
.+"# @6_àA"# 0:.+3*>-&(4%B# 3:.+3*3(4%B# .)/# 3*9%++(4%# 8%&%# akin to the Kuroko-type base metal deposits. The main
found in brecciated andesitic and rhyolitic dikes and in *&%# '()%&.+1B# ,.+%).# .)/# 1>:.+%&(4%# .&%# .33*'>.)(%/# ;-#
Cambrian sandstones along Wadi Abu Khusheiba and ;*=&)*)(4%B#;*=+.),%&(4%B#.&1%)*>-&(4%B#.)/#?.:+*&%#1"1"1"
P./(#O;=#T.&Y.#;*4:#*?#8:(3:#?*&'#>.&4#*?#4:%#%.14%&)#
drainage system tributary to the Wadi Araba. Kao Boh Ngam, ThailandQ#$:%#14&.4(?*&'#.)/#9%()C4->%#
&%>+.3%'%)4#N;CV)#/%>*1(41#.4#e.*#T*:#X,.'B#$:.(+.)/B#
Almalyk, UzbekistanQ# $:%# O+'.+-Z# '()(),# /(14&(34# (1# were emplaced in a series of Cambro-Ordovician sand-
known for its porphyry Cu-Au-Mo ore bodies with sev- 14*)%1B#1:.+%1B#.)/#3.&;*).4%#&*3Z1#@PREMMANEE & JARN-
%&.+#()/(9(/=.+#'()%&.+#.11%';+.,%1B#.'*),#4:%'#K.+)%%# YAHARN# 6__FA"# $%34*)(3.++-B# 4:(1# N;CV)# '()%&.+(H.4(*)#
@0=CO=CO,AB# e.+x'.Z-&# @0=CE*CO=CO,AB# .)/# XP# T.- took place within the S-N trending Shan Thai or Sibu-
lykty (Cu). masu belt. The stratabound Pb-Zn ores developed at low
temperatures within the Ordovician carbonates leading
Kounrad, KazakhstanQ# $:%# e*=)&./# /%>*1(4# (1# .)*4:%&# to what might be called a MVT deposit (GOOSSENS#6_F`B#
porphyry copper-gold deposit of the Central Asian Inte- DIEHL & KERN 1981).
rior in the “Steppe of Hunger” (SINGER et al. 2008).
Pa Daeng, ThailandQ#R=&.11(3C$&(.11(3#.&*=)/#N.#K.%),#
Yazd District, IranQ# W)# 4:(1# 3%)4&.+# W&.)(.)# &%,(*)B# 1%9- are host of the secondary Zn deposits (PREMMANEE &
%&.+# 9%()C4->%B# 3.&;*).4%C:*14%/# N;C0=CV)# /%>*1(41# .)/# JARNYAHARN 1997). Primary MVT Zn-Pb mineralization
porphyry-type copper deposits have been known for ages *33=&&%/#()#4:%#9(3()(4-#*?#4:%#N.#K.%),#'()%B#.4#N:.#K%#
(HUCKRIEDE#%4#.+"#6_b!B#ZARASVANDI#%4#.+"#!GG5B#SINGER et .)/# 7=.# k*)B ?*&'(),# 1'.++C13.+%# *>%)C1>.3%# 2++(),1B#
al. 2008). 9%()1B# .)/# &%>+.3%'%)41 within hydrothermal dolomite
Lachah Meydouk, IranQ# k.3:.:# E*=)4.()# 3*)1(141# *?# (REYNOLDS et al. 2003).
volcaniclastic sediments which were cut by diorite por- Phu Joe-Sankhlaburi, ThailandQ#W)#4:%#)*&4:8%14%&)#>.&4#
>:-&-#;*/(%1#.)/#/-Z%1"#N-&(4%B#3:.+3*>-&(4%#.)/#;*&)(4%# of Karnchanuburi Changwat and beyond the border into
8%&%# (/%)4(2%/# .1# >&('.&-# 1=+2/%1" L*'%# ;.1(3# /-Z%1B# E-.)'.&B# 9%()C4->%# .)/# ;&%33(.4%/# L;C7,# /%>*1(41# *3-
*+(9()%C:*&);+%)/%# ;.1.+4# ()# 3*'>*1(4(*)B# 8%&%# ()4&=/%/# 3=&#.&*=)/#N:=#R*%#.)/#K.;j=%#@E-.)'.&A#@DEPARTMENT
1=;1%Y=%)4+-#.)/#.&%#=)&%+.4%/#4*#4:%#>*&>:-&-C4->%#'()- OF MINERAL RESOURCES 1999). Their country rocks are
eralization. The ore body of Meydouk mineralized with composed of Ordovician and Permian calcareous rocks
3*>>%&#(1#*?#'(//+%#4*#=>>%&#E(*3%)%#.,%B#3*'(),#3+*1%# .)/#K%9*)(.)#1(+(3(3+.14(31"#L4(;)(4%B#;%&4:(%&(4%B#.)/#L;C
4*# 4:%# .,%# *?# 4:%# L.&3:%1:'%:# >*&>:-&-# /%>*1(4# @:44>QUU bearing cinnabar associated with siliceous gangue miner-
mineralresourcemap.com). als make up the primary mineral assemblage.
Al Khod, OmanQ# N.&.+(3# 3.&;*).3%*=1# 1%&(%1B# 3.++%/#
J=1.-+# S*&'.4(*)B# .&%# ()4%&3.+.4%/# .'*),# 3.+3.&%*=1# Ma Ta, Mae Thae, Doi Ngom, Pha Hao and Haii Nai de-
shelf sediments. They developed during the early Eocene posits, ThailandQ# d%()C4->%# L;# /%>*1(41# 8(4:# ?*&'.4(*)#
in front of a low-reliefed hinterland in the Al Khod re- temperatures between 200 °C and 45 °C are hosted by
,(*)B# XM# <'.)"# S&.';*(/.+# >-&(4%B# @?%&&*.)A# /*+*'(4%# Late Paleozoic calcareous rocks in the Lampang-Phrae
with very little siderite are indicative of a diagenetic al- Province in northern Thailand (DILL et al. 2008). After the
teration under high sulfur and carbon fugacities (DILL et /(.,%)%1(1#.)/#/*+*'(4(H.4(*)#*?#3.+3.&%*=1#&*3Z1B#'%1*-
al. 2007c). 4:%&'.+#P#'()%&.+(H.4(*)#8(4:#8*+?&.'(4%#.)/#13:%%+(4%B#
%>(4:%&'.+# L;C@O1A# '()%&.+(H.4(*)# 8(4:# .&1%)*>-&(4%B# .)/#:(,:C1=+2/.4(*)C4->%#0=CO=#'()%&.+(H.4(*)#()9*+9%/#

14(;)(4%B#[=*&(4%B#.)/#'.&3.1(4%#.)/#:*4#1>&(),#L;#/%>*1(- ()#4:%#%'>+.3%'%)4#*?#4:%#*&%#;*/(%1B#3*)4.()(),#1=+2/(3#
tion with pyrite and Fe–W–Sb oxides took place in the .)/# )*)C1=+2/(3# 0=# *&%# '()%&.+1# @HUSTON & KAMPRAD
area (Table 1). It was followed by hypogene and super- !GGGB#CORBETT 2001).
,%)%# .+4%&.4(*)B# &%1=+4(),# ()# 4:%# ?*&'.4(*)# *?# S%hN;hL;#
oxyhydroxides.
2. Supergene ore mineralization as an ore
Kuching, MalaysiaQ#O#,*+/C;%.&(),#:->*,%)%#'()%&.+(H.-
guide
tion containing sarabauite and calcite evolved in the upper
R=&.11(3#T.=#k('%14*)%#8(4:()#4:%#k=3Z-#7(++#'()(),#/(1- The orecretes were also discussed with respect to their
4&(34B#L.&.8.ZB#8:%)#/.3(4%1#.)/#'(3&*,&.)*/(*&(4(3#>*&- parent rocks and mineral deposits as ore guides (Fig. 1s).
phyries of mid-Miocene age intruded into the calcareous Fig. 1s is based on the data listed in Table 1 and shown
series (DILL & HORN#6__bA"#M.&+-#8*++.14*)(4%B#/(*>1(/%B# in one of the maps of Fig. 2. Oxicretes are cast as an ore
.)/#%>(/*4%#.&%#4->(3.+#*?#4:%#1Z.&)#14.,%B#1=33%%/%/#;-#.# guide sensu strictoB#+%./(),#4*#4:%#>&('.&-#*&%#'()%&.+(-
+*8C4%'>%&.4=&%#@0.&+()C4->%A#'()%&.+(H.4(*)"#L.&.;.=(4%B# H.4(*)# .1# .4# L.+.'.)3.B# 0:(+%# *&# ()# 4:%# L;# >&*9()3%1# ()#
14(;)(4%B# 1%).&'*)4(4%B# ).4(9%# .&1%)(3B# &%.+,.&B# .)/# *&>(- Mexico and Thailand (Table 1s). Arsenocretes show a
'%)4B#4:%#3*''*)#*&%#'()%&.+1#()#4:(1#O=CL;#'()%&.+(H.- close relation to certain primary ore types enriched in ar-
tion point to an Fe- and S limitation of the ore-bearing 1%)(3#.)/#'*&%#4:.)#.)-#*4:%&#*&%3&%4%B#'(&&*&#4:%#>.&%)4#
solutions. mineral assemblages which either contain pure arsenides
Desa Toraget-Sulawesi, IndonesiaQ#K%1.#$*&.,%4#(1#.#Z.*- or have arsenic substituting at least for part of the sulfur
+()# /%>*1(4# +*3.4%/# ()# 4:%# X%*,%)%# X*&4:# L=+.8%1(#O&3B# or antimony in some skarn- and carbonate-hosted depos-
W)/*)%1(.B#8:(3:#(1#Z)*8)#?*&#(41#%>(4:%&'.+#O=#/%>*1- its (Fig. 1s). Arsenocretes are proximity indicators at their
its. The deposit lies within the Tondano Caldera that is best when it comes to the discrimination of the parent ma-
rimmed by Quaternary stratovolcanoes (KAVALIERIS et al. terial by means of chemical residues (Fig. 1s). Among the
1992). Its near-surface alteration mineralization mirror 3.&;*3&%4%1B#4:%#1'(4:1*)(4%C*4.9(4%#1"1"1"#(1#3*)4&*++%/#;-#
the transition of hypogene-supergene alteration with alu- the parent material and is useful as an ore guide sensu
nite and woodhouseite-alunite solid solution series (DILL stricto. Fig. 1s shows the distribution of orecretes as a
et al. 1995c) (Table 1). function of the primary ore deposits along a cross section
from the ocean to the continent
Narogong, Java-IndonesiaQ#$:(1#'.&()%#()1=+.&#>:*1>:.4%#
/%>*1(4#?*&'1#>.&4#*?#4:%#E(*3%)%#N.&.(,(#S*&'.4(*)B#4:.4# For literature see references at the end of the main text.
/%9%+*>%/#*)#4:%#1:%+?#*?#4:%#T*,*&#$&*=,:#@KOESOEMADI-
NATAE 1985). In the course of weathering extensively the
Al phosphate wavellite originated from the primary phos-
phate francolite (DILL and KANTOR 1997).
Cho Dien, VietnamQ#L%3*)/.&-#V)#*&%1#:.9%#;%%)#%D>+*(4-

%/#?&*'#0:*#K(%)#/%>*1(4B#aG#Z'#XP#*?#T.#e.)#@KAMI-
TANI#%4#.+"#!GGFA"#$:%1%#N;CV)#*&%1#.+1*#3*)4.()#1*'%#O,B#
0/B# .)/# W)# @KUSNIR# 6_baA"# $:%# V)CN;# 1=+2/%# *&%1# 8(4:#
'.()+-# 1>:.+%&(4%B# >-&(4%B# .)/# ,.+%).# .&%# 14&.4.;*=)/# 4*#
Givetian metamorphosed limestones. The orecretes are
3:.&.34%&(H%/# ;-# 3.&;*3&%4%1# @1'(4:1*)(4%B# 3%&=11(4%B# .=-
&(3:.+3(4%B# '.+.3:(4%AB# 1(+(3.3&%4%1# @:%'('*&>:(4%AB# .)/#
little arsenate-sulfate (beudantite) (Table 1). The Mn ox-
(/%# >&%1%)4# ()# 4:%# *&%# (1# Y=%14(*)%/# 4*# ;%# *?# 1=>%&,%)%#
origin (?).
Tasmania, AustraliaQ#$:%#E*=)4#k-%++#N;CV)C;%.&(),#0=C
O=#/%>*1(4#()#4:%#]=%%)14*8)#.&%.B#$.1'.)(.CO=14&.+(.B#
is located within the hydrothermally altered Cambrian
E*=)4#J%./#d*+3.)(31"#W4#(1#.#3*'>+%DB#:-;&(/#'%4.++*,%-
)%4(3#1-14%'#8(4:#'.11(9%#1=+2/%#@d7ELAB#/(11%'().4%/B#

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N. Jb. Miner. Abh. (J. Min. Geochem.

) 190/2, 123 –195 Article

Metalliferous duricrusts (“orecretes”) – markers of

Harald G. Dill, Berthold Weber, Reiner Botz

With 17 figures and 5 tables

Table of contents 6.2 Climate and the formation of orecretes . . . . . . . . . . . . 155

© 2013 E. Schweizerbart’sche Verlagsbuchhandlung, Stuttgart, Germany www.schweizerbart.de

1. Introduction climatic and related these morphodynamic processes to

El Cobre Cu goethite azurite brochantite tropical humid tropical humid carbocrete-

Ain Sefra, Algeria Cu sediment- malachite tropical semi- arid carbocrete

Heazelwood Hill, Pb-Cu-Zn-Ba brochantite humid mid- warm temper- sulcrete

0.&;*3&%4%1#.&%#.;=)/.)4#()#3.&;*).4%#'()%&.+1B#%","B# <&%3&%4%1C@L%AB# C@E*AB# .)/# @*D.+.4%A# :.9%# )*4# ;%%)#

4*&#8(4:#4&*>(3.+#3+('.4(3#3*)/(4(*)1B#.1#8%++#.1#.4#:(,:%&# tents (Table 1). In the succeeding sections typical super-

and tenorite developed (Fig.#a/B# %A"# 0.&;*3&%4%1C@0=A#

5.1.3 Supergene Cu mineralization in basic magmatic

5.1.4 Supergene Cu mineralization in siliceous

5.1.12 Supergene P-S mineralization in sedimentary NORTHROP & CLAYTON#@6_bbA#?*&#/*+*'(4%B#;-#O’NEIL et

b Fig. 4. Macro- and microtextures of orecretes-(Cu) in siliceous magmatic rocks. a)#E.11(9%#;+=(1:#4=&Y=*(1%#@4=&A#>.&4(.++-#3*9%&%/#8(4:#

O# [*8# 1:%%4# ()# Fig. 9 illustrates the complex interrela-

Fig. 14.#M:C>7#/(.,&.'1#*?#>:*13&%4%1"#L:./%/#.&%.#/%)*4%1#14.;(+(4-#2%+/1#*?#*&%3&%4%1"#a) Eh-pH diagram to show the phoscretes-(Cu)

phosphates in phoscretes-(Cu) of the Congolese deposits (1) Al(OH)3)H3PO4)CuSO4#p#4=&Y=*(1%)H2SO4)H2O

Fig. 15.#M:C>7#/(.,&.'1#*?#.&1%)*3&%4%1#.)/#9.)./*3&%4%1"#L:./%/#.&%.#/%)*4%1#14.;(+(4-#2%+/1#*?#*&%3&%4%1"#a) Eh-pH diagram to show the

Fig. 16.# L*(+# >&*>%&4(%1B# ;%/&*3Z# .)/#

7. Summary and Conclusions 7.2 Second order lithosphere-atmosphere-

Carbocretes and phoscretes are characterized by two +%.14#&%[%34#.)#%.&+-#14.,%#/=&(),#4:%#%)4(&%#?*&'.4(*)#*?#

CANFIELDB#K"#M"#@!GG5AQ#$:%#%.&+-#:(14*&-#*?#.4'*1>:%&(3#*D-,%)"#h# CUMMING, G. L., KRSTIC, D., BJØRLYKKE, A. & AASEN, H. @6__\AQ#

DILLB#7"#o"#@!GG_AQ#N-&*'%4.++=&,(3.+#&%+(31#*?#N;C0=CS%#/%>*1(41# transect from the taiga to the desert in Central Mongolia-Evo-

ROGERS, R. J. & BROWN, F. H.#@6_F_AQ#O=4:(,%)(3#'(4&(/.4(4%#?&*'# H.4(*)1#()#4:%#d.H.)4%B#O';&}1(.#.)/#S.,=)/%1#/%>*1(41B#E().1#

Supplementary material related to economic .&%#3:.&.34%&(H%/#;-#3.9(4(%1#.)/#>*3Z%41#14(++#;%(),#2++%/#

Casapalca, PeruQ# $:%# 1=;9*+3.)(3# O,CN;CV)C0=# 9%()C

Cerro Colorado-Tarapaca region, ChileQ# N*&>:-&-# 3*>- Bidjovagge, NorwayQ#$:(1#(1#.+1*#4&=%#?*&#4:%#0=CO=#/%-

Tirschenreuth-Großklenau, NE-Bavaria-Germany: Si- Bou Azzer, MoroccoQ#$:%# :-/&*4:%&'.+# 0*CX(CO1# 9%()1#

/%>*1(4#:.1#;%%)#()4%&>&%4%/#4*#;%#*?#T%11:(C4->%#@MAIDEN 1.10 Southeast Asia and Australia

Bawdwin, Birma (Myanmar): In a monographic study on

%>(4:%&'.+# L;C@O1A# '()%&.+(H.4(*)# 8(4:# .&1%)*>-&(4%B# .)/#:(,:C1=+2/.4(*)C4->%#0=CO=#'()%&.+(H.4(*)#()9*+9%/#

Cho Dien, VietnamQ#L%3*)/.&-#V)#*&%1#:.9%#;%%)#%D>+*(4-

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0.&;3&%4%1#.&%#.;=)/.)4#()#3.&;).4%#'()%&.+1B#%","B# <&%3&%4%1C@L%AB# C@EAB# .)/# @D.+.4%A# :.9%# )*4# ;%%)#

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