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THE EVOLUTION OF LARAMIDE IGNEOUS ROCKS AND
PORPHYRY COPPER MINERALIZATION IN THE
CANANEA DISTRICT, SONORA, MEXICO

by
Wojtek Alexander Wodzicki

Copyright © Wojtek Alexander Wodzicki 1995

A Dissertation Submitted to the Faculty of

DEPARTMENT OF GEOSCIENCES
In Partial Fulfillment of the Requirements
for the Degree of
DOCTOR OF PHILOSOPHY
In the Graduate College
THE UNIVERSITY OF ARIZONA

1995
 UMI Number: 9531073

Copyright 1995 by
Wodzicki, Wojtek Alexander
All rights reserved.

OMI Microform 9531013

Copyright 1995, by OMI Company. All rights reserved.

This microform edition is protected against unauthorized

copying under Title 11, United States Code.

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 2

THE UNIVERSITY OF ARIZONA

GRADUATE COLLEGE

As members of the Final Examination Committee, we certify that we have

read the dissertation prepared by Wojtek Alexander Wodzicki

entitled THE EVOLUTION OF LARANIDE IGNEOUS ROCKS AND PORPHYRY COPPER

HINERALIZATION IN THE CANANEA DISTRICT, SONORA, MEXICO

and recommend that it be accepted as fulfilling the dissertation

of Doctor of Philosophy

-c::::-
Date

Date --'

'2~2) f/~J 9~
Date

Final approval and acceptance of this dissertation is contingent upon

the candidate's submission of the final copy of the dissertation to the
Graduate College.

I hereby certify that I have read this dissertation prepared under my

direction and recommend that it be accepted as fulfilling the dissertation
requirement.

'-(JtwJ2 D. £()~
Dissertation Director Date
 3

STATEMENT BY AUTHOR
This dissertation has been submitted in partial fulfillment of requirements for an
advanced degree at The University of Arizona and is deposited in the University Library to
be made available to borrowers under rules of the Library.

Brief quotations from this dissertation are allowable without special permission,
provided that accurate acknowledgment of of source is made. Requests for permission for
extended quotation from or reproduction of this manuscript in whole or in part may be
granted by the copyright holder.
 4

ACKNOWLEDGEMENTS
I would like to thank the many people who helped me during the course of this
study. This project would not have been possible without the encouragement and
financial support of Cominco Resources International Ltd. I would specifically like to
acknowledge the late Fred Gill for steering me toward a study in the Cananea District,
and thank John Collins and Myron Osatenko for their consistent support of the project.
I'd also like to thank Ian Paterson for his constructive criticism, and for reading an early
draft of the Maria chapter.
The cooperation and access provided by Minera Maria and Mexicana de Cananea
during the course of this study is gratefully acknowledged. I am particularly grateful to
Ulises Monter, General Manager of Minera Maria, for his consistent support, and to
Alejandro Ramos mine geologist from 1990 to 1993 for all his help. Special thanks are
due to Ramon Ayala, chief geologist, and Moises Menchaca, mine geologist at
Mexicana de Cananea for their cooperation and for introducing me to the tremendous
deposit at Cananea.
I would like to thank the members of my academic committee for their constructive
criticism and for use of their lab facilities. I am especially grateful to my major advisor
Mark Barton for his excellent supervision of this study and for teaching me his
innovative approach to studying ore deposits. Tom McCandless, Jamie Gleason, and
Frank Mazdab helped in various aspects of field and lab work. Antoni Wodzicki, Kate
Gregory, John-Mark Staude, and Bob Ilchik read early versions of the dissertation and
their constructive criticism greatly improved the final product.
Finally I would like to thank my family and my wife Kate for their encouragement
and moral support. Thank you all.
 5

TABLE OF CONTENTS

LIST OF FIGURES ........................................................................................ .... ...... ...... 8

LIST OF TABLES .......................................................................................................... 11

ABSTRACT ................................................................................................................. 12

CHAPTER 1: INTRODUCTION .................................................................................. 14

Background and Purpose of Study ............................................. .............. .... .............. 14
Previous Work ........ ... ................... .... ...................................................................... 15
Cananea District Geology .................................................................... " ................. 15
Present Study ...................................... ,....................................................................... 17
Field work and Sampling .................................................................. ................ ...... 17
Analytical Techniques .................................................................................... ........ 18
Fluid Inclusion Analyses ...................................................................... .................. 18
Major and Trace element Analyses .......................................... .............................. 19
Isotopic Analyses .... .................................................................. .......... ...... ...... ........ 19
X-Ray diffraction .................................................................................................... 21
Electron Microprobe Analysis ...... ........ ................ .................................. ................ 21

CHAPTER 2: THE RELATIONSHIP BETWEEN THE EVOLUTION OF

IGNEOUS ROCKS AND HYDROTHERMAL ALTERATION
IN THE CANANEA DISTRICT, SONORA, MEXICO ....................... 22
Introduction ................................................................................................................. 22
District Geology .................................................................................................. ........ 24
Pre-Laramide Rocks ............................................................................................... 34
Laramide Igneous Rocks .............. .......... ................................................................ 36
Mariquita Fonnation ........................................................................................... 36
Mesa Fonnation .................................................................................................. 37
Tinaja-Cuitaca Batholith ..................................................................................... 38
Late Mafic Dikes ........................... ..................................................................... 40
Quartz Feldspar Porphyries .......... .............................. ........ .......... ...................... 41
Structure and unroofing sequence .......................................................................... 42
Description and Time-Space Distribution of Alteration... ...... ............ ........................ 44
Endo- and Exo- skarn ............................................................................................. 45
Propylitic alteration ................................................................................................ 45
Potassic alteration ................................................................................................... 47
Hydrolytic alteration ............................................................................................... 47
Fluid Inclusions ........ .... ...... ...... ...... ...................... .... ........ ................ .......................... 49
Geochemistry of the Laramide Rocks .. ........ ...... .... ...... ........................ .... .............. .... 51
Major Element Data ................................................................................................ 52
Trace Element Data ................................................................................................ 58
Mineral Compositions .................................. .................. .......... ...... ........................ 64
 6

TABLE OF CONTENTS--Continued

Halogen Contents of Hydrous Minerals ................................... ...... ........ ...... ...... 69

Isotopic Relationships ............................................................................................. 70
Radiogenic Isotopes ............................................................................ .......... ...... 70
Stable Isotopes .................................................................................................... 73
Origin of the Cananea Magmas .................................................................................. 73
Estimation of Intensive Parameters .................................................. .......... ................ 79
Depth Estimates........................................................ .............................................. 80
Oxidation State of Magmas .................... ................ .................. .............................. 82
Evolution of Hydrothermal Fluids.... ............................ ...... ........................................ 89
Summary of Compositional Trends ........................................................ ........ ........ 89
Isotopic evolution of Fluids .................................... ........................ ........................ 90
Discussion ................................................................. .................. ................ ........ ........ 93
Conclusions ................................................................................................................. 98

CHAPTER 3: GEOLOGY AND GENESIS OF THE MARIA SILICATE-

SULFIDE PEGMATITE, SONORA, MEXICO .................................... 101
Introduction ................................................................................................................. 101
Exploration and Mining History ................................................................................. 103
Cananea District Geology ........................................................................................... 104
Geology of the Maria Area ......................................................................................... 107
Mineralization in the Maria Area ............................................................................... 109
The Maria disseminated deposit ............................................................................. 110
Mineral Associations .......................................................................................... 110
Distribution and form of mineralization ............................................................. 115
The Maria silicate-sulfide pegmatite deposit. ......................................................... 116
Mineral Associations .......................................................................................... 117
Chalcopyrite-quartz-biotite associations (early) ............................................. 117
Quartz-biotite-chalcopyrite pegmatitic veins ............................................. 119
Massive chalcopyrite-biotite ....................................................................... 123
Pyrite-quartz-tourmaline associations (late) ................................................... 123
Quartz-tourmaline-pyrite veins and breccia cement.. ................................. 124
Massive pyrite-quartz ................................................................................. 125
Quartz-sericite-pyrite veins ........................................................................ 125
Clay alteration ................................................................................................. 126
Spatial distribution and form of mineralization .................................................. 126
Grade Distribution: ................................................................................................. 132
Time-space development of Mineralization ............................................................... 133
Physical & Chemical Constraints ............................................................................... 136
Fluid inclusion data ................................................................................................. 136
Salinity ................................................................................................................ 137
Temperature ........................................................................................................ 140
 7

TABLE OF CONTENTS--Continued

Stable Isotope data .................................................................................................. 141

Sulfur .................................................................................................................. 141
Hydrogen ............................................................................................................ 143
Oxygen ................................................................................................................ 146
Estimation of Intensive Variables ........................................................................... 146
Source and evolution of hydrothermal fluid ........................................................... 148
Mass and heat balance constraints ...................................................................... 151
Volume of Magma .......................................................................................... 152
Constraints on volume and source of hydrothermal fluid .............................. 152
Discussion of the Comparative Anatomy of Pegmatitic Ore Systems ....................... 155
Comparison with other silicate-sulfide pegmatites ................................................. 155
Thoughts on the origin of Silicate-Sulfide Pegmatites ........................................... 162
Synthesis ................................................................................................................. 166

CHAPTER 4: MAJOR CONCLUSIONS ..................................................................... 169

REFERENCES ................................................................................................................ 175

 8

LIST OF FIGURES

FIGURE 2.1a, Geologic map of the Cananea District. ................................................... 26

FIGURE 2.1 b, Stratigraphic column for the Cananea District ............................... ........ 27

FIGURE 2.1c, Alteration map ........................................................................................ 28

FIGURE 2.1d, Distribution of fluid inclusions ............................................................... 29

FIGURE 2.1e, Location map for Nd, Sr, 0 isotopic analyses of igneous rocks ............. 30

FIGURE 2.lf, Location map for 0 isotope analyses of hyrothermal minerals .............. 30

FIGURE 2.1g, NW-SE and W-E cross sections across Cananea District ...................... 31

FIGURE 2.2, Summary of geochronologic data ............................................................. 33

FIGURE 2.3 a, Plot of K20 VS.Si02 ............................................................................... 55

FIGURE 2.3b, Plot of Na20 + K20 vs. Si02 ................................................................. 55

FIGURE 2.3c, Plot of MgO vs. Si02 .............................................................................. 56

FIGURE 2.3d, Plot of Ti02 and Fe203 VS.Si02 ............................................................. 56

FIGURE 2.3e, Plot of CaO vs. Si02 ............................................................................... 56

FIGURE 2.3f, Plot of P20S vs. Si02 .............................................................................. 56

FIGURE 2.3g, Plot of Cu vs. Si02 ................................................................................. 57

FIGURE 2.4, AFM diagrams of volcanic and plutonic rocks ........................................ 59

FIGURE 2.5, lUGS diagrams based on modal and normative mineralogy .................... 60
FIGURE 2.6, Chondrite normalized Spider diagram ...................................................... 63

FIGURE 2.7, Chondrite normalized REE diagram......................................................... 65

FIGURE 2.8a, Amphibole classification diagram plotting Fe/Fe+Mg vs. Si ................. 67

FIGURE 2.8b, Plot of Fe/Fe+Mg vs. Ti for biotites ....................................................... 67

FIGURE 2.9a, Plot of CI vs. F for apatites ..................................................................... 68

FIGURE 2.9b, Plot of CI vs. F for amphiboles ............................................................... 68

FIGURE 2.9c, Plot of CI vs. F for biotites ...................................................................... 68

FIGURE 2.9d, Plot of Cl/CI+F in hydrous minerals vs. host rock ................................. 68
 9

LIST OF FIGURES-continued

FIGURE 2.lOa, Plot of eNd vs. 87Sf/'86Srinitial....................................................... .... .... 72

FIGURE 2.lOb, Plot of 87Srj86Srinitial vs. B180 igneous feldspar .................................. 72

FIGURE 2.lOc, Plot of 87Srj86Srinitial vs. Si02.......................... ................ .... ................ 72

FIGURE 2.10d, Plot of eNd vs. SiD2 ............................................................................. 72

FIGURE 2.11a, Plot of B180mineral vs. host rock ........................................................ 76

FIGURE 2.11b, Plot of B180H20 vs. host rock .............................................................. 76

FIGURE 2.11c, Plot of B180H20 vs BDH20 ........................................................·........... 77

FIGURE 2.12, Plot of Temperature vs. f02 .................................................................... 84

FIGURE 2.13, Temperature vs. xH20 diagram showing crystallization sequence

of igneous minerals ........................................................................................... .............. 85

FIGURE 2.14, Water saturation curve showing Cananea magmas ................................ 88

FIGURE 3.1, Geologic map of the CananeaDistrict.. .................................................... 106

FIGURE 3.2a, Geologic map of the Maria Mine area .................................................... 108

FIGURE 3.2b, Alteration map of the Maria Mine area .................................................. 108

FIGURE 3.3a, NW-SE cross section showing distribution of ore types and

porphyry .......................................................................................................................... 112

FIGURE 3.3b, NW-SE cross section showing distribution of potassic alteration .......... 113

FIGURE 3.3c, NW-SE cross section showing distribution of sericitic alteration .......... 114

FIGURE 3.4, Summary of mineral associations ............................................................. 118

FIGURE 3.5a, Photo of quartz-biotite-chalcopyrite vein ............................................... 121

FIGURE 3.5b, Photo of quartz-biotite-K feldspar pegmatite ......................................... 121

FIGURE 3.5c, Photo of sericitized quartz-biotite-chalcopyrite vein .............................. 121

FIGURE 3.5d, Photo showing biotite intergrown with chalcopyrite .............................. 121

FIGURE 3.5e, Photo of typical massive sulfide breccia ................................................. 121

FIGURE 3.5f, Photo of an underground exposure of massive sulfide breccia ............... 122
 10

LIST OF FIGURES-continued

FIGURE 3.Sg, Photo of an underground exposure of massive pyrite ............................ 122

FIGURE 3.Sh, Photo of an underground exposure of a pyrite breccia body .................. 122

FIGURE 3.Si, Photo of a handsamp1e of pyrite breccia ................................................. 122

FIGURE 3.Sj, Photo of quartz-sericite-pyrite veins ....................................................... 122

FIGURE 3.Sk, Photo of the contact between massive sulfide breccia and wallrock ...... 122

FIGURE 3.6a, Geologic map of Level 3 ........................................................................ 129

FIGURE 3.6b, Contoured Cu grade map for Level 3 ..................................................... 129

FIGURE 3.7a, Geologic map of LevelS ........................................................................ 130

FIGURE 3.7b, Contoured Cu grade map forLevelS ..................................................... 130

FIGURE 3.8a, Geologic map of Level 7 ........................................................................ 131

FIGURE 3.8b, Contoured Cu grade map for Level 7 ..................................................... 131

FIGURE 3.9a, Space-time evolution diagram for the one fluid model .......................... 135

FIGURE 3.9b, Space-time evolution diagram for the two fluid model .......................... 135

FIGURE 3.lOa, Plot of depth/time vs. salinity ............................................................... 139

FIGURE 3.lOb, Plot of depth/time vs. homogenization temperature ............................. 139

FIGURE 3.lOc, Plot of salinity vs. homogenization temperature .................................. 139

FIGURE 3.11a, Plot of 8DH20 vs. time .......................................................................... 145

FIGURE 3.11b, Plot of 8180 vs. time ............................................................................ 145

FIGURE 3.11c, Plot of 8DH20 vs 8 180H20 ................................................................... 145

FIGURE 3.12, Plot of log f02 vs. log fS2 ...................................................................... .149

FIGURE 3.13, Graph of rade vs. tonnage vs. volume of alteration vs. ore

deposition control ............................................................................................................ 160

FIGURE 3.14, Plot of energy /kilogram of magma vs. pressure .................................... 160
 11

LIST OF TABLES

TABLE 2.1, Modal mineralogy of selected igneous rocks ............................................. 32

TABLE 2.2, Major and trace element analyses and CIPW norms ................................. 53

TABLE 2.3, Rare earth element data ............................................ .................................. 62

TABLE 2.4, Sm-Nd, Rb-Sr, and 0 isotopic data for igneous rocks of the Cananea

District............................................................................................................................. 71

TABLE 2.5, Oxygen and hydrogen isotope data ............................................................ 74

TABLE 2.6, Summary of information on Cananea District plutonic rocks ................... 81

TABLE 3.1, Summary of fluid inclusion data ................................................................ 138

TABLE 3.2, Sulfur isotope results .................................................................................. 142

TABLE 3.3, Oxygen and hydrogen isotope data ............................................................ 144

TABLE 3.4, Comparison of the Maria deposit with other silicate-sulfide

pegmatite deposits ........................................................................................................... 156

TABLE 3.5, Comparison of silicate-sulfide pegmatites with other porphyry-

related deposits ................................................................................................................ 158

 12

ABSTRACT

This study investigates the relationship between the evolution of the igneous and

hydrothermal systems in the Cananea mining district located in northern Sonora,

Mexico. The Cananea district was chosen for this study because post-mineral uplift

and erosion has tilted the Cananea Range -15 0 to the east and exposed an oblique

section through approximately 6 vertical kilometers of a mineralized volcano-plutonic

system and because porphyry-related stockwork, breccia, and pegmatitic silicate-

sulfide mineralization are all well developed and well exposed.

Major, trace element, and isotopic data suggest that the Laramide (-64-56 Ma)

igneous rocks represent a cogenetic calc-alkaline magmatic series ranging in

composition from gabbro to granite. Neodymium isotope (ENd = +0.7 to -5.7) and
strontium isotope (87Srj86Srinitial =0.70570 to 0.71037) values show a smooth inverse
correlation and combined with the major and trace element data suggest that the

Laramide rocks evolved from a mantle-derived parent melt by coupled assimilation and

fractional crystallization.

Phase petrology, mineral compositions, whole rock geochemistry, and alteration

mineralogy indicate water, metal, chlorine, and sulfur content of the magmas increased

with increasing differentiation and reached a maximum in late stage differentiates. The

mineralized quartz-feldspar porphyries represent the rapid upward emplacement of this

enriched differentiate.

Porphyry-related mineralization in the Cananea district includes pegmatitic silicate-

sulfide mineralization represented by the La Colorada and Maria deposits. Detailed

field and geochemical work on the M,aria deposit suggests that the fluids, alteration

assemblages and paragenetic relations in silicate-sulfide pegmatites are similar to those

seen in stockwork- and breccia pipe- hosted porphyry Cu systems, but that silicate-
 13

sulfide mineralization represents transitional conditions in which magmatic fluids are

concentrated in a small volume and undergo efficient cooling and decompression

leading to formation of high-grade telescoped mineralization.

 14

CHAPTER 1: INTRODUCfION

Background and Purpose of Study

Porphyry copper mineralization is the product of magmatic and hydrothermal

processes operating during the evolution of calc-alkaline magmatic systems.

Numerous studies have shown that at least some of the fluids, metals, and sulfur in

porphyry-copper deposits are derived from the associated magma (Gustafson and Hunt,

1975; Burnham, 1979; Dilles, 1987). Therefore information about the evolution of the

igneous rocks provides an insight into the development of the associated mineralization

and alteration. This dissertation addresses the relationship between the evolution of the

igneous and hydrothermal systems through a field, petrological, and geochemical study

of the Cananea mining district in Sonora, Mexico. The Cananea district was chosen for

this study because post-mineral tilting and erosion have exposed a section through

approximately 6 vertical kilometers of a mineralized volcano-plutonic system. This

exposure allowed mapping and geochemical sampling over a significant proportion of

the system.

Cananea is of further interest because of the size and variety of its porphyry-related

ore deposits. Porphyry-related, disseminated, breccia pipe, silicate-sulfide pegmatite,

and skarn mineralization, are all well developed and well exposed in the district.

Silicate-sulfide pegmatites are a rare type of deposit and Cananea is one of the few

mining districts in the world where this type of mineralization is present and well

exposed. The occurrence of pegmatitic mineralization in close association with

disseminated and breccia pipe mineralization provided an opportunity to investigate the

question of how silicate-sulfide pegmatite mineralization forms and how differences

originate among the different styles of porphyry-related mineralization.

 15

Previous Work

Many geologists have studied the Cananea district. Early work focused on defining

the geological framework of the district; notable publications include Emmons' (1910)

monograph on the district as a whole, and Valentine's (1936) study of the geology.

Subsequent studies described the distribution and characteristics of specific styles of

mineralization; notable papers include Perry's (1933; 1961) and Bushnell's (1988)

studies of the breccia pipes, and Meinert's (1982) study of the skarn mineralization.

Anderson and Silver (1977) dated several of the intrusive units resolving a long

standing controversy over the age of the Cananea granite. Damon and Mauger (1983)

dated mineralization at the Cananea mine. McCandless and others (1993) dated

mineralization at the Maria deposit. In addition voluminous observations were made

by Anaconda and other company geologists over the years. Although there are

numerous published studies of porphyry copper districts relatively few workers have

integrated investigation of the geochemistry and evolution of the igneous rocks with

the evolution of alteration. Two notable examples of this type of study are Anthony

and Titley's (1988) publication on the Sierrita deposit in southeastern Arizona and

Dilles and others' (1987; 1992a and b) series of papers on the Yerington, Nevada

deposit. Work on silicate-sulfide pegmatite mineralization, which is the subject of

Chapter 3 is limited to Perry's (1933) description of the La Colorada deposit in

Cananea, Gilluly's (1947) paper on Ajo, Arizona, a few brief descriptions of other

occurrences in the western United States, and my M.S. thesis (Wodzicki, 1992).

Cananea District Geology

The Cananea district is located in northern Sonora, Mexico (Fig. 2.1 a). It is one of

two large copper producers in Mexico and among the largest and most productive
 16

porphyry copper districts in the world. Current production in the district is dominated

by open pit mining of supergene-enriched disseminated mineralization but important

historical production came from breccia pipes, skarn and replacement bodies, and

massive silicate-sulfide pegmatite bodies.

The Cananea district is located within the Basin and Range extensional province

and is part of the SW North American porphyry copper province as defined by Titley

(1982a). The distribution of lithologies and their stratigraphic relations are shown in

Figs. 2.1a and 2.1b. In the Cananea district, as in adjacent parts of southern Arizona,

the basement consists of mid-Proterozoic granitic and metamorphic rocks which are

overlain by Paleozoic sedimentary rocks. These units are overlain and intruded by a

series of Mesozoic and younger intermediate to felsic, calc-alkaline, metaluminous

igneous rocks. These rocks include an older series comprised of Late Triassic-Jurassic

felsic volcanic rocks and a probable Jurassic age pluton. The younger series consists of

intermediate, high-K, calc-alkaline, volcanic and plutonic rocks which were pan of the

late Cretaceous to early Tertiary Laramide volcano-plutonic arc. The oldest Laramide

rocks are andesitic volcanic rocks which are intruded by a mostly equigranular

composite batholith which is grossly granodioritic in composition. Early mapping

established that copper porphyry, breccia pipe, and skarn mineralization in the district

is primarily, if not entirely, related to the quartz-feldspar porphyries which intrude the

entire section including the earlier volcanic and equigranular rocks (Emmons, 1910;

Valentine, 1936; Meinert, 1982). The age of the batholith is 64 ± 3 Ma (Anderson and

Silver, 1977). K-Ar dates on mineralized porphyry stocks range from 59 ± 2 Ma to 54

± 2 Ma and compare well with a Re-Os date of 57.4 ± 1.6 Ma on molybdenite from
Maria (McCandless et aI., 1993). This entire sequence was tilted to the east by Tertiary
 17

basin and range faulting, and subsequent erosion has exposed a section through the

system.

Present Study

The results of this study are presented in four chapters. This first chapter provides

background infonnation concerning, the reasons for this study, geologic setting of the

study area, previous work, the methods used, and the most significant results of this

research. The infonnation presented in this chapter is intended to put the detailed

results discussed in Chapters 2 and 3 into context and to summarize the author's

contribution to the understanding of porphyry-copper mineralization in the Cananea

district. Chapter 2 focuses on the district geology and uses new field and petrographic

observations as well as analytical data to provide insight into the composition and

evolution of the Laramide magmatic-hydrothermal system in the Cananea mining

district. The second part of the study which is presented in Chapter 3, consisted of

detailed mapping and analytical work on the Maria silicate-sulfide pegmatite. The

purpose of this part of the study was to describe the deposit, develop a genetic model

for this unusual and little studied type of mineralization, and to use this information to

discuss origin of differences between different styles of porphyry-related

mineralization. The major conclusions of the entire study are summarized in Chapter

4.

Field work and Sampling

This dissertation is based on approximately 6 months of geological mapping

between 1991 and 1994. The published geological map of Valentine (1936) and

unpublished geological maps by Cominco Ltd. geologists were compiled onto a

1:25,000 topographic base map and contacts and lithologies were field checked and
 18

modified where necessary. The distribution of alteration was mapped at 1: 10,000 and

compiled onto the topographic base map. Primary and alteration mineralogy were

detennined by hand lens and by petrographic examination of approximately 100 thin

sections. Representative samples of the fresh and altered igneous rocks were collected

for whole rock analysis. Representative samples from the alteration assemblages were

collected for fluid inclusion and stable isotope analysis. New workings in the Maria

Mine were mapped at 1:250 as underground development progressed. Samples were

collected for fluid inclusion and stable isotope analysis.

Analytical Techniques

This section describes the analytical techniques used in this study and gives

uncertainties and errors involved in the analyses. Where techniques have been

described by others the appropriate reference is given.

Fluid Inclusion Analyses

Fluid inclusions were classified as primary or secondary based on criteria defined

by Roedder (1984). Heating and freezing experiments were conducted on fluid

inclusions in quartz from each mineral assemblage in the Maria deposit using a

standard University of Arizona designed heating and freezing stage mounted on a

petrographic microscope at Western Washington University. Homogenization

temperatures measured during heating runs are repeatable to 1°C. Freezing

temperatures are generally repeatable to 0.2°C. The accuracy of the stage was

periodically verified using synthetic standards. Salinities for liquid + vapor inclusions

were estimated from the freezing point depression (Roedder, 1984). Salinities for

liquid + vapor + daughter inclusions were estimated from halite dissolution

temperatures (Roedder, 1984). Trapping pressure was estimated from the

 19

homogenization temperatures of co-existing liquid + vapor and vapor + liquid

inclusions.

Major and Trace element Analyses

Powders for whole rock analysis were produced crushing in a tungsten carbide

shatter box at the University of Arizona. A set of 26 representative samples of fresh

and altered igneous rocks was analyzed for major elements and Ba, Nb, Rb, Sr, Y, and

Zr by X-ray fluorescence at XRAL Activation Services in Ann Arbor, Michigan. Ag,

As, Cd, Co, Cu, Mn, Mo, Ni, Pb, and Zn were also analyzed at XRAL by ICP. Rare

earth element analyses were done by solution ICP-MS in the Keck Laboratory at the

University of Arizona. A description of procedures and uncertainties is given in

Roberts and Ruiz (1989). Rocks were classified using the total alkalis-Si02 and the

K20-Si02 diagram of Le Maitre et al. (1989) for orogenic series. Trace element

variations are shown on normalized 'spider' diagrams in which selected trace elements

from Ba to Yb are arranged from left to right in order of increasing incompatibility

during mantle partial melting. Rare earth element abundances were normalized to the

chondrite composition of Anders and Grevesse (1989) and plotted against the element

on standard variation diagrams. CIPW norms were calculated using a spreadsheet

program written by Mark D. Barton.

Isotopic Analyses
A set of 8 samples was analyzed for strontium and neodymium isotopic ratios. The

analyses were done by J. D. Gleason in the Radiogenic Isotope Laboratory at the

University of Arizona. Detailed lab procedures are described in Patchett and Ruiz

(1987) and Gleason (1994). Uncertainties, errors, and normalization values are listed

in the footnotes to Table 2.4.

 20

Oxygen isotope ratios for both fresh igneous rocks and the hydrothermal mineral

assemblages were measured in the Stable Isotope Laboratory at the University of

Arizona. Minerals for analysis were separated by hand-picking. Oxygen was extracted

from - Img single mineral samples in a laser-fluorination extraction line, using

techniques described by Sharp (1990). The precision of isotopic determinations

determined by replicate analysis was 0.2 to 0.5%0. Accuracy was determined by

running 1 internal lab standard (CCI quartz) for every 5 samples. Water was extracted

from 30 to 40 mg of hydrous mineral separates by heating under vacuum and converted

to H2 over hot depleted uranium. The precision determined by analysis of duplicate

samples was 2 to 8 per mil. An internal lab standard (McCullough Butte Muscovite)

was run every 5 samples to monitor accuracy. The isotopic composition of the

extracted gas was measured on a DeltaS gas ratio mass spectrometer at the University

of Arizona. Results are reported relative to SMOW using standard 8 notation in parts

per mil. The 8 18 0 and 8D composition of fluid in equilibrium with the mineral was

calculated using experimentally derived fractionation factors. For samples from the

Maria deposit the temperatures used in the calculations were derived from fluid

inclusion heating experiments. Temperatures used for samples from the Cananea mine

were estimated from average values for the appropriate alteration assemblage taken

from the literature.

Four samples were dated by Matt Heizler at the New Mexico Institute of Mining

and Technology in Socorro, New Mexico using the conventional 40 Arj39Ar step

heating method. The analytical procedures used are outlined by Harrison and Fitz

Gerald (1986). Sample locations are shown in Fig. 2.1a.

 21

X-Ray diffraction

The alteration mineralogy of fine grained samples was determined by X-ray

diffraction using a Siemens powder diffractometer in the X-ray Diffraction Lab at the

University of Arizona. Mineralogy was then determined by comparison with standard

mineral patterns.

Electron Microprobe Analysis

Mineral analyses were performed on -20 standard polished thin sections with a

Cameca SX50 electron microprobe at the University of Arizona using four crystal

spectrometers, natural and synthetic standards and default correction procedures.

Counting time was 10 seconds for major elements and 20 seconds for minor elements

and fluorine and chlorine. Major elements are determined to precisions of <2% for

major elements, and 2-10% for minor elements and> 10% for trace elements.
 22

CHAPTER 2: THE RELATIONSHIP BETWEEN THE EVOLUTION OF IGNEOUS

ROCKS AND HYROTHERMAL ALTERATION IN THE CANANEA DISTRICT,
SONORA, MEXICO

Introduction

The Cananea district located in northern Sonora is one of two large producers of

copper in Mexico and is one of the largest, most productive porphyry copper districts

in the world. Total district production through 1994 exceeds 4 million tons of Cu

(Meinert, 1982; unpub. company reports, 1994). Current production in the district is

dominated by open pit mining of supergene enriched disseminated mineralization at the

Cananea Mine in the southern part of the district. The remainder of district production

in 1994 was from the small (-2 x 1()4 metric tons Cu/yr.) but high-grade Maria deposit

in the central part of the district. (Cominco Resources Annual Report, 1993).

Announced reserves at the Cananea Mine are - 14 x 10 6 tons of Cu (R. Ayala, 1994

personal comm.). Undeveloped resources at the Mariquita and Milpillas deposits in the

northwest part of the district are estimatec to contain an additional 1.5 x 106 tons of

Cu.

Mineralization in the district is associated with early Tertiary quartz-feldspar

porphyry stocks which intrude Paleozoic sediments and Mesozoic to earliest Tertiary

igneous rocks along a NW trending zone -30 km long by 4 km wide. The Cananea

district is of great interest because of the tremendous size and variety of its ore

deposits. Closely associated disseminated, breccia pipe, skarn, and pegmatitic ore

bodies are all well developed and well exposed in the district. Post-mineral tilting and

erosion has exposed an oblique section through approximately 6 vertical kilometers of

a mineralized volcano-plutonic system which provides an opportunity to investigate the

 23

temporal and spatial evolution of both the igneous system and the associated

mineralization. Cross-cutting relationships allow investigation of the evolution of

mineralization from pre-porphyry emplacement of equigranular batholithic rocks to the

late stages of porphyry-related mineralization. New observations and geochemical data

provide insight into the composition and evolution of the Laramide igneous system and

allow estimation of conditions during emplacement and crystallization of the intrusive

rocks. The relationship between composition and crystallization conditions of the

igneous rocks and the type of mineralization/alteration which develops will also be

examined. This information suggests possible answers to the important question of

why some intrusions are associated with mineralization and others are barren.

This study is based on approximately four months of geological mapping between

1991 and 1994. The geological maps of Valentine (1936) as well as unpublished maps

by Cominco Ltd. geologists were compiled onto a 1:25,000 topographic base and

contacts and lithologies were field checked. The distribution of alteration was mapped

at 1:10,000 and compiled onto the 1:25,000 base map. Primary and alteration

mineralogy and paragenetic sequence were determined by petrographic examination of

approximately 100 thin sections. Alteration mineralogy of fine grained samples was

determined by X-ray diffraction. Minerals from 20 fresh and altered rocks were

analyzed with an electron microprobe. Samples of 26 fresh and altered igneous rocks

were analyzed for major and trace elements by XRF and 8 representative samples of

the post- Paleozoic intrusive suite were analyzed for rare earth elements (REE) by ICP-

MS. The same 8 samples were analyzed for Sr and Nd isotopic composition. Feldspar

and quartz from 14 samples were analyzed for their oxygen isotope composition and a

further 12 samples of sericite and clay from mineralized areas were analyzed for both
 24

oxygen and hydrogen isotope composition. Four samples were dated by the 40Ar(39Ar

method.

District Geology

The Cananea district has been studied by many geologists. Notable publications

include Emmons' (1910) and Valentine's (1936) studies of district geology; Perry's

(1933, 1961) and Bushnell's (1988) publications on the breccia pipes, and Meinert's

(1982) study of skarn mineralization. The Cananea district is located within the Basin

and Range extensional province and is part of the SW North American porphyry

copper province. In the Cananea district, as in adjacent parts of southern Arizona, the

basement consists of mid-Proterozoic granitic and metamorphic rocks which are

overlain by Paleozoic sedimentary rocks. These units are overlain and intruded by a

series of Mesozoic and younger intermediate to felsic, calc-alkaline, metaluminous

igneous rocks associated with the late Cretaceous to early Tertiary Laramide volcano-

plutonic arc. This entire sequence was tilted to the east by Tertiary basin and range

faulting. The major rock units and their field relationships are shown in Fig. 2.1 a and

Fig. 2.1 b and described in more detail below. The available geochronologic

information is summarized in Fig. 2.2. Mineralization and alteration in the Cananea

district is closely associated with the Laramide igneous rocks. Therefore these rocks

are of particular interest to this study and are described in greater detail than the older

rocks. The petrographic data summarized in the following two sections provide the

framework for interpretation of the geochemical data which is presented in a

subsequent section. Tables 2.1 and 2.2 summarize the modal mineralogy, major and

trace element data, and CIPW norms for the Cananea rocks.
 25

Figure 2.1

a: Geological map of the Cananea District. Based on Valentine (1936) and unpublished
mapping by Minera Constelacion geologists and this author. Locations of published
and unpublished (this study) radiogenic isotope dates are also shown. A-A' is the
cross section shown in Fig. 1g. Inset shows location of the Cananea district.

b: Stratigraphic column for the Cananea district. Thicknesses of sedimentary and volcanic
units are drawn to scale. Intrusive rocks are schematic.

c: Alteration map showing distribution of hydrothermal alteration based on mapping done

by author during the course of this study. Lithologic units from Fig. la are outlined.

d: Distribution and types of fluid inclusions in igneous and hydrothermal quartz. Size of
the sketched inclusion(s) is a qualitative measure of relative abundance of fluid
inclusions in a particular sample. Lithologic units from Fig. la are outlined.

e: Map showing locations of igneous rocks analyzed for Nd, Sr, and 0 isotopes. Numbers
are 818 0 min Vs SMOW unless otherwise indicated. 8180 measured on single mineral
separates; fsp=feldspar, qtz=quartz. ENd and initial 87Srj86Sr values are whole rock
analyses calculated for 64 Ma (except EI Torre Syenite ENd=.6.4 calculated for 150
Ma). Data is taken from Tables 2.4 and 2.5. Lithologic units from Fig. la are
outlined.

f: Map showing locations of hydrothermal minerals analyzed for 0 isotopic ratio; bt=
biotite, qtz=quartz, ser=sericite. All numbers are 8180 min Vs SMOW. Data is taken
from Table 2.5.

g: NW to SE cross section along A-A' from Fig. 2.1a (upper). E to W section along B-B'
from Fig. 2.1a (lower)
 26

.J
'.
"-\ ....,.....\.
\ 0---
Scale
o Km 400

~
Scale
Km

o Mesa Formalion
;g _ Mariquila Formalion
'.14
I:i%J Henriella Formation ()64 My TInajaiCuila
_ Elenila Formallon _ _ • '<, Granodlorlle
N .;..; CarbonBtes
~~
- -_- _
OlJarlZlllL _ - _
- _ (jMZ EI Torre Syenile
t::.;~ Cananea Granile (1.4 Ga)
69.7± 1 Ma
Ar/Ar Blotile +

Figure 2.1a
 27

Late Mafic dikes

(Early Tert.) ---+--. ~ Dacite flows
Rhyolite Porphyries t
54.2 ±2 Ma ~

Mesa Formation (69.0 ± 0.2 Ma)

Interbedded Volcaniclastic conglomerate,

Quartz-Feldspar POrDt1IVrlles"--I-~ agglomerate, and basaltic andesite flows.
(57.4 ±1.6 Ma to

Mariquita Basaltic-Andesite

Rhyolite flows and tuffs.

Cultaca-Tinaja
Batholith (64 ± 3 Ma)

Henrietta Formation (Jur.?)

Dacite flows and tuffs.

Elenita Formation (Tr.-J)

Rhyolite and Trachyte tuffs and
flows with interbedded sandstones.
(Possibble equivalent to Triassic Mt.
Wrightson Formation).

EI Torre Syenite
JurassIc? ---

Carbonates
E Martin, Abrigo, Escabrosa, and
o Naco Formations
o
o
Bolsa Quartzite

Cananea Granite (1.44 Ga U-Pb zircon)

Figure 2.1b
 28

Explanation
E!:::J ClayaHeralion

CSJ A1unl1a

E::3 Actinolite ± magnetite volnlets

D Epidote ± chlorite assemblage

t::7!J Actinolite ± chlorite assemblage

..-
"
_ SlIica·pyrite gossan
~ Weak pervaslvo and veinlet
L......J controlled quartz·sericite·pyrlte
Weak to moderate quartz·
serlcite·pyrito veining
Intonse quartz·serlcite·pyrite veining

mlJ Potassic Alteration

.... ,~ Gamet ± pyroxene skam/

undifferentiated gamet skam and
martlle

",

.'.

o 1
SCai8
Km

Figure 2.1c
 29

Types of Fluid inclusions

<__> Liquid+Vapor+Daughter (LVD)

CD Liquid+Vapor (LV)
c:J Vapor dominated (VL)
• No fluid inclusions seen

Figure 2.1d
 30

Figure 2.1e

+9.5 eer

+7.9 cloy
+12.7 cloy

+17.4 cia

Figure 2.lf
,..
C')

A'
A
SE
NW Cananea Mine

. '\. ......-,.~~
\:"/"~/.
... ". /
v""
.">-//.,.-. ,..... .'.">-/
. ". /
>..... ".: ..'.\.//
....." / " ..../"
. . ~..' ./~/
," /
.
1km
=

B
W Cananea Mine

1 km
~

I=)){l Mesa Formation

~_ Mariquita Formation ~2-59 My QFP's
lla'=H Henrietta Formation (164 My Ti.naja/Cuitaca
. . Elenita Formation • V GranodiOrite
~ ~ -CartJorfafes - - - - - - - - - -
~ :....: _ Quar.~e _______ _
E] Mz EI Torre Syenite
b::<>1 Cananea Granite (1.4 Ga)

Figure 2.1g
Table 2.1 Modal Mineralogy of Selected Igneous Rocks
Rock Name EI lorre ImaJa ImaJa Dlonte GUitaca GUitaca Deep Lower Hennetta Fm. Opper Mesa
Syenite Gabbro Granodiorite Granodiorite Porphyry Henrietta Elisa Rhyolite Fm
Cananea
Sam~le # 96 151 42.1 Maria Area 224 2397-489 218 216 127

Plagioclase 12% 59% 47% 46% 31% 14% 3% 4% 15%

K feldspar 52% 3% 14% 19% 22% 14% 31% 26% 5%
Quartz 22% 4% 14% 27% 30% 13% 0% 11% 0%
Biotite tr 0% 0% 3% 6% 4% 0% 0% 1%
Hornblende 11% 16% 18% 4% 9% 1% 6% 1% 0%
Magnetite 3% 3% 4% 1% 2% 0% tr 0% 1%
Sphene tr 0% tr 1% 1% 0% 0% 0% 0%
Pyroxene tr 15% 2% 0% 0% 0% 0% 0% 0%
Apatite tr tr tr tr tr 0% 0% 0% tr
Matrix 0% 0% 0% 0% 0% 54% 60% 57% 76%
Rock frags. 0% 0% 0% 0% 0% 0% 0% 0% 3%

2points 284 213 254 604 274 191 222 227 213

(..)
I\)
 25

501-
-
~3
.3 .3 ?,
[_J3
~

:-

~
ro -
I ~5 -~
.5 ~>~
'777Ji

82
4

I-

-
~75 - M
« ?
- I

100)- '.5
?I
.
:-

-
-:7
14501- 771 71L

- /'1

- ~

1500 --.......J_ -- -- -------'

Decreasing Known Relative Ages
- -- ~

o
III
m
m
:c
CD
!!l ~
III
~
CD
::I
::l
0
c: ~
5'
::l
III :!. =!
iii'
0'
....
....
::l.
.0
en
III
~.
III
s= ....CD
::l
CD
W ::: CD 5. "T1
0
III !!!.
W N'
III "T1 III
~ ao·
G> ~ "T1
ii3 ~ ::l
::l

15' I;~ K-Ar Sericite ~ K-Ar Whole Rock

40Ar/39Ar Homblende. Darkest gray is

§ estimated minimum age, lighter grays t~~~:1
".,,,,, Re/Os Molybdenite
represent est. reset ages in same sample

< >U-Pb Zircon &l K-Ar or 40Ar/39A Biotite

Figure 2.2: Summary of published and new geochronologic data for the Cananea district. References: 1. Anderson and Silver,
1977; 2. Damon et aI., 1983; 3. Mexicana de Cananea unpub. data in Meinert, 1982; 4. McCandless et aI., 1993; 5. This study. (..)
(..)
 34

Pre-Laramide Rocks

The oldest unit exposed in the district is the 1440 ± 15 Ma Cananea Granite (U-Pb,

zircon, Anderson and Silver, 1977b). It is found in a northwest trending horst in the

center of the district (Fig. 2.1a). The Cananea Granite is unconformably overlain by

Paleozoic sediments which include the Bolsa, Abrigo, Escabrosa, and Martin

Formations and part of the Permian Naco Group (Mulchay and Velasco, 1954; Meinert,

1982). The Paleozoic carbonate rocks in this sequence host extensive skarn

mineralization described by Meinert (1982).

The Proterozoic and Paleozoic section is unconformably overlain by a thick pile of

Mesozoic to early Tertiary volcanic rocks which were divided into three formations by

Valentine -(1936). The major element data discussed below suggest that they comprise

at least two and perhaps three separate evolutionary series. Field relationships

constrain the relative ages of these units, however unequivocal absolute ages are not

available for the two older units. The stratigraphically oldest volcanic unit is the

Elenita Formation which is composed ofrhyolitic to andesitic tuffs and flows with

interbedded sandstone and quartzite (Valentine, 1936). This section is similar to the

Late Triassic-Mid Jurassic Mt. Wrightson Formation described in the Santa Rita

Mountains of southern Arizona (Drewes, 1971, Riggs and Blakey, 1993). The Elenita

Formation outcrops in the west and southwest parts of the Cananea district (Fig. 2.1 a).

It is estimated to be approximately 1800 m thick (Valentine, 1936) (Fig. 2.1 b).

The Elenita volcanic rocks in the west central portion of the map area are intruded

by the El Torre Syenite (Valentine, 1936). In detail the composition of the El Torre

pluton ranges from quartz-syenite to granite. It is typically a fine to medium grained

(0.5-2 mm), equigranular, quartz-hornblende syenite which contains alkali feldspar (Or
 35

0.6 AbOA) with perthitic exsolution textures, green actinolitic hornblende, quartz, minor

plagioclase(An 15-25), trace biotite (Ann 0.5 PhI 0.5), and accessory ilmenite, apatite.

zircon and sphene. Most of the El Torre is overprinted by weak to moderate propylitic

alteration described in detail below.

The age of the El Torre syenite relative to the Cuitaca and Tinaja plutons discussed

below is problematic. It is texturally and compositionally similar to the Tinaja and

Cuitaca, and Valentine (1936) suggested that all three bodies are phases of the same

batholithic body. Hornblende from the El Torre (Fig. 2.1a) dated by 40Ar/39Ar has a

disturbed spectrum and a plateau age of 58.4 ± 0.5 (± 2) Ma. This is similar to the age

of porphyry copper mineralization in the district and is interpreted as a reset age. A

poorly defined secondary plateau suggests a minimum age of -70 Ma, however the

poor definition of this plateau suggests that this also represents a reset age. Meinert

(1982) suggests an older, perhaps Jurassic age, for the El Torre based on compositional

similarity to Triassic-Jurassic plutons elsewhere in northwest Mexicoand the fact that a

fault which cuts the El Torre syenite does not cut the early Tertiary Tinaja diorite. The

Pima district in southern Arizona has similar composition volcanic rocks and granites

ranging in age from 200-150 Ma then a Laramide cycle beginning at -70 Ma (Titley,

1982a). This field evidence combined with new geochemical data discussed below

suggest that the El Torre is part of an older, possibly Jurassic event.

Medium- to high-K, calc-alkaline, dacite to rhyolite tuffs and flows of the Henrietta

Formation overly the Elenita Formation (Fig. 2.3a). The Henrietta has a less evolved

composition than the Elenita in its basal units and ranges in composition from dacite

and trachy-dacite to rhyolite (Fig. 2.3b). The contact between the Elenita and Henrietta

is a fault, but Valentine (1936) reports clasts of the Elenita Formation within the

lowermost Henrietta. Therefore the Henrietta is generally considered to be younger.

 36

although it is not clear how much younger. An attempt to date hornblende from the

Henrietta by the 40Ar(39Ar method yielded a plateau age of 57.9 ± 0.2 Ma which is

approximately the age of mineralization in the district. This result and the fact that the

Henrietta is intruded by a 64 Ma pluton suggests that this is a reset age and that the

Henrietta is somewhat older. A poorly defined secondary plateau suggests a possible

minimum age of 94 ± ? Ma. The Henrietta Formation occupies a northwest trending,

ENE dipping swath across the center of the Cananea District and hosts part of the

disseminated copper ore body at Cananea (Fig. 2.1 a). The Henrietta Formation is

estimated to be about 1700 m thick (Valentine, 1936)(Fig.2.1 b).

Laramide Igneous Rocks

Mariquita Formation

The oldest Laramide unit is the Mariquita Formation. The Mariquita Fonnation

consists of high K basaltic-andesite (Fig. 2.3a). These rocks plot as basaltic trachy-

andesites on a total alkalis versus Si02 diagram (Fig. 2.3b). In the northern half of the

Cananea Range, the Mariquita Formation occurs as a series of -150 east dipping flows

which fonn the upper 400 m of the Sierra Mariquita (Fig. 2.1a). Between Sierra

Mariquita and Cananea it consists of dikes and small stocks of basaltic-andesite which

intrude the dacitic tuffs of the Henrietta Fonnation, and of a thick basaltic-andesite

flow which overlies the Henrietta Fonnation and grades upward into the overlying

Mesa Formation. From Cananea south, the Henrietta Fornlation is unconformably

overlain by the Mesa Fonnation and the Mariquita flows are missing. Fresh Mariquita

is dark gray to black and typically has a strongly porphyritic 'turkey track' texture

which consists oflarge (10-12 mm) phenocrysts of plagioclase and locally olivine in a

fine grained matrix of plagioclase, hornblende, occasional clinopyroxene, and

 37

magnetite. The plagioclase phenocrysts are commonly partly resorbed. Amygdules

filled with quartz ± magnetite ± epidote are common on Sierra Mariquita.

Mesa Formation

The Mesa Formation ranges in composition from basal trachy-basalt to upper dacite
and trachy-dacite, but is dominantly andesitic in composition (Fig. 2.3b).

The Mesa rocks are medium- to high- K and calc-alkaline. The Mesa Formation

covers the eastern third of the district and is estimated to be -1500 m thick (Valentine,

1936). It is an important host rock for the disseminated copper ore body at Cananea.

The lower Mesa consists of a thick sequence of interbedded agglomerate

(volcaniclastic with volcanic matrix), volcaniclastic sandstone and conglomerate, and

occasional fine-grained, basaltic-andesite flows. In general the andesite flows consist

of small plagioclase phenocrysts in an aphanitic, reddish-brown matrix. Volcaniclastic

sediments and agglomerate form -90% of the volume of the lower Mesa. The average

volcaniclastic sandstone/conglomerate contains abundant clasts of basaltic-andesite

from the Mariquita and lower Mesa Formations, dacite from the Henrietta Formation,

less common clasts of equigranular intrusive rock, quartzite, and occasional clasts of

garnet skarn in a coarse sandy matrix containing quartz, feldspar, and occasional

chlorite. Clasts are typically 1-5 cm across with locally abundant boulders ranging up

to 5 m in diameter. An interesting feature of the volcaniclastic sequence is the

occurrence of apparent blocks of quartzite - 30 m across in two locations near Cananea

(Fig.2.1a). Drilling has confirmed that the blocks are in fact mega-clasts and not

uplifted basement blocks. This type of mega-clast has been described in volcaniclastic

formations of similar age in southern Arizona (Drewes, 1971). In general the grain size

of the volcaniclastic sediments at a given stratigraphic horizon decreases with

increasing distance from Canan ea. There are also repeated fining upward sequences
 38

which grade upward from boulder conglomerate, to conglomeratic sandstone, to well

sorted occasionally cross-bedded fluvial sandstone to thin bedded fine grained

sandstone and siltstone. Cross bedding and channels are locally well developed and

suggest transport to the northeast, away from Cananea. The agglomerate units contain

similar clasts to the sediments but have a volcanic matrix. Outcrops of agglomerate are

concentrated within 2 km of the Cananea Mine. These observations support

Valentine's (1936) suggestion that the Mesa Formation had a source in the approximate

area of the Cananea mine.

To the north of Cananea the volcaniclastic units are overlain by younger gravels,

however to the east of the town and the mine they are overlain by a series of biotite-

bearing rhyodacite flows and pyroclastic units which extend past the east edge of the

map area. These flows consist of -25% phenoc~'sts of plagioclase, K-feldspar, and

biotite, as well as occasional rock fragments in an aphanitic matrix. The relatively

siliceous composition and the abundance of phenocrysts suggests that this unit did not

flow far from its source. Biotite from one flow gave a 40Arj39 Ar age of 69 ± 0.2 Ma.

Tinaja-Cuitaca Batholith

The earliest Laramide intrusive rocks are two spatially distinct, equigranular,

composite intrusive bodies named the Tinaja Diorite, and the Cuitaca Granodiorite by

Valentine (1936). The Tinaja diorite is a large intrusive body which intrudes the

Henrietta and Elenita Formations west of the Cananea Mine (Fig. 2.1 a). It is a

composite pluton with considerable compositional variation ranging from gabbro to

monzodiorite to quartz monzonite. Most workers in the district consider the Tinaja and

the Cuitaca to be part of the same batholithic body (Valentine, 1936; Meinert, 1982;

Bushnell, 1988). Map patterns (Fig. 2.1a) and radiogenic isotope data discussed below

support the idea of a genetically related, polyphase batholithic body. The composition
 39

of the main phase of the Tinaja is grossly monzodioritic., however more quartz-rich

zones grade into quartz monzodiorite and more K-feldspar rich zones are quartz

monzonites. The typical Tinaja is fine grained (0.25 to 1 mm), dark greenish gray, and

generally equigranular although local porphyritic phases are seen near the northwest

margin of the pluton. The typical monzodiorite is composed of euhedral plagioclase

(An30-40) locally overgrown by K-feldspar; green, subhedral actinolitic hornblende

commonly containing abundant magnetite inclusions; euhedral magnetite; minor

euhedral clinopyroxene commonly partly overgrown by hornblende; minor interstitial

K-feldspar and quartz and accessory, ilmenite, apatite, zircon, and sphene. The Tinaja

is widely overprinted by weak to moderate propylitic alteration.

The Tinaja Gabbro crops out in a small area in the east central part of the pluton. It

is coarse grained (2-5 mm), dark gray, and equigranular. It consists of euhedral to

subhedral plagioclase (An30-40), euhedral pale- green clinopyroxene, euhedral

actinolitic hornblende, abundant magnetite associated with the clinopyroxene and

hornblende, and accessory apatite, alkali feldspar, trace interstitial quartz(?).

Clinopyroxene and hornblende are locally replaced by actinolite.

The Cuitaca (64 ± 3 Ma, U-Pb zircon, Anderson and Silver, 1977) is a large

composite intrusive body which crops out in the northern and western part of the map

area. The Cuitaca is composed of monzonitic, granodioritic, and granitic phases which

intrude the Elenita, Henrietta, and Mariquita Formations. The Cuitaca Granodiorite

consists primarily of granodiorite but grades to monzogranite in the Maria Mine area

and to monzonite south of Highway 2 (Fig. 2.1a). The granodiorite is CroSS-Clit by

numerous aplite and quartz-K-feldspar ± magnetite pegmatite dikes as well as locally

abundant basaltic dikes. The Cuitaca is generally equigranular and medium grained (1-

2 mm) but becomes finer grained toward its margins and weakly porphyritic in the
 40

Maria Mine area. The porphyritic texture results from large (3-5 mm) plagioclase and

hornblende phenocrysts in a 0.5 to 2 mm matrix of quartz and K-feldspar. The

granodiorite consists of plagioclase (An20-40), hornblende, biotite, orthoclase, and

quartz. Apatite, magnetite, zircon, and sphene are present as accessory phases,

commonly as inclusions in the mafic minerals.

The monzonite phase consists of early plagioclase, minor clinopyroxene,

hornblende as isolated grains and replacing clinopyroxene, minor biotite (mostly

replacing hornblende), quartz, and orthoclase. Magnetite, apatite, sphene and zircons

are accessory phases and occur as inclusions in plagioclase and the mafic minerals.

A few small biotite-hornblende quartz-monzonite stocks intrude the Mesa

Formation north, south and east of the Cananea mine site. The relationship of these

stocks to the other intrusive units is unclear since there are no cross-cutting

relationships exposed, however Valentine (1936) thought they might be related to the

Tinaja. This study suggests they are compositionally more similar to the Cuitaca,

which implies that the Cuitaca extends under the Mesa volcanic rocks to the area near

Cananea (Fig. 2.1 g).

Late Mafic Dikes

The Tinaja and the Cuitaca are cross-cut by numerous near vertical basaltic dikes

which follow two structural trends; N60-80W and N40E (Valentine, 1936). Similar

basaltic dikes locally cross-cut the Henrietta and Mesa Formations. These dikes were

called the Campana Diabase by Valentine (1936) to distinguish them from the

compositionally similar but older Mariquita Formation. The mafic dikes are fine

grained, typically <5 m wide, and consist of plagioclase, pyroxene, hornblende ±

biotite. Hornblende is commonly partly altered to actinolite. The mafic dikes are not

seen to cross-cut the quartz-feldspar porphyries but those that cross-cut the Cuitaca, are
 41

locally cut off by granodiorite suggesting that they may have been emplaced during

emplacement and solidification of the Cuitaca. This and the fact that they typically

show weak propylitic alteration suggests that the mafic dikes largely pre-date

emplacement of the porphyries and mineralization.

Quartz Feldspar Porpbyries

Two broad varieties of late felsic, porphyritic stock intrude the entire section at

Cananea. The first is a northwest trending series of quartz-feldspar porphyry stocks

which are closely associated with porphyry copper mineralization and the second

consists of barren rhyolitic plugs locally associated with flows. At the Cananea Mine

the porphyry stocks have only been indirectly dated by K-Ar on hydrothermal biotite

and sericite. These dates range from 59.9 ± 2 Ma (K-Ar hydrothermal phlogopite from

the La Colorada deposit, Damon et aI., 1983) to 54.2 ± 2 Ma (K-Ar sericite from the

Teocali rhyolite porphyry, unpublished Mexicana de Cananea data recalculated using

Steiger and Jaeger (1977) decay constants). Mineralization at the Maria deposit has

been dated at 58.2 ± 2 Ma (K-Ar hydrothermal biotite, Cominco Ltd. unpub. data) and

at 57.4 ± 1.6 Ma (Re-Os molybdenite, McCandless et aI, 1993).

The quartz-feldspar porphyries associated with porphyry copper mineralization

range in composition from quartz-monzonite to granite. They typically consist of 3-4

mm quartz, feldspar, and biotite phenocrysts in a matrix of aphanitic to finely

crystalline quartz and orthoclase. Quartz phenocrysts are commonly partly resorbed.

Phenocrysts typically comprise between 20% and 40% of the rock. The proportions of

the phenocrysts and particularly the ratio of quartz to feldspar vary somewhat between

individual stocks, and some workers have noted a correlation between the greater

abundance of quartz and higher grade mineralization (Valentine, 1936, Varela, 1972,
 42

Ochoa-Landin and Echevarri-Perez, 1978). In a few porphyry stocks orthoclase

phenocrysts form prominent mega-crysts (3 cm across) i.e., a phase of the 8-110

porphyry and a phase seen in drill holes below the Kino Pit. Biotite occurs as euhedral

phenocrysts and locally replaces amphibole. The QFP stocks are typically overprinted

by strong sericitic alteration. Most of these stocks lack evidence of devitrified glass

and apparently did not vent (Valentine, 1936; Meinert, 1982)

The second category of porphyritic stock includes three large rhyolitic plugs;

Teocali, El Tordillo, and an unnamed plug west of Cananea (Fig. 2.la) which are

distinguished from quartz-feldspar porphyries on the basis of higher silica content, a

finer grained groundmass which locally contains devitrified glass, flow banding near

intrusive contacts, and close spatial association with apparent flows. The rhyolite

porphyries consist of 2-3 mm K-feldspar, quartz, and occasional biotite phenocrysts in

an aphanitic to glassy (devitrified) groundmass of K-feldspar and quartz. Quartz

phenocrysts are commonly partly resorbed. Feldspar phenocrysts in the rhyolite

porphyries are generally weakly to moderately sericitized and rare pyrite replaces mafic

minerals. However, quartz-sericite-pyrite veins are rare to absent. The rhyolitic plugs

are not associated with extensive copper mineralization at present levels of exposure.

Structure and unroofing sequence

There are two major episodes of faulting evident in the Cananea district; early NW

and NE trending normal faults which are locally followed by quartz-feldspar porphyry
dikes and basaltic dikes, and later NNE trending normal faults which tilt all the rocks

and mineralized breccia pipes to the east. Pre-mineralization faulting in the district

consists of prominent high angle N60-80W faults and a subsidiary set of younger high

angle N40E faults and fractures. These pre-mineralization structures cut the entire pre-
 43

Laramide section and possibly the EI Torre syenite but do not cut the Cuitaca and

Tinaja plutons or the Mariquita and Mesa Formations (Valentine, 1936; Meinert,

1982). On district and local scale the structural grain resulting from this faulting

appears to have controlled the emplacement of the mineralized quartz-feldspar

porphyries (Valentine, 1936).

Post-mineralization faulting in the Cananea district consists of high angle NS-IOE

trending faults which are presumably associated with Basin and Range faulting active

from 20-S Ma. On the eastern side of the Cananea range these faults have minor (1 D's

of meters) displacements but apparently controlled oxidation and supergene enrichment

in the Cananea deposit. Large displacement range front fault(s) are present on the west

side of the Cananea Range. These faults are not well exposed but evidence for their

presence includes: 1) the exposure of equigranular intrusive rocks which geobarometry

discussed below, suggests crystallized at -2kb; 2) juxtaposition of highly altered and

relatively fresh rock near the Mariquita deposit; 3) alluvial deposits west of the inferred

faults which have been rotated during faulting and now dip to the east (Fig. 2.1 a).

Uplift along this fault system has exposed deeper parts of the Cuitaca Batholith and

tilted the entire range -ISO to the east as evidenced by the easterly tilt of the Mesa

Formation (Valentine, 1936) and the easterly tilt of many of the breccia pipes in the

district (Perry, 1961; Bushnell, 1988). An east to west transect across the district

represents an oblique section through the Cananea volcano-plutonic system (Fig. 2.1 f).

The uplift history of the Cananea District is of interest because of its likely impact

on the development of the very thick (>SOO m) supergene enrichment blanket in the

Cananea deposit. Recent K/Ar dates on supergene alunite and jarosite at porphyry

copper deposits in southern Arizona suggest that extensive supergene enrichment

occurred between 9-S Ma (S. Cook, 1994 personal comm.). In Cananea a very thick
 44

chalcocite blanket developed because this enrichment episode apparently coincided

with uplift and tilting of the deposit. The Mid to Late ~ertiary uplift history of the

Cananea Range is recorded in gravel deposits which form extensive dissected alluvial

fans on the steep west side of the range and contain a well preserved unroofing

sequence. The gravels dip to the east but are progressively less tilted up-section and
contain clasts derived from successively deeper stratigraphic levels. The oldest strata
contain clasts of the Mesa Formation and are tilted approximately 8° to the east. The

youngest strata lie flat or dip gently to the west and contain clasts of deeper rocks

including the Cuitaca granodiorite, Paleozoic limestone, and skarn. The alluvial fans

formed by the gravels have been incised by more recent erosion which may have

accompanied the Pleistocene climate change documented in southern Arizona.

Alluvial deposits are less extensively developed on the east side of the range.

However, 1 to 5 m of alluvium containing mineralized boulders derived from the

leached cap at the Cananea Mine record the uplift and partial erosion of the deposit.

Description and Time-Space Distribution of Alteration

The Laramide rocks in the Cananea district record a long (6-10 My) and varied

igneous history. This is accompanied by an equally long and complex sequence of

alteration which began before porphyry copper mineralization and continued afterward

. Early alteration characterized by the development of local areas of proximal endo-

and exo- skarn and hornfels and widespread more distal propylitic alteration

accompanied the emplacement of the equigranular rocks of the Tinaja-Cuitaca

batholith. The subsequent emplacement of quartz-feldspar porphyry stocks was

characterized by the development of focused areas of early proximal potassic alteration

± distal propylitic alteration and, later (more widespread) hydrolytic alteration. The
 45

post-mineral uplift and eastward tilting of the district means that in general deeper

alteration is now exposed on the west side of the district and shallower alteration is

exposed on the east side. Alteration on the west side is characterized by weak to

moderate propylitic alteration. In general the east side has is characterized by sericitic,

advanced argillic and clay alteration. These are generally considered to reflect

shallower environments (e.g. Lowell and Guilbert, 1970; Gustafson and Hunt, 1975).

The principal alteration types and their spatial and temporal relationships to each other

and to the related intrusive rocks are described below.

Endo- and Exo- skarn

Endoskarn characterized by the development of light brown garnet ± clinopyroxene

occurs in a narrow zone along the eastern margin of the El Torre syenite and along the

western margin of the Tinaja (Fig. 2.1c). It is spatially associated with a zone of garnet

± pyroxene exo-skarn which apparently replaces volcanic rock in this area. The skarn

lacks opaque oxide or sulfide minerals. Both endo and exo- skarn in this area are

cross-cut by epidote ± actinolite veinlets. Garnet-pyroxene skarn and extensive marble

is developed in carbonate rock adjacent to the contact with Cuitaca granodiorite at the

Puertecitos mine in the northwestern part of the map area. Extensive skarn and marble

is also present in the Capote Basin in the central part of the district. The Capote Basin

skarns are described in detail by Meinert (1982).

Propylitic alteration

Propylitic alteration is widespread in the Cananea district and it affects most of the

igneous rocks in the map area. Propylitic alteration is characterized by partial

replacement of igneous clinopyroxene and hornblende by actinolite, biotite by chlorite

 46

± sphene ± rutile, and variable alteration of plagioclase to sericite ± clays and epidote.
Epidote ± actinolite ± magnetite ± pyrite veinlets with bleached envelopes are also

common, particularly within or adjacent to contacts with the equigranular plutons. The

alteration assemblage within the bleached envelopes is similar to that seen in

pervasively altered rock. The most intense and pervasive propylitic alteration occurs

within the EI Torre and Tinaja plutons (Fig. 2.1c). Clinopyroxene and hornblende are

commonly altered to actinolite, and locally to chlorite and sphene. Plagioclase is

generally weakly altered to clay ± calcite ± epidote. Propylitic alteration is also well

developed near the margins of the Cuitaca granodiorite and in the adjacent volcanic

rocks. Although weak to moderate propylitic alteration surrounds the Cananea deposit

it is not clear how much of the observed alteration is related to emplacement of the

porphyries and how much is related to the earlier equigranular rocks. However, the

distribution of propylitic alteration appears to be most closely related to the observed

and inferred distribution of the equigranular intrusive rocks (Fig. 2.1c). It does not

increase in intensity with proximity to porphyritic stocks.

Variations in the exact assemblage present depend in part on the original

mineralogy of the rock. The fine grained rhyolitic rocks of the Elenita and Upper

Henrietta Formations manifest propylitic alteration primarily by silicification and

bleaching. The mafic to intermediate rocks of the Mariquita and Mesa Formations

typically show more intense development of actinolite, chlorite, and epidote. Many of

the exposures on Sierra Mariquita are cross-cut by thin quartz-epidote-magnetite

vein lets and have amygdules filled with quartz ± epidote ± tourmaline ± magnetite.

Plagioclase phenocrysts are variably replaced by clay and epidote. In more intensely

altered zones near quartz-feldspar porphyry intrusions the Mariquita is typically

bleached and altered to gray or yellowish clay.

 47

Potassic alteration

Both pervasive and vein controlled potassic alteration are present in the Cananea

district, however at shallow levels it has been extensively overprinted by later

hydrolytic (acid) alteration. Potassic alteration is preserved at depths of -500m below

current pit bottoms in parts of the disseminated ore body at Cananea, and at depths of

-100 m in the disseminated ore bodies at Maria and Mariquita. Potassic alteration

represented by quartz-K-feldspar-biotite pegmatite zones is also present in the La

Colorada and Maria silicate-sulfide pegmatite deposits (Chapter 3). In general the

distribution of potassic alteration is strongly correlated with the distribution of quartz-

feldspar-porphyries, but limited alteration of plagioclase to K-feldspar is seen in the

Cuitaca near the Maria deposit and in the Tinaja monzodiorite. Potassic alteration is

characterized by quartz(-pyrite-chalcopyrite), quartz-bioti te- (chalcopyri te- pyri te-

molybdenite), and tourmaline-pyrite veinlets, typically with pink secondary K-feldspar

envelopes. Pervasive alteration is locally present away from the veinlets. This style of

alteration is characterized by local K-feldspar replacing plagioclase and, in a few

places, shreddy biotite replacing hornblende.

Hydrolytic alteration

Intense quartz-sericite-pyrite alteration characterized by replacement of feldspar by

sericite and mafic minerals by chlorite ± sericite ± sulfide affects most of the quartz-

feldspar porphyries in the Cananea district. At the Cananea mine this type of alteration

extends from the pre-mining surface to depths of -1 km. At shallow levels pervasive

sericite-quartz alteration and quartz-sericite-pyrite ± tourmaline veins cross-cut and

overprint both the potassic and propylitic assemblages. Intensely sericitized rock is

characterized by alteration of original feldspars to sericite, replacement of mafic

 48

minerals by sericite ± pyrite ± chalcopyrite. Sericitically altered rock contains a few

percent pyrite and chalcopyrite and is commonly intensely silicificied. Less intense

generally more distal sericitic alteration is characterized by partial replacement of

feldspar by sericite and replacement of biotite by chlorite and rutile. In areas of high

vein abundance, alteration envelopes overlap, original textures are destroyed, and the

rock consists of just quartz and sericite. Vein density is generally at a maximum at the

margins of an individual dike or stock and decreases with increasing distance. On a

deposit scale proximal randomly oriented stockwork veins grade outward to thorough-

going veins which follow district structural trends. In the Cananea Mine there are

multiple closely spaced porphyry stocks and mUltiple generations of overprinting veins.

Local reversals of the usual paragenetic sequence are common (Varela, 1972; personal

observation) suggesting that there were multiple pulses of mineralizing fluids.

Quartz-tourmaline-sulfide cemented breccia pipes are a prominent feature of the

mineralization at Cananea (Perry, 1961; Bushnell, 1988). These bodies are typically

higher grade than the surrounding disseminated mineralization. The breccia pipes at

Cananea commonly contain mineralized clasts of both volcanic and porphyry wall rock

and are typically spatially associated with sericitic alteration. Many clasts are cut by

early quartz-sericite-pyrite veins which are in turn cross-cut by the quartz-tourmaline ±

pyrite ± chalcopyrite matrix. Quartz-tourmaline-sulfide veins associated with the

breccia pipes cross-cut earlier stockwork veining in the wallrock to the breccia

suggesting that breccia pipe emplacement post-dates the formation of at least some

stockwork mineralization.

Clay (intermediate argillic) alteration characterized by intense bleaching and

pervasive alteration of igneous rocks to clay is developed in patchy structurally

controlled zones in Mesa Formation volcanic rocks to the east and south of Cananea.
 49

Intense texturally destructive clay alteration is locally associated with manganese oxide

and chalcedonic silica veins and is interpreted to be of hypogene origin. Occurrences

of this type of alteration partly surround the sericitic alteration (Fig. 2.1c).

There is also locally important clay and fine sericite alteration within the main zone

of hypogene sericitic alteration. This type of alteration is commonly pervasive and

texturally destructive and is characterized by replacement of feldspars by fine grained

sericite and clay and replacement of pyrite by chalcocite. This type of alteration is

distinguished from hypogene sericitic alteration by its generally finer grain, the lack of

clear control by quartz veins, and significantly lower fresh pyrite content. It is

interpreted to originate by reaction with acid supergene fluids.

Advanced argillic alteration is much less voluminous than sericitic alteration but

was well developed on the upper levels of the La Colorada deposit (Perry, 1961), and

locally at high levels of the disseminated mineralization at the Cananea and Mariquita

deposits (Fig. 2.1c). In the La Colorada ore body this type of alteration was

characterized by alunite ± sulfosalt veins which cross-cut earlier sericitic alteration. In

the stockwork mineralization it is characterized by rare thorough-going crystalline

alunite veins which cross-cut quartz-sericite-pyrite assemblage veins.

Fluid Inclusions

The abundance, distribution, and type of fluid inclusions provides a record of the

presence and composition of hydrothermal fluids and provides insight into the

evolution of those fluids. The spatial distribution of fluid inclusions in igneous and

hydrothermal quartz, together with a qualitative estimate of their abundance is shown

in Fig. 2.1d. The type and abundance of fluid inclusions was determined by

petrographic examination. Three types of inclusions were observed; high salinity

 50

liquid + vapor + daughter crystal(s) (LVD), lower salinity liquid + vapor (LV), and

vapor dominated vapor + liquid(VL). The inclusions were further classified based on

whether they were relatively large and isolated or occurred along fracture zones.

Igneous quartz from each of the intrusive units has at least some high salinity L VD

inclusions containing halite ± other daughter crystals. Isolated high salinity L VD ± LV

inclusions in igneous quartz can be interpreted to represent magmatic aqueous fluid

trapped by recrystallizing quartz during migration of aqueous fluid from deeper parts of

the pluton (Roedder, 1984). In the equigranular rocks the abundance of all types of

fluid inclusions increases toward the upper levels of the intrusions. This trend is

particularly evident in the Cuitaca granodiorite. Deeper levels have minor amounts of

primarily high salinity LVD inclusions whereas upper levels near wall rock contacts

have more abundant high and low salinity inclusions. Igneous quartz from the quartz-

feldspar porphyries has the highest concentration of fluid inclusions of all three types.

Inclusions of all kinds which occur along fractures are generally called secondary,

after Roedder (1984) and interpreted to represent fluid from a variety of possible

sources associated with late overprinting alteration. In the Cananea rocks fluid

inclusions found along fracture planes are typically lower salinity LV inclusions. The

intrusive rocks which have the strongest propylitic alteration, the EI Torre Syenite and

the Tinaja monzodiorite, have abundant low salinity, LV secondary inclusions. Quartz-

actinolite ± chlorite ± epidote veinlets associated with this type of alteration are

dominated by relatively low salinity LV primary inclusions.

Fluid inclusions are most numerous in both igneous and hydrothermal quartz

associated with the quartz-feldspar porphyries. The most striking difference in the

inclusion populations in the quartz-feldspar porphyries compared with those in the

equigranular rocks is the increased abundance of vapor-dominated VL inclusions

 51

coexisting with high salinity inclusions. Igneous quartz and the early potassic

assemblages contain abundant high salinity L VD inclusions which commonly have

multiple daughter crystals including sylvite, and occasional opaque minerals. Also

present though less abundant are coexisting LV and VL inclusions which suggest

widespread phase separation or 'boiling'. Sericitic alteration at the Cananea deposit and

some of the smaller satellite occurrences contains some L VD inclusions particularly in

early veins but is dominated by LV and VL inclusions particularly in more distal and

later assemblages. This suggests a lower salinity fluid was involved in later and distal

alteration. On the other hand deeper exposures of sericitic alteration at the Maria

sulfide pegmatite deposit are dominated by L VD inclusions and even upper level

sericitic alteration at Maria contains abundant L VD inclusions suggesting a more

limited role for late external lower salinity fluids in the formation of this deposit

(Chapter 3).

Geochemistry of the Laramide Rocks

Representative whole-rock samples of each igneous unit were collected for major,

trace element, and isotopic analysis in order classify the rocks and to characterize the

mechanisms which controlled the evolution of the Laramide suite. In addition to the

whole rock data the major minerals were analyzed with an electron microprobe.

Pristine igneous rocks are rare in the district, however, an effort was made to collect the

least altered samples of each rock type. Classification of the rocks and general trends

in the data are treated in this section. The broader implications and interpretation are

presented in a subsequent section. References for techniques and procedures used to

collect the geochemical data are given in the introductory chapter and in footnotes to
 52

the data tables (Tables 2.2, 2.3, 2.4, and 2.5). The sample locations are shown on Fig.
2.1e. Major and trace element variation diagrams are shown in Figs. 2.3a and 2.3b.

Major Element Data

Fresh intrusive and extrusive rocks in the Cananea district are high-K calc-alkaline

rocks with compositions ranging from basalt to rhyolite. The rocks are metaluminous

(Ah03/(K20+Na20»1 and AI203/(K20+Na20+CaO)<1. All the igneous rocks

except a late mafic dike lie within the calc-alkaline field on a plot of FeO/MgO versus

Si02 and follow a calc-alkaline trend on an AFM diagram (Figs. 2.4a and 2.4b). Note

that although the EI Torre Syenite falls along the same compositional trend as the

Laramide rocks, geologic and isotopic data suggest that it may be part of an older

igneous event. Hydrothermal alteration overprints many of the igneous rocks in the

Cananea district, and variably affects their major element compositions, particularly the

abundances of mobile elements such as the alkali metals. For example sericitically

altered rocks are clearly distinguished on the CaO vs Si02 diagram (Fig. 2.3e).

However, fresh rocks from the intrusive suite form coherent compositional trends on

two-element variation diagrams (Fig. 2.3). Ah03, CaO, Ti02, MgO, and P20S all

decrease with increasing Si02. The intrusive rocks also show the typical calc-alkaline

trend of decreasing FeO* with increasing Si02. K20 generally increases linearly with

increasing Si02. Na20 shows a slight increase with differentiation, although values are

scattered due to hydrothermal alteration. The major element data are consistent with

the interpretation that the intrusive rocks form a cogenetic evolving magmatic series.

All three volcanic formations are calc-alkaline trends (Fig. 2.4b) however, the

major element data support the field observations which suggest that the volcanic units

form at least two and perhaps three separate evolutionary series. The older Elenitu
Table 22 Major;n:l Trace E1emenl Analyses and CIPW Norms
ROCiName EJ Tone I. nar a Im.:ll3 blonte CUtaca a-it6 [9 FSP RhYOlIte baKe dike APlite Eieneta fm. Lower HerTletta Fm. Man,,-,ta FfT1 toWer Mesa Mid Mesa Opper Mesa
Syenle Gabbro Granodiorile Porphyry Porphyry Herriena Elisa RhyolllO Fm. Fm. Fm

SaTl>I•• 96 151 421 224 38.3 106.1 228 203 82 83 19 109 156 144 (1) 127
M,neralogyt ksp. qtz.l'bl. plog. pro hbl. plag. qlZ. hbl. plog. qlZ. plog. qtz. qtz. ksp plog. pro qlZ. k5P. bl qlZ. ksp plog. ksp. qlZ. ksp. plog plog. hbl plog plog plag. bl
bt mtilm. mt.lm <;lx. ksp. mt. k5P. bt I'bl. k5P.bl hbl.qtz
ap.zr i1m $ph. ap. zr.

Si02 650 553 600 67.4 657 706 470 784 76.4 642 73.0 51.5 54.3 51.5 65.1
A1203 15 I 150 15.0 14.8 16.7 151 160 11.7 12.0 16.0 13.8 16.2 18.3 16.5 14.8
1.190 163 541 380 1.61 063 066 923 0.14 032 1.56 0.42 4.34 3.57 3.53 2.18
cae 3.08 7.04 506 3.13 0.23 034 954 064 055 2.15 0.71 4.26 5.89 6.16 2.19
Na20 4.17 313 326 321 022 034 2.10 288 0.79 424 424 4.37 4.31 3.40 3.49
K20 437 2.98 348 4.58 525 8.17 176 5.06 625 5.36 5.06 380 1.13 2.68 4.18
Fe203(lotal) 4.14 8.46 650 400 2.11 131 1080 0.59 1.74 4.05 1.50 11.90 6.34 7.53 3.79
li02 064 0.96 075 065 0.31 026 0.99 0.15 0.10 0.52 023 1.52 0.91 0.82 0.55
MnO 008 0.16 0.12 005 0.03 0.03 0.22 000 004 0.11 0.05 0.21 0.17 0.17 0.07
P205 017 028 0.18 0.12 0.14 007 0.00 000 0.03 0.16 0.05 0.38 0.26 0.23 0.19
lOI 130 070 085 0.40 8.65 2.10 0.50 030 1.20 1.20 080 0.60 3.90 6.95 3.10
Total 99.68 9942 99.00 99.95 99.97 98.98 98.14 9986 99.42 99.55 99.86 99.08 99.08 99.37 99.63

Sa 1200 690 730 730 1700 880 220 180 670 1700 1000 970 450 400 1700
Cu 16.3 131 97 31 529 57 44 30 1 43 3 54 6 43 31
Ni <1 50 34 6 <1 <1 79 <1 <1 <1 <1 26 33 26 13
Rb 160 120 220 210 300 640 110 160 310 240 190 180 60 150 160
Sr 250 530 420 260 130 40 230 150 40 270 170 270 1390 370 390
0 270 170 230 270 170 160 80 70 200 160 90 170 140 200 170
y 30 <10 10 30 <10 <10 20 <10 30 20 <10 40 20 20 <10
Nb 20 30 10 10 20 <10 <10 <10 30 20 30 10 10 10 10

K'Rb 273.13 24833 15818 218.10 175.00 127.66 160.00 316.25 201.61 223.33 266 211 188 179 261
RbISr 0.64 023 052 081 2.31 16.00 048 107 7.75 089 1.12 0.67 0.04 0.41 0.41
a..Rb 7.50 575 332 348 5.67 1.38 2.00 1.13 2.16 7.08 5.26 5.39 7.50 2.67 10.63

CIPWNonns
Quartz 16.10 366 11.20 22.17 47.20 35.76 0.00 40.70 46.03 12.26 26.81 0.00 5.31 2.32 21.10
Coruncim 000 000 000 000 11.58 5.25 000 0.32 3.01 0.00 0.18 0.00 0.00 0.00 1.02
Orthoclase 25.82 1761 2056 27.06 33.97 48.28 10.40 29.90 36.93 31.67 29.90 22.46 6.68 17.12 24.70
A1bile 35.29 26.49 27.59 27.16 2.04 2.88 17.n 24.37 6.68 35.88 35.88 33.71 36.47 31.10 29.45
AnorthII. 958 1808 1602 12.45 0.25 1.23 2903 3.18 253 8.90 320 13.36 27.25 23.61 9.62
Diopsido 311 859 442 1.36 000 0.00 10.72 000 0.00 0.54 0.00 2.40 0.15 3.83 0.00
Hodonbe<gile 054 356 1.99 049 0.00 000 404 0.00 000 0.12 000 1.97 0.08 2.56 0.00
Ensla11I. 2.62 949 7.42 338 1.72 1.64 1.11 035 0.80 3.64 1.05 0.00 8.82 7.73 5.43
Ferrosiite 052 451 3.83 1.40 046 0.17 0.49 0.00 0.63 0.95 0.33 0.00 5.32 5.92 0.79
FaBtent. 000 0.00 000 0.00 0.00 000 11.85 0.00 0.00 000 000 6.80 O.CO 0.00 0.00
Fayalite 000 000 0.00 000 0.00 0.00 564 0.00 0.00 0.00 0.00 7.05 0.00 0.00 0.00
Ma!1""ble 3.00 368 2.83 232 1.68 0.95 391 042 126 2.94 1.09 4.31 2.30 2.95 2.75
lime rite 122 1.82 142 1.23 0.64 049 189 0.28 0.19 099 0.44 2.89 1.73 1.68 1.04
Apatl. 0.39 065 042 0.28 0.35 0.16 0.00 0.00 0.07 0.37 0.12 0.88 0.60 0.58 0.44
Sun 9917 98.13 97.70 99 31 99.88 96.91 96.83 99.53 9813 98.15 98.99 97.59 94.71 99.39 96.34

Color Indox 11.00 31.65 21.91 10.19 449 3.25 39.63 1.05 2.89 9.17 2.90 25.41 18.39 24.67 10.01
Dift.lndox 8678 6583 7537 88 85 83.46 88.15 5720 9815 92.19 8861 95.79 69.53 75.71 74.14 84.87

tMain rrinoral phase.: ap-apalll•• bl-biObl•. I'bl· horrtliondo. lI""i_. ksp-K laidspa'. mt-magnollo. pl·plagioda ••• pr- pyroxene, qtz-quatZ. zr·zjrcoo,

1he teas1 altered sart'1'fes available were anaysed but many show' a trace o. atteration. The main alteration phases .e: act·actinolite, c:hI-diorite, ep-ep6dote, ser·serk:i1e

I~
 54

Figure 2.3

a-g: Major and trace element variation diagrams. Data are from Table 2.2. a.) K20 vs.
Si02. Boundaries for the low-, medium-, and high- K fields are from Le Maitre et aI.,
(1989). b.) I.Alkalis vs. Si02. Compositional fields for the diagram are also from
Le Maitre et aI., (1989). c-f) Major and minor element oxides vs. Si02. g.) Shows
Cu increasing with increasing Si02 to a maximum in the upper Cuitaca and relatively
unaltered quartz-feldspar porphyries, then decreasing to a minimum in the late rhyolite
porphyries.
 55

K20

Explanation
10
• PIU10nic Rocks
9 •
•
Mesa Formation
Martquita Formation
•
8 • HenrieUa and Elenna Formations •
7

6 <»

5 0
0 •
4

0
45 55 65 75 85
WI% Si02

a.

Na20+K20

10

2
BasaH

0
45 55 65 75 85
WI%Si02

b.
Figure 2.3
 12
MolO

•
""
10 10
•
•
• ~<.
• • OJ'*
•
.
0
,," Of• ~
• • •
•
.. . • •
Ti02 0
0,\>.4' •
• !" •• • • 0
0
• o 0 <I- o~ 4' 1/1"" 0 0 : : .

45 55 65 75 15 45 55 65 75 15

c. "",-,.s.o2
d. \\1... 002

Ex~!anation
• Plutonic Rocks
• Mesa Formation
" Mariquita Formation
o Henrietta and Elenita Formations
1'205

CaO
0'

10
• 035 "
0.3
" •
• 0.25 •
." • •
•
02
• •
.. 015
o·
" ~o,,;'
0'
~
•
0.1

005
• ,
...•
0
~
o 0 o• •
0 • 0
; •
45 55 65 75 15 c5 55 65 65
\\1"'002 Wl%SlO2
e. f. Figure 2.3
CJ1
en
1000

Ii Aplite

• Maficdike

100 & Mariquita

E o Rhyolite Porphyry
a.
a.
:l
() o QFP

10 Ii Cuitaca Granodiorite

<> Tinaja

• EI Torre

45 55 65 75 85
Figure 2.3g Wr>loSi02

~
 58

Formation is typically extensively altered and only one less altered rhyolitic sample

typical of the composition of the upper part of the formation was analyzed. The

Henrietta Formation forms coherent trends on major element variation diagrams

including, decreasing Ai203, CaO, FeO, MgO, and Ti02 with increasing Si02 and

appears to form a cogenetic series ranging in composition from dacite and trachydacite

to rhyolite. The Mariquita and the conformably overlying Mesa Formation also form

coherent trends on major element variation diagrams with Ab03, CaO, FeO, MgO, and

Ti02 generally decreasing with increasing Si02 (Fig. 2.3). Note that although samples

from the Mariquita Formation and the lower part of the Mesa cluster together at

relatively low Si02 contents, the Mariquita samples are enriched in CaO, MgO, total

Fe, and Ti02.

Trace Element Data

Plots of trace element concentration against Si02 and chondrite normalized spider

diagrams provide insight into the mechanisms by which the igneous suite evolved. All

the igneous rocks including the relatively unevolved the Tinaja Gabbro and the late

mafic dike show significant enrichment in incompatible elements over values that

would be expected for a pure mantle derived melt. Values for compatible elements

such as Ni «80 ppm) and Cr «31 ppm) are relatively low compared to similar rocks

from the Central Volcanic Zone in the Andes, Sierrita, Arizona, and Yerington, Nevada

(Wilson, 1989; Anthony and Titley, 1988; Dilles, 1987). This suggests a relatively

evolved parent magma which has crystallized olivine and clinopyroxene for even the

most primitive rocks. Trends in the trace element data are in the direction which would

be predicted by differentiation alone or differentiation coupled with some assimilation

 59

•
•
• Calc Alkaline

Calc Alkaline

Volcanic Rocks
M
Figure 2.4: AFM plots of plutonic and volcanic rocks. Boundary between
calc-alkaline and tholeitic fields is drawn from Irvine and Baragar (1971).
 60

Volcanic Rocks
Normative mineralogy
<> MesaFm.
A. Mariquita
<> Henrietta and Elenita Fms.

Plutonic Rocks
Normative Mineralogy
e Rhyolite porphyries
o Porphyries
• Mafic dikes-Campana
6 Aplite
.&. Cuitaca
<> EI Torre
4> Tinaja
~+---~------~ __- - - 4 p

Plutonic Rocks
Modal Mineralogy
o Porphyries
6 Aplite
fA Cuitaca
<> EI Torre
<p Tinaja

~~--~~----~----~p

Figure 2.5: Modal and nonnative mineralogy of Cananea rocks plotted on the
lUGS diagram of Streckeisen (1976). Modal mineralogy based on point counts
of thin sections (Table 2.1). Nonnative mineralogy from Table 2.2.
 61

of felsic crust. The isotopic data discussed in the following section help constrain the

relative importance of each process.

Cu values in the Laramide rocks generally increase with increasing differentiation

from -40 ppm in the relatively primitive mafic dikes to a maximum of -500 ppm in

relatively unaltered quartz-feldspar porphyries and in the upper part of the Cuitaca (Fig.

2.3g). Significantly lower Cu values are measured in the deeper parts of the Cuitaca

and in the late aplite dikes and rhyolitic porphyries. Given the low level of

hydrothermal alteration in the samples analyzed, the high Cu content may at least

partly reflect a high primary igneous content. The implications of this trend in Cu

content is discussed in detail below.

The Cananea rocks are strongly enriched in Ba, Rb, and K relative to a mantle

derived melt and have a negative Nb anomalies of varying sizes (Fig. 2.6). The Tinaja

gabbro is the most 'primitive' of the volumetrically important intrusive phases as

shown by lesser enrichment in incompatible elements and higher compatible element

values. In general Ba, Rb, and K values, the size of the negative Nb anomaly and

relative depletion in Sr increase with increasing differentiation (Fig. 2.6). Patterns

formed by the suite are similar to those formed by average upper continental crust and

can be interpreted to reflect significant assimilation of continental crust by even the

relatively less evolved Tinaja Gabbro and Mariquita basaltic-andesite.

The chondrite normalized REE patterns for the Laramide suite cover a small range

and are similar to other continental arc rocks. The patterns are inclined with La/Lu

ranging from 5 to 15 and significant negative Eu anomalies. The late mafic dike is the

exception to the general pattern. It has a distinctly flatter pattern with La/Lu = 2, only
slight light REE enrichment, and lacks a Eu anomaly. Overall the REE patterns of the

Tinaja Gabbro, Tinaja Diorite, and the Cuitaca granodiorite are very similar to each
Table 2.3: Rare Earth Element Data
Rock Name EI TOlTe Syenite Tinaja Gabbro Tinaja Diorite Cuitaca 8-110 Lg Fsp Mariquita Fm. Mafic dike
Graz:Aiorite Porphyry
Sample # 96 151 42.1 224 38.3 109 228

La 31.89 22.62 26.39 29.10 24.87 16.31 7.43

Ce 77.79 60.32 71.40 124.80 53.97 59.43 19.47
Nt 31.83 22.37 27.00 42.15 16.74 24.53 9.81
Sm 6.40 4.56 4.74 9.21 3.15 6.17 2.72
Eu 0.30 0.64 0.33 0.84 1.45 0.75 0.84
Gl 4.12 2.81 2.21 5.67 2.51 5.28 2.83
Tb 0.97 0.62 0.53 1.24 0.33 1.04 0.54
Dy 6.23 3.53 3.45 7.37 1.39 6.65 3.33
Ho 1.29 0.73 0.72 1.54 0.24 1.31 0.79
Er 3.71 2.01 1.99 4.24 0.67 3.82 2.23
Yb 3.87 2.02 2.01 4.34 0.74 3.40 2.07
Lu 0.64 0.38 0.32 0.75 0.16 0.64 0.34

Rare earth elements were analysed by solution ICP-MS in the Keck Laboratory at the University of Arizona. Lab
techniques and uncertainties described in Roberts and Ruiz, 1989. Results are reported in ppm.

~
 - - . - - Mafic dike .. Tinaja Gabbro

- 0 - - 8-110QFP
1000.00
-<>-- Cuitaca

Average Upper Crust

100.00
...
:'~
~ ~

~
~.. --:. mer
~ r ,"
..
-. fill' ,"

Average
'i.
"..~ $ -:.~~~~
~

10.00 Lower Crust

1.00
III
co
.0
c:
.c
I-
~ .0
Z
III
I-
III
...J ()
(I)
en Z~ ~ W E -
N -I -
I-
.0
I-
>- E
I-
.0
>-
Figure 2.6: Chondrite normalized spider diagram. Elements are arranged from left to right in order of
increasing incompatibility during partial melting. Chondritic abundances from Anders and Grevesse
(1989). Average upper crustal value from Taylor and McLennan (1981). Average lower crustal value
from Weaver and Tamey (1984). Note strong enrichment of all magmas in incompatible elements and
similarity to upper crustal pattern.

~
 64

other, however, there is an increase in both light and heavy REE concentrations with

increasing Si02 (Fig. 2.7). On the basis of its major element composition the Mariquita

basaltic-andesite is chemically less evolved than the younger plutonic rocks but has a

similar REE pattern at REE concentrations intermediate between the Tinaja rocks and

the Cuitaca. Like the Cuitaca the Mariquita shows an apparent enrichment in Ceo The

quartz-feldspar porphyry has a more LREE enriched pattern than the equigranular

rocks with La/Lu = 15. The concave upward shape of the pattern from Tb to Lu

suggests that amphibole and/or pyroxene into which the middle and heavy REE are

partitioned was fractionated from the parental melt. The EI Torre Syenite is part of a

different magmatic event but its REE pattern is very similar to that of the Laramide

suite. It has a near flat pattern with La/Lu = 5 and a significant Eu anomaly.

Mineral Compositions

Compositional data on minerals was collected with an electron microprobe to

assess the variation in mineral compositions during magmatic differentiation and

volatile evolution. The compositional data are also used in the following section to

estimate the oxygen fugacity of the magmas. The F and CI contents of hydrous

minerals are used to provide information about the composition of magmatic-

hydrothermal fluids generated by the magmas and the timing of their release.

Plagioclase in the intrusive rocks shows mostly normal zoning with occasional

superimposed oscillatory zoning. Compositions vary within a narrow range from An

(0.4 ± 0.1) in the Tinaja Gabbro to An (0.2 ± 0.1) in the Cuitaca and the porphyries. There

is a general positive correlation between decreasing anorthite content and increasing

differentiation which compares well with the general trends seen on major element

variation diagrams. Alkali feldspars in the Laramide rocks are dominated by the
1000
--a-- Mafic dike A Tinaja Gabbro

- - 0 - - 8-110 QFP
• EI Torre

~Cuitaca - - 0 - - Mariquita
100
Tinaja Diorite

10

Primitive Mantle

La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

Figure 2.7: Chondrite nornlalized REE pattern. Chondrite normalization using values from Anders and
Grevesse (1989). Primitive mantIe pattern from McDonough et aI. (1989) shown for comparison.

m
 66

orthoclase component and are all >Or 0.9 which suggests sub-solidus re-equilibration.

Alkali feldspars in the EI Torre syenite differ from those in the Laramide rocks and

contain up to Ab 0.5.

Magnetite is present in all the intrusive rocks except the porphyries. It occurs as

isolated octahedral grains and is a common inclusion in plagioclase, amphibole and

biotite. Most of the magnetites are pure (Mt 0.99) with very low Mn and Ti contents.

Ti in these rocks is present in sphene and ilmenite. Magnetite compositions are used in

the oxygen fugacity calculations described below.

Amphibole is common to all the intrusive phases, except the porphyries where it is

rare and altered to biotite or replaced by sulfides where present. Amphibole is also

present in the dacites of the Henrietta and Mesa Formations. According to the

classification scheme of Leake (1978), amphibole ranges in composition from

magnesio-hornblende to actinolitic hornblende (Fig. 2.8a). The abundance of actinolite

is a reflection of its common occurrence as an alteration mineral in propylitically

altered rock. The mole fraction Fe/(Fe+Mg) in the amphiboles ranges from 0.6 to 0.8

and does not show a well defined correlation with increasing differentiation of the rock.

Clinopyroxene occurs in the Tinaja gabbro and monzodiorite and in the monzonitic

phase of the Cuitaca. Fe/( Fe+Mg) values in clinopyroxene are lower than in the

amphiboles and they show a slight increase with differentiation.

Biotite is a common igneous phase in the Cuitaca and in some of the quartz

feldspar porphyries. It is present but less common in the EI Torre syenite and Mesa

Formation dacites. Secondary biotite is commonly associated with potassic alteration

in both stockwork mineralization and pegmatitic mineralization (Le., the Maria

Deposit). In contrast to the amphiboles, the mole fraction of Fe/(Fe+Mg) in igneolls

biotite shows a strong correlation with increasing differentiation and decreases with
 67

Amphiboles

0.50

• Mafic Dika
0.45
~ J. () Cuitaca Gd
~
0.40 ()
• ~A ~t
'"+ 0.35
::;: . ,. ()A
.h~
()
A

J ~} ~A
f- i
• Cuitaca Monzonite

A Tinaja Diorita
Q)
u.
CiJ
u.
• •• • lSI> ()
A A
A t A Tinaja Gabbro
0.30 A 6 AA
•• .. A A·
~ EITorra
•
0.25 A
Magnesia-Hornblende Actinolite • Henrietta Fm.
j~tinolitic() () A.
~ornblBnd () ()
0.20
6.50 6.75 7.00 7.25 7.50 7.75 8.00 8.25
a. Si

Biotites

0.45
c
0.40 Increasing 5i02
0.35
c C QFP's and Mineralization

• • •••
0.30
() Cuitaca Gd
0.25 i- c
• Cuitaca MonzonilB
Cc
0.20 c ~
c c
cC ~ EI Torre
0.15 CC
C
0.10 • Mesa Fm
C
C
0.05
c
0.00
0.00 0.10 0.20 0.30 0.40 0.50

b. Fe/Fe+Mg

Figure 2.8: a) Amphibole classification after Leake (1978). Based on electron

microprobe analyses. b) Variation in Fe/Fe+Mg vs. Ti in biotite from Cananea
rocks. Shows decreasing Fe with increasing Si02 in the rock. Based on electron
microprobe analyses.
 Apatite Arrphiboles

:!
035 0.10 • Male Dike

o CUtac.Gd
030 A
D Maria A
•
A.t. • Cuitac:a Monzorite
025 o CUbe.Gd 007 .t.
A linaj. Dioril.
A A 006 .t.
.t.
_ 020
<.>
A linaj. Gabbro A 0\. A Tinli_ Gabtto
<; DOS .t.
iE
015 .t. E1Torr.

. A
.t. E1Torr.

... :
0.0( ." 0 0
A
010 003 A 0 • Henrietta Fm.
A
.t. 002 o· 00•
005 Ql A
O
.t.
001 A
• 0
•
0
0
•
000 000
050 060 0.70 OBO 090 1.00 0.00 0.05 0.10 0.15 0.20 0.25
mo6es F
a. b.
Biot~es

006 II Maria DopooIt o.g

.t.
o QFP'llnd MinwaJiza1ion 08
005
OCUt0c4Gd 07

OO( .t. • 08
0 0 .~ • a
0
• Cuitaca Mentonl•

0 .t. E1Torr. ... 05

<; 003 0
o
0
0 ~
<1>00
0
OFO 0
• MesaFm
g 04
00 ~ iii 0 D
03
002 0
0 <9 ~Do
O IS 02
II a
001 o • D Do
0 01

0 o I
0 01 02 03 O( 8 Tn ... T.,,.a CU .... CU .... CfP Potassic
Ton. Gobl><o t>o<t. Iobnz. QI ~.

S¥ri.

C d.
Figure 2.9: Variation in F and CI contents in a) apatite b) amphibole, c) biotite. Based on electron microprobe analyses.
Note general decrease in CI and increase in F with increasing Si02 in the rock. d) shows the variation in CVCI+F ratio in
hornblende plotted against host rock. The line connects members of the Laramide suite. Note the decrease in the ratio with
increasing Si02.
m
(X)
 69

increasing whole-rock Si02 content (Fig. 2.8b). Secondary biotites from potassic

alteration assemblages have Fe/(Fe+Mg) values similar to apparently igneous biotites

from the porphyries and both are lower in Fe than biotites from the other igneous rocks.

Halogen Contents of Hydrous Minerals

The CI and F contents of apatite, biotite, and amphibole vary between rock types

and between igneous and hydrothermal minerals (Fig. 2.9a, b, c). In general CI content

decreases and F content increases with increasing Si02 in the rock. This trend is

clearly seen as a striking decrease in CVCI + F in igneous hornblende with increasing

Si02 content in the rock (Fig. 2.9d). At magmatic conditions CI is strongly partitioned

into the aqueous phase therefore this trend is important evidence for the early evolution

of magmatic-hydrothermal fluids in the more differentiated rocks.

Apatites show a linear decrease in CI and increase in F with increasing Si02 in the

rock. The highest CI and lowest F values are in apatite from the Tinaja gabbro.

Conversely, apatites from the EI Torre Syenite, the Cuitaca granodiorite, and the

pegmatite zone at the Maria mine are low in CI and high in F. The amphibole data

show considerable scatter but the following general trends are noted. The EI Torre

amphiboles have a range of F values similar to those in the Tinaja but higher Cl. The

Tinaja and Cuitaca amphiboles have a similar range of low CI values but the Tinaja

amphiboles cluster at low F values and the Cuitaca at relatively high F. This

distribution of values suggests a rough positive correlation between Si02 and F

contents. The analyses which lie along the Y axis in Fig. 2.9b are samples with

concentrations of F below the detection limit of the microprobe. All are from the

Tinaja gabbro or monzodiorite. A similar trend of increasing F and decreasing CI with

differentiation is seen in the biotite data. In general relatively low F values are seen in

the Cuitaca biotite and higher values are present in biotites from the quartz-feldspar
 70

porphyries and potassic mineralization. Note that no data is shown for the Tinaja

because it does not contain biotite.

Isotopic Relationships

Radiogenic Isotopes

Sm-Nd and Rb-Sr isotopic data were collected for eight samples representing the

post-Paleozoic igneous suite in the Cananea district. The results are tabulated in Table

2.4. The initial isotopic ratios for the Laramide rocks were calculated for 64 Ma.

ENd(64 Ma) values for the Laramide series range from +0.7 for the mafic dike to -3.1 for

the Tinaja Gabbro to -5.5 ± 0.2 for the Cuitaca, Mariquita, and the two quartz-feldspar

porphyries. Initial 87Srj86Srranges from 0.70579 in the gabbro to 0.71037 in the

Mariquita. ENd calculated for the mafic dike (+0.7) is similar to primitive basalts but

the initial Sr isotope composition (0.70670) is higher than the 0.7020-0.70';0 that is

more typical for such rocks

The series from the mafic dike to the quartz-feldspar porphyries shows an inverse

correlation between ENd and 87Srj86S ro . Note however, that the Mariquita sample has

similar ENd (-5.3) but higher 87Srj86S ro (0.71037) than the Cuitaca granodiorite and the
quartz-feldspar porphyries (Fig. 2.10a). In general ENd decreases and 87Sr/86S ro

increases with increasing Si02 (Figs. 2.10 b, c.) The exception to this trend is the

Mariquita basaltic-andesite which contains 52 wt % Si02 but has ENd =-5.3 similar to

the more evolved Cuitaca granodiorite and porphyries and also has the highest

87Srj86S ro =0.71037 of the samples analyzed.

Initial isotopic ratios for the EI Torre syenite were calculated based on an age of
150 Ma. The values for the EI Torre are ENd= -6.4. and 87Srj86S ro = 0.70952. ENd

becomes even more negative if the initial rado is calculated using an age of 64 Ma
Table 2.4: Sm-Nd. Rb-Sr. and 0 isot02!c data for igneous rocks of the Cananea District
Sample Unit Sma Neil 147Sml 143Ndl144Ndb ENd c Tan Rb Sr 87Rbl 87S r/86 Sr 87Sr/86S a180 vs
(ppm) (ppm) 144Nda measured initial (ppm) (ppm) 86Sr d measured9 r SWfJW
initial felds~r
BD 2397- Qtz-fsp 3.27 19.59 0.1011 0.512307± 6 -5.7 1.00 201 268 2.17 0.710028 ± 0.70805 6.7 ±0.1
489 porphyry 26
38.3 8-110 Porphyry 3.77 20.04 0.1138 0.512322± 7 -5.5 1.10 285 104 7.93 0.715847± 0.70864 9.0 ±0.1
(Lg fsp phase) 37
224 Cuitaca 11.64 60.97 0.1154 0.512333± 6 -5.3 1.11 198 260 2.21 0.708903± 0.70689 6.8 ± 0.1
granodiorite 21
109 Mariquita 7.67 33.72 0.1376 0.512340± 7 -5.3 1.4 189 270 2.02 0.712209± 0.71037 10.0± 0.1
Basaltic· 19
Andesite
42.1 Tinaja 5.77 31.66 0.1101 0.512404±8 ·3.9 0.95 208 385 1.56 0.707497± 0.70608 7.4 ±0.1
monzodiorite 24
151 Tinaja Gabbro 5.71 29.54 .1170 .512444± 6 ·3.1 0.95 122 504 .703 0.706434± 0.70579 n/a
16
228 Mafic dike 3.10 11.66 0.1608 0.512661±6 +0.7 131 236 1.6 0.708148 ± 0.708151 fila
18
96 EI Torre syenite 6.41 32.59 .1188 0.512234± 7 ·6.4 1.30 201 268 2.17 0.710028± 0.70805 8.1 ± 0.1
26

a Uncertainties in 147Sm/144Nd ratios <0.5%

b Ratios normalized to 146Ndl144Nd = 0.7219 (2·sigma error reflect in·run precision)

C ENd = 104[(l43Ndl 144 Nd t sample)/(143Ndl144 Nd t CHUR)·l). using 143Nd/144Nd = 0.512638 as present day CHUR value and 147Sm/144Nd CHUR = 0.1966

d Uncertainties in B7Rb/BGsr ratios <1.0%

e Ratios normalized to 86Sr,sSSr= 0.1194 (2·sigma errors renect in·run precision)

Age used = 64 Ma (except EI Torre syenite = 150 Ma)

T dm model ages calculated from DePaolo. 1981 growth curve

:::i
 72

11

10 D

0 a
g
I •
D

7
o a

·10 I
0.702 0.704 0.706 0.708 0.71 0.712 0.702 0.704 0.706 0.708 0.71 0.712

a. b.

• Mafic dike • Tinaja Diorite

[J Quartz-feldspar Porphyries 11 Tinaja Gabbro

~ Cuitaca Granodiorite • EI Torre Syenite

o Mariquita Fm.

0.711 1

0.71
D
0
•
0.700
a ·1
0708
• a
...i
~ 0706
0.707
. 0 i
~ ·3
·2

i ...
~ 0.70S
·S
0.704 D o
0703 ·8
•
0702
4S SO 5S . 70 7&
·7
4S &0 55 80
wn.So02
os 70

c. d.
Figure 2.10: a) Plot of eNd vs. 87Sr/86Sr initial. Shows inverse correlation
suggesting increasing crustal contamination with time. b) Plot of 87Sr/86Sr
initial vs. d180feldspar. c) Plot of87Sr/86Sr initial vs. Si02 shows initial Sr
increasing with increasing Si02. d) Plot of eNd vs. Si02 shows eNd decreasing
with increasing Si02. From data in Tables 4 and 5.
 73

which supports the field and compositional evidence which suggests that the EI Torre

is part of separate older event. Nd model ages calculated for all the rocks including the

El Torre cluster around 1 Ga (Table 2.4 ).

Stable Isotopes
The results of the stable isotope analyses are tabulated in Table 2.5. Samples from
the plutonic rocks have ~)180fsp values ranging from 5-11%0. There is a general

increase in 818 0 with increasing Si02 content although the value for different samples

from the same rock unit varies by approximately 1%0 (Fig. 2.11a). The range in values

may be due to varying degrees of subsolidus exchange with isotopically heavy external

fluids. The Mariquita basaltic-andesite also stands out with regard to its 0 isotope

composition. Although the Mariquita is quite mafic, plagioclase has 818 0= 10.5%0.

This is a much higher value than is typical for andesitic rocks and may reflect either

subsolidus re-equilibration or alternatively significant assimilation of isotopically

heavy wall rock. In general 818 0 increases with increasing 87Srj86Sr (Fig. 2. lOb).

Origin of the Cananea Magmas

The negative eNd values (except for the mafic dike) and the relatively high

87Sr;86S ro values of even the isotopically primitive mafic dike coupled with the fact

that 87Sr;86S ro increases with increasing differentiation and decreasing eNd, suggests

that the Cananea rocks evolved by progressive contamination of more primitive parent

melt by radiogenic crust. However the relative uniformity of Nd values suggests that

the source of the magmas remained fairly constant over the lifetime of the Laramide

system. The narrow range in eNd values for the Laramide suite and for the Cuitaca,

Mariquita, and the porphyries in particular, supports the hypothesis that they fonn a

cogenetic igneous series. The relatively large decrease in eNd between the Tinuja
 74

Table 2.5: Oxygen and Hydrogen Isotope Data

Me... ured value Calculated water> (SMOW)f
(SMOW)·
Sample # Rock·lype Alleration Mineral 60 6180 6DH20 6D H20 low 6 18 0 H2O 6 18 OlowT TOCused
Assemblage analysed bigh T value Tvalue bigh T value value in calc.
ISneous Rocks (Leost altered .. amples)
109 Mariquita Tr.act. ±mt Plagioclase 10.1 10.8 700
basallic·
andesite
94 EI Torre Syenile Wk acl ± chi K feldspar 8.1 8.5

42.1 Tinaja Diorite WkaCI± chl Plagioclase 7.4 8.1

ISO Tinaja Diorite Wkacl± chi Plagioclase 5.9 6.6
224 Cuitaca Fresh Biolile ·58 4.8 ·42 7.4
Granodiorile
224 Cuilaca Fresh Plagioclase 6.8 7.5
Granodiorite
MCGd·1 Cuitaca Fresh Biolile ·57 ·41
Granodiorile
MCad·3 Cuilaca Wk sericilic Biotile ·80 ·64
Granodiorite
176 Cuilaca Unaltered Plagioclase 7.8 8.5
Granodiorile
202 Cui .. ca Unaltered Plagioclase 7.6 8.3
Granodiorite
203 Aplile Unaltered K feldspar 9.1 9.5
38.3 QFPCanane. Wk sericitic K feldsp.r 6.7 7.1
2397 QFPCananea Wk po .... ic K feldspar 9.0 9.4
33.5 QFPCananea Int. sericllic Quam 10.S 9.5
12b QFPCananea Mod. sericitic Quam 8.2 7.2
230 QFPMaria Int. sericitic Quam 9.S 8.S
LS porph. QFP Maria Wk ..ricitic K feldspar 11.1 11.5
16 Rhyolile Wk .. ricilic Quam 10.5 9.5
Porphyry
106.1 Rhyolile Wk sericitic Quam 12.1 11.0
Porphyry
Potossic Alteration

Average K alt Maria Deposil Quam 8.4

Quartz·K feldspar·biotite pegmatite Biollle ·81 6.7
Sericilic (QSP) Alteration
Average sericilic all. Maria Deposil Quam 10.3
Sericite ·59 8.1
11 QSP Silica·pyrlle Quam 10.S 8.2 5.4 High=SOO
gossaD Low=300
188 QSI' Proximal Quam 10.3 8.0 5.2
33.5 QSP Proximal Sericite 7.3 7.2 4.0
48 QS? D,slal Sericite 11.6 11.5 8.3
125 QSP Proximal Sericite 9.5 9.4 6.1
179 QSP Proximal Sericite 7.0 6.9 3.6
188 QSP Dislal SeriCite 10.0 9.9 6.6
191 QSP Disl.1 Sericite 11.7 11.6 8.3
Argillic Alterotlon
E. Colo. Argillic Proximal Kaohnile 7.3 4.9 ·3.6 IIIgh=300
Low=IOO
122 Argilhc Dislal Kaohnlle 12.7 10.3 1.8
183 Argilhc Dislal Kaolinite .H4 7.9 ·69 ·71 5.S ·3.0
199 Argillic Dislal Kaohn,le ·69 14.6 ·54 ·56 12.2 3.7
E. Can. Argillic Disl.1 Kaohlllle ·79 17.2 ·64 ·66 14.8 6.3
• 0 and II dala collecled in UIC S.. ble lsolope Laboralory al UIC Unlvcrsuy of Arizona. Oxygen was eXlracted from single mUlCrals using a laser·
nuorin.llon line slOlilar 10 Ihal described in Sharp (1990). Willer was CAlIacted from --40 mg of h)'drow: mUlC!'ral by healing under varuwn Dnd
convened 10 liZ aver hal uranium. Reproducib,luy for o.ygen analyse. Was 0.210 O.S'l~ and 2 10 8%0 lor hydrogon. Accur.cy was checled oy
nuuung a lab standard every 5 samples.
t Fractionation ractors rrom the rollowmg sources were wed 10 C3lcuialC' water composillons. Mineral compoSItions (rom electron nllcroJ1ro~
analyses: Oxygen· B,olile from BOllinga and J.voy. 1973 and J.voy. 1977; Quartz from Malmhi ... 1979; K fel(bl'u. plag,od ..« .•eneUe
(extrapolated 10 300'C) from Friedman and O'Neil. 1977: Kaolullte from Kulla and Andcr>On. 1978. lIydrogen· Biollle and senelle lrom Suzuolo:i
and Ep.leUl. 1976; KaoliOlte Lui and Epstein. 1984
 75

Figure 2.11:

a) Measured 618 0 values for minerals plotted against host rock for igneous minerals and
against hydrothermal assemblage for hydrothermal minerals. Si02 increases to the
right for igneous rocks. Hydrothermal assemblages are arranged oldest on the left,
youngest on the right. Data for 2.11 a-c from Table 2.5. References for fractionation
factors also in Table 2.5. b) calculated 6180 of water in equilibrium with minerals
shown in Fig. lla. 6180 calculated for high and low estimate for formation
temperature. Thin vertical lines cover the range of calculated values. Thick gray arrow
shows the inferred evolutionary path for fluids. c) Calculated waters for hydrous
minerals. Meteoric water line and magmatic water 'box' from Taylor (1974) Cananea
meteoric water estimated from Taylor (1979).
"TI
Oti·
c:
@
cr"
. '" a N ~
180 H20

C') CD 0 N ;: m ~
a N
... '"
180 Min.
CD o N ;: m cD
,,
!V

MariquitaFm
-'
,
:, !i
t
3C
Ki
'
~
'

MariquitaFm.
..,,
ii:'
,,,

i-:Oi='
!a
,,, -:,.
Tmaja Diorite : . Tinaja Diorite

I I
'"
.g
Ql EI Torre Syenite
~.
OQ
EI Torre Syenite
2 ~
~
g ~
Cunaca Granodiorrte Cunaca Granodiorrte g
; e! e!
8. 8.
Aplrte Aplrte
'"
o §
Quartz·Feldspar :l: Quartz ·Feldspar ~ .~~.
!'". ".. t~
Porphyries ~ Porphyries 3
,, :r
<II

1:+, ~ ~
:i' , IT!
I~ I~
Potassic Alt. Maria
. ~ ~ ~~~~:i Ht ,:
,
Potassic Alt. Maria ~

~g'f~~
fii;!g~ ex? 00

QSP AIt Maria

"~ . .- ,~.:::>.O QSP Alt. Maria ~
~ I:'"
.:.'
.!
i
QSP Alt. Cananaa • 7: ":-':-D-- I>-
asp Alt Cananea
~ ~<,:::' , ·o~<>~
QSP AIt Maria l :<0..0 : asp Alt. Maria ~g'!?~~ <»<>
[ ,
-g~g'~8:~
r- QSP Alt. Cananaa
u·:- -: .... ~~ • ...cO--o
, , asp A1t. Cananea
~
I» S' ~.
N
. (0 <» <>
~ , ' r- ~
~
..... :,"', I I
Distal Clay AIt ................""':.. :-." .:-.:.:::::.' ....... u<S- •. n n ......... '.<!P' .......~~. Distal Clay A1t. :z: ~ 'II' ~ 'II'

i
.. <IS
~
ii
l
[

~
 77

D vs 180 calculated waters

20
Explanalion
o ~ Extornal Clay Alt. (I00"C)

-20 • External Clay Alt. (300°C)

-40 • Sericile (300°C)

o
-80
o Sericite (5000C)

o Biotite ( 500"C)
-80
Magmallc Waler (Taylor. 19741 f) Biotite ( 600°C)
-100
• Igneous Biotile
-120
-20 -15 -10 -5 o 5 10 15 20
180
Figure 2.11 c
 78

rocks and the rest of the suite correlates with the increase in Si02 between the Tinaja

and Cuitaca and the porphyries. This could reflect evolution by assimilation of older

radiogenic crust coupled with differentiation. The oxygen isotope data which should

ideally be sensitive to crustal contamination are equivocal. The increase in 8 18 0

values with increasing Si02 is especially evident in the aplite, QFP and rhyolite

porphyries and is consistent with either differentiation or progressive assimilation of

crustal material with time (Fig. 2.11a). However, the steep increase in 8180 with

increasing initial 87Srj86Sr suggests assimilation of crustal material (Taylor, 1980)

(Fig.2.IOb).

The major, trace element, and isotopic data suggest the following qualitative model

for the evolution of the igneous suite at Cananea. The positive ENd of the late mafic

dike is distinct from the rest of the igneous suite and suggests a mantle derived melt.

The relatively flat REE pattern and the lack of a Eu anomaly support the idea of a fairly

primitive magma. However the relatively low Mg «6 wt %) and Ni «79 ppm)

contents of the mafic dikes, as well as the enrichment in REE relative to MORB,

suggest that olivine fractionation was important either during partial melting or

crystallization. In either case the mafic dikes may represent a late pulse of magma

similar to that which provided the heat source and the primitive component for the

Laramide magmatism. The Tinaja Gabbro is the most primitive large-volume intrusive

phase in the Cananea district. However, ENd=-3.1, the fact that it has relatively high

concentrations of REE's, a negative Eu anomaly, and a slight hump shape to its HREE

pattern, suggest that it formed from a still less evolved parent, by fractionation of

plagioclase and pyroxene, coupled with assimilation of upper crustal rocks. Continued

assimilation of crustal rocks and crystallization of plagioclase and ferromagnesian

minerals led to the evolution of the Tinaja Diorite and the Cuitaca granodiorite. The
 79

almost identical ENd of the Mariquita basaltic-andesite and the Cuitaca granodiorite

suggest that both were produced by the same magma chamber. However, the

somewhat older, more mafic Mariquita Formation has a significantly higher initial

87Srj86Sr value than the Cuitaca. This somewhat unexpected result can be interpreted

to suggest that the Mariquita represents an early high temperature pulse of magma from

a deeper parent chamber which very efficiently assimilated radiogenic crust during

storage in a higher level magma chamber. The deeper parent magma chamber

continued to evolve but was either in contact with less radiogenic crust or assimilated

radiogenic crust less efficiently. Such a mechanism would explain the lower initial Sr

isotopic ratio in the younger and more evolved Cuitaca granodiorite and porphyries.

An alternative explanation for the high initial 87Srj86Sr in the Mariquita sample could

be hydrothermal alteration which changed the Rb or Sr concentration in the rock. The

ENd of the quartz-feldspar porphyries is similar to that of the Cuitaca granodiorite but

they have a higher initial 87Srj86Sr value which suggests that they were also derived

from the same source as the Cuitaca but that they represent greater assimilation of

radiogenic crust. The quartz-feldspar porphyry is depleted in the heavy rare earths

suggesting that fractionation of pyroxene ± amphibole was an additional evolutionary

mechanism.

Estimation of Intensive Parameters

Depth of emplacement, temperature, and oxidation state of a magma, and timing of

fluid release influence the composition of a magmatic-hydrothermal fluid and the

manner in which it is released and therefore affect the composition and style of the

associated hydrothermal alteration. In this section combined, field, petrographic, and

analytical information is used to estimate depth of emplacement, solidus temperature,

 80

oxidation state, and water content of the intrusive rocks. This infonnation is used in a

subsequent section to examine the relationship between the changes in magmatic

conditions and changes in the nature of the associated hydrothennal fluids. The

estimates of the intensive parameters for each intrusive unit are summarized in Table

2.6.

Depth Estimates

Depths were estimated by restoring the stratigraphy and the 15° to the east tilt in

the district. Where possible depths were estimated by use of the empirical hornblende

geobarometer of Hammarstrom and Zen (1986). This geobarometer depends on the

observation that the amount of Al in the tetrahedral site in hornblende is positively

correlated with the depth of crystallization. The calculated Aliv of igneous hornblendes

is used below to estimate the depth of emplacement of some of the plutons.

The El Torre Syenite is part of an older igneous event but because it is a large body

and associated with a significant area of hydrothennal alteration it will be discussed

along with the younger rocks. Because the older volcanic rocks have not been dated

restoration of stratigraphy gives only a rough estimate of the depth of emplacement of

the EI Torre syenite. A minimum depth of 1.8 km is suggested by the fact that the EI

Torre intrudes the 1800m thick Elenita Formation. However this is a minimum

estimate because an unknown thickness of Elenita may have been eroded after

emplacement of the EI Torre Syenite.

The gabbro and monzodiorite phases of the Tinaja pluton are presently exposed at

approximately the same stratigraphic level so it is assumed that both were emplaced at

a similar depth. The main phase of the Tinaja (West of Cananea) intrudes the upper

Henrietta Formation and is overlain by -200 m of Henrietta Fonnation rocks and by

Table 2.6: Sununary of infomlation on Cananca District plutonic rocks
Unit JIUGS Af1' TnlUn: A.Ju,C1~d o.r<hd Wt%II:O Auidln.;huioo Cl/CI+F in CD content Aucciated Ahentionl
Clauification Empl.accmcnt in igneolls quuu hydrous Mincnliution
mincnh
Rhy('OhlC'
Porrhyrie,
IRhyolite: 52.S! ~ My K-
At sericite
Pol'}'hyntic I-~
mm rheoo.;'f)'Sll
4 tm- O..().S tm
Eviderre of
LV>LVD
sc(('IniUry>pi-
n/. 56 rrm ModeUle 10 ink'nsc
pcrvuive scricitic
(S-S.2 t 2 My arhanitic 10 venting muy aJilcDtioo. local
corrected) gl.luy rmtri .. devitrification.
l.n:al flow

00 ..... fd.hl'"
Porrhyriu
IQuutz
Monz('Initc 10
Granite
1 S9.9 t 2.1 My
K·Ar rhlogor".
58 ! 2 My Re-
INndinS!:
PO'l'hyritic:. 30·
SO%
phcnC'Crylll
S·7.S tm' o.Stbl.Slo2
tm
Raid irx:lusiool
At ic:UI J
hued 00
J"'C5Cntt
"lit'{,

d bt
Primuy LV. ~1.
.nlLVO;
LV>\.VDAm1
Igneou.s bl 0.07
Vein hI 0.11
SOO rrm All: Intense quartz-
sericite-pyrite ± bn
ahcr.ation: loc.J.l dec
en mol)hdr:rute 2·3 mm and Itntignphi.: lVDirrr.VI/ J'OUI,ie ~5Crwcd.
rhcnC'CI}'IlS in ftCoolU'Uction Pou.ibly a5 high der· h POl. di,u{ propylitic.
aphanibc u4 ..5 ....1%if MI.: POlYPhyly·
groundmau lorne bl s.conduy LV related Oiu.. Bx.
",,,bei•• h~ >nlVL Silicale·nlfide pc~
A('iIIC'.jlkcs Gunite n/. 'r Jitie <I tm" o.S tm rrattk W,ler s.. tunlied 30 rrm
cro" CUlling U1dB~n.
CluloKa 1958 rhaIC
~Iations)

Mu..:daus n/. Equignnuw <I tm- I I I 144 rrm

cm" nuing
CuiloKa
CU1UCa nm~m I GDnc>J:tmle to 164 t 3 My U Pb I Mostly 12$ bn· 0.7S·2kb. F.I. BcMttnJ and Ahundant Igneous bt 0.20 31 rrm All: Wiloksrrud Wk
rhne gramte zin;on cquignnulu :.$ aplite comp .• S"1% prinwy esp. in noges uplO hbi to actinollte. bI to
mmph.g. hbl no cpt. bI quru itg wi up 0.32 near chlorite. Ph.g to clay
Low;~ly \IoUy gcobaromctry. R'plxing hbl LV>LVI> CORUCts. and cpo. Local act and cp
rorrhyritic sU"atigraphic Samu!rdcsp .... veins. Loc~ wt K alL
reconsL Maria gnphic IgneOUl hbl Gl stam and marble in
1rJ:tUSC1 E to W tCltu~ 0.13 La, Hnfls nr contact
"'" Fig. X (Map \O\;lh volcanics distal

CuiucI southern
rhne
I Mcnzonite 10
quam:
monzonite
r Ubov
•
1 Equignnulu 3·S 1 included .hove
mmpbg.
r.scction)
12 t 0.3 kb 68
tmhN
gcobaromctry
c3wt%c~ly
blscd on cp),.,
L":r>4.Swl%
t:ued on hbl and
LV»LVD
mOllly
~cond1rie.
Ingeous tool 0.17
IgncoDi hbl
0.24
n/.
acl., ep. chi :t: rY weir..
Wt hbl to actinollle. bl
to ehlonle. Hnfla nea
con~U

min,"" bt t
Tmaja mlin
phue
IQuutz 162 .99 0.37 1Mo.tly
t (1
moruodjClrile to Z) My40ArtlQAr equig,nnuLu
42 tm· Xtb 2·3tm
lU"atigraphic
<3wt%al
emriaccrMnl
Abun.w.1
prinwy «p. in
Ilgneou. hN
0.87
197 rrm I Wide'pread mod hbll
act, ep replacing Flag
quartz hornblende O.2S·lmm reconstruction hilled on early qurtzitgVl/bp and in veinletl
rnonzt"nile locally cpr. ir.:reasing LV>lVD
rorrhyntic to>3wt%w.
r.tallintion hbl
~pl. CpL btc
ulan-tion
recorded by locd
p.n['hic lC'tture
Tinaja nufi .. 1 G.t.bro 10 Ai .above Equigranulu 2·S < Ibn· Similu 10 aN:we <3 VIII'{. J'<U >3 LV»LVD Igneous hbl. 1131 rrm
rhase Quuu·dimte mmplag. wt% later. cpr. mo&t1y 0.76

ElTCIm: I Mode 00"'"

S}~nitc
to
Gr.1nitc
P,,"s. minimum
:r.'Ag39
70 2) My
Ar
(t
MOllJy
eqaignnulu 1·3
mm Ksp.
Jt.m·
blromcuy and
untigraphic
",pi b\o h~.
X tb 2·3 tm hhl 3105"1%
limilCd tit may
luggell early
~cond1riel
LV>\.VD
lome primary
LVm...y
Igneous bl 0.27 116 rrm I\Vide'pread mod hbllo
act, ep replacing plag
and in vrinletl
Igneous hbl
hornblende ttconstruction ""tuntion and scconduy etip 0.42
lou ofwalerfc." on Elide on
bl inlr.

..
CO
 82

1500 m of the Mesa Fonnation. This suggests a minimum depth of emplacement of

1700m.

Along its eastern contact the Cuitaca intrudes the uppennost Henrietta Fonnation

and is overlain by a total of 1800 m of Mariquita and Mesa Fonnation rocks. Fluid

inclusion data from the Maria deposit which is hosted in the Cuitaca near its eastern

contact suggest a depth of 2-3 km (Chapter 3). The eastward tilt of the range and

subsequent erosion exposes progressively deeper parts of the Cuitaca to the west. The

monzonitic phase which is exposed along the range front on the west side of the range

represents the deepest part of the Cuitaca Batholith. Stratigraphic reconstruction and

hornblende geobarometry suggest a depth of 5-6 km.

The quartz-feldspar porphyries in and near the Cananea Mine were emplaced at

depths of between 1 and 2 km based on the fact that they intrude the Mesa Fonnation

and limited fluid inclusion infonnation presented by Bushnell (1988). The rhyolitic

porphyries were apparently intruded to still shallower levels and locally reached the

surface.

Oxidation State of Magmas

For igneous rock containing the assemblage biotite, K-feldspar, quartz, and

magnetite the variation in oxygen fugacity during crystallization can be estimated from

the biotite dehydration reaction:

KFe3AlSi30 lO(OH)2+ 0.502= KAISi30s +Fe304 +H20

annite in biotite + 02 = K-feldspar + magnetite + water

Biotite, K-feldspar, and magnetite compositions were detennined with the electron

microprobe and the fugacity of water was estimated from tables in Burnham et al.,

(1969). Solidus temperatures for each intrusive type were estimated from
 83

experimentally derived temperatures for similar bulk compositions (e.g. Maaloe and

Wyllie, 1975, Whitney, 1988). The oxygen fugacity was then calculated from the

refined biotite stability equation of Wones (1972). The accuracy of this calculation is

sensitive to uncertainties in mineral compositions and estimates of fH20. Sub-solidus

alteration of mineral compositions can also seriously affect results. This effect is

illustrated by the very high oxidation state calculated for the Pinalito porphyry (Fig.

2.12). However, despite the uncertainties, the results do give some idea of the relative

oxidation state of the magmas. In general f02 is higher in the more differentiated

rocks. The results show that oxygen fugacities were above the quartz-fayalite-

magnetite (QFM) buffer at solidus temperatures and approached the magnetite

-hematite buffer at lower temperatures. The high oxygen fugacities suggested for

lower temperatures record conditions during late crystallization and subsolidus cooling.

A similar oxidation trend is seen in many porphyry copper systems and Dilles (1987)

considered it to be a consequence of the ex solution of aqueous fluid. Oxygen

fugacities estimated for both phases of the Cuitaca and the EI Torre Syenite lie on or

just below the H2S-S02 buffer. Oxygen fugacities in the quartz-feldspar porphyry and

in deep potassic alteration are higher and lie above the H2S-S02 buffer. The is

important because sulfur solubility increases with increasing f02 (Burnham and

Ohmoto, 1980).

Water Content of Magmas

Experiments by Maaloe and Wyllie (1975) and Naney (1983) among others,

suggest that the crystallization sequence of ferro-magnesian minerals in granitic and

granodioritic melts at constant pressure is controlled by the water content of the system

(Fig. 2.13). Although the depth estimates discussed above suggest that most of the
 Toe
400 500 600 700 800 900 1000 1100 1200
o

-5

-10

f02 -15 13

o Pinalito
-20 • Deep Cananea Porphyry
o Deep Biotite Veins

-25 <> Cuitaca Granodiorite

• Cuitaca Monzonite
6 EI Torre
-30
Figure 2.12: Temperature vs. f02 diagram showing stability curves for biotite from
various intrusions calculated using equations in Wones (1972). H2S-S02,
magnetite-hematite(MH), Ni-NiO, QFM, and magnetite-wustite curves are shown for
comparison.
~
 85

1100

H20 saturation
L+V
1000

900
Hbl in

Toe Bt in

800
(Opx out)

Hblout
700
Solidus Alk fsp
Plag+Alk fsp+Qtz+Bt+V
600
0 2 4 6 8 10
Wt % Water
Figure 2.13: Temperature vs. xH20 diagram for synthetic granodiorite at 2 kb from
Naney(1983). The Cananea plutons are plotted according to their observed
crystallization sequence.
 86

Cananea intrusive rocks crystallized at less than 2 kb and compositions vary somewhat

from the granite and granodiorite compositions used by Naney, the observed

assemblages are compared with Naney's data at 2 kb because the pressure and

composition may be appropriate for the deeper parts of the Cuitaca and also because

experimental data is not available for lower pressure conditions. Comparison of

Naney's 2 kb data with results for 8 kb suggest that at lower pressures a given change

in crystallization sequence will occur at a lower water content. Therefore using the 2

kb data for plutons which crystallized at S 1 kb results in an over-estimate of initial

water content. However, the estimate made from the crystallization sequence can be

combined with textural observations, depth of emplacement, and water solubility data

to better constrain initial water content. This section concentrates on the data used to

estimate the water contents and presents the results which are summarized in Table 2.6

The most important observation to emerge from a comparison of these estimates is

that in general the water content of the magmas increases with increasing

differentiation. The Tinaja monzodiorite and gabbro are characterized by early

crystallization of the accessory phases, plagioclase, and clinopyroxene, followed by

hornblende, K-feldspar, and quartz. Comparison with Naney's (1983) data suggests

that the initial water content was<3 wt % but increased to >3 wt % (Le., sufficient to

stabilize hornblende) with increasing crystallization. Hornblende does not completely

replace clinopyroxene and the fact that the clinopyroxene to hornblende reaction was

not complete suggests that the higher water content did not occur until the late stages of

crystallization.

Textural relations in the Cuitaca granodiorite indicate early crystallization of

accessory phases and plagioclase followed in sequence by hornblende, biotite, K-

feldspar, and quartz. The crystallization of hornblende before biotite requires a water
 87

content of >4 wt % at 2 kb however, the fact that part of the Cuitaca crystallized at <2

kb suggests that the water content could have been somewhat lower. The lack of

experimental data for the shallower levels precludes an exact estimate of the water

content but the lack of pyroxene cores in the amphiboles suggests that the replacement

of pyroxene by hornblende occurred early and that the granodiorite had a higher initial

water content than the Tinaja gabbro and monzodiorite. Local pegmatite dikes, high

salinity fluid inclusions, graphic texture, and actinolite alteration are common,

particularly at higher levels in the granodiorite near the eastern contact with the

volcanic rocks. These features are further evidence that the granodiorite became

saturated with respect to water and that a magmatic fluid was evolved. The monzonitic

phase of the Cuitaca is a deeper part of the batholith and was apparently a drier magma.

It is characterized by early plagioclase, hornblende with rare augite cores, biotite

locally replacing hornblende. These textures suggest an initial water content of <3 wt

% (hornblende.llQ1 stable), which increased to >4 wt % with progressive crystallization.

The intense sericitic alteration that overprints most of the quartz-feldspar

porphyries typically destroys the ferromagnesian minerals but a few less altered stocks

contain biotite phenocrysts. This suggests biotite crystallized early and is consistent

with a water content of between 3 and 5 wt % H20 (Naney, 1983). However, the

quartz-feldspar porphyries were emplaced at -0.5 kb and a magma with >3 wt % H20

would be oversaturated with respect to water upon emplacement. (Fig. 2.14). The fact

that the porphyries typically contain 20-30% phenocrysts suggests that the magmas

were not saturated on their liquidi and that some crystallization took place prior to final

emplacement. This can be explained by one of two mechanisms; an initial water

content of <3 wt % , 20-30% crystallization at 0.5 kb and subsequent saturation or, a

 88

Wt% H20

8
=f
:::l
~.
COl
7 :::+(j)
0l0l
0e-
Ole-
S:...,
6 00
:::l0l
N:::l
00.
:::l
:::+0
5 CD o·
..0
~
....CD
:::l •

Q)
~

en 4
:::l
en
Q)
~

a..
3

Range of depth est.

1

Figure 2.14: Water saturation curve plotted against pressure from B umham
(1979). The Cananea plutons are shown at their estimated depth of
emplacement and water content.
 89

higher initial water content (3-5 wt % H20), initial crystallization at a greater depth,

then emplacement and saturation at 0.5 kb.

Evolution of Hydrothermal Fluids

Compositional trends in the hydrothermal fluids are compatible with compositional

trends observed in the associated igneous rocks. In the following section those

compositional trends are summarized from the petrographic, fluid inclusion, and

mineral composition data presented above. The stable isotopic evolution of

hydrothermal fluids and possible sources of fluids are also addressed. The relationship

between the evolution of the igneous rocks and the associated magmatic-hydrothermal

fluids is explored more fully in a subsequent section.

Summary of Compositional Trends

The following trends in fluid composition are suggested by the mineralogy of

alteration assemblages, mineral content, and fluid inclusion petrography: sulfur,

chlorine, and copper content of the fluids increased with time to a maximum in early

alteration associated with the quartz-feldspar porphyries and subsequently decreased.

Alteration mineralogy suggests that the pH of fluids decreased with time. Direct

evidence for the enrichment in the chlorine and to a certain extent copper content is

provided by fluid inclusions. Indirect evidence of the sulfur content is provided by the

alteration assemblages.

Based on the observed actinolite ± chlorite ± epidote ± magnetite ± sericite ± clay

assemblage, fluids associated with the early, widespread propylitic alteration were low

in sulfur and weakly acidic. Quartz-actinolite ± chlorite ± epidote veinlets associated

with this assemblage are dominated by relatively low salinity LV primary inclusions.
 90

This suggests that low salinity fluids fonned this alteration. It is important to note that

these low salinity fluids could have been of either magmatic or external origin.

Alteration associated with the emplacement of the quartz-feldspar porphyries

fonned from fluids with higher salinities, and higher metal and sulfur contents. The

early potassic alteration assemblage, which includes quartz-K-feldspar-biotite-

chalcopyrite and pyrite is consistent with near neutral fluids with a high metal content

and abundant sulfur. The presence of halite ± sylvite ± anhydrite in fluid inclusions

suggests high salinity fluids are involved in formation of the potassic alteration as has

been documented in many porphyry copper deposits. A relatively high copper content

for the fluids associated with potassic alteration is supported by the occasional presence

of chalcopyrite as a daughter mineral in the fluid inclusions. Fluids associated with the
porphyries evolved with time toward lower pH and lower salinities. Early sericitic

alteration contains abundant high salinity LVD fluid inclusions but later alteration as

defined by crosscutting relations is dominated by lower salinity LV and VL inclusions.

The greater abundance of lower salinity inclusions in the sericitic alteration suggests

phase separation (boiling) at depth or the influx of a low salinity external fluid. The

fluid inclusion evidence alone does not constrain the relative importance of each

process but the stable isotope data discussed below provide important constraints on

the source(s) of late fluids. Late and distal alteration, including some sericitic

alteration and most clay alteration, record generally lower salinities, and metal contents

and are low in sulfide minerals.

Isotopic evolution of Fluids

The relative importance of magmatic versus meteoric water in the formation of

porphyry copper mineralization has been the subject of considerable debate. Magmatic
 91

hydrothermal fluids are certainly capable of causing both early potassic and later

hydrolytic alteration but in many cases non-magmatic fluids including variably

exchanged meteoric waters have been demonstrated to playa dominant role in the

formation of late alteration (Taylor, 1974, 1979). A reconnaissance study of the

oxygen and hydrogen isotope compositions of hydrothermal minerals was done in

order to investigate the origins of the fluids which formed the various hydrothermal

assemblages in the Cananea district. The isotopic compositions of hydrothermal fluid

in eqUilibrium with both the igneous and hydrothermal minerals were determined using

experimentally derived fractionation factors and independent temperature estimates.

The calculated composition of hydrothermal fluids is strongly influenced by the

temperature used in the fractionation calculation therefore compositions of fluids were

calculated using the typical range of temperatures for each assemblage which was

taken from the literature and fluid inclusion data cited in Chapter 3. The temperatures

and fractionation equations used are cited in Table 2.5.

The isotopic composition of magmatic fluid was calculated based on equilibrium

with magmatic quartz from quartz feldspar porphyries. In Cananea magmatic fluid is

calculated to be B18 0= 8 ± 1%0. Meteoric water in the Cananea district has a present

day isotopic composition of 8 180=-100/00 and BD=-700/00 (estimated from Taylor 1974).

The range of calculated water values for both igneous and hydrothermal minerals is

shown in Figs. 2.11 a, b, and c. In the hydrothermal assemblages there is a trend wi th

time toward isotopically lighter compositions. Fluid calculated to be in equilibrium

with quartz and biotite from early potassic alteration at the Maria Deposit is

isotopically similar to the calculated magmatic fluid using T alt= 600°C from fluid

inclusion data in Chapter 3 and falls within the range of magmatic values defined by

igneous minerals from fresh rocks in the Cananea district.

 92

Fluid associated with sericitic alteration ranges from values similar to those

measured in potassic assemblages to somewhat lighter values. The calculated isotopic

ratio for fluid associated with sericitic alteration in the Maria deposit is also

isotopically similar to that associated with potassic alteration if the maximum

temperature measured in fluid inclusions Talt =500° (see Chapter 3) is used and

somewhat lighter if the average fluid inclusion homogenization temperature of 300°C

is used. Fluid associated with sericitic alteration at Cananea ranges from magmatic

values, (0180= -+8) to isotopically lighter fluid (0180= +4) using Talt = 500° C for

early proximal alteration and Talt= 300°C for later more distal alteration. Fluid

associated with clay (kaolinite) alteration ranges from (0 180= +6 to -4 assuming Talt=

100°C). 180/160 values decrease with increasing distance from the center of

mineralization at Cananea (Figs. 2.1e and 0. The general trend toward isotopically

lighter fluids in later and more distal alteration assemblages is interpreted to reflect the

modest influx of meteoric water. This trend is less pronounced in fluids related to the

Maria deposit which is interpreted to reflect the dominantly magmatic composition of

fluids associated with that mineralization (see Chapter 3). Likewise, relatively early

proximal sericitic alteration at Cananea also reflects a predominantly magmatic

signature. Significantly lighter values are only seen in more distal sericitic alteration

(Fig. 2.10. This suggests that at least some (possibly most, since the samples analyzed

are representative of all the sericitic alteration) sericitic alteration is due to magmatic

fluids. This is in contrast to interpretations of stable isotopic data at other porphyry

copper deposits in the southwestern U.S, e.g. (Taylor, 1974, 1979), which suggest that

large scale influx of meteoric water is typically involved in the development of sericitic

alteration. This data for sericitic alteration at Cananea suggests that meteoric water

only dominates in distal parts of the system. Values obtained from distal clay
 93

alteration are significantly displaced toward meteoric values suggesting that this type

of alteration involves significant meteoric water.

Discussion

While the importance of magmatic fluids in the formation of areally extensive

hydrolytic alteration continues to be debated, many studies have argued in favor of an

orthomagmatic model in which much of the fluid, metal, and sulfur in porphyry copper

deposits is derived from the associated magmatic system. The data presented above are

consistent with an orthomagmatic model for the origin of the porphyry-related deposits

in Cananea. Furthermore, mass balance calculations for the Cananea deposit suggest

that all the Cu, sulfur, and the water necessary to transport them could be derived from

a volume of magma equal to the estimated size of the Tinaja/Cuitaca batholith.

Because the associated intrusive rocks are the source of the critical components which

form mineralization, the evolution of those rocks exerts a strong influence on the

evolution of mineralization. This section summarizes the evolution of the Laramide

magmatic-hydrothermal system in the Cananea district and compares it to observations

on similar systems at Sierrita, Arizona (Anthony and Titley, 1988) and Yerington,

Nevada (Dilles, 1987).

Basin and range faulting have tilted the Cananea range and exposed an oblique

section through the district. The Laramide rocks are a medium- tv high-K metalumious

series which ranges in composition from basalt to rhyolite. Major, trace element, and

isotopic data vary continuously with differentiation and are consistent with evolution of

a mantle derived parent magma by progressive assimilation of radiogenic crust coupled

with differentiation by fractionation of plagioclase and ferromagnesian minerals. The

Cananea igneous system appears to have followed a broadly similar evolutionary path
 94

to that suggested by Anthony and Titley (1988) for the Sierrita Arizona system which

is the same age, contains a similar range of rock compositions, and intrudes similar

Proterozoic to Early Tertiary lithologies. The Cananea rocks have generally higher

ENd than the Sierrita rocks although initial 87Srj86Sr values cover a similar range. This

suggests a different perhaps less depleted source for the Cananea magmas but similar

amounts of crustal assimilation. The pronounced negative Eu anomalies and slight

depletion in the middle and heavy REE's in the Cananea rocks contrast with the lack of

Eu anomalies and smoother REE pattern in the Sierrita rocks suggesting that fractional

crystallization played a more significant role in the evolution of the Cananea rocks.

The relatively low concentrations of compatible elements such as Ni in the Cananea

rocks support an important role for fractional crystallization of ferromagnesian

minerals. By contrast the Yerington Nevada rocks have lower initial 87Srj86Sr than the

Cananea rocks, which is consistent with the location of Yerington to the west of the

inferred limit of pre-Cambrian continental crust (Dilles, 1987). Dilles (1987), suggests

that the evolution of the Yerington batholith was dominated by closed system

differentiation with a relatively limited amount of crustal assimilation, although he

acknowledges that the comparatively unradiogenic wall rocks at Yerington would

make detection of crustal assimilation more difficult. The Cananea system apparently

represents a set of conditions intermediate between the assimilation dominated Sierrita

system and the differentiation dominated Yerington system.

Because the data presented above suggest that the water, metal, and sulfur which

formed the porphyry-related deposits was largely derived from the associated magmas.

the composition of the magma and the conditions under which it is emplaced have a

significant influence on the evolution of mineralization. The important compositional

factors are: water, chlorine, sulfur, and metal content, and oxidation state (Burnham,
 95

1979). The water content of the Laramide magmas increased with differentiation from

<3 wt % H20 in the relatively primitive early magmas to between 3 and 5 wt % in the

Cuitaca granodiorite and the quartz-feldspar porphyries. The CI/F ratio of hydrous

minerals decreases with increasing differentiation. Because CI is strongly partitioned

into the aqueous phase (KD melt-aq =30-40; Kilinc and Burnham, 1972) this trend can

be interpreted to reflect the partitioning of CI into an aqueous phase in the more

evolved magmas. The Cu content of intrusive rocks also increases with increasing

Si02 to a maximum in unaltered porphyries. This is consistent with the CI data

because since Cu is transported as a chloride complex it is partitioned into the aqueous

phase along with the chlorine. The oxidation state of the magmas, as measured from

the biotite stability equation and decreasing Fe/Fe+Mg in other mafic silicates, also

increased with increasing Si02. Oxygen fugacities increased from below the S02fH2S

boundary for the Cuitaca Monzonite (± the Tinaja gabbro and monzodiorite) to above it

in the Cuitaca granodiorite and the quartz-feldspar porphyries. The oxidation state of

the magma is important because it determines oxidation state of sulfur and therefore

helps to determine the sulfur carrying capacity of the magma (Burnham and Ohmoto,

1980). A higher oxidation state increases the amount of sulfur which can be

transported. This in turn influences the amount of sulfur available to precipitate metals

as sulfide minerals. Dilles (1987) suggested that the very high oxidation states

determined for many porphyry magmas were linked to the exsolution of a sulfur-rich

aqueous phase during crystallization and cooling of the magmas. As H2S is partitioned

into the aqueous phase, and the system cools, the reaction S02+H20=H2S+ 1.5 02 is

driven to the right thereby increasing f02 (see also Fig. 2.12).

These observations are important because in tandem with field observations they

help to explain the variations in alteration associated with the different intrusions as
 96

well as the evolution of mineralization in the Laramide system as whole. The initial

water content of the magma is perhaps the most important compositional variable

because it has wide ranging effects on a number of important parameters. Most

important is the effect that water content has on the depth and/or degree of

crystallization at which a magma will saturate (Burnham, 1979). This in tum

determines the amount of mechanical energy available in the magma, and consequently

the amount and style of fracturing the pluton can cause. The timing of water saturation

also influences the composition of the fluid because conditions like T, f02, CI and

metal availability change as crystallization proceeds.

Fig. 2.14 shows the Cananea magmas at their calculated water contents and

estimated depths of emplacement plotted against the water saturation curve from

Burnham (1979). Early relatively dry «3 wt % H20) phases such as the Tinaja gabbro

and monzodiorite ± the Cuitaca monzonite were initially water under-saturated at their

estimated depth of emplacement (-1 kb) and only became saturated after substantial

crystallization (Fig. 2.14). CI is strongly partitioned into any aqueous phase relative to

a granitic melt (KD= 30-40) and Cu is partitioned into the aqueous fluid along with the

chlorine (Kilinc and Burnham, 1972; Candela and Holland, 1986). The Cl/F ratio of

hornblendes from both the Tinaja gabbro and monzodiorite are high suggesting that Cl

may have been sequestered in the hornblendes before saturation occurred and a fluid

phase exsolved. Thl~: suggests relatively late saturation and a low water content for the

Tinaja rocks. The f02 of the gabbro and the monzodiorite have not been calculated,

but because they are the least differentiated rocks, and f02 appears to increase with

differentiation, it may have been similar to or lower than that of the Cuitaca monzonite.

This suggests that f02 in the Tinaja rocks was below the H2S/S02 boundary which

would have inhibited the partitioning of sulfur into any aqueous phase (Burnham, 1979,
 97

Burnham and Ohmoto, 1980). This would limit the amount of sulfide which could be

precipitated from any aqueous phase even if there was sufficient CI to transport

significant quantities of metals. Relatively late saturation at higher levels of

crystallization decreases the PL\ V energy available to fracture rocks. The se two factors

may explain the lack of fracturing and sulfide mineralization immediately associated

with the Tinaja. The Cl/Cl+F ratio in hornblende from the Cuitaca monzonite is about

1/3 of those in the Tinaja suggesting that Cl may have been partitioned into a late

aqueous phase prior to the crystallization of hornblende. The margins of the monzonite

are associated with small Cu bearing skarns suggesting that the ex solved Cl-rich fluid

was capable of carrying metal and precipitating sulfides.

The biotite and hornblende bearing igneous assemblages in more differentiated

rocks like the Cuitaca granodiorite are consistent with a higher water content (3-5 wt %

H20) and saturation at an earlier stage of crystallization. The relatively low CI

contents of hydrous minerals in the Cuitaca support the idea of relatively early

saturation and ex solution of a Cl-rich aqueous phase. Bodnar et al. (1985) and Cline

and Bodnar (1991) suggest that a fluid exsolving at 1-2 kb would be within the two

phase field in the NaCI-H20 system and that this would lead to the formation of a low

salinity vapor plume and a high salinity Cu-rich aqueous phase. The locally high Cu

content of upper levels of the Cuitaca may reflect the collection of this Cl-rich aqueous

phase in local apices of the Cuitaca. The widespread propylitic alteration found around

the upper margins of the Cuitaca may have been caused by the release of the low

salinity vapor plume.

Another important process is suggested by the increasing water, metal, and sulfur

content with differentiation and the isotope data which suggest that the quartz-feldspar

porphyries and evolved from a Cuitacaffinaja parent melt. If the Laramide system
 98

evolved from one parent magma then, as chlorine, sulfur, and metals are partitioned

into the aqueous phase and may be progressively concentrated in the differentiated melt

fraction along with the ex solving fluid leaving the parent depleted in these components.

This may explain the high Cu content of the upper parts of the Cuitaca and some of the

unaltered quartz-feldspar porphyries and the low Cu content of deeper parts of the

Cuitaca. The quartz-feldspar porphyries may represent the rapid upward emplacement

and pressure quenching of this enriched differentiate. They contained between 3 and

4.5 wt % H20 and were emplaced at between 0.5 and 1 kb. This means that they

developed the maximum available P~V energy and produced abundant fracturing upon

emplacement. The low Cl/CI+F in the igneous mafic silicates and high proportion of

high salinity inclusions in the early potassic alteration is consistent with a high chlorine

content in the fluids. A high chlorine content would have made the fluids efficient at

transporting Cu and other metals. The high oxidation state was well with the S02 field

and made them very efficient at transporting the sulfur required to precipitate sulfides.

The late rhyolitic porphyries and aplites may represent the last Cu-depleted melt

fraction which remain after emplacement of the mineralized porphyries.

Conclusions

The major findings of this part of the study are as follows:

1) The Cananea district is a major porphyry copper system with multiple centers of

mineralization associated with a major Laramide volcano-plutonic complex. Post

mineral uplift and erosion have exposed an oblique section through the system.

Shallower rocks and alteration are exposed in the eastern part of the district and

progressively deeper rocks and alteration are exposed to the west.

 99

2) The igneous rocks in the district represent a cogenetic magmatic series ranging

in age from 64 ±3 Ma to - 56 Ma. Igneous compositions range from gabbro to quartz-

monzonite and have ENd values ranging from -3.8 for the gabbro to -5.7 for a late stage

quartz-feldspar porphyry. A late mafic dike with ENd= +0.7 may represent an original

mantle-derived parent melt and heat source. The isotopic relationships suggest that the

Laramide magmatic series evolved by assimilation of radiogenic upper crust along with

fractional crystallization of plagioclase and ferromagnesian minerals.

3) There is a general trend toward higher water contents, more oxidizing

conditions, and enrichment in metals and sulfur with increasing differentiation. The

quartz-feldspar porphyries may represent rapid upward emplacement of this enriched

differentiate.

4) Alteration and mineralization developed in close association with the evolution

of the igneous rocks. Early alteration associated with relatively deep equigranular

plutons is widespread and broadly propylitic. It is characterized by a sulfur poor

actinolite ± chlorite ± epidote ± magnetite assemblage and typically features

replacement of hornblende by actinolite, biotite by chlorite, and plagioclase by clay and

epidote. This early assemblage is cross-cut by sulfur-rich alteration that is spatially and

temporally associated with the younger quartz-feldspar porphyry stocks. The later

alteration is characterized by early, deep, potassic alteration and overprinting,

shallower, hydrolytic alteration. Extensive stockwork, breccia pipe, and pegmatitic

mineralization is associated with this stage of alteration.

 100

5) Early fluids associated with potassic alteration and pegmatitic copper

mineralization were highly saline and have a stable isotopic signature similar to that of

the associated porphyry stocks. Fluids associated with proximal quartz-sericite-pyrite

alteration associated with both disseminated and pegmatitic mineralization also have

magmatic stable isotope signatures. Fluids associated with more distal sericitic

alteration have isotopically lighter signatures which may represent the limited influx of

isotopically exchanged meteoric waters in the distal parts of the system. Late fluids

associated with distal hypogene clay alteration show distinct displacement toward

meteoric water values.

 101

CHAPTER 3: THE GEOLOGY AND GENESIS OF THE MARIA SILICATE-

SULFIDE PEGMATITE, SONORA, MEXICO

Introduction

The Maria deposit is located in the Cananea district, approximately 10 km

northwest of the town of Cananea, in the state of Sonora, Mexico (Fig. 3.1). The

Cananea district is of great interest not only for its world-class orebodies, but for the

combination of porphyry, breccia pipe, skarn, and pegmatitic mineralization all related

to a cogenetic set of early Tertiary intrusive rocks. Mineralization is distributed along a

zone approximately 30 km long and 4 km wide, and follows a northwest-striking belt

of quartz-feldspar porphyry stocks. The Cananea district is one of the two principal

copper producers in Mexico and one of the largest in the world. It currently produces

-54 Mt I year, and has announced reserves of - 2 Gt in disseminated ore (R. Ayala,

personal comm., 1994). Most production presently comes from supergene-enriched

disseminated ore bodies (-0.65% Cu) in the southern part of the district. Historically,

about one-third of total district production has come from 1) vertically continuous

rock-fragment-rich breccia pipes (1-2% Cu), 2) variably brecciated skarns (-2% Cu),

and 3) the brecciated La Colorada and Maria massive silicate-sulfide pegmatite bodies

(-7% Cu). Apart from the Maria deposit and occasional breccia and pegmatitic bodies

encountered in the open pits all current production in the district is obtained from the

disseminated ores.

The district has been studied by many geologists; notable publications include

Emmon's (1910) monograph on the district as a whole, Valentine's (1936) study of the

geology, Perry's (1933, 1961) and Bushnell's (1988) studies of the breccia pipes, and

Meinert's (1982) study of the skarn mineralization. In addition voluminous

 102

observations were made by Anaconda and other company geologists over the years.

Some of this information is available in the collections of the University of Wyoming.

The early work focused on the distribution and characteristics of the different styles

of mineralization in district. The recent discovery and development of the Maria

silicate-sulfide pegmatite deposit has allowed new examination of an exceptionally rich

end-member of porphyry-related mineralization in the district. This paper describes the

field relations and petrogenesis of the Maria silicate-sulfide pegmatite ore body.

Furthermore, these results yield insight into the broader question of how differences

originate in the range of porphyry-related mineralization styles from disseminated to

breccia to pegmatite. Porphyry-related systems display broadly similar paragenetic

relationships regardless of style of mineralization or metal content. Although

porphyry-related systems typically show common evolutionary trends in their chemical

characteristics, there are significant differences in their physical characteristics. In

particular, the amount of hydrothermal fracturing and ultimate distribution of metals

and alteration differs profoundly between stockwork, breccia pipe, and pegmatitic

mineralization styles.

This study is based on approximately 4 months of detailed surface and underground

geologic mapping between 1989 and 1993. Surface geology and alteration were

mapped at 1: 1000. The underground workings were mapped at 1:250 and selected

areas were mapped at 1:50. Approximately 4000m of drill core was logged at 1:250.

Additional work completed includes; petrographic study of some 150 thin sections,

electron microprobe analysis of selected minerals, and fluid inclusion analysis.

Previous geologic studies on the Maria deposit include work by Wodzicki (1992),

internal reports prepared by Compania Minera Constelacion, Cominco Limited, and

Minera Maria geologists, during delineation, development, and mining of the ore body.
 103

Exploration and Mining History

Although large scale mining in the Cananea district dates back to the late 19 th

century, the Maria high-grade deposit was not discovered until 1979. Early workers in

the district noted the presence of iron oxide staining and intense quartz-sericite-pyrite

alteration on the prominent hill which lies approximately 150 m northwest of the high-

grade body, but the area was initially passed over due to the limited size of the altered

zone and more promising prospects in the immediate Cananea mine area (Y. D. Perry

personal communication). Such altered zones are abundant in the district and generally

correspond to altered, oxidized quartz-feldspar porphyry plugs.

In 1971, regional geologic mapping and geochemical sampling by Minera

Constelacion and Cominco Ltd. geologists identified an undrilled copper anomaly in

the Maria area. Between 1974 and 1976 a 14 hole diamond drilling program delineated

a small disseminated Cu-Mo ore body centered on a small porphyry plug that forms the

hill northwest of the present mine. Work on the property resumed in 1979 after

resolution of land status and step-out drilling designed to increase reserves of the Maria

disseminated ore body encountered high-grade chalcopyrite-pyrite breccia which

corresponded to the northwest corner of the Maria silicate-sulfide pegmatite. Between

1979 and 1982 a Max-Min electro-magnetic survey, a University of Toronto Electro-

Magnetic (UTEM) survey, and an additional 31 diamond drill holes defined the limits

of the high-grade mineralization. The UTEM survey showed a strong, flat-lying

conductor which was coincident with the lateral extent of massive sulfide

mineralization. Infill drilling on 35 m centers was completed in 1983.

Initial tonnage and grade estimates indicated that the deposit was economic, and a

joint venture agreement with Empresas Frisco S.A. de C.Y., was signed in 1988. A

production decline was started in early 1989 and the first ore was shipped to the
 104

smelter in October, 1990. The Maria deposit is being mined underground by undercut

and flU methods, and current production is approximately 500 Tpd (Reuss and Olivier,

1991). Most of the massive sulflde breccia was mined in the flrst three years of

operation, but production from pegmatitic quartz veins is anticipated through 1995.

The Maria mine and concentrator are operated by Minera Maria, a joint venture

between Empresas Frisco (51 %), and Cominco Resources International (49%).

Cananea District Geology

The Cananea district is located within the Basin and Range extensional province

and is part of the SW North American porphyry copper province (Titley, 1982). Like

adjacent parts of southern Arizona, the section in northern Sonora consists of Paleozoic

sedimentary rocks overlying a mid-Proterozoic granitic and metamorphic basement. In

the Cananea district these rocks are intruded and overlain by intermediate to felsic

composition igneous rocks. Older igneous rock include probable Jurassic age

intrusions (EI Torre Syenite) and volcanic rocks of the Elenita and Henrietta

Formations (Meinert, 1982). The older rocks are intruded by Laramide (64-56 Ma)

igneous rocks which include quartz-feldspar porphyry plugs and dikes that intrude

older equigranular rocks and a composite volcanic sequence (Fig. 3.1). The older

Laramide plutons are mostly equigranular members of a district-scale composite

batholith which is grossly granodioritic in composition. Early mapping established that

copper porphyry, breccia pipe and skarn mineralization in the district is primarily, if

not entirely, related to the quartz-feldspar porphyries (Emmons, 1910; Valentine, 1936;

Meinert, 1982). K-Ar dates on mineralized porphyry stocks range from 59 ±2 Ma

(phlogopite from the La Colorada deposit, Damon, 1983) to 54 ± 2 my (sericite from

the Teocali porphyry, recalculated from unpub. Mexicana de Cananea data using Stein
 105

Figure 3.1: Geologic map ofthe Cananea district compiled from Valentine, (1936),
unpublished Minera Constelacion maps, and mapping by the first author. Note the
locations of Maria, La Colorada, and the Cananea open pits. The inset shows the
location of the Cananea district and other districts in the region which host silicate-
sulfide pegmatite mineralization.
 106

Scale
o Km 400

D Mesa Formation
~_ Mariquita Formation
-;14
(~'J64 My TinaJaiCuita

~
- Henriella Formation
_ ~ ~Je~it~ ~o~~iO~ ____
S Carnonates
-CI \:/ Granodiollto
Mz EJ Torre Syenite
___ OlJa.rlZlt!L _ _ _ _ _
~~:J Cananea Granite (1.4 Ga)

Figure 3.1
 107

and Jaeger, 1977 decay constants) and compare well with a Re-Os date of 57.4 ± 1.6

Ma on molybdenite from Maria (McCandless et al., 1993).

Older structures in the district consist of small-displacement faults oriented WNW

and NE; these locally host porphyry dikes and mineralization. Post-mineral NNE

faults tilt all rocks and mineralized breccia pipes about 15° to the east (Perry, 1961).

Overall, the main ore bodies are on the east side of the Cananea Range, with

intermediate and deeper rocks exposed in the central and western portions, and

terminated on the west by range-bounding and tilting faults (Fig. 3.1). This regular

progression, apparently undisrupted by major faulting, may represent an eroded oblique

section through a Laramide volcano-plutonic system.

Geology of the Maria Area

The Maria Deposit is located in the central part of the Cananea district, 8 km

northwest of the town of Cananea near the intrusive contact of the granodiorite

batholith with the older Mesozoic volcanic rocks (Fig. 3.2a). The dacitic tuffs and

flows of the lower Henrietta Formation are intruded by the 64 ±3 my Cuitaca

granodiorite (Anderson and Silver, 1977) which is the host rock for the both the Maria

disseminated and silicate-sulfide pegmatite deposits. Near the intrusive contact, the

volcanic rocks are altered to hornfels and locally cross cut by quartz-sericite veins.

Away from the contact, the volcanic rocks show weak propylitic alteration

characterized by alteration of hornblende to actinolite or chlorite, alteration of

plagioclase to epidote and clay, and local concentration of epidote on fractures.

The composite Cuitaca pluton shows some compositional variation from

granodiorite to monzogranite; in the Maria area it is predominantly a medium to coarse

grained (1-3 mm), equigranular, hornblende-biotite granodiorite, typically containing

24% quartz, 20% K feldspar, 45% plagioclase, 2-3% biotite, 2-3% hornblende with
 108

I~o
m m m
~
limits of disseminated -:::j -31m it"-
mineralization : ",..;..>~.:
" ~~, -'" '" Ii
~--""- fr':U) " ~ .....
~ ", , \.. 1-3/m ::1::1, . . . Projection of limits

I
/
/ , '7.'.

~ "~';·I/ 5/~
.. ....,
3/nt+,
~
, 1':'
~
• • 3/",~
...
high-grade m
~ ~

, ~~m / - • \". .'1

\, ~/'-~· ~ I •
" .....
~
~I·~ ~
1,-....1..·

9/~t:;" 9/~ ~
~. I,
~., :,)
,,~
- -.........
'~,,-,,,,
,-,' ~ f$
-.. ~
~
,
~~15/m~;!
. ,~, .
' ..'

~ ~
lIm~~
3/~ ....
.- \
t
~~
~t?/~
51,
•

•
/Iv • • ::I)

• '/ "/
')' •
Explanation
Quartz·feldspar porphyry &~t
~~
~1/m D Cultaca Granodiorite Outcrop with
QSPvein
a. " • Henrietta Fm. abundance

,,
I~o I~o I~o I~o I~o 6500
m m m ,- m
\
,, m
Limits of disseminated
.
mlneraliz~0.!1 ____ - - - - - - - - - -,- --- I
\

"
, , . I
. '\ "
t" " ".... ",
i
I , --....
1 , / -""".
,

Limits of high·grade ,
,
6400
'1\_~~:~raIiZatiOn; \
I .'
r '/ " \"
I
iA
\ , " '\"~ \ \ I
\
\
'M51; "M66 :""
I
\ I
\
\ I /', ,..,
\
, / ," \ 6300 N

" _f Explanation
-------, A
M50
" -__ I \ / o Weak, veinlet controlled
sericitic alteration
• Drill hole

\ I , ~/ o Moderate vein controlled

•
serictic alteration
\ \. ,-7 Mod. to in!. selectively pervasive and vein
\ --.,."., :,.; controlled seridtic alteration
"
b.
"-'-~-'- - ,..-
II Texturally destructive sericitic
alteration

Figure 3.2: a.) Geologic map of the Maria Mine area showing the major rock types,
quartz-sericite-pyrite vein abundance, and the surface projections of the limits of
high-grade and disseminated mineralization. Note that the pattern for the Cuitaca
granodiorite has been changed to a white background for clarity. b.) Alteration map of
the Maria Mine area showing the surface distribution of sericitic alteration, at the same
scale as a. A-A' is the line of section shown in figure 3.3a-c.
 109

accessory, apatite, magnetite, sphene, and zircon. Weakly porphyritic zones with large

(2-6 mm) plagioclase and orthoclase phenocrysts, in a finer grained (1-2 mm) quartz

and feldspar matrix, are common. Orthoclase locally displays graphic texture. The

Cuitaca is relatively fresh away from the mine area showing only local development of

chlorite ± actinolite after hornblende, chlorite after biotite, and traces of pyrite.

Feldspars are fairly fresh, although plagioclase is usually chalky, occasionally

containing sericite and epidote. High salinity fluid inclusions are common in igneous

quartz in the Maria area. Intense alteration is observed in the Cuitaca only adjacent to

younger quartz-feldspar porphyry stocks.

In the Maria area the Cuitaca is intruded by a quartz-feldspar porphyry (QFP) stock

which outcrops as a series of dikes and forms a prominent hill NW of the Maria Mine.

The QFP consists of two phases, a more abundant type with obvious quartz

phenocrysts and a less abundant type with large (6 mm) feldspars but few quartz

phenocrysts. The former contains large (5-6 mm) resorbed quartz (90%), plagioclase

(8%) ± minor K-feldspar (2%) and biotite (trace) phenocrysts, in a fine grained

groundmass (-80%) of quartz and feldspar. Both types of porphyry are intensely

altered in both outcrop and drill core making identification of primary features difficult.

Feldspars are largely replaced by sericite with very little plagioclase remaining. The

rare biotite phenocrysts are ragged and typically chloritized but still recognizable as

biotite.

Mineralization in the Maria Area

Mineralization in the Maria area occurs in two distinct bodies. The two bodies

contain similar total contents of copper and molybdenum, have similar parageneses,

but very different forms and grades. The first is stockwork-controlled mineralization

centered on the composite QFP stock, whereas the second is cross-cutting, variably
 110

brecciated massive silicate-sulfide pegmatite (Fig. 3.3a). Alteration around both bodies

is distributed in two distinct but overlapping zones. These two ore bodies are

conveniently described in sequence, first a brief description of the disseminated body,

followed by a more thorough treatment of the silicate-sulfide pegmatite.

The Maria disseminated deposit

The Maria disseminated deposit consists of a chalcopyrite-bearing stockwork of

potassic and sericitic veins that roughly coincides with the quartz-feldspar porphyry

stock (Fig. 3.2b). This body contains approximately 7x106 metric tons of 0.8% eu and

0.04% Mo (Reuss and Olivier, 1991). Alteration grades upward and outward from

deeper potassic assemblages to shallower hydrolytic assemblages with a near-surface

supergene overprint.

Mineral Associations
The earliest and deepest alteration consists of potassic assemblages that are

subsequently overprinted by sericitic assemblages. Early vein lets are of three main

types: q uartz(± pyrite-chalcopyrite), quartz-tourmaline(± bioti te-chalcopyri te- pyri te-

molybdenite), and tourmaline-pyrite. These veins have pink secondary K-feldspar

envelopes. Away from the veinlets, K-feldspar locally replaces plagioclase, and in the

Cuitaca, shreddy biotite locally replaces hornblende.

Quartz-sericite-pyrite veins and pervasive sericite-quartz alteration overprint the

potassic veins at shallow levels. These veins contain a few percent total disseminated

tourmaline and sulfides (pyrite ± chalcopyrite ± molybdenite). Thin (2-3 mm vein/l

cm ~nvelope) randomly oriented stockwork veins are found proximal to the QFP stock.

In the vein envelopes, both plagioclase and K-feldspar are largely replaced by sericite +

quartz and biotite is replaced by sulfides ± chlorite. In areas of high vein abundance
 111

Figure 3.3

a: NW-SE cross-section showing the distribution of quartz-feldspar porphyry (QFP), and

of ore types within the high-grade mineralization. The QFP occurs as a series of dikes
cross cutting the granodiorite and the shaded region outlines the area with >50 vol. %
porphyry dikes. The QSP veins overlying the deposit are shown schematically as
dashed lines.

b: NW-SE cross-section at the same scale as Fig. 3a showing the distribution of potassic
alteration. Note that within the high-grade mineralization potassic alteration is
represented by the quartz-biotite-chalcopyrite assemblage The limits of the QFP and
the high-grade mineralization are outlined by the solid black line.

c: NW-SE cross. section at the same scale as Fig. 3a showing the distribution of sericitic
alteration. Note that sericitic alteration extensively overprints the potassic alteration
shown in Fig. 3b. The QFP and the high-grade mineralization are outlined by the
solid black line.
 A A'
NW 7 SE

50 66
I
,
,,
\
\
\ I
I
I

.... , I
, ,
I \
\
I
I
I

I
I

, ---
I I'
, I
\ ,, I

I I
I' \
j..-"'( ""
.... _ - -r-

I
~I
L. 25m-

!TIl Quartz-dominated 1Diamond Drill Hole

breccia
\ Qu!1f1Z-s.ericile-
>50 vol. % QFP dikes • Massive-sulfide pynte veins
and sills breccia Schematic.

o Cuitaca Granodiorite 0
Quartz-rich pegmatite.
Dark lines are veins
intercepted in DOH.

Figure 3.3a
-"
-"
N
 A
NW 10
7 41
I r A'
SE

50 66

I
~I
"'Sm-

Outline of high-grade
ore bodies
0 Weak •. veinlet controlled potassic
alterabon
• Mode~te vein controlled potassic
R~limits of >50 vol% alteration
(/'\? quartz-feldspar porPhyry. Massive quartz-biotite ±
K feldspar- chalcopyrite pegmatite
-- .. _---

~
~
(,.)
A A'
NW SE

Distribution of Sericitic Alteration

Outline of high-grade D Weak, veinlet controlled ser alteration
ore bodies
D Moderate vein controlled ser alteration

R_ Limits of >50 vol% • Moderate to intense selectively

CI\? quartz-feldspar pervasive and vein controlled ser alt
/
/
porphyry III Texturally destructive ser alteration

..
~
 115

overlapping envelopes obscure igneous textures. However, it is possible to distinguish

granodiorite from porphyry in thin section. A greisen-like assemblage of quartz-

tourmaline-pyrite veins and vug fIllings with coarse (2-3mm) muscovite envelopes is

locally present.

External to the sericitically altered rocks, propylitic alteration is variably developed

in the granodiorite. It is characterized by plagioclase altering to clay ± sericite ±

epidote. K-feldspar in this zone usually shows a trace of sericite, and hornblende and

biotite are commonly rimmed with chlorite. A trace to 1% pyrite as fine

disseminations and thin vein lets is common.

Sulfides within -50 m of the surface are oxidized and residual feldspars are

converted to clays ± pink calcite. In the area of intense sericitic alteration, which

approximately coincides with the limits of the Maria disseminated ore body, secondary

chalcocite is abundant as a coating on pyrite at depths between 40 m and 60m.

Distribution and form of mineralization

The overall form of alteration in the disseminated deposit is that of an upward

widening cylinder centered on the QFP stock. A zone of deep potassic and sparse

sericitic vein lets is overlain by intense sericitic alteration in the upper 125 m (Fig. 3.3b

and c). Stockwork quartz veins with potassic envelopes constitute 1-5% of the deeper

zone, with a more restricted region on the west side of the stock of abundant coarse

veins with pegmatitic quartz-biotite-feldspar (inferred from chips, now altered to

quartz-sericite). The abundance of molybdenite in quartz veins increases with depth.

To the base of drilling (-250 m) in this deeper zone, sericitic alteration is widely

distributed but comprises <10% by volume of the rock, with intense development only

near the western pegmatitic zone (Fig. 3.3c). At <125 m depth within 25 meters of the

QFP stock, intense sericitic alteration obliterates most evidence of earlier potassic
 116

alteration, although rare quartz veinlets with partially sericitized pink K feldspar

envelopes are seen at intennediate depths. Alteration intensity diminishes rapidly

peripheral to the QFP stock, except in close proximity to the Maria deposit to the east

and the small silicate-sulfide pegmatite body to the west. Peripheral alteration at all

levels is weakly propylitic with minor potassic veinlets and scattered quartz-sericite-

pyrite zones.

Hypogene and supergene mineralization are primarily controlled by the form of the

stock with a pronounced E-W fracture control only in the periphery. Brecciation and

faulting is rare and exerts little control on mineralization. Average grades in the

supergene enriched zone which lies almost entirely within quartz-sericite pyrite

alteration, are 1.0% Cu and 0.05% Mo with local intercepts as high as 2% Cu. Grades

within the QSP altered zone but below the supergene enrichment zone average 0.8%

Cu and 0.04% Mo. Grades below extensive QSP alteration average 0.35% Cu and

0.04% Mo.

The Maria silicate-sulfide pegmatite deposit

The Maria silicate-sulfide pegmatite deposit consists of a complex of variably

brecciated massive sulfides interfingering with and overlying a mass of quartz-rich

pegmatitic veins (Fig. 3.3a). The deposit contained an initial resource of 1.6 x lO6

metric tons of 6% Cu, 0.36% Mo, and 31 glmetric ton Ag with accessory Wand Au.

Mineable reserves in January 1991 were 465,000 metric tons of 12.8% Cu, 0.25% Mo

and 62 glt Ag; and 390,000 metric tons of 1.8% Cu, 0.67% Mo and 10 glt Ag (Reuss

and Olivier, 1991).

Although much of the upper part of the orebody underwent extensive brecciation

and disruption which juxtaposed various stages of the paragenesis, consistent mineral
 117

associations can be identified throughout, and are best preserved in marginal and deep

parts of the deposit. Zoning in the silicate-sulfide pegmatite is similar to that seen in

the disseminated deposit. Early mineral associations are potassic and copper-rich.

Overprinting and shallower associations are pyrite-rich and exhibit hydrolytic

alteration. The entire ore zone is surrounded by weakly propylitized Cuitaca

granodiorite. The following section focuses on description of the mineral associations

and their mode of occurrence. The spatial and temporal distribution of those

assemblages and fabrics are discussed in a subsequent section.

Mineral Associations

There are two broad suites of mineral associations - an early chalcopyrite-quartz-

biotite suite, and a later pyrite-quartz-tourmaline suite - which exhibit a wide range of

modes, textures, associated minerals, and wall-rock alteration (Fig. 3.4). In both suites,

there are massive sulfide-rich varieties, which are generally brecciated and occur high

in the deposit, and pegmatitic silicate-rich varieties which predominate at depth. The

mineral associations are discussed in order from early to late and generally from deep

to shallow.

Cha!c0l2Yrite-Quartz-biQtite associations (early)

Two styles of mineralization comprise early copper-rich chalcopyrite-quartz-biotite

mineral associations: (1) quartz + biotite + chalcopyrite ± K-feldspar ± apatite ±

magnetite pegmatitic veins, and (2) massive chalcopyrite + biotite ± quartz ± pyrite.

Deeper or proximal quartz-rich veins interfinger with shallower or distal chalcopyrite-

rich bodies (Fig. 3.4). Biotite is phlogopitic (Ann0.3O±O.OSPhIO.70±O.OS), K-feldspar is

mildly sodic orthoclase (OrO.95AbO.oS), apatites are fluorine rich (F/F+CI =0.96).
 en
c
-0 Mineralogy Morphology
CIl--
~-
a>_CIl Open-space /I envelope degree of brecciation thickness (m) elevation relative
co to massive sulfide
~g unbroken - crackle - monolithic - heterolithic
I J J5K, u=;:::J DL ) > it.,..,. > )
0.01 - 0.1 - 1 - 10 below - within - above

~ ~
Sph - 91 - py - qtz 1/ ~
-===-
Clay
1/ CI (chlr -mont) - py - cal <= =- <::::::>
Otz - py ± tm 1/ ser - py
<> <>
Pyrite -
quartz -
tourmaline
Py - qtz ± tm ± moly 1/
ser - qtz - py o
Otz - tm - py ± sch /I
ser - chlr - tm ± moly <>
Chalcopyrite
- biotite -
Cpy - bt - qtz ± py
-=:::::::::====.> <>
quartz Otz - bt - cpy - ap ± Kspar /I
K-spar(?) ± bt <>
Figure 3.4: Summary of mineral associations Cap =apatite, bt =biotite, cal =calcite, chlr =chlorite,
cl = clay, cpy =chalcopyrite, gl = galena, Kspar =potassium feldspar, moly =molybdenite, py =
pyrite, qtz =quartz, sch =scheelite, ser = sericite, sph =sphalerite, tm =tourmaline) their mode of
occurrence, and distribution relative to the massive sulfide. Thickness of polygon is related to the
proportion of a particular assemblage which exhibits the morphology read off the top line.

...a.
...a.
0)
 119

Quartz-biotite-chalcopyrite pegmatitic veins

The quartz-biotite-chalcopyrite pegmatite occurs as variably brecciated 1-3 m wide

veins in the upper portions of the system and grades downward and laterally into a

stockwork of 1-30 cm veins in granodiorite and porphyry (Fig. 3.3a). Modal

mineralogy varies considerably, particularly in the minor minerals. The larger veins

consist of 2-25 cm euhedral to subhedral quartz ± K feldspar ± apatite crystals and 0.1-

2 m bunches of 2-5 cm books of biotite (Fig. 3.5a and 5b). These crystals clearly grow

in from one or both margins, implying open-space filling. Biotite and quartz are

ubiquitous components (5-40 vol. %,50-90 vol. %, respectively) whereas the

abundance of K-feldspar and apatite apparently increase to the east and with depth in

the massive orebody from <5% to -10%. Coarse-grained (> 1 cm) chalcopyrite is

prominent ranging in abundance from <1-30%, typically 5-10%. Magnetite is

widespread in trace quantities intergrown with chalcopyrite. Anhydrite has been

observed in fluid inclusions from this association, and tabular casts in chalcopyrite

suggest a more widespread original presence. Biotite increases in abundance (to 90%),

whereas K-feldspar, quartz, and sulfides decrease in abundance (trace, 5-80%, trace-

5%, respectively) in the thinner stockwork veins beneath the deposit.

The quartz-biotite-chalcopyrite veins almost always contain vug-fillings of pyrite

and fibrous tourmaline with or without minor molybdenite and scheelite. Where

associated with these later minerals, biotite is commonly altered to chlorite, toumlaline

or sericite; K-feldspar is altered to sericite. The extreme in this overprinting process

may be represented by intensely brecciated quartz- and sericite-rich horizons in the

upper portions of the deposit. Subhorizontal zones of coarse-grained quartz + chlorite

± sericite breccia consisting of 0.5-2 cm quartz crystals -60-70% by volume, sericite

 120

Figure 3.5

a: Underground photo showing a quartz-biotite-chalcopyrite vein cross-cutting

granodiorite wallrock (Level 10). Photo is - 5m across

b: A typical sample of quartz-biotite-K feldspar pegmatite (Level 8). Scale is in

centimeters.

c: Underground photo showing a horizontal, brecciated, sericitized quartz-biotite-

chalcopyrite vein (Level 3). Light-colored material is the vein. Dark-colored material
is massive sulfide breccia.

d: A handsample showing biotite intergrown with massive chalcopyrite (Level 5). Black
crystals are biotite, gray crystals are chalcopyrite, white crystal is quartz. Scale is in
centimeters.

e: A handsample of typical massive sulfide breccia (Level 3).. Larger gray clasts are
chalcopyrite, smaller gray clasts are pyrite. Matrix material is quartz and fine pyrite.

f: A typical underground exposure of chalcopyrite-pyrite breccia (Level 3).

g: An underground exposure of massive pyrite (Level 8).

h: An underground exposure of a pyrite breccia body (behind the hammer) cross- cutting
chalcopyrite-pyrite breccia (Level 3).

1: A handsample taken from the contact between the pyrite breccia body and chalcopyrite-
pyrite breccia shown in Fig. 3.5h (Level 3). Material on left is chalcopyrite breccia.
Material on right is pyrite dominated breccia. Scale is in centimeters.

j: Surface exposure of the quartz-sericite-pyrite veins (dark vertical lines) which overlie the
high-grade mineralization. Back pack shown for scale.

k: An underground exposure of the contact between massive sulfide breccia (dark material)
and brecciated granodiorite wallrock (lighter material) (Level 3).
 121

e
 122

,,
j
 123

-20-30 % by volume, sulfides -10 % by volume are commonly observed overlying and

underlying sulfide dominated breccia (Fig. 3.5c).

Massive chalcopyrite-biotite
Massive chalcopyrite with intergrown biotite and less commonly, quartz, pyrite,

and magnetite comprises the second early association. This type of material is

commonly intergrown with the silicate dominated veins described above. Enormous
chalcopyrite crystals (up to 1 m, as defined by continuity of twin planes) are common

in the massive zones. Glassy quartz crystals and 1-2 cm fresh biotite are locally

embedded in solid chalcopyrite and become quite common at the margins of massive

chalcopyrite bodies where the massive sulfide interfingers with quartz-biotite-K-

feldspar pegmatite (Fig. 3.5d).

Unbrecciated massive sulfide is locally preserved in the deeper and marginal pans

of the deposit. These zones typically consist of chalcopyrite (75-100 vol. %), with
lesser biotite (0-15 vol. %), quanz (0-10 vol. %), and euhedral pyrite (0-5 vol %).

However, in most of the deposit, this assemblage is strongly brecciated and disrupted.

Typical sulfide breccia consists of chalcopyrite, pyrite, and quanz fragments of various

sizes cemented by later quanz ± tourmaline (Fig. 3.5e and Sf). Less common clasts

include scheelite, intergrown quanz-chalcopyrite, chalcopyrite-magnetite, sericitized

igneous rock, and traces of intergrown sphalerite + galena ± chalcopyrite. As

documented below, there is a continuum in modal mineralogy between breccias

developed from massive chalcopyrite-biotite and pyrite-quanz-tourmaline protoliths.

Pyrite-Quartz-tourmaline associations (late)

Pyrite, quanz, and tourmaline dominate later hydrothermal assemblages, typically

with sericitic alteration of feldspar and chloritic alteration of biotite. In form, these
 124

assemblages range from deeper pegmatitic quartz-rich veins through pyrite-dominated

massive sulfide, sulfide breccia, and breccia cement, to distal quartz + pyrite ±

tourmaline veins with prominent sericitic envelopes (Fig. 3.4) Accessory molybdenite,

chalcopyrite, and scheelite are commonly present.

Quartz-tourmaline-pyrite veins and breccia cement

The quartz-tourmaline-pyrite assemblage is well developed both within and

immediately above the deposit. At deeper levels of the deposit, this assemblage occurs

as 1-3 m wide veins composed of euhedral2-25 cm quartz crystals with abundant open

space filled with fine fibrous tourmaline (drvO.70±O.05scho.30±O.05, ::;; 5 %), pyrite (1-10

%), chalcopyrite «2 %), and rare scheelite. Individual vugs tend to be monomineralic.

Scheelite occurrence is highly irregular but where it is found it may comprise up to 5 %

of the rock. Wallrock (Cuitaca, porphyry, quartz-biotite-feldspar pegmatite) is

typically converted to coarse (0.1-1 mm) sericite + quartz ± chlorite ± tourmaline.

Chlorite and tourmaline replace biotite, whereas the sericite replaces feldspars and,

where best developed, biotite. Most molybdenite in the deposit occurs within the

intensely sericitized zones.

This assemblage differs in form over the vertical extent of the mineralization. The

massive veins in the core of the deposit grade downward into a stockwork containing

unbrecciated quartz-tourmaline-pyrite veins of diminishing thickness and abundance.

In the overlying sulfide-dominated breccia the quartz-tourmaline assemblage occurs as

fine grained cement and euhedral crystals overgrowing breccia clasts. Clasts of quartz-

tourmaline and disrupted zones of quartz-tourmaline-pyrite are also common. Rare

scheelite clasts are also seen. In a few instances massive quartz-tourmaline veins have

sharp linear contacts with and apparently crosscut chalcopyrite-dominated breccia.

Mineralogically similar veins cement wall-rock breccias over the margins of the
 125

massive sulfide breccia culminating in a 2-3 m thick quartz-dominated breccia capping

the massive sulfide breccia (Fig. 3.3a). This overlying breccia contains 80-90% quartz,

5-20% open space, 10-15% pyrite, 0-5% chalcopyrite, trace to 1% tourmaline, trace to

2% molybdenite, and rare scheelite. Fragments consist of brecciated euhedral quartz ±

tourmaline crystals, 1-5 em long, partly cemented with quartz and minor tourmaline

and pyrite. Quartz, tourmaline, and pyrite that cement the massive sulfide breccia may

be part of this assemblage or reflect a continuum into the pyrite-dominated

assemblages described below.

Massive pyrite-quartz

Massive pyrite with lesser quartz and accessory molybdenite and tourmaline forms

a modally distinct assemblage within the pyrite-quartz-tourmaline suite. Pyrite-rich

material comprises about half of the massive sulfide breccia. Within this assemblage

sericite, quartz, molybdenite, and pyrite replace inclusions of host rock. Pyrite-rich

bodies are generally coherent, 1-5 m wide, and show varying degrees of brecciation.

At deeper levels of the deposit, massive pyrite bodies are relatively little brecciated and

contain >80% pyrite in crystals 1 to 10 cm in size with interstitial coarse-grained quartz

intergrown with tourmaline (Fig. 3.5g). In the upper parts of the deposit, pyrite-

dominated breccia zones cross cut massive and brecciated chalcopyrite-biotite-quartz

rocks (Fig. 3.5h). These contain 80-85% pyrite, 5% quartz ± tourmaline (clasts), 5%

quartz + tourmaline cement, and 5-10% open space (Fig. 3.5i). The tourmaline occurs

as fine thin needles surrounded by quartz. Molybdenite crystals up 1 cm across grow

on chalcopyrite, pyrite, and quartz breccia clasts.

Quartz-sericite-pyrite veins

Closely spaced (5 to 101m) fractures and quartz ± tourmaline ± pyrite-sericite

(QSP) veins cut the Cuitaca immediately over the high-grade mineralization and are the
 126

only surface expression of the mineralization at depth (Fig. 3.2, 3.3a, and 3.5j). There

are three generations of QSP veins: thin early veins forming a randomly oriented

stockwork, later, thicker, through-going veins. A near-horizontal set of open space-

filling veins cross cuts the stockwork veins and both cross cuts and is cross cut by the

vertical veins. The abundance of horizontal veins increases with depth to -1- 21m.

Both vertical and horizontal QSP veins are most abundant directly over the deposit and

diminish abruptly lateral to the vertical projection of the deposit. The QSP veins

consist of a thin (0.1-1 cm) quartz-tourmaline-pyrite vein with an up to 15 em wide

sericite alteration envelope. Vein + envelope locally exceed 50% of the rock by

volume. Pyrite in QSP veins is oxidized to iron oxide to a depth of approximately 20

m. The overlying QSP veins can be traced to within 2-5m of the high-grade

mineralization where they are lost in a zone of intense, texturally, destructive, sericitic

alteration and brecciation which immediately overlies the ore body.

Clay alteration

Clay alteration is concentrated in the granodiorite walIrock and localized along sub

horizontal and near vertical fractures and in parts of the wallrock breccia adjacent to

high-grade mineralization. It is characterized by pervasive alteration of feldspar to, and

partial alteration of biotite to chlorite. The centers of these zones of intense

argillization are commonly cored by pink Fe carbonate ± orange stilbite (identified by

Cominco Ltd. XRD analysis).

Spatial distribution and form of mineralization

The overall form of the high-grade deposit is that of a flat to 10-15" west dipping

lens approximately 125 m by 100m by 25m thick (Fig. 3.3a). The massive

mineralization grades with depth into a WNW plunging zone, consisting of massive
 127

pegmatitic quartz veins cutting granodiorite which disappear into the QFP at the limits

of present drilling. Approximately 90% of the high-grade ore body is brecciated and

variably disrupted and in general the degree of brecciation, disruption, and mixing of

different assemblages increases upward in the deposit. In less brecciated generally

deeper parts of the deposit massive quartz-biotite pegmatite is intergrown with massive

chalcopyrite and biotite of the quartz-biotite-sulfide assemblage and massive quartz-

tourmaline veins of the quartz-tourmaline-pyrite assemblage contain massive

unbrecciated pyrite. Good exposures of this sort of rock were present on Level 8 of the

mine (Figs. 3.5a and g). This deep zone of relatively unbrecciated veins interfingers

with an extensively disrupted breccia zone consisting primarily of chalcopyrite, pyrite,

and quartz fragments.

A heterolithic sulfide dominated breccia containing fragments of the wall rock, as

well as the early quartz-biotite and later quartz-tourmaline assemblages forms

approximately 50% of the high-grade ore body (Fig. 3.5e and f). Modal composition

of this type of breccia is quite variable. It ranges from 10-90% chalcopyrite, 10-80%

pyrite, 0-40% quartz ± tourmaline, 0-30% wall rock fragments, with minor scheelite,

galena, sphalerite, molybdenite, and sericite. An average composition which is

representative of heterolithic breccia is 50% chalcopyrite, 25% pyrite, 20% quartz ±

tourmaline (both clasts and cement), 5% other including variable proportions of wall

rock, tourmaline, molybdenite, scheelite, galena, sphalerite. Average clast size varies

between 1 and 50 cm with the majority of clasts in the 1-10 cm range. The abundance

of fine matrix material, defined as fragments <2 mm across, varies from 10-40 volume

%. In some cases late euhedral quartz, tourmaline, and pyrite of the pyrite dominated

association grow into open space and between breccia fragments; in other cases they

form a hard crystalline cement.

 128

As mentioned above variably brecciated variably altered quartz-biotite and quartz

tourmaline veins are present within the massive sulfide breccia. Examples of such

veins were well exposed on Levels 3, 5, and 8 (Figs. 3.6a, 3.7a, and 3.8a). The massive

sulfide breccia is locally cross cut by 1-5 m wide breccia bodies of the pyrite-quartz

assemblage (Figs. 3.6a and 3.7a). These breccia bodies appear to root in massive

pyrite zones exposed in deeper parts of the deposit (Figs. 3.8a and 3.5g).

The massive sulfide breccia lens grades outward into variably brecciated and

altered granodiorite. The percentage of wall rock fragments increases as the contact is

approached, but the transition from sulfide dominated breccia with <5% wall rock

fragments to wall rock dominated breccia is quite abrupt; generally <1m (Fig. 3.5k).

Matrix supported wallrock breccia with rotated fragments grades outward to crackle

breccia and finally variably sericitized and veined but unbrecciated granodiorite. In the

upper part of the system the transition upward from massive sulfide breccia to

unbrecciated relatively unaltered granodiorite cross cut by the QSP veins described

above, occurs over 5-15 meters. On the north, east, and south sides of the deposi t the

lateral transition to unaltered wallrock with no QSP veining occurs over <5 meters.

The matrix, lithology, and alteration of fragments, in the wallrock breccia show

systematic variation around the ore body. The west side of the ore body is adjacent to

the QFP and the disseminated mineralization and the wall rock breccia consists of
variably sericitized granodiorite and QFP fragments. Sericitized clasts on the west side

of the deposit are commonly cut by several generations of quartz-sulfide veins which

are in turn cross cut by matrix material. These veins are similar to those seen in the

disseminated ore body. The wall rock breccia on the north, east, and south sides of the

deposit, away from the QFP consists of a mixture of sericitized and argillized

granodiorite fragments. The close spatial association of sericitized and argillized

 (Jl
'"'"
I\)
(Jl
!\)

6350 N I'"rn 6350 N I~

/'
/
I
I \
I J
I I
1
6300 N 6300 N I
/
I
/
/ /
/
I
,,
I
\
,
6250Nt\ 6250Nt\ \" __ \.'i:.."".:;;;;:;:;;;;:;:';j)..'"

N
'-
I N I
"-
---- ----
-•
_ Massive Sulfide Breccia. >75%
iml Late pyrite breccia bodies Cp.0-15% Py. 0-100/. all. Explanation
c:
.g CJ Marginal pyrite breccia zone I2Sa auartz·~iotite-K feldspar > 25% Cu
~ .. (BO-l00% pyrite) pegmante
.!!!
~
CJ Massive sulfide breccia <50% Cpo
20·60% Py. 5-30%all. 0-5% rock Irag.
IDi Brecciated variably altered
20-25% Cu
D 1-10% Cu
Granodiorite
W [m Massive sulfide breccia 50-75% Cpo
, .. 20-40% Py. 5-30% all CJ Unbrecciated Granodiorite
Wlli] 10-20% Cu D <l%Cu

a. /00 Fault. with dip .. ' Geologic contact

b.
Figure 3.6: a.) Geologic map of Level 3. The larger body of quartz-biotite-K feldspar
pegmatite in the NE comer of the map is extensively brecciated and sericitically altered whereas
the body in the SE is essentially unbrecciated and unaltered. Note that massive sulfide breccia
makes up most of the ore body on this level. Also note the distribution of pyrite dominated
breccia bodies which cross-cut massive sulfide breccia. b.) Contoured Cu grade for Level 3
with outline of quartz-biotite-K feldspar pegmatite from Fig. 3.6a shown. Note the sharply
lower Cu grades within the pegmatite, the marginal pyrite zone, and the wallrock breccia.
iG
CD
 I\
~ ~

.- .-I~ -- - - - - -- ~--...
(It ( 1 1 , - - - - __ ....... U'I
It;: 1-
IS!:CS .g-- - - - - - ~
--.~--...

ro+ /~.:.-- ~<&f%%D7

- -
m _ - - ./"m (_J m ..............
" .- - ......".. ...-:-.. 'Ii....:::/ \ \
6375~1--"" _~. : (1:& ,L

I
-:f ,~! ~ Ii
I I \ I I
I
I
I
I
I
L
,
, \
\
I I
\ ,
6325N
...,.... 63kN\ \L
I I I . JI
/ I I ~/I
{
/ I \ / /
\ { \ \ I I
"
'\ I ',\ \ I
\ I \I \1
I )/
6275N II
" '/

t
6275 N J /
/ - /,
I / II /1
\
/
/
, \\ . '. : .._.:/1
:;) /1
\
\~~0>'
-- .... ~
/ /'t<J Fault, with dip
\

'---- --
./ , Geologic contact
\. - \. _ _ _"1- - - 25m I N
!tQLate pynte breccia bodies ~ Ouartz-biotite-K feldspar
Q .Masslve Sulfide Breccia. >75%
iii Cp,0-15% Py, 0-10% Otz.
pegmatite
Brecciated variably altered Granodiorite.
5 • >25%Cu D HO%Cu
c: . .
.!!l ~Masslve sulfide brecoa 50-75%
~ . Cp, 20-40"10 Py, 5-30% atz
bia Interior blocks of granodiorite are locally
cross cut by pegmatitic veins.
i • 2D-25%Cu D <1"1oCu
a• w OMassive sulfide breccia <50% Cp,
20-60"10 Py, 5-30"/oOtz, 0-5% rock trag.
CJ Unbrecciated Granodiorite b.
C.
~ !:}}}j 10-20"/. Cu
J) Outline of pegmatite

Figure 3.7: a.) Geologic map of Level 5. Compare the larger area of quartz-biotite- K
feldspar pegmatite exposed with Fig. 3.3a. b.) Contoured Cu grade for Level 5 with outline
of quartz-biotite-K feldspar pegmatite from Fig. 3.7a shown. Again note the sharply lower
Cu grades within the pegmatite.
..4
W
.0
 ,. ,.
----- .....
I ,
- , ....
I .,...- "' "-

~~'1\\ ",

, \ " ,
\ ", '
I
I , '
\
,, \
\
\
\ t
I I
I I
f I
II
I
I
I
I
\ \
,,
\ ,

t ~
\ \

t~~mffi
\ \

N
"m•• I
\ I
~ '?l::W ':: .:.1,1
\ I f I
\ \ f I
,-----.==;::::-.::::-------, \ \ I
Explanation \ " ,',
Ifi Massive pyrite l!lS >70"10 qtz-bt-ksp veins cross
• >25%Cu D1-4%CU \ ' I I
locally brecciated cutting granodiorite
Massive sulfide variably
brecciated> 75% chalcopyrite ~ 20-700/0 qtz-bt-ksp pegmatite
veins crosscutting granodiorite m 1Q-25%CUDo.5-1%CU
\
, ...." _-- /','
/

Massive sulfde breccia 50-75% §)

chalcopynte
5-20% qlZ-bt-ksp pegmatite
crosscutting granodiorile " [ill 4-10% Cu (J Outline of Pegmatite
a. Massive sulfide breccia <50"10
o Granodiorite wall rock
b. " Grade contour

Figure 3.8: a.) Geologic map of Level 7. Note that most of this level is made up of
massive pegmatite and pegmatitic veins cross-cutting granodiorite with variably
brecciated massive sulfide forming a ring surrounding a pegmatitic core. b.) Contoured
eu grade for Level 7.

-"
~
 132

fragments is possibly explained by a degree of collapse brecciation which juxtaposed

sericitized wallrock which was in immediate contact with the high-grade

mineralization, with less altered more distal wall rock.

Grade Distribution:

The fIrst order control on the distribution and tenor of grades within the high-grade

deposit is the distribution of massive sulfide breccia and quartz dominated pegmatite.

The brecciated massive sulfide zone, which generally overlies the pegmatite dominated

mineralization, had initial mineable reserves of 465,000 metric tons of 12.8% Cu,

0.25% Mo and 62 glt Ag, and contains -90% of the copper and 30% of the

molybdenum contained in the high-grade ore body (Reuss and Olivier, 1991). This

reserve fIgure includes zones of the relatively low grade quartz and pyrite dominated

assemblages as internal waste and a significant portion of the massive sulfide breccia

assays >20% Cu, with channel samples up to 10 m long assaying >25% Cu (Figs. 3.6b,

3.7b,3.8b). Additional mineable reserves of 390,000 tons of 1.8% Cu, 0.67% Mo and

lOgit Ag are contained within the underlying quartz dominated pegmatite zone (Reuss

and Olivier, 1991).

Cu grade is strongly controlled by the distribution of the massive sulfide breccia

(Compare Figs. 3.6a-b, 3.7a-b, 3.8a-b). Within the massive sulfide dominated part of

the ore body copper grade generally correlates with degree of brecciation. More

disrupted and brecciated material generally has a smaller average clast size, more

matrix material, higher quartz and pyrite content, and therefore lower Cu grade. The

highest grades are found in unbrecciated or weakly brecciated zones of massive sulfide

containing large tabular blocks of chalcopyrite and only minor matrix material. Mo is

distributed through the massive sulfide breccia especially as an aureole around some
 133

pyrite-quartz breccia zones. However, significantly higher grades, and approximately

2.5 times as much total Mo is present in the deeper quartz dominated pegmatite.

Time-space development of Mineralization

An interpretation of the sequence of events responsible for the formation of the

high-grade deposit is possible despite the complexity imposed by the degree of

brecciation and disruption in the ore body. The earliest event was the emplacement of

the QFP stock and the associated stockwork mineralization. This assertion is supported

by the presence of mineralized fragments of both granodiorite and QFP in the wall rock

breccia on the west side of the high-grade mineralization, and by the fact that many of

the wall rock breccia fragments are cut by a stockwork of early quartz ± pyrite ±

chalcopyrite ± tourmaline/sericite veinlets which are cut off by matrix material. The
plunge of the pegmatitic veins toward the QFP, and the approximate coincidence of the

mineralization with an apophyse of the QFP suggests that the high-grade

mineralization is related to a later phase of the QFP stock(Fig. 3.3a), and that

mineralizing fluids may have followed a zone of weakness in the Cuitaca along the

QFP apophyse.

Cross-cutting relationships suggest that within the high-grade mineralization, the

quartz-tourmaline-sulfide assemblage post-dates the quartz-biotite-chalcopyrite

assemblage. The evidence for this relationship includes: First, the widespread

overprint of the quartz-biotite-chalcopyrite assemblage by hydrolytic alteration

associated with the quartz-tourmaline assemblage. For example K feldspar in the

pegmatitic veins is widely replaced by sericite, biotite is commonly replaced by

chlorite and locally by tourmaline. Second, in a few places quartz-tourmaline veins

and massive pyrite-quartz breccia bodies cross cut massive or weakly brecciated

chalcopyrite belonging to the quartz-biotite-sulfide assemblage. Lastly much of the

 134

material cementing the massive sulfide breccia consists of quartz, tourmaline, and

pyrite.

Within this general time sequence, emplacement of each assemblage occurred as

multiple pulses rather than a single event. For example, on Level 3 a quartz-biotite

pegmatite vein cross cuts massive sulfide breccia suggesting more than one episode of

quartz-biotite vein emplacement within the quartz-biotite-sulfide assemblage (Fig.

3.6a). Furthermore, a few zones within the massive sulfide breccia are cemented by

quartz-biotite material which is further evidence for multiple episodes of quartz-biotite

± chalcopyrite emplacement. The presence of quartz-tourmaline clasts in the sulfide

breccia suggests several stages of quartz-tourmaline veining and multiple phases of

brecciation.

In summary, at a given point in the deposit mineralization evolves from an early,

massive quartz-biotite-K feldspar-chalcopyrite assemblage to brecciation and dilution

by the variants of the quartz-tourmaline-pyrite-sericite assemblage (Fig. 3.9a and b).

This evolution of mineralization through time can be explained in several ways: 1) The

single, evolving fluid model: Mineralization forms from multiple pulses of similar

composition fluid. Each batch of fluid forms the quartz-biotite-sulfide assemblage at

depth and forms the overprinting quartz-tourmaline-pyrite assemblages as it cools and

decompresses. Within each cooling pulse of fluid the process envisioned is analogolls

to the classic model for the evolution of alteration in veins (e.g. Meyer and Hemley,

1967). The model envisioned for the Maria deposit is similar to a strictly

orthomagmatic model for the evolution of mineralization in porphyry copper deposits.

2) The two fluid model envisions a process in which early mineralization is callsed by

one fluid and later mineralization is caused by a second fluid with a different

composition. This process would be analogous to that proposed for many porphyry
 One fluid Model Two fluid model

c: c:
o o
~ ~
> >
Q)
Q)
iIi iIi

a. Time ~ b. Time ~

Figure 3.9: a) Space-time evolution diagram for the one fluid model. At a time t1 quartz- biotite-
chalcopyrite ± K feldspar is being precipitated at deep levels and the various assemblages within the
quartz- tourmaIine- pyrite association are being deposited at shallower levels. At a time t2
quartz-tourmaline-pyrite is deposited over the entire vertical extent of the deposit. At any given point in
space mineralization evolves through time from quartz- biotite -chalcopyrite to quartz- tourmaline -pyrite.
b) Space-time evolution diagram for the two fluid model. At a time tl quartz-biotite-chalcopyrite is
deposited over the entire vertical extent of the deposit. At a time t2 the quartz- tourmaline- pyrite is
deposited over the entire vertical extent of the deposit. At any given point in space the mineralization
evolves through time from quartz-biotite-chalcopyrite to quartz- tourmaline- pyrite.
...a.
Co)
CJ1
 136

copper deposits in which early alteration is due to magmatic fluids and later alteration

results from the influx of meteoric waters (Taylor, 1974). The physical consequences

of each alternative are summarized below and in (Fig. 3.9a and 9b)

The single fluid model (Fig. 3.9a): At any given time, deep (proximal) quartz-

biotite-K feldspar and chalcopyrite-biotite, intermediate quartz-tourmaline-pyrite-

sericite, and shallow(distal) quartz-sericite-pyrite are forming. Repetition of this

evolutionary pattern by successive pulses of fluid of similar composition leads to

precipitation of quartz-biotite-K feldspar and chalcopyrite-biotite, at depth and

brecciation of earlier, overlying mineralization by the decompressing fluid. As this

fluid rises and cools, it precipitates quartz and pyrite ± chalcopyrite, alters K feldspar to

sericite and biotite to chlorite ± sericite. The fluid's source may evolve with time for

example as a magma chamber crystallizes and cools and the composition (e.g. sulfur,

chlorine, metal content etc.) of the fluid ex solved would also change.

Two fluid model (Fig. 3.9b): An early perhaps magmatic fluid precipitating the

quartz-biotite-sulfide assemblage and a second fluid, possibly external meteoric water

precipitating the quartz-tourmaline-sulfide assemblage.

Both scenarios are consistent with the geologic observations and fluid inclusion and

stable isotope data are needed to determine which best explains the evolution of

mineralization at Maria.

Physical & Chemical Constraints

Fluid inclusion data

Quartz containing abundant primary and secondary fluid inclusions is present

throughout the paragenetic sequence at Maria. Micro-thermometric measurements

were performed on primary inclusions in quartz from each mineral assemblage using a

standard heating and freezing stage. Glass windows were used on the stage so heating
 137

runs were limited to <500°C. Inclusions were determined to be primary or secondary

based on petrographic criteria established by Roedder (1984). Isolated, relatively large

inclusions and rare inclusions occurring along growth zones in quartz were considered

to be primary. Clusters of small inclusions occurring along fracture planes were

considered to be secondary. Three types of primary and secondary fluid inclusions are

seen; liquid + vapor + daughter(s) (L VD), liquid + vapor (liquid dominated)(L V), and

vapor + liquid (vapor dominated)(VL). The most common daughter crystal seen in the

three phase inclusions is halite. However inclusions with multiple daughter crystals

including sylvite, hematite, anhydrite, and possible chalcopyrite in addition to halite are

common. In a number of samples, both liquid and vapor dominated inclusions are

found in close spatial association suggesting phase separation or 'boiling' took place at

certain times in the paragenesis. All 3 types of inclusions are present in varying

proportions throughout the paragenetic sequence.

Salinity
L VD inclusions and LV inclusions are present throughout the paragenesis and the

vertical extent of the Maria deposit. However, the relative abundance of L VD high

salinity inclusions increases with depth. Table 3.1 shows how the proportion of L VO

inclusions increases from an estimated 10% of the total inclusion population in QSP

veins overlying the deposit to -70 % of the inclusion population in quartz intergrown

with chalcopyrite in quartz-biotite-sulfide veins and in quartz-tourmaline-sulfide veins.

The quantitative salinity data show a similar trend, with maximum salinity increasing

with depth (Fig. 3.lOa). Note also that inclusions in both the early quartz-biotite-

sulfide and the late quartz-tourmaline-sulfide assemblages fall into 3 distinct

populations. Both assemblages have a high salinity population clustered around 50 wt

% NaCI equivalent, a medium salinity population clustered around 30 wt % NaCI and a

Table 3.1: Summary of Ruid Inclusion Data
Assemblage Petrography Homogenization Salinitiy (wt % Boiling Pressure
Temperature (0C) NaCI)
HigM-owlAverage High/LowlAverage
Wallrock L+V>L+V+D 410/147/315 34.1/8.7/21.5 yes 320 bars
Cement 70:30

Sulfide bx L+V=L+V+D 425/198/329 48/10/32 yes

cement

Massive Qlz- L+V>L+V+D >500/323/250 56/28/45 yes 664 bars

trn-sulfide 752 bars
veins 720 bars

Higher level L+V=L+V+D >500/215/331 36/5/21 yes 800 bars

QIZ-bt-cp 592 bars

Lower level L+V>L+V+D >500/265/268 55/30/38 yes 800 bars

QIZ-bt-cp 592 bars

...J.

~
 139

60

50

40
.
z"
30
~
.~
c
~
20 ..
10 ... ~

0
a. O!
Early • Lalo
Incroasing Doplh

° OIz·bl·suK. voins

IJ. OIz·lm·sul!. voins

• SuKide Broccia Cemonl

<> Wallrock Broccia Cemonl

100

o +-----------------------------------~
b. Early ,. LalO
. Incroasing Doplh

55 .0 I;.
Th vs. Salinity o!i
50 .... IJ. ••
45
•• •
~35
40
4Il.. .. . 0
b. •
~I;.I;.
c3 30 ~
. 0 I;. • o. I;. ~ o
o/p 0
~25
!20
.~
0
~15
10 .0 80 o(/>
<>
5 ~o--~--------~--------~1--------r-------~--------~
200 250 300 350 400 450 500
Homogenization temperature °C
c.
Figure 3.10: Fluid inclusion data. Samples are arranged from deepest and
earliest assemblage on the right to youngest and shallowest assemblage on
the left. Legend shown with b. also applies to a. and b. a) Plot of salinity vs.
time and depth. b) Plot of homogenization temperature vs. time and depth.
c) Plot of salinity vs. homogenization temperature.
 140

low salinity population clustered around 15 wt % NaCl. A bimodal distribution of

salinities is especially marked in the sulfide and wallrock breccia cement at shallow

levels in the deposit. This observation is consistent with petrography which suggests

that several generations of quartz cement are present in the massive sulfide and

wallrock breccia. The high salinity population from the sulfide breccia cement lies

along the NaCI saturation line and overlaps the range of the higher salinity inclusions

from massive quartz-tourmaline-sulfide veins. The shallower (more distal) wallrock

breccia cement has lower maximum, minimum, and average salinities than the sulfide

breccia.

Temperature

Most homogenization temperatures fall within a broad band between 200 aC and

>sooaC (Fig. 3.10b). Some variation in homogenization temperature is seen between

the different types of inclusions. In most LVD inclusions, final homogenization was

by halite dissolution at temperatures of between 300aC and Sooac. Liquid + vapor

inclusions which homogenize to liquid generally did so at temperatures below 400 aC.

Measured homogenization temperatures for inclusions homogenizing to vapor, range

from 317 aC to 500aC (Table 3.1).

A similar range of homogenization temperatures is seen in both the quartz-biotite-

sulfide and quartz-tourmaline-sulfide assemblages. Similar maximum temperatures are

seen in massive quartz-tourmaline-sulfide veins and in quartz intergrown with massive

chalcopyrite from the quartz-biotite-sulfide assemblage. Note that the maximum

temperatures for these samples are at the detection limit of the heating-freezing stage

used, so the true maximum and mean temperatures are probably somewhat higher than

shown. Although little temperature variation is recorded between assemblages,

maximum recorded temperatures show a slight increase with depth in the quartz-
 141

tounnaline sulfide assemblage (Fig. 3.lOb). Note that higher maximum temperatures

are found in the massive quartz-tounnaline-sulfide veins than in the slightly shallower

quartz cementing massive sulfide and wallrock breccia.

Stable Isotope data

25 samples from the high-grade ore zone, the QFP, and the Cuitaca granodiorite

were analyzed for 180/ 160 and DIH in order to better define the sources of

hydrothennal fluids. Water was extracted from 30-40 mg of biotite, sericite, and

chlorite by heating under vacuum and was converted to H2 over heated uranium. 02

was extracted from -1 mg of quartz, biotite, sericite, feldspar, and chlorite by heating

with a laser and reaction with bromine-pentafluoride using techniques described by

Sharp (1990). The 02 was converted to CD2 on a hot carbon rod. The 180/ 160 and

DIH isotopic ratios were measured on a Delta S gas ratio mass spectrometer at the
University of Arizona. The oxygen and hydrogen isotopic composition of fluid which

would have been in equilibrium with the minerals was calculated using experimentally

derived fractionation factors and temperatures derived from the fluid inclusion data

discussed above. In addition 11 sulfide samples were analyzed for 34S;32S. Gas was

extracted by heating crushed sulfide together with copper oxide in a uranium furnace.

Sulfur

The results of sulfur isotope analyses perfonned on sulfides from the ore zone at

Maria are summarized in Table 3.2. The analyses show a narrow range of 834 S values

ranging from -1.36 to 0.2 per mil. The restricted range of these results suggests that the

hydrothennal fluids had a single source of sulfur. The clustering of the results around

834 S= 0 suggests that the sulfur was derived from a magmatic source. Temperatures
were calculated using equations from Ohmoto and Rye (1979) on analyses from two
 142

Table 3.2: Sulfur IsotoEe Results.

Sample# Description Mineral 034S Calculated
Analysed 0/00· temperature OCt
S4PY L3 Pyrite breccia Pyrite -1.0
body
S5CP L3 Intergrown Chalcopyrite -1.1
pyrite and
chalcopyrite

S5PY L3 Intergrown Pyrite -1.1

pyrite and
chalcopyrite

S9CP L3 Intergrown Chalcopyrite -0.7

quartz-biotite-
chalcopyrite

L3CP L3 chalcopyrite Chalcopyrite -1.4

clast from
sulfide breccia

L3PY L3 pyrite clast Pyrite -0.7 571

from sulfide
breccia

S6CP L4 massive Chalcopyrite -0.5

chalcopyrite
intergrown with
quartz

S2CP L8 intergrown Chalcopyrite -0.5

chalcopyrite and
pyrite

S2PY L8 intergrown Pyrite 0.2 528

chalcopyrite and
pyrite

S3MO L8 molybdenite Molybdenite -0.6

from pegmatitic
quartz vein

S3CP L8 molybdenite Chalcopyrite 0

from pegmatitic
quartz vein

·S isotope data was collected in the Stable Isotope Laboratory at the

University of Arizona. Gas for analysis was extracted by heating crushed
sulfide with copper oxide in a uranium furnace. Reproducibility ± 0.10/00.
Accuracy checked by running an internal galena standard every 5 samples.
Results reported in per mil vs Canyon Diablo Troilite.

I Temperature for coexisting sulfides calculated from equations derived by

Ohmoto and Rye (1979) from experimental data.
 143

samples containing intergrown chalcopyrite and pyrite. While this pair is not

considered ideal for sulfur isotope thermometry, the results, 528 ± 40°C and 571± 40

°C, fall within the range of temperatures obtained from fluid inclusions. These

temperatures provide a check on the accuracy of the fluid inclusion measurements and

provide an independent estimate of trapping temperature which can be used to estimate

pressure and depth of formation.

Hydrogen

The results of hydrogen isotopic analyses are summarized in Table 3.3. The

hydrogen isotopic composition of local magmatic water is 8D= --7C1'1oo. This

composition is based on fluid calculated to be in equilibrium with biotite from

unaltered Cuitaca granodiorite. The calculated fluids for 6 isotopic analyses of biotite

from the quartz-biotite assemblage in the Maria ore body have somewhat lighter
8DH20 values which range from -54 to -74 using an estimated Talt= 600°C. An

analysis of biotite taken from Cuitaca overlying the high-grade mineralization (Sample

MCGd-3; Table 3.3) had a 8D mineral isotopic value of -79 similar to that seen in

biotites from the quartz-biotite assemblage. The values for the quartz-biotite

assemblage are somewhat lighter than those for the igneous minerals but still fall

within the range of magmatic values and within the range of values for biotites in

porphyry copper deposits both defined by Taylor (1974). The 4 analyses of sericite

from the QSP assemblage have 8D values which show some overlap but are generally

slightly D enriched relative to the biotites (Fig. 3.11a). The values for fluid in
equilibrium with sericite at T alt = 500°C range from -29 to -56. These values fall

within the range of magmatic values defined by Taylor (1974) for muscovite, as well as

within the range of values seen in sericites from the southwestern U.S. porphyry

copper deposits. One analysis of a clay altered feldspar site from the Cuitaca
 144

Table 3.3: Ox~ien and H~droien Isoto~ Data

Measured value Calculated waten; (SMOW)t
(SMOW)°
Sample # Rock.type Mineral 00 olSO liD 00 0 180 0 180 TOCused
analysed H2O H2OH20 high 10wT in calc.
highT 10wT Tvalue value
value value
Igneous Rocks
224 Fresh Biotite ·58 4.8 42 7.4 700
Granodiorite
MCGd·1 Fresh Biotite ·57 41
Granodiorite
MCGd·3 A!lered Biotite ·80 -64
Granodiorite
224 Fresh Plagioclase 6.8 7.5
Granodiorite
230 Fresh Quartz 9.5 8.5
Granodiorite
Quartz-biotite-chalcopyrite Assemblage
LlO Level 10, vein Quartz 8.4 6.8 6.1 Hi=6oo;
Low=500
LlO Biotite ·90 7.0 -74 ·66 9.5 9.4

1.8-1 Level 8, vein Quartz 8.4 6.8 6.1

1.8-1 Biotite ·70 6.3 ·54 46 8.9 8.7

92·6 levelS, vein Biotite ·72 ·55 47

MP3 Level 4, vein Biotite ·88 ·71 ·63

MP5 Level 3, vein Quartz 8.5 7.0 6.2

MP5 Biotite -85 7.0 ·69 ·61 9.5 9.4

L2tL3 Level 2, vein Quartz 8.3 6.7 6.0

L2tL3 Biotite -79 6.5 -63 ·55 9.0 8.9
Quartz-tourmaline-pyrite-sericite
LlObx Level 10, vein Quartz 10.0 7.7 5.9 Hi=500;
Low=3oo
LlObx Sericite ·74 7.5 ·56 42 7.4 4.1

126.1 Level 8, vein Quartz 10.7 8.4 6.7

135b Level 8, vein Quartz 10.5 8.2 6.5

LScp levelS, Sericite -47 ·29 ·15

sericitized rock
f/'3g.

L5bx levelS breccia Quartz 10.5 8.2 6.5

LSbx Sericite ·50 8.9 ·32 ·18 8.8 5.5

QSP Surface, veins Quartz 9.7 7.4 5.7

QSP Sericite ·67 7.9 -49 ·35 7.8 4.6
Distal Clay Alteration
ArgGd Drill core 4001 Clay (chi, ·72 13.8 ·57 ·59 11 3
~th mont!

• 0 and H data collected in the Stable Isotope Laboratory at the University of Arizona. Oxygen was
extracted from single minerals using a laser·nuorination line similar to that described in Sharp (1990).
Water was extracted from --40 mg of hydrous mineral by heating under vacuum and converted to H2 over
hot uranium. Reproducibility for oxygen analyses was 0.2 to 0.5%0 and 2 to 8%0 for hydrogen. Accuracy
was checked by running a lab standard every 5 samples.
t Fractionation factors from the following sources were used to calculate water compositions. Mine/'31
compositions from electron microprobe analyses: Oxygen· Biotite from Botlinga and Javoy (1973) and
Javoy (1977); Quartz from Ma15uhisa (1979); K feldspar, plagioclase, sericite (extrapolated to 300°C)
from Friedman and O'Neil (1977); Kaolinite from Kulla and Anderson (1978). Hydrogen· Biotite and
sericite from Suzuoki and Epstein (1976); Kaolinite Lui and Epstein (1984).
 145

o
80 Calculated water vs. time
-10

-20

----------i-------~ ---~
-30 • Igneous biotite

E-4O
l;~~';~;;-
•

~-50 •
L-:_:_:_:_:_,:_,:_:_'_bio_t_ite_...I
o
<0-60

-70 •

-60 --------------------------------
-90

a. Time
14.0
8180 Calculated H20 VS, time
12.0

100
r------------------~---------- • Igneous Minerals

E 80
1»Co
0 6 .0
!Xl
l_~~~~:~~ ___ ~ ___ ~ ___;___ ~ __ _ C Quartz-biotite

• Quartz-sericite

;Q o Cu~aca, Clay
4.0

2.0

0.0 " - - - - - - - - - - - - - - - - - - - - - -
Time
b.
-20
Isotopic Composition of Calculated Waters
-30 o
-40

'E

0
...
<Il
Co

<0
-50

-60

-70

-80

-90
Cananea Meteoric Water
[JC~ OC

Magmatic water (Taylor, 1974)

C

o
Igneous biotite

Quartz-biotite

Quartz-sericito

Cu~aca, Clay
-100

-110

-120
-20.0 -10.0 00 10.0 20.0
C. 0180 per mil
Figure 3.11: 0 and H Isotope results. Samples are arranged from deepest and earliest
assemblage on the right to youngest and shallowest assemblage on the left. References
for fractionation factors shown in footnote to Table 3.3. a) Plot of calculated dD H20
vs. time and depth. b) Plot of d180 H20 vs. time and depth. c) Plot of calculated
d180 vs. dD H20 values.
 146

granodiorite immediately overlying the deposit has a 8D mineral value of -71 which

corresponds to a fluid value of -59 at Talt = 100°C.

Oxygen
20 samples of quartz, feldspar, biotite, sericite, and chlorite + clay from the ore

body and the intrusive rocks were analyzed for 180/16Q. Calculated fluid values for

both quartz and the micas plot within the hypothetical 'magmatic' range and the fields

defined for SW U.S. porphyry copper deposits by Taylor (1974) (Fig. 3.11 b). Fluid

associated with both quartz-biotite and quartz-sericite alteration has a broadly similar

oxygen isotope composition and neither shows significant displacement toward local

meteoric values which are 8180 = --10. Only a sample oflate clay alteration shows

significant displacement toward meteoric values ( Fig. 3.11c). Temperatures calculated

from quartz-biotite and quartz-sericite pairs are geologically unreasonable suggesting

isotopic equilibrium was not achieved.

Estimation of Intensive Variables

In this section we estimate the pressure, temperature, and composition of the

hydrothermal fluids from the fluid inclusion and stable isotope data and from the

observed phase relationships. Estimates of fluid pressure were made using

homogenization temperatures from closely associated LV and VL inclusions which

presumably formed under boiling conditions. Measurements on this type of inclusion

were obtained from the quartz-biotite assemblage, the massive quartz-tourmaline-

sulfide veins, and the quartz-tourmaline-sulfide wallrock breccia cement (Table 3.1)

Salinity measurements on vapor dominated inclusions were not made; however

Roedder (1984) suggests that assuming a salinity of 10 wt % NaCI equivalent

 147

introduces minimal error into pressure estimates. Trapping pressures were then

estimated using procedures outlined by Crawford (1981).

Homogenization temperatures from coexisting LV and VL fluid inclusions in the

massive veins from both the quartz-biotite-sulfide and the quartz-tourmaline-sulfide

assemblages suggest trapping pressures ranging from 600 bars to 800 bars (Table 3.1).

Temperatures from the quartz-tourmaline-sulfide material cementing the wallrock

breccia indicate a trapping pressure of 320 bars. The higher pressures are interpreted as

corresponding to lithostatic pressure at a depth of 2.5 to 3 km. The lower pressure is

interpreted as corresponding to hydrostatic pressure at a similar depth. A similar depth

is estimated from stratigraphic reconstruction over the deposit.

As discussed above, the proportion of LV to L VD inclusions varies between

samples (Table 3.1) which may affect the mean temperature for a particular assemblage

because LV inclusions have lower homogenization temperatures. The mean

temperature for an assemblage may also be affected by inadvertent bias in selection of

inclusions for measurement, e.g. a cluster of lower temperature inclusions in a clear

part of the sample chip, so the maximum temperature recorded may reflect the

temperature of the assemblage more accurately than the mean. Using the maximum

temperatures obtained for each assemblage and correcting for a pressure of 700 bars

suggests that the fluid inclusion homogenization temperatures represent trapping

temperatures of between 550 and 600°C for both the early quartz-biotite-sulfide

assemblage and the later quartz-tourmaline-sulfide assemblage. These temperatures

are consistent with the sulfur isotope results. The temperatures obtained from quartz

intergrown with chalcopyrite are especially important because they constrain the

temperature range over which chalcopyrite precipitated. Measurements on these

 148

samples suggest chalcopyrite precipitation over a temperature range of approximately

600 to 400°C.

Observed temporal relationships among mineral assemblages in the Maria deposit

show similar trends to those seen in disseminated/stockwork and breccia pipe deposits.

The general trend in all three types of deposit is toward lower temperature and lower

pH assemblages with time. As in many disseminated/stockwork and breccia pipe

systems the dominant sulfide minerals are pyrite, chalcopyrite, and molybdenite. There

is no evidence of advanced argillic alteration, which is consistent with the

predominance of intennediate sulfidation minerals.

The stability field of hydrothennal biotite(Ann. 0.30 PhI. 0.70), coexisting with K

feldspar and magnetite or pyrite defines the limits of sulfur and oxygen fugacities

during fonnation of the quartz-biotite-K feldspar-chalcopyrite assemblage. Cu-Fe-S-O

minerals in the Maria deposit are limited to pyrite, chalcopyrite, and magnetite.

Therefore, sulfur and oxygen fugacities during the rest of the paragenesis are limited to

the stability field of chalcopyrite-pyrite ± magnetite (Fig. 3.12). The absence of more

sulfidized Cu-Fe sulfides, and the absence of hypogene alunite, places an upper limit

on fS2. The absence of pyrrhotite places the lower limits of f02 and fS2 above the

pyrite-pyrrhotite boundary.

Source and evolution of hydrothermal fluid

With the fluid inclusion and stable isotope data, we can now discuss the source and

reexamine the three models for the evolution of the hydrothennal fluids. The high

salinity, high temperature fluid inclusions from the quartz-biotite-sulfide and the

quartz-tounnaline-sulfide assemblages are consistent with a magmatic fluid. However,

the low salinity inclusions seen in higher level quartz-biotite-chalcopyrite veins and in
 149

log f02
-35 -30 -25 -20 -15
0.0
Covellite
-2.5 &m~---------------------;7~C~~oc~-----
-5.0
I--------------~~::::.:$;'-:r ,,"'"" "
Chalcopyrite ~
.. ~¢1~tP ,,""
•..,.'1;", ~ Range

C\J
-7.5
~-'----~r.-7·-'''''''
..,'
,_~,(,'o

:. I
/I
!!2.C) -10.0
"."
",'
,II'''
/ ..~..
.tJ''''
/"
"
:

t:
..Q ...................... r. ..... ~ ..... .."v- I.
-12.5

-15.0
", ,'/"
, •• "
/
//

I
I:
I
/
I

I
I
: Bioti,e xFe= 0.3

-17.5

-20.0
Figure 3.12: Plot of f02 vs. fS2. The range of conditions during the
fonnation of the Maria deposit are indicated by the gray arrow.
 150

breccia cement could be interpreted to represent involvement of a second low salinity

fluid, possibly meteoric water in the upper part of the deposit. However, if mixing with

meteoric water had occurred one would expect to see a mixing line between the high

salinity inclusions and the low salinity inclusions instead of the two separate

populations which are actually seen. The favored inte!pretation for the observed

distribution of salinities is decompression or 'boiling' of an intermediate salinity fluid

during the transition from litho static to hydrostatic pressures and separation into a very

high salinity liquid phase containing most of the metal, and a lower salinity vapor

phase (Fig. 3.lOa). Experimental work by Cygan et al., (1994) suggests that in this

situation, Cu is strongly partitioned into the aqueous brine. The widespread occurrence

of coexisting LV and VL inclusions and the presence of very high salinity inclusions in

quartz intergrown with chalcopyrite supports this scenario.

The stable isotope data are also consistent with a magmatic fluid. The calculated

waters in eqUilibrium with quartz, biotite, and sericite in the ore body have values

which are broadly similar to those calculated to be in equilibrium with minerals from

unaltered igneous rocks. Only late clay alteration shows significant displacement

toward local meteoric water values (Fig. 3.11c). The sulfur isotope data indicate that

the sulfur had a magmatic source, but because the deposit is surrounded by igneous

rocks, available sulfur is likely to have a magmatic signature regardless of water

source. Nevertheless, taken together, the high temperature high salinity fluid

inclusions, and stable isotope data suggest a magmatic source for fluid and sulfur in the

deposit.

The stable isotope and fluid inclusion data can also be used to evaluate possible

fluid evolution models. The fact that 8180 of quartz from the quartz-tourmaline

assemblage is slightly heavier than quartz from the quartz-biotite assemblage is

 151

consistent with a magmatic fluid evolving with time. The data and arguments

summarized above do not show clear evidence for the involvement of large amounts of
meteoric water and support an evolving magmatic source for hydrothel1l1al fluid. An
orthomagmatic fluid with an evolving composition is consistent with early quartz-

biotite-K feldspar assemblages being brecciated and altered by fluids associated with

precipitation of the later quartz-tourmaline assemblage.

Mass and heat balance constraints

Geologic observations and mass balance considerations detailed below provide

further constraints on possible sources of hydrothermal fluids and metals in the deposit

and are consistent with a largely magmatic source for both. The limited amount of

alteration in the host rock to both the stockwork and the high-grade deposits suggests

that extensive leaching of wall rock did not occur and therefore the hypothesis that the

source of metal contained in the Maria deposit was the associated intrusion is

reasonable. The physical and chemical data described above are consistent with a

largely magmatic source of metals and hydrothermal fluids in the Maria deposit. Mass

and heat balance calculations can be used to check whether a magmatic source of

metals and hydrothel1l1al fluids is geologically reasonable. The calculations described

below test the hypothesis that all the copper, quartz, and hydrothermal fluid in the

Maria deposit were derived from a magmatic source. First the volume of magma

required is estimated from the copper content of the deposit and the copper content of

an average granitic magma. Second the volume of fluid required is estimated from the

volume of copper and quartz in the deposit and experimentally derived copper and

quartz solubilities.
 152

Volume QfMagma

The fIrst step in the mass balance calculations is to estimate the volume of magma

required if the copper contained in the deposit was derived from a magmatic source.

Calculations based on reserve fIgures indicate that the Maria high-grade deposit

contains approximately -10 5 metric tons of Cu. Data in Banks (1982) suggest that the

average unaltered Laramide-age granitoid in the region contains 10 ppm Cu. Using

this conservative estimate of the Cu content of the source pluton and assuming that all

the copper in the deposit was derived from the source magma, suggests that the Cu

present in the Maria deposit could reasonably be derived from -3.5 km 3 of magma. If

the initial Cu content of the source magma was higher than the 10 ppm average and/or

some Cu was scavenged from the wallrock in deeper portions of the system not reached

in drilling to date, then the amount of magma needed to supply the necessary Cu would

be decreased.

Constraints on volume and sOurce Qfhydrothermai fluid

The amount of copper in the deposit and an estimate of copper solubility can help

constrain the amount of hydrothermal fluid need to form the deposit. Assuming an

average copper solubility of 1000 ppm (Crerar and Barnes, 1976) the mass of

hydrothermal fluid needed to form the deposit can be estimated by the relationship,

1011 g Cu in deposit x 1000g solution/lg eu in solution = 10 14 g (l08 tons

solution)

The amount of quartz in the deposit can also help constrain the amount of

hydrothermal fluid needed. The ore reserve numbers and estimates of average quartz
 153

abundance based on observations made during mapping, indicate that the high-grade

deposit contains -6x10 5 tons of quartz. Fournier (1985) calculated silica solubilities of

-1800 ppm in pure water at the temperature and pressure indicated for the Maria

deposit. However, at a temperature of -5OO·C, a pressure of 500 bars and a salinity of

18 wt % NaCI silica solubility approximately triples (Fournier, 1985). If a similar

relationship holds for the slightly higher pressures indicated for the Maria

mineralization then Maria fluids may have been able to carry as much as 5400 ppm

silica in solution. A similar mass balance calculation to that performed for the

contained Cu shows that the -6x10 5 metric tons of quartz in the Maria deposit could

also have been carried by -108 metric tons of fluid. This amount of solution could be

readily derived by second boiling from 1-3.5 km3 of source magma containing 2-4 wt

% H20.
The above calculations suggest that a magmatic source for metals and hydrothermal

fluids is reasonable, however,. they do not preclude significant participation of meteoric

water. The following calculation based on equations and models detailed by Cathles

(1980), and estimates of the volume of alteration surrounding the deposit, sheds light

on this question. This calculation suggests that the thermal energy of 0.15 km 3 of

magma would be sufficient to circulate the necessary 108 tons of solution

A similar calculation for the Maria deposit suggests that a 1-3.5 km 3 pluton,

intruded into host rock containing appreciable meteoric water would be expected to

circulate considerably more than 108 metric tons of fluid causing a similarly greater

volume of alteration. The volume of sericitically altered rock associated with the high-

grade ore body including immediately adjacent wallrock and overlying and underlying

veins is estimated to be -2 x 10-3 km3. The volume of alteration associated with the

stockwork! disseminated body is -6 x 10-3 km 3 The relatively limited volume of

 154

alteration around both the high-grade and the stockwork deposits suggests that a large

hydrothermal circulation cell did not develop. The lack of areally extensive sericitic

alteration may indicate emplacement into relatively dry and/or impermeable wall rocks

and limited involvement of meteoric water in mineralization. This in turn limits the

amount of metal which could be scavenged from the wall rocks by hydrothermal fluids

and supports the hypothesis that the causative intrusion was the source of most of the

contained metal in the deposit.

The fact that the high-grade mineralization is concentrated into a relatively small

volume rather than distributed through a large volume of hydrothermally fractured rock

suggests that extreme over-pressuring of hydrothermal fluid did not occur. A possible

reason for this is that, as the mineralization was emplaced hydrothermal fluid was

efficiently removed before over pressuring occurred. The question of whether the QSP

veins overlying the deposit were sufficient to remove the required volume of

hydrothermal fluid quickly enough can also be tested by mass balance calculations.

The lifetime of a hydrothermal system formed by magmatic fluids is related to the time

it takes the pluton to cool below its H20 saturated solidus. Calculations using the

equations for conductive cooling of Jaeger, (1961) suggest that an equidimensional 3.5

km3 intrusion would cool to temperatures below its H20 saturated solidus in <1()4

years and therefore would exsolve its contained H20 over that approximate time

interval. Calculations using estimates of the abundance veins above the high-grade
body (average -5/m), an estimate of the average width of fractures (-1 mm), and

equations for fluid flow through a crack (Turcotte and Schubert, 1982), suggest that all

the fluid necessary to form the deposit could be removed in a small fraction of that

time.
 155

Discussion ("Comparative Anatomy ofPegmatitic Ore Systems")

Mineralization in porphyry-related systems encompasses a wide range of deposit

styles, including; disseminated/stockwork Cu-Mo deposits, Cu-Mo breccia pipes,

Cordilleran lode veins, Climax-type Mo deposits, and silicate-sulfide pegmatite bodies

similar to the Maria and La Colorada deposits. This section will compare the

characteristics of the Maria deposit with those of other silicate-sulfide pegmatites and

then with those of other porphyry-related deposits in order to gain insight into the

origin of silicate-sulfide pegmatites.

Comparison with other silicate-sulfide pegmatites

The Maria deposit represents an unusual, though not unique, style of porphyry-

related pegmatitic mineralization which has direct analogs in porphyry Cu-related

systems throughout the North and South American Cordillera (Table 3.4). Similar

mineralization has been described at the La Colorada deposit and other smaller

occurrences at Cananea (Perry, 1933, 1961), at Ajo-New Cornelia, Arizona (Gilluly,

1946), in the Childs-Aid winkle and Copper Prince deposits in the Copper Creek

district, Arizona (Kuhn, 1941), the OK mine in the San Francisco district, Utah (Butler.

1913), the Shakan deposit, Alaska (Buddington, 1930), Chuquicamata, Chile (Sales,

1954), Cumobabi, Sonora (Scherkenbach et aI., 1985), and a few small occurrences in

southern Arizona mentioned by Lutton (1959). All the occurrences are spatially

associated with at least some disseminated and/or breccia pipe hosted porphyry

mineralization and closely associated with a porphyritic stock. The mineralization

described at the other silicate-sulfide pegmatites appears mineralogically and texturally

similar to that seen at Maria, that is, it is characterized by sulfide bearing quartz-biotite

± K feldspar pegmatite ± closely associated massive Cu-Fe sulfide mineralization.

Table 3.4: ComEarison of silicate-sulfide pegmatite deEosits.
Deposit Size and grade are mineralogy Alteration Intrusion! relationship P, depth, T Morphology References
evolution & zonin~ to ~!Eh~~ Cu min.
Maria, Cananea 1.6 x lOb metric tons 6% Cu, cp, py, mo, scheelite Early ± proximal Isolated Qtz·feldspar 700·300 brecciated sub horizontal This study
District, Sonora, Mex. 0.36% Mo, 31 gimetric ton Incr late mo with qtz.bt·ksp porphyryl near but bars, -2.75 massive sulfide lens with
Ag traceW. depth, Incr. cp:py Later± distal qtz· lateral to large Jan,>500to moderately dipping
with deEth tnl·ser·E~ chI stockwork deposit 250·C pegmatite extension at depth
La Colorada, Cananca 6xlOb metric tons 7% Cu, cp·bn-chalc, mo-cp- Early proximal qtz· Qtz·feldspar porphyryl <I Jan? Brecciated massive sulfide Kelly, 1935;
District, Sonora, Mex. 0.8% Mo. py bt·l;sp int distal high grade zonewithin body overlying qtz·bt·ksp Perry 1933,
late luz·tenn·cov.sph· qtz·ser·py large stockwork peg. cross cut by late breccia 1961
sal Late 9tz.al·E~ deposit with alunite
Cumobabi district, 1.2 X lO(}melric tons 1.7% cp, py, mo, scheelite Early ± proximal Isolated qtz·monz. 220-80 bars, sub vertical pipe deep qtz·ht· Scherkenbach
Sonora, Mex. Cu, 0.058% Mo, 0.14% W, Incr mo with depth, qtz·bt·ksp, distal porphyry stock One in -0.9 Jan, ksp peg with interstitial et aI, 1985
15..8gff Ag Deer. py ,,;th depth propyl. cluster of >35 pipes >50010 suI fides sha 1I0wer breccia
Later± distal qtz- 250·C cemented by qtz·\m·sulfides
\m·ser·E~
Ajo-New Cornelia, -204 xJ06 tons 3.66% Cu cp, py,bn Early proximal qtz· Multiphase qtz monz. moderately dipping GilluIy, 1946
Arizona ksp-bt stock? high grade zone pegmatite with interstitial
within 15xJ06 tons Io49C Cu minor la te mo
within large stockwork sulfides
Later qtz·ser·py
chI deposit
Chuquicamata, Chile small cp, py, bn, mo Early qtz·ksp Qtz·monz porphyry ? small dike· like bodies Sales, 1954
<Pegmatite Later qtz·ser·py small high grade zones
occurrence only) within large stockwork
deEosit
Shakan, Alaska I x 104 tons?% Cu. 1.58% py, cpo po, mo, minor Early qtz·ksp±bt isolated stock within lens? Buddington,
Mo sph, gal Later qtz·ser? chI. diorite wall rock? 1930
early py to cp to py. minor stockwork?
sEh·~al·£2:m~
Copper Creek, Production 5.8x I O(} lbs Cu, cp, py, bn, chalc, mo, Early qtz.ksp±bt Isolated? stock sub vertical pipe pegmatitic KuIut,1941
Arizona enarg·tenn(Ir.) one of cluster of I ()(). body wi interstitial sulfides
7x I 06 lbs Mo, 27x J06 oz Later qtz·ser? chI
Incr. mo with depth, 125 bx pipes at depth. Massive sulfide
AS Jncr. cp:py with lens. Shallow breccia?
depth, Incr chalc, bn
with deEth
OK mine,San -I x JO(} Ibs Cu PY,cp,mo Isolated? Qtz·monz subvertical pipe pegmatitic Butler, 1913
Fransisco District, porphyry. Some quartz with interstitial
Utah stockwork. sulfide, massive sulfide
lenese?

-4

~
 157

The deposits are zoned from early proximal biotite and K feldspar, to generally later

more distal quartz-sericite-pyrite alteration. The major sulfide minerals reported are

chalcopyrite ± bornite, pyrite, and molybdenite. In most of the deposits including

Maria, molybdenite is relatively late and is reported as growing on chalcopyrite. It is

commonly associated with sericitic alteration which may reflect its remobilization in

acid solutions. Sphalerite and galena are generally present in minor q~antities and are

late and peripheral. La Colorada differs from the other known systems in size and in

development of a more complete alteration system which includes bornite, covellite,

and digenite as well as advanced argillic alteration including extensive, late, hypogene

alunite and sulfosalts. Massive sulfide bodies were reported in the Copper Creek

occurrences, La Colorada, Shakan, the OK mine, and some of the small southern
Arizona occurrences. At Cumobabi, the Chuquicamata occurrence, and at Ajo, Cu-Fe

sulfide minerals occurred as open space filling material in the pegmatite and no large

massive sulfide bodies were reported.

Silicate-sulfide deposits are a distinct style of porphyry-related mineralization but

there are enough similarities that comparison with more extensively studied porphyry-

related deposits, is logical place to begin thinking about a general genetic model. The

described mineralogy and zoning of silicate-sulfide pegmatite mineralization is similar

to that seen in disseminated and breccia pipe hosted porphyry copper deposits (Table

3.5). Quantitative pressure estimates for silicate sulfide pegmatites are limited to the

Maria deposit where depth of emplacement is estimated at -3 km based on boiling in

fluid inclusions and stratigraphic reconstruction. Stratigraphic reconstruction suggests

that the La Colorada deposit formed at -1 km depth. This is within the 1 to 4 km range

of depths of emplacement calculated for many disseminated and breccia pipe hosted

deposits. Fluid compositions vary considerably, however, all three types of deposit
Table 3.5 Comparison of silicate-sulfide pegmatites with other porphyry-related deposits
Deposil Size and grade Ore mineralogy Alteration mineralogy P.depth. T Fluid Composition Area References
Plulon/Alteralion
Silicale-Sulfidc Small 10 7 xl06 10ns 110 cpo py. bn. mo ± Early proximal K qtz- (Dala for Maria) 20-50 WI % NaCI equiv. (Dala for Maria) This study; Perry.
Pegmalile. (eg. 7% Cu. 0.05 10 2% Mo. sch. chalc. gal. sph. ksp-bl ± dislal 800-300 bars. and 5-10 wI % NaCI 3 xlO· 2 km2 / 1961; Kelly. 1935;
Maria. La leon .• letr. propylilic 10 QSP qtz-ser 2.5-3km. equiv. halile. sylvile. hcm. Kuhn. 1954;
Colorada)
locally 10 35%Cu
occ 10 Adv Arg qlZ- 10- 1 km2 Buddinglon. 1930
>500 10 250'C cp daughler xlalls
alunile
Porphyry Cu 107 t;IO"IO~--- cpo py.b.... lno ± Early proximal K qtz- 350-80 bars. Early 26-50 wI % NaCI 10-2 _10- 1 km 2/ Bushnell. 1988
-relaled Bx pipe 0.5.2% Cu 100.025%Mo sch. chalc. gal. sph. ksp-bl. '!' dislal 1·1.5 km. equiv. I km2
(eg. Cananea- lenn .• letr. propylillc 10 QSP qtz·ser 300->500'C Lale 5- 10 WI % NaCI 10
Duluth. Mex. ) occ 10 Adv Arg qlZ- equiv. halile. sylvile.
alunile hem. cp daughler xtalls
Slockwork/Dissemi i
1051~ns 10 0 9 (ons cpo py. bn. mo Early proximal K qtz- <I kb. Early 26-50 wI % NaCI generally multiple Gustafson and
naled Porphyry Cu 0.3510 I%Cu. 0.015% Mo ksp-bl ± dislal 1-2 km, equiv. intr. 1-3 km2 Hunl.1975
(eg. EI Salvador) propylilic 10 QSP qtz-ser mosI350-400'C Lale 5-10 WI % NaCI individual intr./
occ ~o Adv Arg qlZ- max 6OO'C equiv. halile, sylvile.
alunlle hem, ;:p daughler xtalls 15km2
Porphyry Cu skarn 106 10 108 Ions cp, bn, py Early proximal garnel, 0.2-1 kb, Early 26-50 wI % NaCI 1-3 km 2 individual Einaudi, 1982
1-2% Cu ±Pb. Zn ml, tun inl px. dislal woo <1-3.75 km, equiv. intr/
laler acl-chl >500 10 250'C Lale 5-10 WI % NaCI? 3-10 km2
Qtz-Monz-Iype Mo 50 xl06 10 1O"lons 0.1- mo. minorcp Early prox. albitic 10 inl. >1 kb, Early mod 10 low sal. _I km 2/ Shaver. 1988;1990
(eg. Hall. Nevada) 0.2%Mo K 10 greisen. LaIC chl+ 2.2-5 km. Laler high salinily 4-6 km 2
0.£»-0.1 %Cu basemetal 750-330'C
Climax-Iype Mo 50 X lOt> 10 10'J Ions 0.3 10 mo Early K + distal 350-800 bars. Early 30-65 wI % NaCI 0.1 10 1 km2/ Carten el aI., 1988
(eg.Climax, 0.51% Mo propylilic, QSP inlense 0.5-3.1 km, equiv. 4-6km 2
Colorado) silie laIc argillic. Main stage 650- Laler 0-5",1 % NaCI
500'C equiv.
SnoW 0.3 W03 wolf, cass; minor qlZ-lm-musc 10 oxides <0.5 leb. 5-10 wt % NaCI equiv. Multiple intr. Kelly and Rye.
(eg. Panasquiera, aspy, cp, sph, gal and silicales 10 base 1-2km. Individual intr. -10 1979
Portugal) melal sulfides. po. 360-230'C km2/
carbonale veins
»IOkm 2

Cordilleran Vein IO Slons 6% Cu 10 5 x I 08 enarg. bn. py, cp, Central Adv argillic distal to small stock Einaudi. 1977;
(eg. Cerro de Ions 2% Cu. minor Mo 50- sph Inlermediale Sericitic 1982
Pasco, Peru) 150gIT Ag minor Bi, Sn and W Distallnlermediale Arg 500-250'C
variable PbZn and others mins. and Prop.
Rare elemenl U, Th, Ti, Zr, Nb, Typically» I high salinily widely variable intr Cerny, 1984
Pegmalile REE leb, size
(Black Hills. Soulh magmalic limiled wallrock
Dakota) temperatures all.

...I.

~
 159

have early high salinity fluids, which both fluid inclusion and stable isotope data

suggest represents either a magmatic fluid or at least a fluid in equilibrium with a

magma. The significant role of meteoric water in remobilization of metals and

formation of large areas of acid alteration is well documented in many disseminated/

stockwork Cu-Mo deposits (Gustafson and Hunt, 1975, Taylor, 1974, Brimhall, 1979,

Norton 1982). However, the fluid inclusion and stable isotope data at Maria suggest

that the role of meteoric water may be much more limited in the silicate-sulfide

pegmatite mineralization.

Relationships between grade, size, and extent of alteration are shown in (Fig. 3.13)

and detailed in Table 3.5. Average grades in silicate-sulfide pegmatites are -10 times

the average hypogene grades in disseminated deposits and typically 5 times the grade

seen in conventional breccia pipes. The pegmatites are also typically much smaller,

generally 105 to 106 tons, and contain less total metal than the average disseminated

deposit. La Colorada, by far the biggest deposit found to date, contained -6mT of 7%

Cu, 0.8%Mo. Nevertheless the total metal content of even the huge La Colorada

deposit is only equivalent to a small to moderate disseminated deposit. Mineralization

in stockwork and breccia pipe deposits may be distributed over vertical distances of

over 1 km, and lateral distances of several kilometers, whereas silicate sulfide

pegmatites are typically telescoped into less than a few hundred meters. Mineralization

in silicate sulfide pegmatites is concentrated into a small volume and wall rock

alteration is similarly concentrated into a lesser volume. Wall rock is commonly

sericitized and silicified, however, intense alteration is generally limited to within

<20m of the ore zone. Even at the large Ajo and La Colorada deposits, alteration

related to the pegmatitic mineralization is limited to within 60 meters of the contact

(Gilluly, 1946; Perry, 1961).

 160

Volume of Alteration

Physical
e Silicate-Sulfide Pegmatites

_ Breccia pipes
c
o
E
en
o
Cl.
Disseminated Deposits CIt Q)
"0
~
o

Chemical
~------------------------------------------------------------~

Tonnage
Figure 3.13: Graph showing the relative volume of alteration, grade, and
tonnage among silicate-sulfide pegmatites, breccia pipes, and stockwork
deposits.

PilV Energy ergs/kg magma

0 2 3 4 5 6 7 8 9 10
0

250

~ 500 2
ctI 1 wt% H20
OJ 750 3 E
ai
.... "'-5"
::J 1000
U)
U)
2.7wt%H20 4 8'
....
Q) 1250
5
c...
1500 c
''""
::;;
6
1750
7
2000

Figure 3.14: Plot of energy per kilogram of magma vs. depth of crystallization
for complete crystallization of magmas containing 1 and 2.7 wt% H20.
Calculated from equations in Burnham, 1985.
 161

Other porphyry-related deposits differ from silicate sulfide pegmatites in

mineralogy, zoning, and fluid composition, however, comparison is still instructive.

Cordilleran lode vein deposits have similar grades and coarse, open-space filling ore

textures but differ from silicate-sulfide pegmatites in ore mineralogy, dominant style of

alteration, and geometry. The Cordilleran lode vein deposits range in size from 10

million tons of 6% Cu to 500 million tons of 2% Cu with no large tonnage of ~0.5%

Cu material (Einaudi, 1982). Enargite and bornite occurring in massive open space

filling veins are the major ore minerals. Sphalerite and galena are commonly present.

Mineralization is typically associated with advanced argillic alteration. Lode deposits

like silicate-sulfide pegmatites, represent concentration of hydrothermal fluids into a

relatively small volume, commonly along pre-existing structures. However the vein

deposits are typically distal to any source intrusion and generally lack the close

association with pegmatitic quartz, K feldspar, and biotite, observed at Maria. There

may however, be some deposits which are transitional between the two types including

some of the occurrences at Chuquicamata and the deep quartz-Mo zones reported at

Butte (Sales, 1954, Sales and Meyer, 1956). More examples of transitional deposits

may exist, although additional investigation would be necessary to confirm this

relationship.

Silicate-sulfide pegmatites differ significantly from Climax-type Mo deposits

which are much larger, contain molybdenite with very little chalcopyrite, and are

associated with quite different intrusion compositions. But, episodic and/or cyclic fluid

release events have been well documented in Climax-type and quartz-monzonite-type

Mo deposits (Shaver, 1988, 1991; Carten et aI., 1988) and the evidence for cyclic or
 162

episodic pulses of mineralizing fluids in the Maria deposit implies possible similarity to

mechanisms suggested for the formation of the Mo systems.

Thoughts on the origin of Silicate-Sulfide Pegmatites

The details of the origin of silicate sulfide pegmatite mineralization remain a

subject for future investigation but the results of this study allow presentation of a

preliminary model for the formation of this type of mineralization. The data and

arguments presented above suggest that the Maria high-grade deposit formed from

fluids of predominantly magmatic origin at temperatures and pressures similar to those

reported in both breccia hosted and stockwork mineralization in many porphyry Cu

deposits. The Maria high-grade deposit and the nearby stockwork mineralization both

contain -10 5 tons of Cu, but the amount of hydrothermal fracturing and the distribution

of metals and alteration differs profoundly between stockwork and pegmatitic

mineralization styles. The stockwork mineralization is distributed through -3 x 107 m3

of rock, and in the case of the high-grade deposit the hydrothermal fluids were

concentrated into -5 x 105 m 3 ofrock. Determining the factors which control this

difference in mineralization style is an important part of any genetic model for the

formation of silicate sulfide mineralization.

The amount of hydrothermal fracturing and therefore the style of mineralization

depends on rate and mechanism of mechanical energy release from the source

intrusion. Therefore an energetic model based on ideas developed by Burnham (1979,

1985) is one approach to developing a physical model for the formation of the Maria

deposit. The total amount of energy available in a magma depends on among other

things, the water content, the efficiency of collection of the water, the total mass of the

magma, and the manner in which the hydrothermal fluid is released.

 163

Water solubility in melts is strongly controlled by pressure. The initial water

content of a magma and the depth of emplacement determine at what stage of

crystallization a given magma will saturate with respect to water. In general the higher

the initial water content of a magma the greater the pressure and so depth at which it

will saturate. Higher initial water content generally means greater P.1V energy released

when the magma becomes saturated with respect to water as a result of decreased

pressure and/or crystallization of anhydrous phases. Maximum energy is released by

melts with initial water contents near to their water saturated liquidi (Burnham, 1979,

1985). Therefore at a given depth a melt emplaced near its water saturated liquidus

will generate the maximum amount of energy during complete cooling. A melt which

is significantly undersaturated with respect to water at the same depth of emplacement

will undergo a greater degree of crystallization before saturation and generate

significantly less energy. The amount of energy which would be generated by

complete crystallization of melts of varying water composition was calculated using

equations 1-3 in Burnham (1985) and the results are plotted in Fig. 3.14.

The amount of energy generated by a near saturation melt emplaced at the

approximate depth suggested for the Maria deposit, -3 km, is more than adequate to

exceed the mean tensile strength of the average homogenous wall rock, and cause the

stockwork fracturing typical of porphyry deposits (Mean Tensile Strength of rock

adopted from Burnham, 1985). Continued crystallization, with additional pulses of

water rich magma from a parent magma chamber, and subsequent saturation events

would cause repeated high energy fracturing events causing additional stockwork

veining or leading to the fonnation of intra-mineral breccia pipes as proposed by

Burnham (1985). Without substantial addition of new water saturated magma the melt

would now contain less water and be significantly undersaturated with respect to water.
 164

This means that later saturation events would take place from a melt with a lower

absolute water content and would liberate less energy to cause fracturing. The energy

released as a result of saturation at higher degrees of crystallization is significantly less

and may not be sufficient to extensively fracture wall rock. However, considerably less

energy, on the order of a few bars would be required to exploit pre-existing zones of

weakness with the wall rock. At the Maria deposit the pre-existing zones of weakness

may have been fracturing which developed during cooling of the Cuitaca granodiorite

or zones of weakness along earlier QFP dikes or sills.

Pi\ V yields energy per unit mass, therefore another important factor affecting the

energy budget of an intrusion is its total mass. The Maria deposit appears to be related

to a relatively small intrusive system and a smaller system would have a lower energy

content than a large one. How the energy released by this volume change is dispersed

is one factor which determines the style of mineralization which develops. Whether

the aqueous phase is concentrated efficiently and released rapidly, ex solves more

gradually, or perhaps expands into a zone of pre-existing weakness, plays a significant

role in determining the resulting style of mineralization. At one end of the spectrum

are stockwork and breccia pipe hosted Cu-Mo deposits, which represent rapid fluid

release. Climax-type Mo systems may represent a transitional set of conditions which

allow gradual or episodic fluid release. Silicate-sulfide pegmatite bodies similar to the

Maria and La Colorada deposits, ± some Cordilleran lode systems may represent

gradual or episodic fluid release into a zone of structural weakness. At the other end of

the spectrum are 'barren' intrusives in which a separate aqueous phase was not

concentrated and metals are disseminated throughout the intrusive in sub economic

concentrations--mostly in mafic minerals.

 165

The model favored for the Maria deposit proposes an early pulse of magma at or

near H20 saturation which caused the stockwork style mineralization, subsequent

saturation events at lower absolute water contents and higher degrees of crystallization

released lower levels of P8.V energy. This energy was insufficient to cause stockwork

fracturing but the accumulated fluid had enough energy to exploit pre-existing zones of

weakness. The Hall Mo deposit in Nevada provides an instructive analog to this

process. Decreasing vein density with time at the Hall (Nevada Mo) deposit has been

attributed to progressively weaker and deeper fluid release events resulting from

inward crystallization of the causative intrusion (Shaver, 1988, 1991). A tilted section

at Hall exposes the deeper portions of the system, allowing documentation of

progressive fluid release events with increasing crystallization. The lack of exposure of

the intrusive rocks believed responsible for the high-grade mineralization at Maria,

precludes convincing documentation of the above mechanism, however the cyclic

nature of mineralization and brecciation within the high-grade body suggest that

episodic fluid release events possibly resulting from the above mechanism, were

important in the formation of the Maria deposit.

Insufficient information is available on most of the other silicate-sulfide deposits in

order to evaluate whether the model developed for Maria is generally applicable An

important question in the study of this type of deposit is how the volume now occupied

by massive mineralization was created. This problem was especially perplexing in the

case of the huge La Colorada deposit. After exhaustive mapping and observation

Perry, (1933, 1961) suggested that the massive mineralization formed in the cupola of

the underlying intrusion, and that the necessary space was created by magma

withdrawal as the magma chamber was tapped to form dikes elsewhere. The Maria

deposit lies lateral to the known intrusion and the geometry of the deposit does not
 166

require creation of a large open space, so magma withdrawal does not appear to be a

necessary mechanism in this particular case. However, it may well be the best

explanation at La Colorada.

The limited amount of wall rock alteration around Maria and the other silicate-

sulfide pegmatites suggests that chemical control on precipitation of mineralization was

relatively minor and that physical controls such as changes in temperature and pressure

were the dominant controls on ore precipitation. In disseminated/ stockwork systems

ore bearing veinlets are evenly distributed through large volumes of rock. The large

volume of wall rock alteration and the relatively small scale of individual mineralized

veins in disseminated! stockwork bodies reflect the influence of both chemical control,

i.e., wall rock reaction and physical controls i.e. changes in temperature and pressure.

Silicate-sulfide pegmatites may be a good example of systems in which physical

controls predominate.

Synthesis

The major findings of this study are as follows:

1) The Maria deposit is a silicate sulfide pegmatite. At depth, the deposit consists

of early pegmatitic quartz-K feldspar-biotite veins which interfinger with massive

chalcopyrite-biotite. This early assemblage is crosscut by a quartz-tourmaline-pyrite-

sericite assemblage. Mineralization is zoned from outer quartz-sericite-pyrite to pyrite

>chalcopyrite, to chalcopyrite>pyrite, to molybdenite>chalcopyrite in a potassic core.

The Maria deposit has direct analogs in porphyry Cu-related systems throughout the

North and South American Cordillera.

 167

2) Mineralization was episodic. This point is supported by the occurrence of

quartz-K feldspar-biotite veins which cut slightly earlier massive sulfide breccia and by

evidence for multiple episodes of brecciation within the massive sulfide breccia.

3) The degree of brecciation and disruption increases upwards in the deposit. There

is a gradation over <10m from massive, unbrecciated veins at depth to extensively

brecciated and dismpted material at shallower levels. This brecciation of the overlying

mineralization may be due to fluid released during the crystallization of deeper, later

pegmatitic veins.

4) Coexisting liquid and vapor dominated inclusions throughout the paragenesis

suggest that boiling was widespread and indicate early pressures of -800 bars and later

pressure of -300 bars, corresponding to early litho static and later hydrostatic

conditions respectively. These pressures indicate mineralization at a depth of -3 km.

Pressure corrected homogenization temperatures and limited S isotope geothermometry

indicate that mineralization occurred over a temperature range of 600°C to 250°C.

5) Salinities of 20-55 wt % NaCI equivalent, calculated ol80fluid= 8 ± 1 %0 and

oDfluid=-50 ± 10%0 as well as mass balance considerations, suggest a dominantly

magmatic source for hydrothermal fluid, metals, and sulfur.

6) The composition of the fluid changed with time. Early fluids deposited quartz,

biotite and chalcopyrite and later fluids brecciated and hydrolitically altered the early

assemblages and deposited quartz, tourmaline, and pyrite. The evidence for boiling

and the limited volume of alteration suggest that physical factors such as cooling and

decompression controlled precipitation of sulfides.

7)Although mineralization is telescoped into 75 vertical meters, the mineral

assemblages, zoning, general paragenesis, pressures, and temperatures observed in the

 168

Maria deposit are similar to those seen in stockwork- and breccia pipe- hosted porphyry

Cu systems.

8) The evidence for repeated pulses of mineralizing fluid in the deposit, comparison

with Climax-type and Quartz-monzonite Mo deposits, and calculations of magma

energy are consistent with formation of the high-grade deposit by successively lower

energy pulses of fluid released from a progressively cooling pluton.

 169

CHAPTER 4: MAJOR CONCLUSIONS

Numerous studies of porphyry copper systems have shown that at least some of the

fluid, metal, and sulfur are derived from the associated magma. Therefore knowledge

about the evolution of the igneous rocks provides an insight into the development of

the associated mineralization. This study represents a significant advance in the

understanding of the evolution of both the igneous system and porphyry copper

mineralization in the Cananea District. The major conclusions are strictly applicable to

the Cananea system but also shed light on general processes involved in the

development of igneous related mineralization. The work summarized in Chapter 2

shows that the porphyry-related mineralization at Cananea is the end result of typical

magmatic and hydrothennal processes operating during the evolution of an average

calc-alkaline magmatic systems. The study of the Maria deposit (Chapter 3) represents

one of very few detailed descriptions and genetic models for this unusual type of

mineralization

Mapping conducted during this study led to the insight that the Cananea district

represents a tilted and eroded section through a Laramide volcano-plutonic complex

and associated porphyry copper system. The record of this uplift and unroofing

sequence is preserved in alluvial fans on the west side of the Cananea range. Older fan

material has higher dips to the east than younger material, suggesting that fan

deposition was coeval with tectonism.

The stratigraphic section in the Cananea district consists of a Proterozoic to early

Mesozoic basement intruded and overlain by late Mesozoic to early Tertiary igneous

rocks which include a large granodioritic batholith and younger quartz monzonite

porphyry stocks. The younger rocks were emplaced during the Laramide orogeny from
 170

64 to -56 Ma. Porphyry-related mineralization is associated with the Laramide rocks.

Major and trace element geochemistry discussed in Chapter 2, shows that the Laramide

rocks are typical medium- to high- K calc-alkaline arc magmas. The igneous rocks

have compositions ranging from gabbro to quartz-monzonite and form coherent trends

on major element variation diagrams (Fig. 2.3). REE data show a prominent negative

Eu anomaly and a slight concave shape in the heavy REE's suggesting fractionation of

plagioclase and amphibole or pyroxene respectively (Fig. 2.7). ENd values range from

-3.8 for an early gabbroic phase to -5.7 for a late-stage quartz-feldspar porphyry. A

late mafic dike with ENd = +0.7 may represent an original mantle-derived parent melt

and heat source for the Laramide magmatic event. ENd show a smooth inverse

correlation with initial 87S rj86S r suggesting mixing of isotopic reservoirs (Fig. 2.10).

Taken together, the major, trace element, and isotopic data suggest that the Laramide

igneous rocks represent a cogenetic magmatic series which evolved by open system

assimilation of wall rock coupled with fractional crystallization of plagioclase and

ferromagnesian minerals.

Water, metal, chlorine, and sulfur are all critical ingredients in the formation of ore

deposits. Water content is critical because it controls whether or not the magma will

saturate and if so at what depth and degree of crystallization. It is possible to get an

idea of the water content from the sequence of crystallization of ferromagnesian

minerals. Petrographic observations of the crystallization sequence for the Cananea

rocks show that water content increased with increasing differentiation. One

consequence of increasing water content is progressively earlier saturation at a given

depth of emplacement.

This trend of progressively earlier saturation is supported by the sharp decrease in

CI content of hydrous minerals with increasing Si02 content of the rock (Fig. 2.9d).
 171

Experimental studies have shown that CI is strongly partitioned into the exsolving

aqueous fluid relative to the melt. The high chlorine content of hydrous minerals from

the less evolved rocks suggests that water saturation occurred late in the crystallization
history, and that much of the available CI was structurally bound up in hydrous mineral

before saturation. The low CI content of the more evolved rocks is consistent with

early exsolution of a CI rich aqueous phase and removal of much of the available

chlorine before amphibole crystallization.

Evidence for the early evolution of a Cl-rich aqueous phase is important because

Cu in hydrothermal fluids is transported as a Cl- complex. Therefore if an aqueous

phase develops, Cu is also strongly partitioned into it. Cu content increases with

differentiation to a maximum in the upper part of the granodiorite batholith and in

unaltered quartz-feldspar porphyry stocks (Fig. 2.3g). Later rocks, such as aplites and

rhyolitic porphyries have much lower Cu contents. These data suggest that as the

magma chamber differentiated fluid and elements like CI and Cu which are partitioned

into the fluid were concentrated in the upper parts of the magma chamber and in the

remaining melt. Further evidence for the collection of fluid in the upper parts of the

plutons and in the later rocks is seen in the distribution of fluid inclusions found in

igneous quartz. The abundance of high salinity inclusions increases at shallower levels

of the granodiorite batholith and reaches a maximum in the quartz-feldspar porphyries

(Fig. 2.ld). The upward emplacement of this enriched differentiate leads to the

formation of mineralization.

Alteration and mineralization developed in close association with the evolution of

the igneous rocks and changes in the type of alteration reflect changes in the magmatic

system. Early assemblages are broadly propylitic and low in metals and sulfur. They

are widely distributed but concentrated at shallower levels of the granodioritic batholith
 172

and in rocks which overlie the inferred subsurface extensions of the batholith (Fig.

2.1c). The distribution of propylitic alteration appears to reflect widespread diffuse

fluid flow. Later assemblages including early potassic and later sericitic alteration are

more metal and sulfur rich and are associated with high salinity fluid inclusions. Their
distribution is strongly correlated with the quartz feldspar porphyries and their limited

areal extent suggests highly focused fluid flow (Fig. 2.1c). The distribution of

alteration reflects a transition with time from diffuse fluid flow associated with

emplacement of the batholith, to highly focused fluid flow associated with the

emplacement of the porphyries.

Evidence presented in Chapter 2 and summarized here suggests a strong correlation

between magmatic processes and the evolution of hydrothermal alteration in the

Cananea District. The stable isotope data provide further evidence for a connection to

magmatic processes. The early high temperature potassic and early proximal sericitic

alteration which is associated with most eu mineralization has magmatic values (Fig.

2.11). Only the later distal sericitic and clay alteration shows a significant

displacement toward meteoric water values. In contrast with interpretations in many

other porphyry-copper districts, fluids associated with main stage proximal

mineralization in Cananea are dominantly magmatic with only limited involvement of

meteoric water.

The second half of this study presented in Chapter 3, focused on describing the

Maria silicate-sulfide pegmatite deposit and develops a preliminary genetic model for

this unusual style of mineralization. The mineralization at Maria consists of early

stockwork Cu-Mo mineralization and a later massive lens of variably brecciated

chalcopyrite-pyrite-(quartz ± molybdenite) and quartz-rich pegmatite. Within the

pegmatitic lens early quartz-K-feldspar-biotite-sulfide assemblage veins are cross cut

 173

by a later quartz-tourmaline-pyrite-sericite assemblage. Cross cutting relationships are

consistent with repeated pulses of mineralizing fluids. Fluid released during the

formation of later pegmatite appears to have been responsible for the hydrothermal

brecciation of overlying mineralization.

Microthermometric measurements on fluid inclusions and sulfur isotope

geothermometry suggest that mineralization formed from fluids with temperatures

between 600 and 200°C and salinities of 26-55 wt % NaCI. Fluid inclusion, H, 0, S

stable isotope data, and the limited volume of hydrothermal alteration surrounding the

Maria deposit suggest the deposit formed from a dominantly magmatic fluid (Tables

3.1, 3.2, and 3.3). Coexisting liquid and vapor dominated inclusions suggest early

pressure of -800 bars and later pressure of -300 bars, corresponding to early lithostati<:

and later hydrostatic conditions respectively. These pressures indicate mineralization

at a depth of -3 km.

Mineralization at Maria appears to have formed as a result of episodic fluid release

events, implying similar genetic mechanisms to those suggested for Climax- and

Quartz Monzonite- type Mo deposits. The evidence of repeated pulses of mineralizing

fluid in the deposit, comparison with Climax-type and quartz -monzonite Mo deposits,

and energy balance calculations, are consistent with formation of both the stockwork

and high grade deposits by successively lower energy pulses of fluid released from a

progressively cooling pluton.

Both the district scale study and my work at Maria have shown that magmatic

fluids are important in the formation of the ore deposits at Cananea. How those fluids

are released determines the style of mineralization that develops. Silicate-sulfide

pegmatites like the Maria and La Colorada deposits represent transitional conditions in

which magmatic fluids are concentrated in a small volume and undergo efficient
 174

cooling and decompression leading to formation of telescoped, silicate and high-grade,

sulfide mineralization. My work at the Maria deposit suggests that the fluids, alteration

assemblages and paragenetic relations in silicate sulfide pegmatites are similar to those

seen in stockwork- and breccia pipe- hosted porphyry eu systems, but the pegmatites

are lower tonnage, higher grade, and are associated with a lower volume of

hydrothermal alteration and reflect dominantly physical precipitation mechanism like

cooling and decompression. Stockwork deposits and breccia pipes reflect a

combination of physical mechanism and chemical mechanism such as wall rock

reaction.
 175

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