UDH Report Chapter

The Magma-Metal Series ClassificationFoundational to the UDH Model

The UDH model grew out of the Magma-Metal Series Chemical Classification of Igneous Rocks and Mineral Deposits. The development and testing of this classification began in the 1970’s. Since the early 1980’s development and testing of the classification has been done by MagmaChem Exploration, Inc. This classification provides the empirical basis and logical framework for the UDH model. The MagmaChem Classification was originally applied to mineral exploration, leading to the discovery of 21 metal deposits on 3 continents, and has been used as a predictive tool to help unravel the complex geology of regions such as the western United States.

This chapter is an historical overview and generalized description of the MagmaChem Classification, how it contributed to the mineral deposit discoveries and led to the development of the UDH model. The overview is written chronologically and divided into four decades (Figure 1). The history of the work leading up to the UDH model provides the empirical and conceptual basis required for truly understanding the model and for effectively applying it to petroleum exploration. It is important to note that it also illustrates the great diversity of data types and the integration of multiple geoscience disciplines that were required to develop the UDH model. For a more detailed description of the MagmaChem Classification and history of its development (see Appendices 1-4).

Figure 1: Historical timeline of the MagmaChem Classification and the UDH model

MagmaChem is not the first to attempt to empirically link mineral deposits to magmatism and geotectonic setting. However, MagmaChem’s work constitutes a more specific, logically organized empirical proof that builds on many earlier, more qualitative observations and classification. The earliest description relating magma and mineral deposits was made by Decartes in 1644. He considered that most mineral deposits were epigenetic in character and constituted addition of metallic elements into a chilled upper crust from a still hot interior sub-crust. Hutton’s classic work “Theory of the Earth” in 1788 was much more specific. In 1847, de Beaumont published a comprehensive treatise entitled “Note sur les emanations volcaniqes et metalliferes.” The next major statement supporting magmatism as a source for ore deposits came with the publication of “The Genesis of Ore Deposits” by Posepny in 1894. J.E. Spurr in 1903 took Posepny’s speculations a major step further in his paper entitled “A Consideration of Igneous Rocks and Their Segregation or Differentiation as Related to the Occurrence of Ores.”

This early work set the stage for Waldemar Lindgren--one of the most outstanding students of ore deposits of all time. At the end of his life Lindgren was conceptually far beyond his famous thermodynamically-based classification and was in the process of linking the compositional parameter of his thermodynamic classification to the chemistry of closely associated magma series to mineral deposits. If Lindgren had lived another decade or

if M.A. Peacock had published his alkalinity classification of igneous rocks titled “Classification of Igneous Rock Series” ten years earlier in 1921, the framework of a comprehensive, specific and predictive classification for mineral deposits and their associated magma series might have emerged much earlier and the MagmaChem Classification would have been unnecessary. Not only did Lindgren make fundamental linkages in 1933 between igneous rocks and mineral deposits, be conjoined them with what we now call subduction in plate tectonic parlance. The following words were written by Lindgren and published posthumously in 1933 thirty years before the plate tectonic revolution:

“It is held that the whole Cordilleran metallization is based on the gradual eastward movement of deep-seated magma beginning with the original impulse from the Pacific. That impulse is no doubt caused by the reaction between the North American continent and the deep sima layers of the Pacific, but this question had better be left to the geophysicists.”

After Lindgren died in, his successors especially L.C. Graton and R. H. Sales from 1933 to 1968 refined his earlier thermodynamic classification. Their work now shares the spotlight with structural classifications based on ore deposit form by Buddington, 1935; Bateman, 1942; Newhouse, 1942; Park and MacDiarmid, 1964. The advent of the plate tectonic paradigm in the late 1960’s turned the attention of ore deposit thinking away from the classical Lindgren approach toward the linkage between geotectonic setting and mineral deposit phenomena. Important contributors include: Guilbert, 1981; and Guilbert and Park, 1986, and finally linking geotectonics, magmatism and mineral deposits or some variation on this theme; I. Baragar, 1971; Hutchinson, 1973; Naldrett and Cabri, 1976; Jensen, 1976; Fox, 1979; Naldrett, 1981; Westra and Keith, 1981; Guilbert, 1981; Mitchell and Garson, 1981; Hutchinson, 1982; and Guilbert and Park, 1986.

In the 1970 several events set the stage for the development of the Magma-Metal Series classification. These included: the new paradigm of plate tectonics, the proliferation of multi-elements and whole rock geochemistry, a growing data base of isotopic age dates, and the fact that no one had followed up on Lindgren’s prophetic words concerning the relationship between magmas and mineral deposits and plate tectonics.

1970-1980 Pre-MagmaChem and Discovery of Magma-Metal Series

Project topics listed by year:38 publications, 6 unpublished works

1970 Geologic mapping, Arizona 1971 Geologic mapping, Arizona 1972 Mineralogical studies 1973 Recumbent folds 1975 Basement kinematic analysis, Arizona

Precambrian orogeny, NA Regional geotectonic analysis, southwestern US

1977 Radiometric age date compilation, ArizonaDevonian tectonism, ArizonaBasement structure and magmatism

1978 Metamorphic core complex discovery, western USCopper production in, ArizonaPorphyry Cu genesis, southwestern USPaleosubduction and magmatism, NAGeologic road logs, Arizona

1979 Subduction to transform tectonics, southwestern NAArizona overthrust oil playSubduction, magmatism, metallogeny, southwestern NAJurassic-Triassic sedimentation/paleotectonics, ArizonaGeologic quad maps, Arizona

The beginnings of the UDH model can be traced back to the 1970s’ when Stan Keith, who would later co-found MagmaChem, was mapping the geology of several Arizona porphyry copper deposits and recognized a relationship between Laramide-age igneous stratigraphy and the metal content of associated mineralization. In the field he observed, mineralogically, that older more potassic-rich igneous rocks were associated with Pb-Zn-Ag mineralization and that younger less potassic-rich rocks were associated with Cu-Mo mineralization. To chemically confirm this observation he collected samples of the igneous rocks for whole rock analysis and samples of the associated mineralization for multi-element analysis. He then plotted the data on a K2O-SiO2 variation diagram to graphically quantify the relationship. The plots confirmed his mapping and mineralogical observations (Figure 2).

Figure 2: K2O versus SiO2 variation diagram for plutonic data associated with various base metal metallogeny in southeastern Arizona

To test this igneous rock metallogenic correlation over a broader area, Keith obtained data for the entire western US and northern Mexico for Cretaceous through Cenozoic magmatic systems and associated mineralization. The result was that the correlation recognized in the field and in the chemistry of the Arizona igneous rocks and mineralization continued to hold up. The variation diagram K2O versus SiO2 for plutonic data associated with metallogeny in the western US and northern Mexico confirmed that plutons associated with Pb-Zn-Ag metallogeny consistently plot more potassic at a given silica content than plutons associated with porphyry Cu-Mo metallogeny. The differences in potassium content were of a serial character; that is, the igneous suite of rocks associated with Pb-Zn-Ag deposits had consistently higher potassium contents compared to igneous rocks associated with Cu-Mo deposits, and comprised a mafic through silicic differentiation sequence. This discovery of the serial nature of igneous suites and their associated metallogeny, referred to as “Magma-Metal Series” and first seen in Arizona, became the core concept of the MagmaChem Classification and the fundamental paradigmatic parameter around which it revolves. In a sense, mineral deposits are simply the products of “dirty magma”--the dregs left over at various stages during differentiation of a particular magma series. It follows that these left-over metals may be used to referee the chemical classification of a magma series based on the magma series’ own major and trace element content.

In the early 1970’s Monte Swan, who would later co-found MagmaChem with Stan Keith, met him at the University of Arizona and began following the conceptual development of the Magma-Metal Series idea and Keith’s field work. He was particularly interested in applying Stan’s work to his basement structural work for Kennecott’s Geologic Research Group, which was focused on the structural control of the emplacement of porphyry Cu deposits. He was attempting to relate magmatism and the mineralizing fluids to the kinematic history of basement structures. When he met Keith, he was just completing a five year field-based study of the basement structural of Arizona and New Mexico, the infamous Texas Zone (which in later work became a “Crack of the World”) and a kinematic analysis of a Precambrian shear zone. The results of this research was presented and published by Swan in the late 1970’s. Most importantly it expanded and stimulated Keith’s thinking regarding the basement structural control of magma emplacement and migration of mineralizing fluids and the value of kinematic analysis.

The field observation by Keith that led to the discovery and development of the Magma-Metal Series concept also led to a formal igneous rock and mineral deposit classification, and a layered Earth model. In combination

with Swan’s structural work and the work of many other colleagues, it led to the development of new exploration tools, the discovery of 21 mineral deposits on three continents totally $65 billion in metal value and finally the development of the UDH model. This connection, to a field observation by Keith, makes the point that the UDH model is ultimately about geology. But it’s also about collaboration with many individuals and companies to the point of MagmaChem becoming a virtual “clearing house” for industry geologic data and ideas. This philosophy of openness with both ideas and data was a key to the success of MagmaChem. Complete documentation of the people, companies and institutions that have contributed to the Magma-Series Classification and the UDH model can be found in various Appendices.

Beginning in 1978, more than 160 papers have been presented and published, 200 company reports written, and 11 theses sponsored on various subjects related to the MagmaChem Classification. The first Magma-Metal Series publication was written by Keith and published in Geology magazine by the Geological Society of America in 1978. It is entitled, “Paleosubduction Geometries Inferred from Cretaceous and Tertiary Magmatic Patterns in Southwestern North America.” Keith’s paper links subduction to continental geology using a preliminary version of Magma-Metal Series and isotopic age dates and demonstrated how the new paradigm of plate tectonics had the potential to integrate oceanic and continental data in a predictive way. In this paper Keith adapted M.A. Peacock’s (1931) fourfold chemical classification of igneous rocks based on the alkali-lime index, i.e. calcic, calc-alkalic, H-K calc-alkalic, alkali-calcic, and alkalic. This nomenclature was later officially adapted into the MagmaChem Classification. In the paper Keith used these alkalinity types to describe the composition of melts generated at various melting depths along the subducting oceanic slab.

1980-1990 The Earth’s Mantle and Founding of MagmaChem

1 Au deposit discovery:

Trout Creek (Valmy), Nevada 1988 179,000 ounces Au

62 publications and 90 unpublished worksMagmaChem project topics listed by year:

1980 Molybdenum mineral associations, ArizonaUranium and western US metamorphic core complexesStacked thrust faults west-central, Arizona

Intrusion/deformation, western US metamorphic core complexes 1981 Molybdenum classification and genesis

Greenstone gold exploration, central ArizonaPeraluminous magmatism and low-angle subduction,

southwestern USSedimentational-tectonic patterns of Sonora and ArizonaPlate tectonics and mineral deposits, northern Mexico

1982 Exhalative gold exploration modelPeraluminous igneous rock classification

1983 Mineral district compilation Basin and RangeSW-directed thrusting in metamorphic core complexes, ArizonaMagma-Metal Series Classification and geotectonic setting

1984 Sevier-Laramide paleo-tectonic petroleum maps, western USGold exploration models, Mojave regionEarly Jurassic stratigraphy/paleogeography southeastern,

Arizona1985 Magma-Metal Series and greenstone gold metallogeny

Western Washington mineral system assessmentK-Ar age date compilation ArizonaField trip guidebooks: low-angle tectonics of ArizonaStrato-tectonic analysis, southwestern USCordilleran decretion, western US Late Cenozoic igneous rocks, geotectonics, metallogeny of

ArizonaBorate deposits and Magma-Metal Series, western US

1986 Precambrian 1.4 b.y. orogenyOxidation fugacity control of base metals and gold, ArizonaStrato-tectonic analysis of the Idaho BatholithLaramide magmatism, tectonics, metallogeny, southwestern US

1987 Magma-Metal Series and Geotectonics (1000 page manuscript)Peraluminous Au deposits classificationPaleo-tectonic strato-tectonic petroleum analysis, Columbia

1988 MagmaChem Handbook of Geochemical Models (300 page manuscript)

Volcanogenic massive sulfides, ColoradoMagmaChem “call” decision treeMagma-Metal Series applied to Nevada gold

1989 Distribution of metals in modal mineralogyStrato-tectonic section thermal petroleum history, Colorado Strato-tectonic section, California, Arizona, New MexicoWestern US oxidation state mapGeochemical zoning of Nevada gold systems

Continued work in the 1980’s on the Magma-Metal Series concept, by Keith and Swan, MagmaChem employees and associates, focused on the Earth’s mantle resulting in the development of:

1. The Magma-Metal Series Classification 2. An 8-layered mantle model 3. The technique of strato-tectonic analysis4. Crustal oxidation state concept

This work was funded primarily by the mineral industry, although the petroleum industry and the USGS provided funds. Keith and Swan co-founded MagmaChem Exploration, Inc as the research and business vehicle for this work. The bulk of the work focused on data compilation that continued throughout the 1980’s and included global “hard” (empirical) igneous rock and mineral deposit data gathered from all published sources (primary and gray literature) and augmented by a large volume of unpublished data generated by MagmaChem’s clients. The data types included: geochemistry, mineralogy, isotopic age dates, stratigraphy, geologic field relationships and especially geologic maps. From this data Magma-Metal Series relationship were tested and refined. As a result thousands of mineral systems were geographically and geologically defined. This includes data from more than 12,000 mineral systems. (In 1986, the USGS consider adopting this approach to their mineral data base). Many compilation products were provided for the mineral and petroleum industries. The philosophy behind this massive undertaking was inductive in nature i.e. empirical data was assembled from scratch revealing natural patterns. Through these patterns, among many other discoveries and developments, crustal magma and metal sources were identified, plate tectonics was linked to continental geology and mineral deposits, the slab segmentation of subducting oceanic lithosphere was recognized, crustal oxidation state maps were created, and Expert System software was written. These are only a few of a long list of discoveries, exploration tools and products that are described in detail in the Appendices. Most importantly, of interest in this report, they were applied to mineral and petroleum and lowered exploration risk, often dramatically.

In the early 1980’s the notion of Magma-Metal Series was expanded beyond the calc-alkalic/alkali-calcic serial distinction through several projects and publications. By the 2000’s, 194 Magma-Metal Series had been defined and 442 rock systems, of which 91 are economically favorable and the definition of Magma-Metal Series was expanded to:

A co-genetic sequence of igneous rocks and metal deposits linked by a process of fractional differentiation along a petrochemically-distinct mafic to felsic path of liquid descent from and controlled

by the initial silicate, volatile, and metal composition of a more primitive parent magma.

The concept for the first publication in the 1980’s began when the Magma-Metal Series concept attracted the attention of Gerhard Westra of Exxon Minerals. Discussions led to the expansion of the alkalinity fields to include porphyry molybdenum metallogeney and associated igneous rocks and the discovery that the driving process behind lithophile enrichment in molybdenum related igneous rock series was differentiation. Included in this work was the creation of time-slice maps based on molybdenum metallogeny, igneous rock, and isotopic age date data which brought plate tectonics into the model. Out of this work in 1982 Westra and Keith published “Classification and Genesis of Stockwork Molybdenum Deposits” in Economic Geology. Because the paper supported the minority position at the time, which identified the mantle as the source of molybdenum rather than the crust, it caused a spirited discussion by Christiansen and Wilson in 1982 which Westra and Keith wrote an extended reply to in 1982 that significantly expanded their model.

Concurrently, with the porphyry molybdenum work, Stan Keith teamed up with Steve Reynolds and conducted a uranium favorability study of the potential of the newly discovered metamorphic core complexes of the southwestern US for the Arizona Bureau of Geology. The primary result of this work was a recast of the “I” (mantle-sourced) versus “S” (sediment-sourced; usually pelitic) granite distinction into “metaluminous” (mantle-sourced) versus “peraluminous” (crustal-sourced) granite distinction. This important distinction was presented in the 1983 GSA paper entitled, “A Geochemical Classification of Peraluminous Granitoids”. This advanced existing peraluminous work by Shand (1927) and Chappell and White (1974) and shed new light on the petrologic nature of flat subduction.

About the same time in 1982 Exxon funded the compilation of 15 time-slice maps of the Cretaceous to Recent magmatic and metallogenic history of the southwestern US. Massive sulfide data from Mike Fellows of Exxon and gold and base metal data from Hutchinson (1973) and Fox (1978) added more fields to the K2O versus SiO2 variation diagrams. This work also resulted in the creation of several variation diagrams that helped to better define additional Magma-Metal Series. This work was tested with geology and advanced the integration of geotectonics into the Magma-Metal Series concept.

In 1982 Kennecott Exploration funded a greenstone gold project which showed that Magma-Metal series and metallogeney are independent of time and geotectonic setting, which had both been used in published classifications. The project showed that the same Magma-Metal Series relationships we see today operated in Archean time. In a related gold study

in 1983, Michael Parr brought leading-edge data and knowledge of high-magnesium ultramafic magmatism to the concept. Data from Naldrett and Cabi (1976) and Nardrett (1981) was also added at this time. This ultramafic contribution to the Magma-Metal Series concept became the basis for MagmaChem’s understanding of serpentinization in the UDH model. More variation diagrams were developed.

Also in 1983, during a workshop for Mobile Minerals and work on the metallogeny of the Pacific Northwest for Billiton Exploration, Dick Mishimori based on work in the coastal batholiths provided insight into the water content of magmas that led to the eventual creation of an iron enrichment variation diagram that measures the amount of water in a magma series and a re-interpretation of the AFM ternary diagram. This turned out to be an incredibly valuable tool in determining and predicting geotectonic setting, mantle melting mechanisms, and economic potential of mineral systems and some petroleum system. This is also an important tool in the evaluation of geothermal potential.

By this time the screening of mineral systems for specific metal type and economic potential had begun and was routinely being applied to the evaluation of mineral systems. A Magma-Metal Series determination for a mineral system was referred to as a “Call”. The primary motivation in making a “Call” was to identify the system type according to the Magma-Metal Series, which would connect that particular system to a specific economic track record, thus lowering exploration risk.

Also in 1984 several companies (i.e. Exxon Minerals, Gulf Minerals, and Kennecott Copper) questioned the statistical treatment of altered igneous rocks. This led to the development of a series of alteration filter variation diagrams one of which defined the metaluminous/peraluminous distinction Reynolds and Keith had discussed in their 1983 paper . Additional alkalinity distinctions were made in 1984 based on data and discussions with Felix Mutschler. This resulted in the identification of Te-poor Au deposits associated with quartz-bearing alkaline rhyolite systems and Te-rich Au deposits associated with nepheline-bearing and/or nepheline normative syenite, monzonite, and phonolites.

By 1984 it was apparent to Stan Keith and Monte Swan that the Magma-Metal Series concept was paradigmatic and had significant potential as an exploration tool, so they co-founded MagmaChem Exploration, Inc as a research and business vehicle to facilitate its development. This greatly accelerated the data base compilation. At one time nearly the whole graduate geology department was working for MagmaChem in Phoenix compiling and plotting data. One of MagmaChem’ first projects was the creation of the “MegaChart”, which depicted a layered mantle (Appendix 5). This was a concept that had been apparent in the Magma-Metal Series

data for some time. The chart graphically presents independently-determined and geophysically-defined layers of the mantle next to independently-determined Magma-Metal Series layers of the mantle. The near perfect match of the two layer models together with a survey of mantle xenoliths data was a solid geologic proof of the layered nature of the mantle. Metallogeny was soon added to the MegaChart at the request of several mineral companies which expanded the size of the chart to 3 by 13 feet. The layered mantle, as a geologic layered reference frame of 8 physically immiscible and chemically distinct layers extending 1000 km into the Earth comprising the Athenospheric mantle. There are 4 way to melt the various layers: hydrous melting during subduction, adiabatic decompression melting during rifting, thermal melting during generation of a hotspot. And compressional melting during crustal thickening usually due to continental collision or flat subduction. By chemically identifying which melting occurred predictions and correlation with geotectonic settings can be made. So the layered mantle model soon became the basis for regional mineral and petroleum exploration applications that led to discoveries and for many geotectonic and plate tectonic insights. Figure 4 and Appendix 6 is the 2008 version of the MegaChart.

Figure 4: Magma-Metal Series petrochemical model for a layered earth

During the development of the MegaChart, Stan Keith began applying his philosophy background to the Magma-Metal Series concept and data base, not only in his graphical organization of the Magma-Metal Series data but in roughing out the logical framework for what would become the Magma-Metal Series Geochemical Classification of Igneous Rocks and Mineral Deposits. This classification continued to be refined over the next 15 years. Presented below is a table summarizing the detailed quantitative conventions and definitions employed at each logical level. A narrative describing the Classification can be found on pages 1-16 of Appendix 2 Text. Taxonomic clarity is also aided by the employment of a series of chemical variation diagrams referred to in the narrative. (Appendix 2 Supporting Figures).

LOGICAL ORDER

CLASSIFICATION LEVEL TYPE OF CRITERIAKey References

NOMENCLATURE FOR CRITERIA DETERMINATION OF CRITERIA

Distinctions based on chemistry of magmatism associated spatially and temporally with the mineral system

1st Megaseries aluminum content

Shand (1927)Chappell and White (1974)Reynolds and Keith (1982)Keith and others (1991)Mitchell and Bergman (1991) Sorenson (1970)

peraluminous/metaluminous broadly equivalent to ("S" vs "I" granitoid distinction) peralkaline/metaluminous (subaluminous)

peralkaline/subaluminous (for subalkaline and quartz alkaline metaluminous)

agpaitic/miaskitic (for nepheline alkaline and leucite alkaline)

agpaitic/perpotassic (for leucite alkaline superseries)

A/CNK vs. SiO2 variation diagram1 presence of muscovite and garnet, and monazite (peraluminous) versus olivine, pyoxene, amphibole, or sphene (metaluminous)

A/NK vs. SiO2 variation digram2 presence of one feldspar (anorthoclase), presence of Na pyroxene or Na amphibole mol. (K2O + Na2O vs. Al2O3); mol. (Na2O vs. K2O)2

A/K vs. SiO2 variation diagram3 presence of leuci te

2nd Superseries (2A) potassium-calcium-sodium-magnesium-silica and Nb-Zr-Ba-Rb-Sr contents.

Silica saturation

peraluminous subalkaline, alkaline

metaluminous subalkaline, quartz alkaline, nepheline alkaline, leucite alkaline

For Peraluminous CaO vs. SiO2, Na2O/K2O vs. SiO2, Rb vs. Sr, Ba vs. Sr, and CaO vs. Sr plots.

For Metaluminous K20 vs. SiO2, K2O vs. SiO2, K2O + Na2O vs. SiO2, K20+ MgO vs. Si02, CaO vs. SiO2, LREE vs. Silica Nb vs. Zr, Rb vs. Sr plots. Rb-Sr and Sm-Nd isotopes.

Series (2B) potassium-calcium-sodium-magnesium-silica LREE and Nb-Zr-Ba-Rb-Sr

Peacock (1931)Kuno (1966)Dickinson and Hatherton (1967)Keith (1978, 1982)Dawson (1980)Arndt and Nisbet (1981)Keith and others (1991)Mitchell and Bergman (1991)Sorenson (1970)

peraluminous subalkaline superseries; calcic, calc-alkalic series

peraluminous alkaline superseries; alkali-calcic, alkalic series

metaluminous subalkaline superseries; magnesian, calcic, calc-alkalic series

metaluminous quartz alkaline super-series; alkali-calcic, quartz or hypersthene normative alkalic

metaluminous nepheline alkaline super-series; nepheline alkalic, melilite alkalic series

metaluminious leucite alkaline super-series; phlogopite alkalic, leucite alkalic series

For Peraluminous CaO vs. SiO2, Na2O/K2O vs. SiO2, Rb vs. Sr, Ba vs. Sr, and CaO vs. Sr plots.

For Metaluminous K20 vs. SiO2, K20-CaO vs. SiO2, K2O + Na2O vs. SiO2, K20+Na2O-CaO vs. SiO2. K2O-MgO vs. Si02, CaO vs. SiO2, LREE vs. Silica Nb vs.Zr, and Rb vs. Sr plots. Rb-Sr and Sm-Nd isotopes.

K57.5 index4; Peacock alkali-lime index5; K-Ca index6; K-Mg index7

magnesian series plagioclase only

calcic series plagioclase dominant with microcline

appearing in granitic differentiates; quartz oversaturated

calc-alkalic series plagioclase dominant with orthoclase

appearing in granitic differentiates; quartz oversaturated

alkali-calcic seriesplagioclase ~K-feldspar with K- feldspar appearing in monzodiorite system onward; quartz oversaturated

quartz alkalic seriesK-feldspar > plagioclase with K- spar occurring in the syreno-gabbro system onward; quartz saturated; hypersthene normative

nepheline alkalic series two feldspars; no quartz; nepheline appears

in differentiatesmelilite alkalic series

no feldspar (except for orthoclase in high-F Foyaitic differentiates). No quartz. Nepheline throughout sequence. Melilite throughout much of sequence (especially early).

LOGICAL ORDER

CLASSIFICATION LEVEL

TYPE OF CRITERIAKey References

NOMENCLATURE FOR CRITERIA DETERMINATION OF CRITERIA

Distinctions based on chemistry of magmatism associated spatially and temporally with the mineral system

2nd (cont.) Series (cont.) phlogopite alkalic phlogopite occurs in all rock systems; leucite

occurs in differentiates (lamproites); no feldspar

leucite alkalic leucite can occur in all rock systems

generally no feldspar (except minor sanidine in some differentiates)

3rd Subseries iron content; REE sample/REE chondrite HFSE (Nb, Zr, Y, Ta, V, Hf, Ti, HREE) content

water content

Wager and Deer (1939)Nockholds and Allen (1953)Thompson and others (1984)Miyashiro (1974)Keith and others (1991)Rock (1992)

Fe-rich (also Ti, Y, and V rich)

Fe-poor (also, Ti, Y, and V poor)

Various REE patterns on chondrite normalized plots such as:

convex upward REE (early rift anhydrous low K tholeiites)

convex downward REE (mature high speed anhydrous rift komatiites)

LREE enriched (vs. flat HREE) (oceanic and continental weakly hydrous to hydrous arcs)

LREE depleted (vs. flat HREE) (mature moderate sppd rift anhydrous NMORB)

Linear HREE to LREE enrichment (EMORB and OIB’s of various alkalinities)

positive Eu anomaly (anorthositic subseries)

negative Eu anomaly (ongonitic and rapakivine mini-series)

anorthositic/anhydrous (tholeiitic)/weakly hydrous (island arc tholeiitic)/hydrous (calc-alkaline) /strongly hydrous (lamprophyric)

Iron enrichment characterizes anorthositic, and anhydrous clinopyroxene rich magma series. Weak iron enrichment characterizes weakly hydrous magma series. No iron enrichment is featured in hydrous and strongly hydrous magma series.

AFM8 ternary diagram or SiO2 vs. FeO*/MgO variation diagram (Miyashiro plot); Y vs. Zr, Nb vs. Zr. TiO2 vs. FeO*/MgO, and V vs. FeO*/MgO plots; REE sample/REE chrondrite plots HFSE spidergrams

Presence of OH-bearing minerals vs. clinopyroxene and/or orthopyroxene; LOI and total H2O histograms; oxygen isotopes

4th Mini-series Halogen (F, Cl) contents

Barberi and others (1975)Bailey (1977)MacDonald (1974)Christiansen and others (1983)Keith and others (1991)

F-rich, Cl rich (peralkaline in subalkaline or quartz alkaline superseries or agpaitic in nepheline alkaline or leucite alkaline superseries) vs. moderate F, Cl poor (miaskitic in nepheline and leucite alkaline superseries ) vs. F-rich, Cl poor (ongonitic in quartz alkaline superseries) vs. F-poor, Cl poor (normal metaluminous) vs. moderate F, Cl poor (rapakivine)

F vs. Cl; Rb vs. Zr plots.

A/NK vs. SiO2 plot

Fluorite is restricted to peralkaline/agpaitic, ongonitic, or rapakivine miniseries

For ongonitic (presence of topaz)

For rapakivine (presence of rapakivi orthoclase)

For peralkaline (presence of one feldspar and Na pyroxene or Na amphibole; sodalite may occur in basaltic rocks with 'peralkaline'/agpaitic ‘potential')

LOGICAL ORDER

CLASSIFICATION LEVEL

TYPE OF CRITERIAKey References

NOMENCLATURE FOR CRITERIA DETERMINATION OF CRITERIA

peralkaline terminology is applied to quartz bearing and quartz saturated sequences. Agpaitic terminology is applied to quartz undersaturated, feldspathoid bearing sequences

LOGICAL ORDER

CLASSIFICATION LEVEL

TYPE OF CRITERIAKey References

NOMENCLATURE FOR CRITERIA DETERMINATION OF CRITERIA

Distinctions based on chemistry of magmatism associated spatially and temporally with the mineral system

5th Micro-series oxygen contentsulfur contentcarbon dioxidemethane

Osborne (1962)Wones and Eugster (1965)Ishihara (1981)Czaimanski and others (1981)Leveille and others (1988)Wones (1989)Keith and others (1991)

oxidized/reduced--equivalent to magnetite/ilmenite series distinction of Ishihary (1981). Specific terminology is: very strongly reduced; strongly reduced; reduced; weakly oxidized, moderately oxidized; oxidized; strongly oxidized

Fe2O3-FeO ratios, accessory sulfide and opaque oxide mineralogy; sphene presence (or absence); magnetic susceptibility; volume percent of opaque oxides. Fe2O3/FeO vs. SiO2, A/CNK, and FeO*/MgO plots; S histograms, sulfur isotopes, hydrogen isotopes F, Cl, C total, and CO2 histograms; F vs. Cl plots

6th Nano-series emplacement level/geologic setting

Buddington (1959)Hammarstrom and Zen (1986)

Intra/supracrustal Emplacement Levels: hypabyssal (0-1 km) epizonal (1-3 km) mesozonal (3-6 km) katazonal (>6 km)Submarine Emplacement Levels: littoral/neritic (0-.2 km) bathal (.2-4 km) abyssal (>4 km)

Geobarometry based on hornblende, or garnet-feldspar geochemistry; wallrock setting of associated intrusions. For example, volcanic, hostrocks may be consistent with shallow level 'hypabyssal' intrusions.

7th Rock System/Stage degree of fractional differentiationHarker (1909)Larsen (1938)Thornton and Tuttle (1960)Keith and Swan (1996)

gabbro (basalt)quartz diorite (andesite); granodiorite (rhyodacite);granite (rhyolite)etc.

silica content; differentiation index (D.I.)9; Larsen Factor (L.F.)10; A/NK (inverse; Agpaitic Index); granite (rhyolite) or element ratio on Y axis vs. D.I., L.F., SiO2, or A/NK plots; oxygen isotopes; compositional gaps on Harker variation plots

LOGICAL ORDER

CLASSIFICATION LEVEL

TYPE OF CRITERIAKey References

NOMENCLATURE FOR CRITERIA DETERMINATION OF CRITERIA

Distinctions based on environment of deposition of the mineral system

8th Megatype Setting of deposition spherical setting [i.e. atmosphere-lithosphere (subaerial), lithosphere (intraplate), lithosphere-hydrosphere (submarine)]

geological interpretations of all available relevant data

9th Supertype Type of deposition hydrothermal/magmatic [epigenetic-syngenetic/syngenetic only (exhalitive)]

interpretation of whether fluid deposited (hydrothermal) or solid deposited (magmatic)

10th Type Stage within a fractional differentiation sequence and conditions of deposition (P, T, fO2, pH, fS, emplacement level, etc.)

Selected serial nomenclature of associated igneous rocks. Hotspring/epithermal/mesothermal/Hypothermal for hydrothermal, epigenetic, metaluminous systems in subaerial (atmosphere-lithosphere) settings; hypomesothermal for hydrothermal peraluminous systems in lithosphere settings; and littoral/bathyal/abyssal for hydrothermal metaluminous systems in submarine (hydrosphere-lithosphere) exhalitive systems. Mineral deposit place name for the mineral deposit considered to be the type location for that particular deposit (eg. Carlin type).

Mineralogy and chemistry of associated igneous rock at the rock system level and fluid inclusion, isotope, microfossil, mineral stability, mineralogical, paragenetic data, etc.

11th Subtype Form of deposition (morphological and structural characterics)

Massive sulfide; stratabound, strata-form; vein; stockwork; disseminated; porphyry; skarn; replacement, manto; nodular, cumulate, etc.

geologic mapping; structural analysis; interpretation of mineral textures, etc.; i.e. analysis of the physical properties of the mineral system

12th Zone Composition as a function of geographic position within a specific mineral deposit type (eg. distal Ag-Mn leptothermal zone/fringe of a mesothermal Pb-Zn-Ag deposit type)

Principal and minor commodities that occur within the zone and deposit name for the mineral deposit considered to be the type locality for that particular zone (eg. Prompter Ag-Mn zone of the Tintic Pb-Zn-Ag type)

Mineralogy and chemistry of mineral deposit metal and alteration materials relative to that of neighboring mineral deposit material deposited during the same formational event.

NOTES:

1A/CNK molecular ratio = wt% Al2O3/102 ; when A/CNK > 1.0, the rock is peraluminous. When A/CNK < 1.0, the rockwt% CaO/56 + wt% Na2O/62 + wt% K2O/94 is metaluminous. From Shand (1927).

2A/NK molecular ratio = wt% Al2O3/102 ; A/NK > is the inverse of the more familiar agpaitic index (NK/A). When A/NK < 1.0, the rock is wt% Na2O/62 + wt% K2O/94 peralkaline in subalkaline and quartz alkaline cases and agpaitic in nepheline alkaline cases.

From Shand (1927). In nepheline alkaline and leucite alkaline superseries when mol (Na2O + K2O<Al2O3) rock is miaskitic; when mol (Na2O+K2O)>Al2O3 and mol (Na2O>K2O), rock is agpaitic.

3A/K molecular ratio = wt% Al2O3/102 ; when A/K < 1.0, the rock is perpotassic. All perpotassic rocks may be viewed as a subset of agpaitic rocks (see

wt% K2O/94 above) and are restricted in occurence to leucite alkaline superseries (see Figure 1). From Mitchell and Bergman (1991).

4K57.5 index: weight percent K2O value at 57.5 weight % silica for a suite of igneous rocks plotted on a K2O versus SiO2 Harker variation diagram. From Dickinson and Hatherton (1967).

5Peacock alkali-lime index: the silica where the quality K2O+Na2O-CaO equals zero for a suite of igneous rocks plotted on a K2O+Na2O-CaO versus SiO2 variation diagram (all values are in weight percent major element oxide). Modified from Peacock (1931).

6K-Ca index: the silica value where the quantity K2O-CaO versus SiO2 variation diagram (all values are in weight percent major element oxide).

7K-Mg index: the silica value where the quantity K2O-MgO equals zero for a suite of igneous rocks plotted on a K2O-MgO versus SiO2 variation diagram (all values are in weight percent major element oxide).

8AFM ternary = triangular compositional plot where A = Na2O + K2O at lower left corner, F = total iron as FeO (FeO*) at apex, and M = MgO at lower right corner (all oxides in weight percent). From Wager and Deer (1939).

9Differentiation Index (D.I.) = sum of normative (C.I.P.W. or Barth-Niggli) plus albite quartz or nepheline or kalisilite and/or orthoclase. From Thornton and Tuttle (1960).

10Larsen Factor (L.F.) = 1/3(SiO2 + K2O - (CaO + MgO + FeO). From Larsen (1938).

Table 1: Criteria for classification of Magma-Metal Series

The MegaChart and the Classification caught the attention of several companies and in 1985 Ray Morley of Utah Minerals (BHP) requested that MagmaChem catalogue the geochemical threshold values or “switches” in the Classification and compile them in a geochemical handbook that could be used for screening exploration plays. An important ratio that came out of this work was the Ag:Au ratio of 40:1, which identified a mineral system as either a Ag or a Au system. This led to the search for other “threshold” or “magic” numbers that are characteristic of specific Magma-Metal Series. It wouldn’t be until nine years later that FMC funded the development of the Expert System Adviser software to more rigorously document and develop for routine use the empirical relationships emerging from the Magma-Metal Series Classification. The empiricism which a MagmaChem “Call” is based on was doubled as a result of this work.

Through discussion with numerous clients from 1984-1986, especially Nigel Grant of Billiton and with geologists at the United States Geological Survey during a MagmaChem workshop, oxidation state of a magma series

emerged as an important parameter in the tradition of Ishahara (1977). After several data oxidation state compilation it was discovered that oxidation state for a metal deposit can be calculated from the ferric:ferrous ratio of the associate igneous rock and directly related to Au:Ag ratios and in general to the relative abundances (ratios) of metals in mineral systems. In reduced crust for example where the ferric:ferrous ratio is low (below 1) gold deposits, diamonds, tin, and hydrocarbon can be present, but are rare in crust where the ratio is above 1. In oxidized crust with a ferric/ferrous ratio above 1 base metals are maximized and gold is less abundant, and no economic concentration of diamonds or hydrocarbons occur. Oxidation state also defines strato-tectonic terranes, major crustal sutures and basement faults and lithology.

One of the greatest challenges facing oil and gas exploration in the WUS is the region's complex geology. A good example is found in its Sevier-Laramide history (125-43 Ma) which records a bewildering series of tectonic and hydrocarbon events characterized by diachronous (time-transgressive) geologic sequential overprinting. The term diachronous has been traditionally used to describe, "similar material in a sedimentary formation varying in age from place to place, usually due to transgression or regression". The sequence-stratigraphic approach, originally used by Sloss in 1963, was developed to address diachronous sedimentation. This approach, however, limits analysis to sedimentary rocks and is unable to rigorously address the diachronous complexity of the overall geology.

To address this challenge during 1984 Rick Livaccari and Stan Keith began a tectonic analysis of the Sevier (145-85 Ma) and Laramide (85-43 Ma) orogenies in western North America. They constructed paleo-tectonic time-slice maps and sections. Using Magma-Metal Series they were able to link oceanic plate motion with continental geology in the western US via petrology and isotopic age dates--something that had never been done before. They also developed strato-tectonic analysis to help sort out the diachronous complexity

Strato-tectonic analysis, in contrast to sequence stratigraphy, incorporates structure, metamorphism, mineral deposits, igneous rocks, isotopic age dates, and plate tectonic data into strato-tectonic assemblages in a sequence-stratigraphic column-like fashion. An early version of this technique was first used by Coney (1973) in the form of a chart that combined western US stratigraphic information with structural phenomena. When these strato-tectonic columns are plotted on time-distance sections, the diachronous complexity and sequential overprinting become obvious. The individual elements of the overall geology are apparent as is their unique positions in geologic time and space. The result is a better-constrained tectonic model for the orogenic events.

In several publications and reports strato-tectonic charts of Mesozoic-Cenozoic geology were combined in time-distance diagrams for the western US (Keith and Wilt, 1985, 1986; Livacarri and Keith, 1986, 1990). Igneous rock series are a key element of the strato-tectonic charts when petrochemically-classified as Keith did in 1978 and 1982 using the Magma-Metal Series Classification. Such treatment allows the division of a generic subduction-related arc complex into a more resolved petrochemical stratigraphy that is absolutely calibrated to the geologic time scale using isotopically-dated magmatic rock assemblages. These form an orderly igneous chemical stratigraphic absolute time/space framework onto which all other data can be plotted and then integrated with plate tectonic data.

Where the data is poorly constrained, it can be put into regional context on the time-distance section by analogy with nearby areas adding a testable specify not found in other more generic tectonic approaches. Tectonic data with varying degrees of confidence can then be synoptically integrated into regional tectonic models. This brings data not normally used in basin analysis to the basin, resulting in a more complete and dynamic basin model. Most importantly, tying hydrocarbon events to strato-tectonic assemblages, not only maps hydrocarbons through time and space, but provides insights into possible relationships to basement structure and deep-earth processes such as serpentinization.

In 1985-1986 the Sevier and Laramide paleotectonic maps and sections, 216 page report, annotated bibliography and seminar was purchased by: Pennzoil, Anschutz, Exxon, Mobil, Texaco, AMACO, Marathon, Elf Aquitaine, Tenneco, Phillips, Chevron, Unical, Kerr McGee, Exxon Research, and the United States Geologic Survey.

In late 1986 market conditions shifted in favor of the platinum group elements (PGE). In reaction to this MagmaChem focused on platinoids. With the help of George Smith correlations between magma chemistry and precipitation of immiscible sulfide segregations were recognized to be a function of not only Magma-Metal Series but oxidation state.

In 1987 a Karl Albert with expertise in diamond and kimberlite-lamproite rock systems facilitated a breakthrough that resulted in the identification of the new Magma-Metal Series of kimberlite-lamprophere.

1990-2000 The Earth’s Crust and Mineral Deposit Discoveries

9 Cu-Au-Ag deposit discoveries:

SE Ajo, Arizona 1998 2 billion pounds CuEspanola, Chile 1997 6 billion pounds CuEspanola, Chile 1997 2 million ounces Au

South Alcaparrosa, Chile 1996 60 million pounds CuSouth Alcaparrosa, Chile 1996 0.15 million ounces Au

Pascua, Chile, 1995 700 million ounces AgTyrone, New Mexico 1994 2.4 billion pounds CuSouth Meikle, Nevada 1992 2 million ounces Au

Vinasale Mountain, Alaska 1992 655,000 ounces Au

26 publications and 52 unpublished works MagmaChem project topics listed by year:

1990 Geochemical vectoring technique--correlated element assemblages

Geochemical zoning and vectoring of Carlin-type depositsAssimilation of crustal fluids by magmas

1991 Metal dispersion, sea floor isopachs and exhalite Au, ColoradoVectoring Vinnsale Mtn, AlaskaMagma-Metal Series and metallogeny, NevadaMid-crustal formation fluidsCrust versus mantle as source for metals

1992 Geochemical vectoring Au targeting, Nevada1993 Mexico metallogenic and Magma-Metal Series compilation

Neural network confirmation of Magma-Metal Series1994 Pluton vectoring--staged fractionation rock system and metal

sequencePluton vectoring porphyry Cu targets, Arizona, MexicoGenesis of the southwestern porphyry Cu clusterMagma-Metal Series “Call” Expert System Adviser Software

1995 Giant oil fields and crustal oxidation state and slab segmentation

1996 Geochemical-pluton vectoring, Chile, Arizona1997 Geochemical-pluton vectoring, Chile, Peru1998 Tectono-metallogenic evolution of Mexico

Thermal infrared emission spectroscopy and granitoid pertrology

1999 Flat plate subduction and continental deformationMagma-metal differentiation sequenceStrike-slip faults, wet magmas and giant mineral depositsCracks of the World, oxidation state, and petroleum

Continued work in the 1990’s by Keith and Swan, MagmaChem employees and associates, focused on the affect the Earth’s crustal fluids have on Magma-Metal Series traveling through the crust to its points of deposition.

This work resulted in the conceptual development and exploration application of:

1. Metamorphogenic crustal formational fluids 2. Fault zones as fluid conduits for Magma-Metal Series 4. Fractionation of Magma-Metal Series Fluid migration (mapping of fluid plumes) Geochemical assemblage (statistical determination) Kinematic analysis (predicting fluid migration) Magnetics and gravity (mapping magma and fluids in basement)

Magma-Metal Series development in the 1980’s was concerned primarily with the source of magma and associated metal deposits, while Magma-Metal Series development in the 1990’s focused on the process of the magma and associated metalliferous fluids traveling through and depositing in the Earth’s crust. The 1990’s work directly addresses the long-standing debate concerning the role of source and process that can be traced back at least 500 years to Decartes (1644) and Agricola (1556). In the 1990’s it was discovered that the key to resolving the debate is found in the interaction between crustal metamorphogenic formationl fluids and rising magmas. Mass-balance calculations, petrology, Magma-Metal Series fractionation patterns, and structural kinematics applied to fluid migration demonstrated how source and process integrate. The most spectacular result of this work and economic proof of concept was the discovery of nine economic Cu-Au-Ag deposits on two continents.

In 1990 geochemical vectoring was applied to a number of gold prospects in Nevada and from this work a zoning model for Carlin gold systems was created. Strato-tectonic analysis was applied in detail to the region from southern California to West Texas. Apparent from this was the crustal thinning or decretion caused by the flat subduction and the influence this thinned crust had on middle Tertiary magmatism and deformation as the slab collapsed at 43 Ma. The most significant discovery was evidence for assimilation of crustal fluids by magmas moving from the mantle through the crust. It was discovered that the fluid greatly influenced the fractionation of the Magma-Metal Series causing magmas to fractionate along any of seven tracks in a spectrum from oxidized to reduced. In 1990 MagmaChem compared the economic track records of various gold deposit types based on Magma-Metal Series and found profound differences that had important exploration implications.

In 1991 geochemical vectoring studies continued to be applied to Nevada gold prospects and a formalized geochemical procedure was written by Steve Ruff and Stan Keith using the Ledge Ridge volcanogenic massive sulfide deposit in Maine as a case history. A

layered earth model was developed by Monte Swan and Stan Keith to highlight the four primary ways to melt the mantle and the Earth’s crust. This demonstrated the value of Magma-Metal Series in predicting and unraveling geotectonic settings. Nevada was used as a case history for demonstrating the application of Magma-Metal Series logic to a world-class gold province. A resolution for the crust versus mantle source debate was presented by Stan Keith at the Left Lateral Leap Session at the Northwest Miners Convention in Spokane Washington.

2000-2010 Serpentinization and the Ultra Deep Hydrocarbon Model

13 Cu-Au discoveries and 1 geothermal discovery:

San Luis Potosi, Mexico 2009 (to be determined)* Lookout Mountain, Nevada 2006 (to be determined?)**

Jewett (Crown Zone), Oregon 2005-6 several thousand tons of +1 opt AuBig Springs (701/601), Nevada 2005 (to be determined?)***

Rio Figueroa, Chile 2005 (to be determined!?)****Big Springs (Crusher), Nevada 2005 (to be determined!?)*****

Chuquicamata, Chile 2004 4 billion pounds CuRen, Nevada 2003 1.3 million ounces Au

Storm-Dee Forty Niner, Nevada 2003 1 million ounces AuLightning Dock, New Mexico 2002 geothermal test flow 320-325 gpm @ 137°C

Ntotorosa, Ghana, West Africa 2000 2 million onces AuPascua, Chile, 2000 26 million ounces Au

*Discovery quality holes for Au**Discovery quality holes for Au announced December 19, 2005, January 4, 2006 and March 15, 2006 ***Discovery quality holes for Au announced November 8, 2005 ****Discovery quality holes for Cu-Au announced August 16, 2005 and February 22, 2006 *****Discovery quality holes for Au announced by press releases dated August 11, 2005 and October 18, 2005

22 publications and 38 unpublished works Project topics listed by year:

2000 Magma-Meta Series chemical classification of Ag depositsStrike-slip faulting and later differentiation of porphyriesGenesis of Carlin giant Au depositsGold deposit models, eastern Russia

2001 Initial work on the UDH Model

Basin analysis--strato-tectonic, oxidation state, fluid zone structures

Hydrocarbons in the earth--petrologic approach2002 Petroleum geology of Mexico

Petroleum fluid formation, movement and depositionBasement structure of ancestral Rockies and petroleum western

USCarlin Au analysis, New FoundlandGeochemical vectoring of Lightening Dock geothermal systemMetal production grade/tonnage data baseMagma-Metal Series four volume set (1100 page manuscript)

2003 Strike-slip faulting and reservoir development, New YorkGeochemical vectoring Glodes Corner gas field, New YorkHTD exploration model and Mg-hydrocarbon sourceCracks of the World, strike-slip faults and giant resource

accumulationsGulf of California source rock studyFive-staged HTD reaction sequenceCarlin geologic maps of the North Carlin Trend Magma-Metal Series of a Mongolian gold depositHTD, white smokers and Cambrian life explosion

2004 Global Cracks of the World map in multiple projectionsHydrothermal oil--integration of hydrocarbons into Magma-

Metal SeriesPluton vectoring Au systems, Mexico and Nevada

2005 Basement structure/lithology, petroleum and mineral systems, western US

Metal dispersion structure, Grant Canyon oil field, NevadaGeochemical and pluton vectoring Cu-Au, ChileHydrothermal hydrocarbons--mineral deposit geology to

hydrocarbonsGeochemical and pluton vectoring Carlin Au systems, Nevada

2006 Peridotites, serpentinization and hydrocarbonsMagma-Metal Series contributions to discovery

2007

Continued work in the 2000’s by Keith and Swan, MagmaChem employees and associates, focused on petroleum the process of serpeninization while continuing application of Magma-Metal Series to exploration, not only mineral exploration but also geothermal and petroleum exploration. This work resulted in the conceptual development and exploration application of:

1. Serpentinization (discovered to be a first-order Earth process)2. Oil and serpentinite chemistry3. Serpentinization mass balance calculations4. HTD Story (relationship to Green River Oil Shale, Ghawar, etc.)

5. Source rock (black shale) exhalative timeline 6. Re-Os isotopic age dates7. Supercritical water8. “Biomarkers” in serpentinite and HTD9. Serpentinite-hydrocarbon association10. Kerogen in serpentinites (TOC up to 0.5%)11. HTD ‘Just-in-Time” arrival of hydrocarbon12. Mapping hydrocarbon plume fractionation13. Strato-tectonic analysis of hydrocarbon events

Although MagmaChem did geotectonic work for most of the major oil and gas companies in the 1980's and continued to present papers on the subject in the 1990's, MagmaChem did not begin to focus on petroleum projects until the UDH project began in 2001. (This was about the time that the mineral industry experienced a prolong depression in metal prices).

In 2001 MagmaChem prepared a paper for the AAPG meeting in Denver for the purpose of updating the petroleum industry on MagmaChem’s last ten years of geotectonic work. The subject of that paper was the application of MagmaChem's geotectonic and deep-Earth story to dynamic basin modeling. One of the people in the room was the Exxon new-venture leader Barbara Rassman. She approached MagmaChem and indicated that Exxon had an "accounting" problem for hydrocarbons in super-giant petroleum systems and perhaps MagmaChem’s deep-Earth story might provide some insight. She told MagmaChem she had been specifically sent to the conference to find an answer. Her exact words were, "When we do the accounting for super-giant oil and gas accumulations the books don't balance. Do you have any ideas from your deep-Earth work how we can balance the books?"

This led to two short courses with Exxon Research personnel in Houston. While many of the geologists and geochemists were intrigued with the Magma-Metal Series ideas, a couple of the geochemists were not and the subsequent interactions with Exxon over the matter stalled.

Encouraged by Exxon’s original question, MagmaChem did an in-house compilation to see if and how hydrocarbons might fit into the Magma-Metal Series Classification. About this time John Caprara with EOG expressed an interest in applying Magma-Metal Series to HTD. He introduced MagmaChem to John Martin of NYSERDA (New York State Energy Research Development Authority) and together MagmaChem and John Caprara applied for a NYSERDA grant for mineral deposit thinking to be applied to petroleum geologic problems in New York State--specifically to address the age and HTD connection of petroleum systems with HTD reservoirs and MVT (Mississippi valley Type Zn deposits). The team won a grant in 2002. The upshot of that project was the identification of possible

high-magnetic, low-gravity serpentinite sources in the Rhone Trough (and other rifts) for the fluids that produced the HTD reservoir for HTD gas plays such as Glodes Corner in Stuben County, New York and the host rocks for the MVT Zn deposits. But MagmaChem had a surprising result that lead to identification of the natural gas resource some 8,000 feet beneath the ground surface.

Early in the project, basement structural control for the Glodes Corner gas field was recognized and a kinematic migration model was constructed using aeromagnetic, gravity, remote sensing, geologic mapping, structural data and kinematic analysis techniques developed in the mineral industry. Unlike sampling mineral systems, sampling the Glodes Corner gas field directly was not possible, so it was assumed that a structural kinematic analysis would be the extent of the study. But a surface soil gas and trace-element data base generated by Direct Geochemical, another NYSERDA research group, was made available, although not actually released for examination until the results of the kinematic structural analysis and predicted geochemical patterns were reported to Direct Geochemical. The result of this “test” was that the patterns were correctly predicted. Although soil gas geochemical surveys had a good exploration track record at the time, trace-elements and especially metals, had apparently not been used in this exploration context and especially had not been used to geochemically “vector” an oil or gas system. The mechanism for transporting metal to the surface above hydrocarbon accumulations was a new and untested exploration concept, but the data appeared to be real and was interpreted, revealing patterns that correlated closely with production and with the kinematic migration model constructed before the geochemical data was examined. Most importantly, these patterns were reminiscent of patterns seen in mineral systems

Since this work was supported by the New York State government, they encouraged MagmaChem to put the story out, which MagmaChem did at a NYSERDA conference in Albany New York in 2002; at the AAPG in Salt Lake City, Utah convention in 2003; and at the AAPG convention in Houston in 2006.

In 2003 Jim Villeneuve of Direct Geochemical in Denver (now Vista Geoscience), introduced MagmaChem to Brian Crooks of Noble Energy. This interaction was a product of a combination of MagmaChem’s and Direct Geochemical’s follow-up research regarding the multi-element geochemical exploration tool for soil geochemical samples taken at Glodes Corner, New York. Brian Crooks was also interested in other MagmaChem technologies such as the serpentinite-source model. This gave MagmaChem an audience with Susan Cunningham (formerly with Statoil) who was especially impressed with an earlier version of our Cracks of the World map that had been initially supported by Gary Heinmeyer at Phelps Dodge (Cu

company) and later by John-Mark Staude at BHP. Noble Energy then paid MagmaChem to upgrade the Cracks of the World Map and apply the geochemical exploration tool to suspected hydrothermal hydrocarbon occurrences in the Great Basin. MagmaChem discovered a spectacular geochemical vectoring pattern at Grant Canyon. (Subsequent application of this technology by Direct Geochemical to the Snake Valley Play has led to it becoming a geochemical vectoring case history and exploration play).

The Noble Energy project was initiated in late 2004 and was ongoing in June 2005 when MagmaChem met Martin Hovland of Statoil at the AAPG Hedburg conference on the origin of petroleum in Calgary. At that time, Martin asked MagmaChem if they would be interested in looking at how supercritical water might fit into the Magma-Metal Series concept from a petroleum perspective. MagmaChem completed the project with Noble in late-2005 and in mid-2006 began the Statoil UDH project.

Appendices (for MagmaChem History chapter)

1. Contributions of the Magma-Metal Series Approach to the Discovery Process, with sections on The Magma Metal Series Technical Approach, Magma Metal Series Tools Developed by MagmaChem to Assist in the Identification and Discovery of Mineral and Petroleum Resources, and Hydrothermal Hydrocarbons: Keith, S.B and Swan, M.M., 2006,:

2. Magma-Metal Series 4 Volume Set; Text: Keith, S.B., 2002, MagmaChem unpublished manuscript, 66 pp; Appendix I--76 supporting figures; Appendix II--Model Table, Classification Chart and Explanatory Text, 347 pp; Appendix III--Grade/Tonnage Table 178 pp.

3. Mineral Deposits, and Geotectonics: Keith, S.B., Magma Series, 1984, Unpublished Report (in review and under contract for a time with John Wiley and Sons), MagmaChem Exploration, Inc., 500 pp.

4. MagmaChem Handbook--Geochemical Models of Precious Metal Deposits and Their Empirical Relationship to Magma Series or How to make MagmaChem “Calls”: Keith, S.B., Swan, M.M. and Maughan, J.R., 1988, , 250 pp..

5. Metallogeny, Magma Series and Geotectonic Setting of Igneous Rocks: Keith, S.B., 1984, Unpublished 3 by 13 foot Megachart, Phoenix, AZ, MagmaChem Exploration, Inc.

6. Magma-Metal Series Petrotectonic Model for a Layered Earth: Keith S.B. and Swan, M.M., 2009, Unpublished chart.

7. Pluton Vectoring for Porphyry Metal Deposits: Keith, S.B., 1994, MagmaChem unpublished report, 112 pp.

References (for MagmaChem History chapter)

Keith, S.B., 1978, Origins of Arizona Copper Deposits; Hypotheses: Arizona Bureau of Geology and Mineral Technology, Fieldnotes, v. 8, no. 1-2, pp. 9, 17.

Keith, S.B., 1978, Paleosubduction Geometries Inferred from Cretaceous and Tertiary Magmatic Patterns in Southwestern North America: Geology (Boulder), v. 6, no. 9, pp. 516-521.

Keith, S.B., 1979, Spatial, Temporal, Chemical, and Structural Evolution of the Southeast Arizona-Southwest New Mexico Porphyry Copper Cluster: Society of Economic Geologists Field Conference on Tucson Area Porphyry Copper Deposits, April 1979 Guidebook.

Westra, G. and Keith, S.B., 1981, Classification and Genesis of Stockwork Molybdenum Deposits: Economic Geology, v.70, no. 4, June-July 1981, pp. 844-873.

Westra, G., and Keith, S.B., 1982, Classification and Genesis of Stockwork Molybdenum Deposits: Reply: Economic Geology, v. 77, no. 5, pp. 1252-1263.

Keith, S.B., 1982, Paleoconvergence Rates Determined form K2O/SiO2 Ratios in Magmatic Rocks and their Application to Cretaceous and Tertiary Tectonic Patterns in Southwestern North America: Geological Society of America Bulletin, v. 93, no. 6, pp. 524-532.

Reynolds, S.J., and Keith, S.B., 1982, Geochemistry & Mineral Potential of Peraluminous Granitoids: Arizona Bureau of Geology and Mineral Technology Fieldnotes, v. 12, no. 4, pp. 4-6.

Sloss, L.L., 1963, Sequences in the Cratonic Interior of NA: Geol Soc. America Bull., v. 74, no. 2, p. 93-114.

Coney, P.J., 1973, Cordilleran Tectonics and NA Plate Motions: American Journal of Science, v. 272, p. 603-628.

Coney, P. J. and Reynolds, S.J., 1977, Cordilleran Benioff Zones: Nature, v. 270, p. 403-406.

Livaccari, R.F., and Keith, S.B., 1985, Tectonic Analysis of the Sevier (145-85 Ma) and Laramide (85-43 Ma) Orogenies in WNA: Paleo-Tectonic (Time Slices) Map Folio with Corresponding Cross-Sections and 3-D Block Diagrams of the Crust and Mantle, Bellevue, WA, MagmaChem Exploration, Inc., 220 pages.

Keith, S.B. and Wilt, J.C., 1985, Late Cretaceous and Cenozoic Orogenesis of Arizona and Adjacent Regions; a Strato-Tectonic Approach: in Flores, R.M., and Kaplan, S.S., Editors, Cenozoic Paleogeography of the West-Central US: Rocky Mountain Section, Society of Economic Paleontologists and Mineralogists, Denver, CO, pp. 403-437.

Keith S.B. and Wilt, J.C., 1986, Laramide Orogeny in Arizona and Adjacent Regions: a Strato-Tectonic Synthesis, in Beatty, B and Wilkinson, P.A.K., editors, Frontiers in Geology and Ore deposits of Arizona and the Southwest: Arizona Geological Society Digest, v. 16, pp. 502-554.

Livaccari, R.F. and Keith, S.B., 1990, Detailed Strato-Tectonic Analysis of the Southern Cordillera from Trans-Pecos Texas to Southwestern California (abstract): Geological Society of America Abstracts with Programs, v 22, no. 3, p. 37.