Chapter 10 Geology and Rare Earth Element Geochemistry of Magnetite Deposits at El Laco, Chile Any LARSON RiiopEs,* NOAM ORESKES,"* AND SOSSIrY SHEETS*** Department of Barth Sciences, Dartmouth Calege, Hanover, New Hampshire 03755, Abstract ‘The magnetite deposits at El Laco, Chile, have been widely cited as the type example of an iron deposit formed from direct consolidation of a magma. This study presents field, petro- graphic, and rare earth element (REE) evidence that shows that magnetite deposition was largely the result of hydrothermal activity. Hydrothermal activity at El Laco i clearly manifested in alteration assemblages observed in hostrock andesite: magnetite occurs in association with a series of hydrothermal alteration assemblages. The earliest-formed alteration assemblages in- ‘lude weak propylitic (chloritesericite-lay), sodic-potassic mineral phases (scapolite-albite-K feldsparsphene), and silicification by cation leaching. Alteration of andesite to calcium-tich py- roxene (diopside) + magnetite followed. Bulk iron-oxide mineralization then occurred, pro- ducing an assemblage of magnetite + apatite + quartz + calcite. The final stages of hydrothermal alteration of andesite included argillic alteration (kaolinite-sericite-alunite), silcfication assoc ated with anhydrite, and retrograde alteration (sericite-clinozoisite-alcillite /smectite-biotite) of sodic and calcic alteration phases. Oxidation of magnetite to hematite (+ jarosite + goethite) postcated magnetite emplacement. ‘Textural evidence also supports the interpretation of a metasomatic hydrothermal origin: 1. Abundant layers of magnetite mimic the morphology of andesite flow layers, suggesting di rect replacement of andesite by magnetite. 2, Porous textures in magnetite resemble andesite breccia fragments that were partially or completely replaced by magnetite. These textures are associated with bladed diopside and py- roxene casts, confirming that, prior to iron mineralization, andesite experienced calcic alter- ation. Porous regions in magnetite that occur on a larger scale than typical breccia fragments (210 cm) indicate direct replacement of unbrecciated andesite. 3, Microscopy shows direct replacement of diopside by both magnetite and apatite. 4, Abundant hydrothermal magnetite textures include coarse-grained magnetite octahedra encrustations, magnetite veins occurring with drusy quartz, brecciation, geyserlike magnetite terraces, and fumarole-like tube structures. 5, Magnetite veins crosscut diopside-rich altered breccia fragments, indicating that hydraulic fracturing of footwall andesite was followed by hydrothermal precipitation of magnetite, REE patterns of magnetite and andesite alteration assemblages show negative Eu anomalies during early alteration (diopside and scapolite) and magnetite apatite phases, and positive Eu anomalies in later alteration. This likely reflects a change in oxidation state from Eu* to Eu® as the system developed. REE concentrations in magnetite are the same as REE concentrations in ‘unaltered country rocks, suggesting that the total REE content of magnetite was inherited from precursor andesite during replacement processes, These results are most consistent with the in- terpretation that magnetite-apatite formation represents a hydrothermatalteration event, in \which iron-or phosphorousrich fluids reacted with and replaced host-rock andesite and formed by hydrothermal open-space filling. Silica that was removed during replacement was later de- posited as quartz veins and as siliceous alteration associated with argillic and sulfate deposition. {Corresponding author: email arhodestscence smithedy * Present address: Depart * Present addres: Deparunent of Geology, Smith College, Northampton, Diego, 9500 Gilman Drive, % Massachusetts 01068 ‘Present addresx Departnent of Material Science and Engineering, Mas chusets Intute of Technology, Cambridge, Massachusetts 02159, nt of History, University of California, San 209300 Introduction ‘The majority of giant iron ore deposits of magmatic or ‘magmatic-hydrothermal association are found in rocks of Early to Middle Proterozoic age (1.8-1.1 Ga). These de- posits, which include the ore provinces of southeast Mis- souri in the United States, Inner Mongolia of China, the Great Bear magmatic zone in the Northwest Territories of Canada, and northern Sweden, are often classified together as Kiruna-ype, based on textural and compositional simi- larities with the giant iron ore deposits in Kiruna, Sweden, However, given the wide range of formation models and in- terpretations proposed for the various deposit, classifying these and other similar deposits together presents signif cant interpretive difficulties (Hitzman etal, 1992; Oreskes and Hitzman, 1998). The formation mechanism of magnetite deposits of ‘magmatic association has been the subject of much contro- versy. A wide range of geological processes has been pro- posed, including formation by hydrothermal processes (Geijer, 1915, 1931; Bookstrom, 1977, 1994; Panno and Hood, 1983; Hildebrand, 1986; Hitzman etal., 1992), mag- matic intrusion (Gefjer, 1910, 1967; Henriquez and Martin, 1978; Nystrém and Henriquez, 1994), liquid immiscibility ofan iron-rich melt (Philpotts, 1967; Frietsch, 1978; Lund- berg and Smellie, 1979), voleanicsedimentary exhalative processes (Parsk, 1975, 1984, 1985), and remobilization of Older, iron-and phosphorousrich sedimentary rocks (Park, 1961, 1973; Frutos and Oyarziin, 1975). Furthermore, a number of workers have postulated a link to the Olympic Dam-type deposits. Recent work on the Olympic Dam Fe- oxide, Cu-U-AuREE deposit of South Australia has illus- trated formation of early magnetite by deep-seated hy- drothermal fluids of possible magmatic origin, followed by later hematite deposition in breccias from fluids of signifi cantly lower temperature and of probable meteoric origin Hematite-rich breccias are the principal hosts for copper and uranium mineralization at Olympic Dam (Oreskes and Einaudi, 1990, 1992; Reeve etal, 1990) ‘Younger magnetite-bearing, iron oxide deposits are typ- ically much smaller than their giant Proterozoic counter- parts. Several deposits, ranging in size from fewer than 2 Me to more than 100 Mt of ore with 60 percent iron, lie within the Chilean iron province, a belt of Cretaceous mag- netite and magnetite-apatite deposits that extends along the Pacific coast for about 600 km between 25° Sand 31° S (Park, 1972; Bookstrom, 1977; Espinoza, 1990; Nystrom and Henriquez, 1994). The El Laco iron deposits are still younger, dated at Pliocene-Pleistocene age. These deposits are located approximately 280 km east of Antofagasta, Chile (23°48" S, 67°30’ W) and contain 500 Mt of up to 98 ppercent iron oxide, and rarely less than 80 percent iron ox- ide. Due to remarkable textures in the magnetite that in some respects resemble those of basalt lava flows, El Laco has been described as the extrusive counterpart of the Kiruna iron ores. Thus, itis widely cited as the type exam- ple ofa magmatic iron oxide deposit formed by magmatic liquid immiscibility. RHODES ET AL, Several workershave pointed outinconsistencies with the liquid immiscibilty hypothesis, however. Haggerty (1970a), Frutos and Oyarziin (1975), Frutos etal. (1990), and Hitz ‘man etal, (1992) have noted that the low concentrations of titanium in E1Laco magnetites are inconsistent with normal trace-metal contents of iron-rich magmas. Frutos et a (1990) observed a negative europium anomaly in the rare carth element (REE) content of El Laco apatite and con- cluded that the deposits, although magmatic, formed by fractional crystallization rather than liquid immiscibilty There is no known mechanism, however, to produce iron- dominated magmas by fractional crystallization. Haggerty (1970a) and Hitzman etal. (1992) have argued that the tex- tures described at El Laco are not entirely consistent with what would be expected from a high-temperature, low-vis cosity, poorly polymerized iron oxide lava. Experimental ‘work has suggested that segregation of an immiscible iron oxide magma occurs at apatite concentrations of about 30 percent by volume (Philpotts, 1967). Naslund (1983) demonstrated immiscibility with low phosphate contents at 1465°C, but noted that immiscibility in natural systems is ‘most likely to occur in bulk compositions high in total iron, titanium, and phosphate. Yet the apatite content at El Laco is extremely variable, and apatite is absent in some mag- netite bodies (Larson, 1994). As a result of these inconsis- tencies, Hildebrand (1986) and Hitzman etal. (1992) sug- gested that the magnetite deposits at El Laco may have formed by hydrothermal, rather than magmatic processes Haggerty (1970a) proposed an important role for gaseous phases. Clearly more work is needed. Thanks to their young age and relatively complete preservation, the El Laco de- posits permit detailed field study, which can help resolve the relative importance of these various suggested mechanisms. ‘This in turn may help us to better understand their relax tionship to the giant iron deposit ofthe Proterozoic. ark (1961) was the first to describe the El Laco deposits, and proposed a genetic interpretation in the ttle of his pa: per: “A Magnetite ‘Flow’ in Northern Chile.” He consid- ered his proposal to be a working hypothesis, however (Park, pers. commun., 1985). More recently, Henriquez and Martin (1978) and Nystrom and Henriquez (1994) have classified the deposit as either lava flows with feeder dikes, dikes, or intrusive domes. Their interpretation is based on specific magnetite textures that resemble spinifex textures observed in ultramafic rocks, such as the Archean komatiites of South Africa and Western Australia, However, they do not describe many other textures present at El Laco, nor do they describe the overall morphology of the deposits, the distribution of mineralogic and textural varie ability, or contact and other field relations, all of which are critical to any genetic interpretation. Before drawing ge- netic conclusions, itis essential to have a full description of the morphologies and textures of the iron deposits at El Laco and their relationships to surrounding host rocks and hydrothermal alteration assemblages. ‘This paper presents new field, petrographic, and REE, data from the El Laco deposits. A companion paper (Rhodesand Oreskes, 1999) discusses oxygen isotope rela-GEOLOGY AND REE GEOCHEMISTRY OF MAGNETITE DEPOSITS AT EL LACO, CHILE tionships within the deposits. The work presented is based. ‘on two field seasons at El Laco in 1993 and 1994, during which the textural occurrences of the magnetite, the dis. tibution of mineralogic assemblages associated with mag- netite, and the veining, brecciation, and alteration assem- blages in the surrounding andesite were mapped. Particular attention was focused on the relationship be- ‘ween iron ore and surrounding andesite as evidence of the processes of formation. We believe that the detailed ge- ologic, petrographic, and analytical data presented here clearly indicate that the El Laco magnetite was deposited from vaporich fluids in a magmatic-hydrothermal system. Most, if not all, of the magnetite formed as a result of the ‘metasomatic replacement of andesite flows. We suggest that many of the flowJike features observed by previous workers are palimpsest features, inherited from the an- desitic protolith. Geologic Description of El Laco The El Laco voleanic complex is located in the central Andean cordillera (23°48" S, 67°30" W) in the Antofagasta province of northern Chile (Fig. 1). The iron oxide deposits, are hosted in Tertiary andesitic rocks, dated by K-Ar whole- rock methods at 2.0 + 0.3 Ma (Maksaev ct al., 1988). The de- posits consist of seven distinct concentrations of iron oxide surrounding an andesite-rhyodlacite peak, Pico Laco (Fig. 1; Park, 1961; Ruiz Fuller et al., 1965; Haggerty, 1970a; Frutos and Oyarztin, 1975; Henriquez and Martin, 1978; Gardeweg and Ramirez, 1985; Frutos et al., 1990; Larson and Oreskes, 1993; Henriquez etal., 1994; Larson, 1994; Nystrom and Henriquez, 1994; Oreskes et al., 1994, 1995; Rhodes and Oreskes, 1994, 1995a, 1995b, 1996). The seven iron deposits at El Laco are: Laco Norte, Laquito, Laco Sur, San Vincente Alto, San Vincente Bajo, Cristales Grandes, and Rodados ‘Negros. The andesites surrounding the magnetite bodies are intensely and pervasively altered. Large sulfate-domi- nated mounds, which appear to be fossil fumaroles, are pres- ent around the complex and represent the youngest stage of | hydrothermal activity at El Laco. Locally, glacial and fluvial deposits overlie parts of the complex. Extensive Tertiary ig- nimbrite deposits are present within the region of the com- plex; playa lakes and Neogene evaporite deposits are pres ‘ent locally and regionally (Ruiz Fuller etal, 1965; Gardeweg and Ramirez, 1985; Alonso et al., 1991), Summary of Hydrothermal Alteration Assemblages ‘The hydrothermal alteration assemblages observed in host-rock andesite is described first because of the close spatial relationship between alteration type and the distri- bution of magnetite. Alteration of the andesite is pervasive throughout the complex; there is very litle andesite at El Laco that has not experienced some form of hydrothermal alteration. Weakly altered andesite preserves the original ‘mineralogy, which consists of phenocrysts of wellleveloped plagioclase and poorly developed orthopyroxene with an Fe-Ti oxide phase in a fine-grained matrix. Glass is not pres- cnt in the andesite matrix. These observations are consis- 301 JAntofagasta ELLACO’ Santiago [Ep reset state Fumaroles Iron Onde Bodies / Magneto Foat Hy Hydrothermal Alteration in Andesites [Bil Ancesite Flows, Glacial / Fluvial Doposts, Mic Exrusives Fc. 1. Geologic map of iron oxide depos and asocated hydrothermal alteration, El Laco, Chile. LN Laco Norte, L5= Laco Su, LQ= Laquito, 'SVA = San Vincente Alt, SVB = San Vincente Bajo, CG ~ Crivales ‘Grandes, RN = Rodados Negros, adapted from Ruiz Fuller etl (1965). tent with the observations of Gardeweg and Ramirez. (1985) in their regional study of the geology around El Laco. ‘Atleast seven possible alteration assemblages are present at El Laco, and they differ significantly from the typical al teration assemblages often described in hydrothermal de- posits such as porphyry copper or epithermal gold deposits ‘Many of the minerals we have identified in the following al- teration assemblages have also been recognized by Vivallo et, al, (1994). The timing relationships of the alteration assem- blages at El Laco are presented schematically in Figure 2. Propyltic alteration, Regionally, the andesite displays weak propylitic alteration characterized by a general greenish ap- pearance of the andesite matrix. In this assemblage, or- thopyroxene is altered to chlorite and plagioclase is altered, to sericite and clay minerals (Vivallo et al., 1994; Rhodes, 1996). Disseminated magnetite also increases in abundance with this weak alteration type.302 RHODES ET AL. Mineral Time_———» ‘Weak propylitic Sodic-(Potassic) Albite, scapolite, K-spar, sphene Ca-metasomatiem Diopside: Iron oxide mineralization Magnetite Apatite Quartz Calcite Retrograde Serio, clinozois, tite, biotite, al, smectte Siliceous Argillic + Anhydrite/Sulfate Hematite onene fragments, Pyroxene appears shredded and partially replaced by ‘magnetite reflected ight; Laco Nore. B. Pseudomorph of magnetite a ter pyroxene, Laco Su netite at El Laco are evidence of rapid crystallization, but not necessarily from a magma. The experiments of Turner. cecal. (1986) proved that spinifex textures can result from, rapid crystallization of aqueous solutions as well 'AtEL Laco, columnar magnetite commonly occurs as 4-to 6-cm-thick horizons located within close proximity to an- desite breccia zones. This texture is also observed at mag- netite-andesite contacts at Cristales Grandes and Rodados ‘Negros. Petrographic examination of columnar magnetite in contact with an andesite breccia fragment (Fig. 22C) reveals, that bladed magnetite zones consist ofthe subparallel growth, of coarse, elongated diopside crystals infilled by magnetite. The pyroxene most likely formed during calcic metasoma- tism, with magnetite later infiling between pyroxene grains. Icthus appears that the pyroxene defines the bladed texture observed in the magnetite, The fact that the majority of ‘columnar magnetite occurs in contact with andesite suggests that some bladed magnetite forms.asa result of an iron met somatic reaction front with diopside assemblages.ic. 22. A. Porous region in magnetite sample resembles diopside breccia fragments exceptthat no diopside present A thin, relic reaction rm su. rounds the bree fragment San Vincente Bajo. B: Close up of magaetite in porous zone has a rectangular morphology sinew pyroxene and ex hibits growth along former pyroxene cleavage planes indeting that bre Cia fragment was formerly mposed of aiopride reflected ight C, Cols har magnetite rimming altered andesite breccia Iragment, Cristales Grandes: Hand sample shows potascaly altered andesite rimmed by py. roxene and bladed magnetite. Asocated thin section shows columnar tx ture thatinay have rele from magnetite infiling between blade pron ene gains, representing a magnetite replacement reaction front RHODES ET AL. Discussion of Hydrothermal Alteration and Processes of Magnetite Formation The hydrothermal activity at El Laco is clearly mani- fested in the alteration assemblages observed in the at desite. Weak propylitic and argillic alteration is pervasive throughout the complex. Sodie, potassic, and calcic alter- ation assemblages are associated with magnetite formation and occur as alteration envelopes around magnetite veins or bodies (Fig. 23). Propylitic, sodic-potassic, and calcic al- ‘eration and magnetite mineralization may have occurred simultaneously in different portions of the system. Alter ation assemblages overprinted each other in a regular se- ‘quence: first, weak propylitic alteration, then sodic-potassie alteration or silicification by cation leaching, then calcic al: teration, and, finally, magnetite = apatite + quartz = calcite alteration, Argillic alteration forming kaolinite, sericite, and alunite dominantly postdated magnetite emplacement. Siliceous alteration is observed as an overprint of sodic- potassic and argillic alteration, but itis also observed in as- sociation with argillic alteration; most likely it postdates magnetite emplacement but may overlap in time with argillic alteration. Formation of quartz and caleite veins in magnetite may be contemporaneous with siliceous altei ation, Retrograde alteration of scapolite and diopside phases to sericite, clinozoisite, ale, illite-smectite, and bi. tite may have occurred during both magnetite formation and argillic alteration, as hydrothermal fluids cooled, The alteration assemblages at El Laco are similar to those described by Hitzman et al. (1992) in their compila- tion of geological and alteration features of Proterozoic iron oxide deposits. At El Laco, however, the alteration zones appear to be telescoped: all of the alteration assem- blages described by Hitzman et al. (1992), and interpreted, by them to reflect vertical zonation within these systems, are observed together at El Laco. This may have occurred be- cause El Laco formed at very high crustal levels—where flu ids cooled rapidly—and it may be analogous to the tele scoping of alteration zones of epithermal precious and base metal deposits described by Sillitoe (1994) Hi tice a Daj Dy coe pn oot ° ; 4 ¢ ~) 7 Hyena Pid Patsy (clio "ic. 28, Schematic diagram of metsomatic reaction envelopes that formed from continued interaction of hydrothermal luis with andestic host rock,GEOLOGY AND REE GEOCHEMISTRY OF MAGNETITE DEPOSITS AT EL LACO, CHILE 323 The field relations and petrographic evidence outlined above demonstrate that hydrothermal processes were impor- tant at El Laco, and that magnetite formation occurred as part of a complex series of hydrothermal events. We believe the evidence is most consistent with the interpretation that ‘magnetite formation was one of these events. Evidence of this ineludes: (1) abundant magnetite beds that point to forma- tion by replacement of andesite flows; (2) porous textures in ‘magnetite that resemble anclesite breccia fragments partially ‘or completely replaced by magnetite and that are associated with bladed pyroxene and pyroxene casts; (3) porous regions, in magnetite that occur on a larger scale than the typical brec- cia fragments and that indicate direct replacement of u brecciated andesite (Fig. 24); (4) petrographic evidence for the direct replacement of diopside by magnetite and apatite: (5) abundant coarsegrained magnetite octahedra encrusta- tions, magnetite veins, brecciation, geyserlike magnetite ter- races, and other hydrothermal textures in magnetite; and (6) footwall breccias beneath ore horizons suggesting hydrother- ‘mal fluid flow beneath magnetite emplacement. EDS analyses of iron-phosphate alteration phases associ- ated with apatite, pyroxene, and magnetite indicate an in- troduction of iron and phosphorous to the pyroxene assem- blage with subsequent removal of silica and calcium. The calcium may have reacted with phosphate to form apatite, sometimes in place of the original pyroxene. Introduction, of iron would result in magnetite formation. A possible chemical reaction describing the replacement of diopside by magnetite and apatite is as follows: diopside + fluid —> magnetite + apatite + 2quartz Ca(Mg.Fe)Sig0, +96FeCl, + 4Ca®* + 3(PO,)* SFr 40, +H, Fe,0, Ce, ),(F) + 28i0,)9) + 5Cl-+ Vedigh +3 i « Sica remeed in this reaction could manifest self as te quartz veins or a8 regional aliceous alteration of an- estes Siitied pyroxene has abo been identified by EDS Smalyes Fluid eottaining less clelum and phosphate wll mot sreate apatite: Only magnetite wil form, as described Dye folowing reaction: diopside + fluid + magnetite + quartz Ca(Mg.Fe)Si,0, +54FeCl, + 40, + H,0 > FeO, +2510, +5CE + Cal + Mae + 2H 2) ‘Thus, field and petrographic data suggest that iron oxide deposition could have resulted from the progres. sive replacement of host-rock andesite, beginning with the formation of sodium and potassium-bearing alter- ation phases, continuing with the formation of diopside followed by magnetite = apatite, and concluding with siliceous and argillic alteration. Corroboration of this in- terpretation may be possible through the analysis of REE contents of the andesite and iron-ore assemblages pre- sented in the next section, Fro. 24, Possible sequence of alteration assemblages during replacement ‘of andesite by magnesite; samples from Laco Norte and San Vincente Bajo. A. Weaky propsltialy altered or fesh andesite i he inital sage, B. Alteration of andes by acidic Huds leaches major mineral phases and ‘ations to form a porous ind permeable rock C. Later alteration includes Ca metasomatism to cinopyroxene * magnetite and quart. This sample iscomposed of coarsely grained, bladed pyroxene. Sodic and potas a teration of andesite (not shown) may precede Ca metasomatism. D, Bladed texture of magnet sngest pseudomorphsafter pyroxene, Thin fof magaetite through sample indicates hat replacement oceurted by hydrothermal fluids, . Porous magnetite with thin magnetite veins exposed inside massive magnetite. This texture suggests replacement of Sndesite by hydrothermal magnetite Rare Earth Element Analyses ‘Methods Rare earth element contents of magnetite and of andesite whole-rock samples were determined by neutronactivation, analysis. The REE contents of apatite and pyroxene mineral, separates and of one iron oxide sample were measured by fur inductively coupled plasmasmass spectrometry (ICP-MS Activation Laboratories Ltd, Ontario, Canada, conducted all analyses. Magnetite samples were categorized by texture types (Table 2) that included ostensibly magmatic textures (bladed, finegrained, massive, and vesicular magnetite), replacement textures (porous fragments of former andesite, intergrowths. with pyroxene and pyroxene casts, and layers from the mag- netite-andesite contact at San Vincente Bajo), and hydrother- mal textures (magnetite octahedra, veins, and thinly lami- nated layers). Andesite samples included apparently unaltered, andesite, in which no alteration minerals were visible in hand, sample. However, oxygen isotope results show that even these rocks have interacted with hydrothermal fluids (Rhodes and,324 ‘Taste 2, Clasfication of Magnette, Andesite, and Mineral Separate Samples (Gasification Description ‘Mineral separates ‘AP Apatite mineral separate P Glinopyroxene mineral separate « Sulfate wholerock sample (gypsum * sulfur, ‘quartz, anyarite) Magnetve whole rock MI Bladed magnetite: parallel vertical growth of ‘magnetite occurring in columns, radial blades, and subhedgal columns that form layers; mage Mz “Masive magnetite: fine grained, massive mag. petite, vesicular magnetite, and fine-grained f- able magnetite; magmatic texture Ms Porous magnetite: finegrained magnetite = encrusted magnetite octahedra, = porous ‘egione that resemble andesite replaced by ‘magnetite + relict andesite fragments repace- ‘meat texture + hydrothermal magnetite Ma Contact zone: irom oxide layers from mag netiteandeste contact at San Vincente Bajo: whole rock includes hematite + magnetite + Jarosite; replacement texture M5, “Magnette + pyroxene: magnetite intergrown with clinopyroxene and altered relict epx sum pled from veins and andesite breeca zones, oF magnetite with pyroxene cats; replacement ted layers: iron oxide occurring as fine- Iy laminated layers suggesting deposiuon in an slqucous envionment: hydrothermal wexcure M7 Octahedral magnetite: magnetite octahedra Separated from massive magnetite and mage nette veins; hydrothermal texture Al Unaltered and weak propylie alteration a2 Partial or complete Ca metasomatism; includes samples that alo contain potasc alteration, Seapolite, and porous, leached, siliceous Andesite all simples contain clinopyroxene a3 Parial or complet agi alteration; includes samples that are most propylitally ater bu have an agile rind MM Silceous alteration atsociated with slate ost; whole rock contains quart, tidy, sf, and gypeum Oreskes, 1999). REE contents of the following alteration as- semblages in andesite were also measured: weak propylti sodicpotassic, Ca metasomatic, argc, and siliceous al ation associated with sulfate deposits. Apatite mineral sepa rates consisted of coarse, euedral crystals: one crystal was col lected from a magnetite layer at San Vincente Bajo and the other from a weathered andesite outcrop below Cristales Grandes. Pyroxene was sampled from Laco Norte magnetite and from Cametasomatically altered andesite rock from Laguito. Both apatve and pyroxene grains were separated us ing magnetic and heavy liquid methods. RHODES ET AL, REE Results REE data for all analyses are shown in Tables $ to 5. Chondritenormalized (Wheatley and Rock, 1988) distri bution patterns of apparently unaltered andesite whole- rock samples (Fig. 25) are the same as those of other Chilean andesites (Thorpe etal, 1976). They are slightly enriched in the light REE (La, Ge, Nd) and reveal a small negative to flat Eu anomaly. The distribution patterns of other andesite alteration assemblages (Fig. 26) are de- scribed generally as follows: (1) samples displaying weak propytic alteration resemble unaltered andesite and have weak, negative Eu anomaly, (2) samples partially or com pletely altered to clinopyroxene (Ca metasom: feldspar or scapolite) are depleted in light REE, s riched in heavy REE, and have a negative Eu anomaly; (3) samples exhibiting weak to intense argillic alteration ex- hibit light REE enrichmentand a strong, positive Eu anom- aly; and (4) silicified samples associated with sulfate de- poxits have a positive Eu anomaly as wel. ‘Magnetite REE distribution patterns are essentially the same in all texture types and localities (Fig. 27). All mag- netite samples have a negative Eu anomaly, and most are enriched in the light REE. Exceptions occur in samples containing pyroxene inchisions. As would be expected, these samples are depleted in the light REE relative to the intermediate and heavy REE. In general, the total REE con- tent of the magnetite samples is similar to or less than the REE content of the andesite samples. ‘The distribution patterns of the REE in apatite and py- roxene mineral separates (Fig. 28) have negative Eu anom- ales. Apatite exhibits strong light REE enrichment, and it haas the greatest concentration of REE of all the samples an- alyzed. One pyroxene sample is enriched in light REE, and the other is depleted. ‘The magnitude and direction of europium anomalies are illustrated by Eu/Eu" ratios (Fig. 29), where Eu is the ‘measured value in a sample, and Eu" is a theoretical value calculated by interpolating the distribution pattern be- tween Sm and Tb. For samples having Tb concentrations below the analytical detection limit, Eu” is calculated by ex: tending the slope of the pattern between Nd and Sm. Sev ‘eral magnetite samples have Eu concentrations below the analytical detection limit. Therefore, for these samples, culated Eu/Eu' ratios represent maximum values, and the actual Eu/Eu value could be lower. Chondrite-normalized (Wheatley and Rock, 1988) La/Sm ratios were calculated to compare enrichment in the light REE between samples relative to the middle REE (Fig. 30). The average La/Sm ratio in the magnetite sam ples is greater than in the andesites, (8.5 + 2.5 and 4.6 + 116, respectively), indicating that the majority of magnetite samples are more enriched in light REE than the hostrock andesite. However, many of the argillically altered andesite samples have higher La/Sm ratios than unaltered andesite and fall within the range of the average magnetite La/Sm ratios, Magnetite and andesite samples containing clinopy- roxene have the lowest La/Sm ratios of all the whole-rock samples, which reflects the La/Sm ratio of pyroxene min-GEOLOGY AND REE GEOCHEMISTRY OF MAGNETITE DEPOSITS AT EL LACO, CHILE 325 ‘thous 8, Rare Earth Element Concentrations and Calculated Bu/Bu" and La/Sm Ratios for Magnetite Samples lass Locality Lc Na Ea T x Lx Eu/Eu'_La/Sm Mm 1Qens |S 8 9 14 <02<05 016054 GGL Mo LOLs ~ 56 5 23 05 <05, oat 035-630 mM 1gon2 794 8 07 <02 £05, 009 1456.06 MI RNOG 27 “ 6 es a 02300 TL ML SVAOD 18 31 13 moa ah ay kos a Mi CG 9405 2h 3 3 12 £02 £05 025 0551080 M2 LQ 1a 20 57 18 27 “04 05, 04 08768 Me LQ 15 31 63 5 22805, bay 0826S M2 LOL 3 % 30 ok a, 03 © 04s GIT Mz RNOWA 0170 33 6902 <5, 15700084 Me INMOT | Bs 1 03 <5 008 100 Ba Me INOS 58 98 26 25) 08, ost 0777 Me INO 51 4 2 as oe con 058 Oot 87H Me LN OB 77180 2% ing] 0s) con 105053 Ot M2 INO 85 or 1 2 08 cos, ost 075745 M2 IS 940516 3 6 1 «ag cone . fs cc corra F 00 cece | 3 100 5 mvon_| € : XY =, 2 6 & zo i] god a 3) B= svamose pan : a) Suna to Some to Ge Md Smee eo Th Ge HN” Sm EvGi Te Oyo ETmYO ‘Rc. 26, REE distribution patterns of whole rock andesite samples For di {erentalteration assemblages at Laco, Patterns are normalized to mean chondrite vales (Wheatley and Rock, 1985); (1) weak propyl alter ‘tion; (2) seapolite + clinopyroxene alteration; (3 sliceos alteration a- sociated with sulfate deposits, (2) poasicalterason rimmed by clinopy- roxene; (5) Ca metasomatinm to clinopyroxene; (6) agile alteration, ation did not produce minerals that incorporated REE, or propylitic alteration was unrelated to the REE-bearing fluid that produced later alteration assemblages; (2) Ca metaso- matism excluded the light REE but incorporated the mid- dle and heavy REE; and (8) later argillie alteration incor- porated both the light REE and Eu. Distribution patterns of REE in magnetite, The various tex- tural types of magnetite at El Laco exhibit essentially the same REE distribution, Most are enriched in the light REE, and all have a negative Fu anomaly. There is no difference between magnetite in veins, coarse-grained octahedra, and ‘massive magnetite. The only significant exception occursin clinopyroxene-rich samples, where this mineral controls the REE distribution pattern. The uniformity of the mag- netite REE patterns strongly suggests that all of the differ- Fic, 28, REE distribution patterns of apatite and clinopyroxene (eps) ‘mineral separates, normalized to mean chondtite values (Wheatley nd Rock, 1988). cent forms of magnetite formed by the same process. Had these samples formed at different times and by different processes (e-g., early magmatic magnetite followed by mag- ‘matic-hydrothermal veins), one might expect differences in REE distribution patterns as the system evolved. Such dif ferences are not observed. These results thus cast serious doubt on the hypothesis that any significant portion of the ‘magnetite at El Laco formed by direct consolidation of an iron oxide magma. Normalizing the magnetite distribution patterns to unal- tered andesite shows the differences in REE contents from andesite (Fig. 32). Except for one sample containing pyrox- ene, all of the different magnetite textural types have nega- tive Fu anomalies and show enrichment in both light REE and heavy REE relative to andesite. The normalized distri328 RHODES ET AL. ‘SAMPLE CLASSIFICATION ‘ic. 29. Musation of Eu anomalyin mineral separates, magnetite, and an- {deste wholerock amples: Dark ccs represent simples having messed Eu concentrations below the analytical detection mit and that represent ‘maximum Eu/Eu" rao, Deseription of sample clsfications ii Table 2 Moet inte ek Wot eck sepa Iaet odes ‘SAMPLE CLASSIFICATION ic 80, Light REE ensichments of apatite, clinopyroxene, and gypsum mineral separates, and of magnetite and andesite wholerock samples a, ‘lastrated by La/Sn radios. Shaded regions define average magnetite and andesite La/Sm ratios Is standard deviation, La and Sa aze normalized to average chondrite values (Wheatley and Rock, 1988). Description of sample classifications isin Table 2 bution patterns of the majority of magnetite textures fll around a value of I, indicating that the total REE content of the magnetite is close to that of the unaltered andesite Again, this is consistent with the interpretation that mag- netite formed by replacing hostrock andesite the REE may have been largely inherited from the protolith and redis- tributed during hydrothermal alteration Evolution of REE concentrations in reforming fluids, Sev- eral studies have discussed the introduction, depletion, or remobilization of REE during hydrothermal alteration of hhost rocks associated with ore emplacement (Humphris et, al., 1978; Martin etal, 1978; Alderton et al, 1980; Leroy and Turpin, 1988; Whitford et al, 1988; Oreskes and Ein aul, 1990). Mobilization of REE in fluids is controlled by: (1) the REE concentrations of reacting minerals; (2) the stability of these mineral phases with respect to the fli (8) the availabilty of sites within secondary minerals for ac- commodating REE released during alteration; (4) the REE, FREE plot (rocklandesite) 8 (ade Ne" Smey Te Yet Foo. $1, REE distribution patterns of whotesock andesite samples for dit ferent alteration assemblages at #1 Laco. Patterns are normalized tothe ‘composition of unaltered Et Laco andesite, Nonzera slopes indicate REE enrichment or depetion from the orignal andesite due to inrodiction ‘of hydrothermal alteration fluids; (1) weak propyitie alteration; (2) lic alteration; (3) Ca metasomatism to clinopyroxene; (4) potas ak {eration rimmed by clinopyroxene; (5) scapolie+ clinopyroxene; (8) siliceous alteration asociated with slate deposits concentrations of incoming fluid; and (5) the ability of the fluid phase to transport REE out of the system (Alderton et al,, 1980). Humphris et al. (1978) emphasized that crystal- lographic controls in metasomatic minerals may largely de- termine which REE are precipitated and which are trans- ported out of the system. REE may be transported by saline alteration fluids; however, transport is enhanced by F be- ‘cause itforms more stable aqueous REE complexes than Cl (Alderton etal, 1980). Apatite at El Laco is predominantly fluorapatite, and SEM/EDS analyses of minerals of several andesite alteration assemblages detected trace concentra- tions of F. Evidently, F was present in the fluid during both alteration of andesite and ore deposition at El Laco, indi- cating that the ore-forming fluids were suitable for mobi- ing the REE, The REE distribution patterns at El Laco indicate that hydrothermal fluids carried or remobilized REE, and that these REE were partitioned from the fluid into alteration assemblages, iron-ore, and apatite. The negative Eu anom- aly observed in clinopyroxene, apatite, and magnetite (Figs, 82 and 88) is consistent with a low fo aystem, where Eu would have been present primarily as Eu®* and therefore not readily accommodated in the lattice structures of the available minerals, including the Ca site of apatite Puchelt and Emmermann, 1976). Eu is stable in high-tempera- ture fluids (>250°C) over a wide range of pH values at the ‘magnetite-hematite buffer (Sverjensky, 1984). In contrast, the positive Eu anomalies in argillically and siliceously al- tered andesite assemblages likely reflect cooling and oxida-GEOLOGY AND REE GEOCHEMISTRY OF MAGNETITE DEPOSITS AT EL LACO, CHILE 329 REE (rock/andesite) © LO.9413 bladed mt, (M1) ‘© LNo27B massive, tg. mt (M2) 12 LN tube porous + oct mt (M3) = ANOO7 t+ relict py (MS) 4 SVBO14 pyxcast + replaced and. fragment (MS) 8 LNO1GB mt + abundant pyx (M6) X LOLA mtoct. + fine grained mt (M3) 12 LNS#O7 fine-grained mt + vesicles (2) 1 SVAO05 magnetite octahedra (1-2 em; M7) + 669405 _magnatte octaheda (4 om; M7) La ce Nd" SmEu TD Rc. 32. REE patterns of magnetite with different textures normalized to REE contents of unaltered El Laco andesite, Nonzero slopes indicate enrich ‘Mentor depletion ia REE relate wo andesite. Dashed lines represent estimated slopes where the REE content was below analytical detection imi v0 0 He i t este on _ Sac team) Since Go S018 eon oor Uh Go na ‘sm eu” To Yo uy ic. $8, REE distribution patterns of apatite and clinopyroxene (cpx) ‘mineral separates normalized to unaltered E Laco andesite. tion of hydrothermal fluids at El Laco following iron depo sition, Eu°* would have become stable when the system, cooled and became oxidized (Sverjensky, 1984), and there- fore would have incorporated into hydrothermal minerals formed at that time. Thus, Eu was anomalously low in con- centration during the high-temperature alteration and ore ‘mineralization stages, butis observed in anomalously high amounts in the cooler, argillic alteration assemblages that ‘are widespread throughout El Laco. Magnetite is not normally thought of as a major REE- bearing mineral due to the small ionic radius of Fe. How- ever, Schock (1979) argued that titanomagnetite from ‘ocean-floor basalts is an important carrier of REE in mafic, volcanic rocks, which show chondrite-normalized patterns similar to the El Laco magnetite samples. Schock (1979) cited other magnetite analyses that have randomly distrib- ‘uted Ca?" ions in the magnetite structure, noting the plau- sibility that REE ions with comparable ionic radii to Ca®* could enter the same lattice sites. AtEl Laco, the magnetite and andesite whole-rock REE totals are comparable to one another, which indicates that the bulk of the REE concen- tration in magnetite is inherited from precursor andesite during the replacement process. In fact, El Laco magnetite isno more REE-rich than the associated igneous rocks. Nor have any REE poor igneous rocks been found in the region. Both of these observations contradict what would be ex- pected had the REE partitioned into an iron-rich melt that formed by liquid immiscibility. They also indicate that, con- trary to expectation, the fluids that formed magnetite at El Laco were not particularly rich in REE. If liquid immiscibility had occurred, we might expect to see higher concentrations of REE in octahedral magnetite— the textural type that shows least evidence of wall-rock re- placement. In fact, octahedral magnetite shows lower con- centrations of REE, similar to the concentrations foun vein-style magnetite. This strongly suggests that both vein. and octahedral magnetite formed from hydrothermal fluids, and that these fluids were not especially enriched in REE. Summary Field, petrographic, and SEM evidence indicate that El Laco was once a large hydrothermal system and that hy- drothermal activity was contemporaneous with magnetite ‘emplacement. Itis indisputable that some of the magnetite apatite assemblages at El Laco formed by direct precipita- tion and wallrock replacement by hydrothermal or pneu-330 RHODES ET AL. tmatolytic Aids, The question that remains is whether all of the magnetite at EI Laco is hydrothermal in origin, While it 4s not possible to rule out conclusively a magmatic compo- nent, we believe available evidence is most consistent with the interpretation that magnetite formation was a hy- Grothermabalteration event, in which iron- and phospho- rousrich fluids reacted with and replaced hostrock an- desite. Sodicpotassic and Cametasomatic alteration preceded magnetite formation. Silica that was removed during replacement was redeposited in late quarta-mag- netite veins, quartz veins, and in siliceous alteration assoc ated with argillic and sulfate deposition. REE data are consistent with this interpretation, and in- dicate that REE were mobile during Ca metasomatism, ion-apatite formation, and argillie alteration. Fluotine in the hydrothermal fluids facilitated the redistribution of REE and reaction with Ca to form apatite. The change from negative Eu anomalies in clinopyroxene, magnetite, and apatite to positive anomalies in minerals formed during later alteration events reflects change in oxidation state as the system evolved In arguing for the role of hydrothermal fluids at El Laco, wwe do not mean to suggest that the nature of such fluids is understood. On the contrary, itis clear that highly unusval fluids—rich in volatile anions such as Fand Clbut low in S and metallic cations other than iron—are required. Barton and Johnson (1996) have suggested a model for the genera- tion of such fluids. They proposed that very high salinity hy- drothermal fluids originate from evaporite sources, such as salars or buried evaporites, transport large amounts of Fe, and produce sodic alteration assemblages, Such uids would have low sulfur activites as reflected by the absence or very ‘minor occurrence of sulfides in these ypes of iron deposits, “Magmatic activity at depth would heat the fluids and drive a hydrothermal system (Barton and Johnson, 1996). Barton and Johnson's (1996) model is consistent with several aspects at El Laco: the arid climate, the proximity to playa lakes and evaporite deposits, the occurrence of sodium-bearing alteration phases (albite and scapolite), and the observation of halite inclusions in apatite that indi- cates high chlorine availability. Perhaps most critically itex- plains the abundance of Fe and the dearth of other met als—Cu, Pb, Zn, Ag or Au—that would normally be ‘expected in hydrothermal fluids of magmatic origin, How: ever, one aspect that is not explained by this model is the presence of gas-escape structures throughout El Laco. It ‘may be that the hydrothermal fluids were more fluid than hydrous—perhaps more akin to the fluids that form peg- aatites than those that cause mineralization inthe more fa ial interpretation differs from the origin by ‘magmatic intrusions and flows previously proposed for the ElLaco magnetite deposits. We argue that many of the mag- netite textures previously proposed as unequivocally mag- ‘matic are in fact not unique, and that alternate interpreta tions that include the involvement of hydrothermal and replacement processes are better to explain all of the fea- tures at El Laco, Given the longstanding controversy over the origins of the Kiruna iron ores, the ascription of El aco to a magmatic origin, based on textural similarities with. Kiruna, risks proof by circular reasoning. The El Laco de- posits need to be evaluated in their own right, rather than by comparing their common features with Kiruna—or with any other deposit whose origins are not well understood. Itis interesting to note that the giantiron deposits of the Proterozoic are often referred to as being REE-cnriched, or REE-bearing; the present authors have also used that ap- pellation. Although apatite is an important accessory min- cral at El Laco—and in some portions of the system itis vi- sually conspicuous—the deposits are not particularly rich in. REE. In fact, they may not be enriched at all, The evidence. presented here suggests that the REE in the system were re- mobilized from the andesite protolith and country rock. F in the hydrothermal fluids helped to dissolve protolith min- crals and facilitated local REE mobility. Dissolved REE re- acted with P (in the fluid) and Ca (either in the fluid or re- leased from the protolith) to form apatite, This question of how REE-tich the Proterozoic iron oxide de- posits actually are, and further strongly distinguishes El Laco from Olympic Dam. At Olympic Dam, sulfide-bearing hematite breccias are highly enriched in light REE—in some cases up to 10,000 times chondrites—and the con- centrations and ratios are such that they could not have been derived from local country rock (Oreskes and Ein- audi, 1990). This conspicuous difference between mag- netite at El Laco, with REE signatures that are consistent with derivation from the protolith, and hematite at Olympic Dam, with REE signatures that are not, strongly supports the interpretation of Oreskes and Einaudi (1990; 1992) and Haynes ct al. (1995) that mineralization at Olympic Dam involved two fluid sources: one that was hot and deep-seated, the other that was cool and surficial. The interaction of these two fluids is critical in terms of gener- ating economically significant deposits. Iron may come from hypersaline fluids interacting with mafic rocks at depth, but base metals, REE, and sulfur in these systems are largely absent unless supplied from elsewhere. The lack ofa surficial luid source at El Laco may well account for the lack of economic base metal miner exploration standpoint, hematite-ich zones may be impor- tant locales for base (or precious) metal mineralization pre- cisely because they represent the zones where oxidized wa- ters infiltrated these systems. ‘Our goal in this paper has been to point out that many of the magnetite textures at El Laco, which were previously interpreted as unequivocally magmatic, are not. Alternative interpretations that include the involvement of hydrother- ‘mal and replacement processes are equally if not more plausible, and other textures are unambiguously hy- drothermal. The questions that remain to be answered are the extent to which magnetite at El Laco formed by hy- drothermal processes, and the nature of the fluids involved. Distinguishing between hydrothermal and possible mag- ‘matic magnetite, aswell as understanding the nature of the hydrothermal fluid(s), isthe subject of our accompanying Paper (Rhodes and Oreskes, 1999). | fGEOLOGY AND REE GEOCHEMISTRY OF MAGNETITE DEPOSITS AT EL LACO, CHILE Acknowledgments, ‘We thank L. Vergara and H. Salder, Compaiiia Minera del Pacifico, Chile, L. Bullemore, Plaza, S.A., 8. Espinoza, Universidad de Antofagasta Catlotica del Norte, and J. Arias for logistical support while at El Laco. M. Astengo, J. Furr, K. Rainville, and C. Zamora assisted with fieldwork and mapping. Suggestions by H. Zantop, colleagues from IGCP 342, and a critical review by M. Hitzman have improved this ‘manuscript. Financial support for this project was provided by NSF Grant no. EAR 92:19887 to N.O., the Geological So- ciety of America, Sigma Xi Research Society, and the Stoiber Ficld Fund. 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