Economic Geology Models 1. Geochemical Exploration and Metallogenic Studies, Northern Chile

Research was initiated in 1998 on geo-chemical methods of exploration for copper porphyry deposits buried under thick, lithified piedmont gravel cover in the Atacama Desert, Chile. Early data suggest that mineralized, saline groundwater has been episodically forced up through fracture zones to the surface during earthquakes, creating geochemical anomalies above ore deposits. Follow-up research supported by the Canadian Mining Industry Research Organization (CAMIRO) examined the composition of both groundwater and surface anomalies, confirming a link between the two. Further work suggests that the geo-chemical anomalies are the surface expression of a process common to the metallogenic evolution of many deposits. Porphyry intrusion and hypo-gene mineralization are controlled by faults, and are followed by supergene enrichment in a semi-arid climate. After burial by Miocene gravels, the climate changed to hyper-arid; estimates of the onset of hyperaridity vary from mid-Miocene (11–14 Ma) to Pliocene (~3–5 Ma). Since then, saline dewatering of the basement along long-lived faults has converted the original super-gene copper oxide assemblage, formed in equilibrium with meteoric water and lacking atacamite, to one containing atacamite [Cu2Cl(OH)3], the copper mineral especially associated with northern Chile. This interpretation is supported by studies showing that the salinity of fluid inclusions in atacamite is similar to that of local groundwater and that atacamite is considerably younger than the co-existing supergene alteration. SOMMAIRE La recherche décrite ici et initiée en 1998 visait à mettre au point des méth-odes d'exploration de gisements de porphyres cuprifères enfouis sous d'épaisses couches lithifiées de graviers dans le désert d'Atacama au Chili. Des données préliminaires indiquent que des eaux souterraines salines minéralisées ont été poussées épisodiquement jusqu'à la surface, à travers des zones de fractures, à l'occasion de séismes, créant ainsi des anomalies au-dessus de gisements minéraux. Une recherche subséquente appuyée par la Canadian Mining Industry Research Organization (CAMIRO) qui a porté sur la composition de l'eau souterraine et des anomalies de surface, a permis de confirmer l'existence d'un lien entre les deux. Les résultats de travaux subséquents permettent de croire que ces anomalies géochimiques sont l'expression en surface d'un processus commun à l'évolution métallogénique de nombreux gisements. L'intrusion porphyrique et la minéralisation hypogène sont tributaires de failles, auxquelles s'est ensuite ajouté un enrichissement supergène sous climat semi-aride. Après l'enfouissement au Miocène par des graviers, le climat est devenu hyper-aride; selon les estimations le climat serait devenu hyperaride entre le Miocène moyen (11-14 Ma) et le Pliocène (~3-5 Ma). Depuis, l'assèchement des eaux salines du socle le long de failles persistantes a entraîné une conversion de l'assemblage original d'oxydes de cuivre supergène - lequel s'était formé en état d'équilibre en milieu d'eau météorique et qui était dépourvu d'atacamite - en un assemblage contenant de l'atacamite [Cu2Cl(OH)3], ce minéral de cuivre typique du Chili du nord. Cette interprétation est corroboré par des études montrant que la salinité des inclusions fluides dans l'atacamite est semblable à celle de l'eau souterraine locale et que l'atacamite est significativement plus jeune que l'altération supergène coexistante

Spatiotemporal and multi-isotope assessment of metal sedimentation in the Great Lakes.

This study investigates spatiotemporal dynamics in metal sedimentation in the North American Great Lakes and their underlying biogeochemical controls. Bulk geochemical and isotope analyses of n=72 surface and core sediment samples show that metal (Cu, Zn, Pb) concentrations and their isotopic compositions vary spatially across oligotrophic to mesotrophic settings, with intra-lake heterogeneity being similar or higher than inter-lake (basin-scale) variability. Concentrations of Cu, Zn, and Pb in sediments from Lake Huron and Lake Erie vary from 5 to 73 mg/kg, 18 to 580 mg/kg, and 5 to 168 mg/kg, respectively, but metal enrichment factors were small (<2) across the surface- and core sediments. The isotopic signatures of surface sediment Cu (δ65Cu between -1.19‰ and +0.96‰), Zn (δ66Zn between -0.09‰ and +0.41‰) and Pb (206/207Pb from 1.200 to 1.263) indicate predominantly lithogenic metal sourcing. In addition, temporal trends in sediment cores from Lake Huron and Lake Erie show uniform metal concentrations, minor enrichment, and Zn and Pb isotopic signatures suggestive of negligible in-lake biogeochemical fractionation. In contrast, Cu isotopic signatures and correlation to chlorophyll and macronutrient levels suggest more differentiation from source variability and/or redox-dependent fractionation, likely related to biological scavenging. Our results are used to derive baseline metal sedimentation fluxes and will help optimize water quality management and strategies for reducing metal loads and enrichment in the Great Lakes and beyond

Atud Gabbro-Diorite Complex: Glimpse of the Cryogenian Mixing, Assimilation, Storage, and Homogenization Zone beneath the Eastern Desert of Egypt

We analysed gabbroic and dioritic rocks from the Atud igneous complex in the Eastern Desert of Egypt to understand better the formation of juvenile continental crust of the Arabian–Nubian Shield. Our results show that the rocks are the same age (U–Pb zircon ages of 694.5 ± 2.1 Ma for two diorites and 695.3 ± 3.4 Ma for one gabbronorite). These are partial melts of the mantle and related fractionates (εNd₆₉₀ = +4.2 to +7.3, ⁸⁷Sr/⁸⁶Sr_i = 0.70246–0.70268, zircon δ¹⁸O ∼ +5‰). Trace element patterns indicate that Atud magmas formed above a subduction zone as part of a large and long-lived (c. 60 myr) convergent margin. Atud complex igneous rocks belong to a larger metagabbro–epidiorite–diorite complex that formed as a deep crustal mush into which new pulses of mafic magma were periodically emplaced, incorporated and evolved. The petrological evolution can be explained by fractional crystallization of mafic magma plus variable plagioclase accumulation in a mid- to lower crustal MASH zone. The Atud igneous complex shows that mantle partial melting and fractional crystallization and plagioclase accumulation were important for Cryogenian crust formation in this part of the Arabian–Nubian Shield

Fractionation of sulfide phases controls the chalcophile metal budget of arc magmas: evidence from the Chilas complex, Kohistan arc, Pakistan

Some arc magmas lead to the formation of porphyry deposits in the relatively shallow upper crust (<5 km). Porphyry deposits are major sources of Cu and an important Au source but lack significant amounts of platinum group elements (PGE). Sulfide phases control the behavior of chalcophile elements and affect the potential to form ore deposits either by remaining in the mantle residue or by fractionating from arc magmas at lower crustal levels, although in detail the role of sulfide saturation in the lower crust remains poorly understood. Lower crustal cumulate rocks from the 85 Ma Chilas Complex of the Kohistan arc, Pakistan, provide insight into processes that occur at depth in arcs. Here we provide Cu, Ni, Au, and PGE concentrations and Os isotope ratios of the Chilas Complex in order to constrain the extent of sulfide saturation in the lower crust and the effect of sulfide saturation on the metal budget of evolved melts that ascend to the upper crust. The Chilas rock suite contains less than 0.17 wt % sulfides and low PGE concentrations. In situ laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) measurements of the sulfide inclusions in silicate minerals show enrichment in several chalcophile elements (up to 34 wt % Cu, 23 ppm Au, 245 ppm Pd, and 20 ppm Pt), whereas iridium group PGE (IPGE- Os, Ir, Ru) are mainly below detection limits. The metal content of the parental melt was modeled based on the elemental concentrations of the sulfides. The modeled parental arc magmas contain 70 to 140 ppm Cu, 0.2 to 1.5 ppb Au, and 1.2 to 8 ppb Pd, but low concentrations of IPGE, suggesting that IPGE were likely retained in the mantle source. Mass balance calculations show that segregation of a sulfide melt in the lower crust could further deplete the melt by more than 95% in Pd and Pt, 33 to 85% in Au, and 13 to 60% in Cu. Thus, magmas that ascend to the upper crust would contain very low concentrations of Au (< 0.2 ppb) and Pd (< 0.04 ppb), but they would retain sufficient concentration of Cu (~45–57 ppm) to form porphyry Cu deposits upon emplacement in the upper crust, as is commonly observed in arc settings

Louisville seamount subduction and its implication on mantle flow beneath the central Tonga–Kermadec arc

Subduction of intraplate seamounts beneath a geochemically depleted mantle wedge provides a seldom opportunity to trace element recycling and mantle flow in subduction zones. Here we present trace element and Sr, Nd and Pb isotopic compositions of lavas from the central Tonga–Kermadec arc, west of the contemporary Louisville–Tonga trench intersection, to provide new insights into the effects of Louisville seamount subduction. Elevated 206Pb/204Pb, 208Pb/204Pb, 86Sr/87Sr in lavas from the central Tonga–Kermadec arc front are consistent with localized input of subducted alkaline Louisville material (lavas and volcaniclastics) into sub-arc partial melts. Furthermore, absolute Pacific Plate motion models indicate an anticlockwise rotation in the subducted Louisville seamount chain that, combined with estimates of the timing of fluid release from the subducting slab, suggests primarily trench-normal mantle flow beneath the central Tonga–Kermadec arc system

New Insights into the mineralogy of the Atlantis II deep metalliferous sediments, Red Sea

The Atlantis II Deep of the Red Sea hosts the largest known hydrothermal ore deposit on the ocean floor and the only modern analog of brine pool-type metal deposition. The deposit consists mainly of chemical-clastic sediments with input from basin-scale hydrothermal and detrital sources. A characteristic feature is the millimeter-scale layering of the sediments, which bears a strong resemblance to banded iron formation (BIF). Quantitative assessment of the mineralogy based on relogging of archived cores, detailed petrography, and sequential leaching experiments shows that Fe-(oxy)hydroxides, hydrothermal carbonates, sulfides, and authigenic clays are the main “ore” minerals. Mn-oxides were mainly deposited when the brine pool was more oxidized than it is today, but detailed logging shows that Fe-deposition and Mn-deposition also alternated at the scale of individual laminae, reflecting short-term fluctuations in the Lower Brine. Previous studies underestimated the importance of nonsulfide metal-bearing components, which formed by metal adsorption onto poorly crystalline Si-Fe-OOH particles. During diagenesis, the crystallinity of all phases increased, and the fine layering of the sediment was enhanced. Within a few meters of burial (corresponding to a few thousand years of deposition), biogenic (Ca)-carbonate was dissolved, manganosiderite formed, and metals originally in poorly crystalline phases or in pore water were incorporated into diagenetic sulfides, clays, and Fe-oxides. Permeable layers with abundant radiolarian tests were the focus for late-stage hydrothermal alteration and replacement, including deposition of amorphous silica and enrichment in elements such as Ba and Au

Submarine Magmatic-Hydrothermal Systems at the Monowai Volcanic Centre, Kermadec Arc

Authors listed on this Accepted Manuscript vary slightly from those listed on the Version of Record. Harold L. Gibson is an additional author on the published version.The Monowai volcanic centre (MVC) is located at the mid-point along the ~2530 km long Tonga-Kermadec arc system, is probably the most hydrothermally active submarine volcanic system globally. The MVC is comprised of a large elongate caldera (Monowai caldera, 7.9 x 5.7 km; 35 km²; depth to caldera floor is 1590 m), which has formed within an older caldera some 84 km² in area. To the south of the nested caldera system is a large composite volcano, Monowai cone, which rises to within ~ 100 m of the sea surface and has been volcanically active for at least several decades. Despite the large size, mafic volcanic rocks dominate the MVC; basalts are the most common rock type recovered; less common are basaltic andesites and andesites. Hydrothermal plume mapping during the 2004 NZAPLUME III cruise showed at least three major hydrothermal systems associated with the caldera and cone. Monowai cone has hydrothermal venting from the summit. This summit plume is gas-rich and acidic; plume samples show a pH shift of -2.00 pH units, δ³He up to 358 ‰, H₂S concentrations up to 32 μM and CH₄ concentrations up to 900 nM. The summit plume is also metal-rich with elevated total dissolvable Fe (TDFe up to 4200 nM), TDMn (up to 412 nM), and TDFe/TDMn (up to 20.4). Monowai caldera has a major hydrothermal vent system with plumes extending from ~ 1000 to 1400 m depth. The caldera plume has lower values for TDFe, although ranges to higher TDMn concentrations than the summit plume, and is relatively gas-poor (no H₂S detected, pH shift of -0.06 pH units, CH₄ concentrations up to 26 nM). Hydrothermal vents have been observed associated with prominent basaltic andesite ridges (Mussel Ridge) proximal to the southwest wall of the caldera (1025 – 1171 m depth). However, the composition of the hydrothermal plumes in the caldera are different to the vents, indicating that the source of the caldera plumes is at greater depth and is more metal-rich and therefore likely higher temperature. Minor plumes detected as light scattering anomalies down the northern flank of Monowai caldera most likely represent resuspension of volcanic debris. Particulate samples from both the cone sites and the caldera site are enriched in Al, Ti, Ca, Mg, Si, and S, with the cone summit plume especially enriched in K, As, W and Cu, Pb, Zn. The elevated Ti and Al suggest acidic water-rock reactions and intense high-sulfidation alteration of the host volcanic rocks. Observations from submersible dives with Pisces V in 2005 and the remotely operated vehicle ROPOS in 2007 of Mussel Ridge indicate numerous low temperature vents (< 60°C), with a large biomass of vent-associated fauna, in particular large accumulations of the mussel Bathymodiolus sp. and the tubeworm Lamellibrachia sp. We interpret the Monowai volcanic centre as possessing a robust high-sulfidation magmatic-hydrothermal system, with significant differences in the style and composition of venting at the cone and caldera sites. At Monowai cone, the large shifts in pH, elevated TDFe and TDFe/TDMn, and H₂S-, CH₄- and ³He-rich nature of the plume fluids coupled with elevated Ti, P, V, S and Al in the particulates indicates significant magmatic volatile ± metal contributions to the hydrothermal system and aggressive acidic water-rock interaction. By contrast, Monowai caldera has low TDFe/TDMn in hydrothermal plumes; however, end-member vent fluid compositions, combined with presence of alunite, sulfide minerals and native sulfur in samples from Mussel Ridge suggest recent acid volatile-rich venting and active Fe-sulfide formation in the subsurface, and the potential for the presence of significant SMS mineralization

A new approach to laser-ablation inductively-coupled-plasma mass-spectrometry (LA-ICP-MS) using the flexible map interrogation tool 'Monocle'

A new flexible interrogation tool for 2-dimensional LA-ICP-MS element and isotope maps is presented. Called Monocle, the tool works as an add-on in the software Iolite. Initial inspection of map data is undertaken with a size and shape adjustable loupe that is moved across the map. As the loupe is panned over the map, histograms and density/probability plots of the element concentration (or ratio, or age) contained within the area under the loupe are displayed. The data of any loupe position can be saved as a region of interest (ROI) in a table. For maps with rare earth element (REE) data a live normalised REE graph can be shown. Similarly, live graphs (e.g. Wetherill or Tera-Wasserburg concordiae) can be displayed for U/Pb data. The second step of map interpretation refines the initial data selection, for example by drawing polygons over irregular zones of similar chemistry. Where areas are separated (e.g. by cracks) several polygons can be nested into one ROI to improve counting statistics. Additional means of data pooling exist. Firstly, by growing a ROI from a seed, whereby the data distribution in the seed is used to find adjacent pixels that are within a user defined statistical boundary (e.g. 1 standard deviation). Secondly, multiple criteria can be set (e.g. element A > 0.1 ppm and element B < 40 wt%) to determine which pixels (connected or unconnected) are included in a ROI. This new approach is illustrated with several examples. A Mariana Arc oceanic Mn crust is used to show how elemental maps resolve alternating periods of precipitation from variably intense hydrothermal input and how their REE systematics reflect mixing between two distinct sources. A map of a garnet from a lherzolite illustrates that with modern LA-ICP-MS instruments it is possible to obtain reproducible REE data from strongly depleted mantle minerals (e.g. La approximate to 14 ppb) with a 20 x 20 mu m(2) beam and how mineral inclusions, metasomatism and serpentinisation can be avoided to obtain data from the most pristine parts of a grain. A map of a zoned augite crystal from Mt. Etna was used to examine the distribution of Ni and Cr, whose interrelationship in the strong oscillatory zoning can be modelled with extreme fractional crystallisation. A U/Pb map of a complex zircon was used to separate data from the complex inherited core and the much younger magmatic rim. Extraction of data from 2-dimensional maps ( < 1 mu m deep) avoids limitations of conventional LA-ICP-MS analysis that typically ablates much deeper. In combination with fast aerosol transfer systems that permit high repetition rate mapping (50-80 Hz), extraction of quantitative data with map analysis tools heralds a new era of in situ chemical and isotopic analysis