Mineral thermometry and fluid inclusion studies of the Pea Ridge iron oxide-apatite–rare earth element deposit, Mesoproterozoic St. Francois Mountains Terrane, southeast Missouri, USA
Mineral thermometry and fluid inclusion studies were conducted on variably altered and mineralized samples from the Mesoproterozoic Pea Ridge iron oxide-apatite (IOA)-rare earth element (REE) deposit in order to constrain P-T conditions, fluid chemistry, and the source of salt and volatiles during early magnetite and later REE mineralization.
Scanning electron microscopy (SEM)-cathodoluminescence and SEM-backscatter electron images show that quartz and rutile precipitated before, during, and after magnetite and REE mineral growth. Ti-in-quartz and Zr-in-rutile equilibration temperatures range from ≤350° to 750°C in the amphibole, magnetite, hematite, and silicified zones where T increased during magnetite and quartz growth and dropped precipitously after fracturing and brecciation. Late drusy quartz cements within a REE-rich breccia pipe record the lowest T (≤315°–400°C).
Liquid-, vapor-rich, and hypersaline (±hematite, calcite) fluid inclusions are common and liquid CO2 is present locally. Salinities define three populations: saline (10–27 wt % NaCl equiv), hypersaline (34–>60 wt % NaCl equiv), and dilute (0–10 wt % NaCl equiv ). The wide range of eutectic melting temperatures (−67° to −19°C) suggests that saline inclusions trapped variable proportions of a CaCl-MgCl-FeCl-bearing fluid end member and an NaCl-KCl fluid end member. Homogenization temperatures and pressures of these saline inclusions suggest they were trapped when fluids unmixed into brine and vapor at T <350°C, P <15 MPa, and a depth of ~1.5 km. Hypersaline inclusions were trapped at low T and P (~200°C and ~1 MPa) along the V + L + H curve when the system vented to the paleosurface. Data for dilute inclusions in late drusy quartz from the REE-rich breccia pipe are indicative of a boiling epithermal environment.
The Na/Cl, Na/K, and Cl/Br ratios of fluid inclusion extracts provide evidence for mixtures of magmatic hydrothermal fluids and evaporated seawater. Extracts from magnetite, hematite, and pyrite plot in the magmatic-hydrothermal field, indicating that Fe was derived from a magmatic source. Their enrichments in Mg and Ca are consistent with a mafic magmatic source. The positive correlation between Na/Mg and Na/Ca ratios may be due to halite saturation or albitization of igneous rocks. Extracts from barite in the REE-rich breccia pipes are enriched in Na and Br and plot near the seawater evaporation trend.
He is highly enriched relative to Ne and Ar in fluid inclusion extracts, which precludes air as a source of He. Although the He is mostly of crustal origin, pyrite with a 3He/4He (R/RA) of 0.1 contains up to 12% mantle He. Many extracts have low 20Ne/22Ne ratios due to nucleogenic production of 22Ne in high F/O minerals such as fluorapatite or F biotite. The arrays of data for 3He/4He (R/RA) and 22Ne/20Ne suggest that volatiles were derived from two sources, a moderate F mafic magma containing mantle He and a high F silicic magma with crustal He.
Together with other evidence cited in this report, these data (1) support a magmatic hydrothermal origin for the Mesoproterozoic magnetite-apatite deposit with ore fluids derived from a concealed mafic to intermediate-composition intrusion, (2) suggest that the REE minerals in breccia pipes were either derived from apatite or precipitated in response to decompression and cooling during breccia pipe formation, (3) provide evidence for the influx of basinal brine, magmatic fluids from granitic intrusions, and meteoric water after breccia pipe formation, and (4) show that Pea Ridge was relatively unaffected by the late Paleozoic Mississippi Valley-type (MVT) Pb-Zn system in overlying Cambrian sedimentary rocks.