Nora K. Foley

The principal rare earth elements deposits of the United States-A summary of domestic deposits and a global perspective

Demand for the rare earth elements (REE, lanthanide elements) is estimated to be increasing at a rate of about 8% per year due to increasing applications in consumer products, computers, automobiles, aircraft, and other advanced technology products. Much of this demand growth is driven by new technologies that increase energy efficiency and substitute away from fossil fuels. Production of these elements is highly concentrated in China, which is reducing its exports of REE raw materials as part of its industrial policy. The ability of the rest of the world to replace supply from China depends on the quality of known REE resources and the degree to which those resources have been explored and evaluated. A review of United States resources in a global context finds that the United States could make significant contributions to future REE production. Aside from two advanced projects in the United States and Australia, however, there are no REE projects advanced enough to meet short-term demand.

Mineral sources and transport pathways for arsenic release in a coastal watershed, USA

Metasedimentary bedrock of coastal Maine contains a diverse suite of As-bearing minerals that act as significant sources of elements found in ground and surface waters in the region. Arsenic sources in the Penobscot Formation include, in order of decreasing As content by weight: löllingite and realgar (c. 70%), arsenopyrite, cobaltite, glaucodot, and gersdorffite (in the range of 34–45%), arsenian pyrite (<4%), and pyrrhotite (<0.15%). In the Penobscot Formation, the relative stability of primary As-bearing minerals follows a pattern where the most commonly observed highly altered minerals are pyrrhotite, realgar, niccolite, löllingite > glaucodot, arsenopyrite-cobaltian > arsenopyrite, cobaltite, gersdorffite, fine-grained pyrite, Ni-pyrite > coarse-grained pyrite. Reactions illustrate that oxidation of Fe-As disulphide group and As-sulphide minerals is the primary release process for As. Liberation of As by carbonation of realgar and orpiment in contact with high-pH groundwaters may contribute locally to elevated contents of As in groundwater, especially where As is decoupled from Fe. Released metals are sequestered in secondary minerals by sorption or by incorporation in crystal structures. Secondary minerals acting as intermediate As reservoirs include claudetite (c. 75%), orpiment (61%), scorodite (c. 45%), secondary arsenopyrite (c. 46%), goethite (<4490 ppm), natrojarosite (<42 ppm), rosenite, melanterite, ferrihydrite, and Mn-hydroxide coatings. Some soils also contain Fe-Co-Ni-arsenate, Ca-arsenate, and carbonate minerals. Reductive dissolution of Fe-oxide minerals may govern the ultimate release of iron and arsenic – especially As(V) – to groundwater; however, dissolution of claudetite (arsenic trioxide) may directly contribute As(III). Processes thought to explain the release of As from minerals in bedrock include oxidation of arsenian pyrite or arsenopyrite, or carbonation of As-sulphides, and most models based on these generally rely on discrete minerals or on a fairly limited series of minerals. In contrast, in the Penobscot Formation and other metasedimentary rocks of coastal Maine, oxidation of As-bearing Fe-cobalt-nickel-sulphide minerals, dissolution (by reduction) of As-bearing secondary As and Fe hydroxide and sulphate minerals, carbonation and/or oxidation of As-sulphide minerals, and desorption of As from Fe-hydroxide mineral surfaces are all thought to be involved. All of these processes contribute to the occurrence of As in groundwaters in coastal Maine, as a result of variability in composition and in stability of the As source minerals. Arsenic contents of soils and groundwater thus reflect the predominant influence and integration of a spectrum of primary mineral reservoirs (instead of single or unique mineral reservoirs). Cycling of As through metasedimentary bedrock aquifers may therefore depend on consecutive stages of carbonation, oxidation and reductive dissolution of primary and secondary As host minerals.

Anthropogenic and natural lead isotopes in Fe-hydroxides and Fe-sulphates in a watershed associated with arsenic-enriched groundwater, Maine, USA

A survey of the natural and anthropogenic sources of lead contributing to secondary minerals in sulphidic schists associated with arsenic-enriched groundwater in Coastal Maine shows that the most likely source is natural Pb, particularly from coexisting sulphide minerals. The secondary minerals also reflect notable contributions from anthropogenic Pb. The Pb isotopes establish pathways by which Pb, and by inference As, could have been transported from As-bearing minerals (arsenian pyrite, arsenopyrite, lollingite, orpiment, arsenic oxide and others), via sulphide oxidation or carbonation reactions into multiple generations of secondary minerals (goethite, hematite, jarosite, natrojarosite and others). Lead isotopic compositions of the sulphides and secondary minerals determined by thermal ionization mass spectrometry (n=53) range widely. Lead and As contents of the sulphides and secondary minerals overlap, and are generally positively correlated. Pyrite, the dominant sulphide in sulphidic schists associated with As-enriched groundwater in Coastal Maine, has values of 206Pb/204Pb from 18.186 to 18.391, 207Pb/204Pb from 15.617 to 15.657, 208Pb/204Pb from 38.052 to 38.210, 206Pb/207Pb from c. 1.1625 to 1.1760 and 208Pb/207Pb from c. 2.4276 to 2.4394. Mixtures of Fe-hydroxide and oxide minerals (predominantly goethite and hematite) and secondary Fe-sulphate minerals (jarosite, natrojarosite, rozenite and melanterite) in the sulphidic schists have overlapping but generally higher values of 206Pb/204Pb from 18.495 to 19.747 (one sample at 21.495), 207Pb/204Pb from 15.595 to 15.722 (one sample at 15.839), 208Pb/204Pb from 38.186 to 39.162, 206Pb/207Pb from c.1.1860 to 1.2575 (one sample at 1.3855) and 208Pb/207Pb from c. 2.4441 to 2.4865 than the sulphides. Sulphides from Zn-Pb metal mines are somewhat less radiogenic than sulphides from the schists. Other sulphides (mostly pyrite) associated with pegmatites and granitic rocks are heterogeneous and more radiogenic than the pyrite-rich sulphidic schists. Sulphides from other regional bedrock units also have heterogeneous isotope values. Lead isotopic compositions of the sulphides from the sulphidic schists and coexisting Fe-oxides and Fe-sulphates produced by weathering and alteration overlap, but the secondary minerals extend toward more radiogenic values that broadly indicate the addition of Pb from anthropogenic origin. As a component of Pb from extensively used arsenical pesticides may also be present in the secondary minerals, the range in Pb isotope values is consistent with multiple sources: natural Pb from the schists and anthropogenic Pb (industrial and possibly from agricultural activities). Contributions from past mining activities or from other bedrock sources are not implicated.

Soil geochemical survey of abandoned mining sites in the Eastern-Central Peloritani Mountains, Sicily, Italy

This investigation focused on topsoils (n = 122) and vertical profiles (n = 6) distributed over an area of 250 km2 in the eastern-central Peloritani Mountains, northeastern Sicily. Georeferenced concentration of 53 elements (including potentially harmful ones), determined by ICP-MS after an aqua regia leach, were used to produce geochemical maps by means of a GIS-aided spatial interpolation process. Results show that there are two distinct areas: the larger, located between the Fiumendinisi, Budali and Ali villages, and the other between C. Postlioni and Femmina Morta, which contain anomalous As (up to 727 mg/kg), Sb (up to 60 mg/kg), Ag (up to 1 mg/kg) and Au (up to 0.1 mg/kg) concentrations. Most of the investigated areas have high contamination levels for As, Zn, Sb, and Pb that exceed the threshold values (As = 20 mg/kg, Zn = 150 mg/kg, Sb = 10 mg/kg and Pb = 100 mg/kg) established for soils by the Italian Environmental Law (Decreto Legislativo 2006, number 152). The isotopic ratios of 206Pb/207Pb and 208Pb/207Pb have been measured in selected soils on both leaches [using 1M HNO3–1.75M HCl (50:50)] and residues thereof. Soil leach reflects possible anthropogenic contamination, whereas soil residues indicate geogenic contributions. Results suggest that most of contamination in the soils is related to the presence of sulphide and sulphosalt rock-forming minerals in the surveyed area. The soil fraction contains a Pb value >1600 mg/kg and has ratios of 1.1695 for 206Pb/207Pb and 2.4606 for 208Pb/207Pb. Only one soil leach isotopic composition could reflect possible anthropogenic contamination. The correlation among As, Zn, Pb contents v. Pb isotopic signatures of 206Pb/207Pb indicates that surface and deep soils collected from profiles are dominated by geogenic compositions.

REE Distribution and Mobility in Regolith Formed on Granite Bedrock of the Southeast United States

Rare earth elements (REE) ion-adsorption clay deposits are of global economic importance. There is considerable ambiguity regarding the origin and global distribution of the deposit type, which is currently mined only in South China. While all weathered materials may contain some exchangeable REE, the importance of weathering of REEenriched parent material is in the generation of high concentrations of selected REE. Ionadsorption clay deposits of China have grades from ~500 to over 3000 ppm total rare earth oxide. South China clay deposits enriched in heavy REE relative to light REE currently supply virtually all of the heavy REE to global markets (Yang et al., 2013). We present results of mineralogical, REE geochemistry and radiogenic isotope (Nd-Sr-Pb) studies of weathered metaluminous-to-alkaline igneous rocks of the Southeast United States. Our studies are aimed at understanding the genesis of REE-enriched regolith profiles and how that information can be used to discern whether there is significant potential for economic REE ion-adsorption clay deposits in the United States. The main criteria of this deposit model include the presence of large igneous suites, generally granitic rocks; long periods of intense weathering with little subsequent erosion; and evidence for mobility and enrichment of REE within the developing regolith profile. Source rocks for the South China deposits are described mainly as granitic rocks that range from calc-alkaline to alkaline compositions. REE mobilization processes are thought to include late-magmatic-to-deuteric alteration and deep lateritic weathering. The REEs can occur as ionic REE adsorbed to clay, and as secondary REE-carbonate and/or phosphate minerals. 2 Weathered Granites from the Southeast United States

Geologic, geochemical, and isotopic studies of a carbonate- and siliciclastic-hosted Pb-Zn deposit at Lion Hill, Vermont

A report about the potential for Irish-type Pb-Zn deposits in a platform rocks of western Vermont; however, at Lion Hill they contain enrichments of Pb, Zn, and Cu rather than a Pb, Zn, and Ag association.