Long-Term Arsenic Sequestration in Biogenic Pyrite from Contaminated Groundwater: Insights from Field and Laboratory Studies

Pumping groundwater from arsenic (As)-contaminated aquifers exposes millions of people, especially those in developing countries, to high doses of the toxic contaminant. Previous studies have investigated cost-effective techniques to remove groundwater arsenic by stimulating sulfate-reducing bacteria (SRB) to form biogenic arsenian pyrite. This study intends to improve upon these past methods to demonstrate the effectiveness of SRB arsenic remediation at an industrial site in Florida. This study developed a ferrous sulfate and molasses mixture to sequester groundwater arsenic in arsenian pyrite over nine months. The optimal dosage of the remediating mixture consisted of 5 kg of ferrous sulfate, ~27 kg (60 lbs) of molasses, and ~1 kg (2 lbs) of fertilizer per 3785.4 L (1000 gallons) of water. The remediating mixture was injected into 11 wells hydrologically upgradient of the arsenic plume in an attempt to obtain full-scale remediation. Groundwater samples and precipitated biominerals were collected from June 2018 to March 2019. X-ray diffraction (XRD), X-ray fluorescence (XRF), electron microprobe (EMP), and scanning electron microscope (SEM) analyses determined that As has been sequestered mainly in the form of arsenian pyrite, which rapidly precipitated as euhedral crystals and spherical aggregates (framboids) 1–30 μm in diameter within two weeks of the injection. The analyses confirmed that the remediating mixture and injection scheme reduced As concentrations to near or below the site’s clean-up standard of 0.05 mg/L over the nine months. Moreover, the arsenian pyrite contained 0.03–0.89 weight percentage (wt%) of sequestered arsenic, with >80% of groundwater arsenic removed by SRB biomineralization. Considering these promising findings, the study is close to optimizing an affordable procedure for sequestrating dissolved As in industry settings.

EVOLUTION OF INVISIBLE Au IN ARSENIAN PYRITE IN CARLIN-TYPE Au DEPOSITS

A significant characteristic distinguishing Carlin-type Au deposits from other Au deposits is the abundance of invisible Au in arsenian pyrite. Gold occurs primarily as ionic Au1+ in arsenian pyrite and is unstable during subsequent thermal events. In this study, we used the focused ion beam combined with scanning electron microscope (FIB-SEM) techniques, and a transmission electron microscope (TEM) to examine invisible Au and how it evolved through later geologic events that eventually led to the formation of Au nanoparticles. FIB-SEM techniques were used to prepare site-specific TEM foils from four Carlin-type gold deposits, including Getchell and Cortez Hills, Nevada, USA, and Shuiyindong and Jinfeng, Guizhou Province, China. These samples were analyzed to quantify ore pyrite chemistry and evaluate textures at the nanometer scale. In 17 examined TEM foils, we observed widespread Au-rich domains in high-grade Au arsenian pyrites from the Getchell and Cortez Hills Au deposits and the Jinfeng deposit but only 10 Au-bearing nanoparticles, ~10 to 20 nm in diameter. The Au-rich domains exhibit Au (Sb), (Tl), (Hg), and (Cu) peaks in the energy dispersive X-ray (EDX) spectrum without the presence of recognizable nanoparticles. This confirms that Au is invisible even at a nanometer scale and is most likely present in the crystal structure of arsenian pyrite. Stacking faults and nanometer-sized fluid inclusions were commonly observed in Au-bearing arsenian pyrite from the four deposits, implying rapid crystallization. Moreover, unlike the coarsely crystalline arsenian pyrite from Guizhou Carlin-type Au deposits, arsenian pyrite from Carlin-type deposits in Nevada consists of fine-grained polycrystalline aggregates, further implying rapid crystallization. Additionally, curved dislocations were commonly pinned by solid inclusions, reflecting a former annealing process. Combining nanoscale textures with geologic information previously reported for Carlin-type deposits, invisible ionic Au was initially incorporated into the crystal structure of arsenian pyrite during rapid precipitation. Subsequent post-ore magmatic events in both districts initiated the annealing of the ionic Au-bearing arsenian pyrite, leading to the redistribution of trace elements and formation of Au-bearing nanoparticles in the arsenian pyrite. The presence of predominantly ionically bonded Au in arsenian pyrite confirms that ore fluids were not saturated in Au when Au-bearing arsenian pyrite formed, as previously reported for Carlin-type deposits. Ionic Au that was scavenged from an undersaturated ore fluid and incorporated into the arsenian pyrite crystal structure formed the giant Carlin-type Au deposits.

Chapter 15: Goldstrike Gold System, North Carlin Trend, Nevada, USA

The Eocene Goldstrike system on the Carlin Trend in Nevada is the largest known Carlin-type gold system, with an endowment of 58 million ounces (Moz) distributed among several coalesced deposits in a structural window of gently dipping carbonate rocks below the regional Roberts Mountains thrust. The 3.5- × 2.5-km Goldstrike system is bounded to the east by the Post normal fault system and to the south by the Jurassic Goldstrike diorite stock and is partly hosted in the favorable slope-facies apron of the Bootstrap reef margin that passes through the system. The carbonate and clastic sedimentary sequence is openly folded, cut by sets of reverse and normal faults, and intruded by the Jurassic Goldstrike stock and swarms of Jurassic and Eocene dikes, establishing the structural architecture that controlled fluid flow and distribution of Eocene mineralization. A proximal zone of permeability-enhancing decarbonatization with anomalous gold (>0.1 ppm) extends a few hundreds of meters beyond the ore footprint and lies within a carbonate δ18O depletion anomaly extending ~1.4 km farther outboard. The full extent of the larger hydrothermal system hosting Goldstrike and adjacent deposits on the northern Carlin Trend is outlined by a 20- × 40-km thermal anomaly defined by apatite fission-track analyses. The bulk of the mineralization is hosted in decarbonatized sedimentary units with elevated iron contents and abundant diagenetic pyrite relative to background. Gold is associated with elevated concentrations of As, Tl, Hg, and Sb, and occurs in micron-sized arsenian pyrite grains or in arsenian pyrite overgrowths on older, principally diagenetic pyrite, with sulfidation of available iron as the main gold precipitation mechanism. The intersection of a swarm of Jurassic lamprophyre dikes with the edge of the limestone reef provided a favorable deeply penetrating structural conduit within which a Jurassic stock acted as a structural buttress, whereas the reef’s slope-facies apron of carbonate units, with high available iron content, provided a fertile setting for Carlin-type mineralization. The onset of Eocene extension coupled with a southwestward-sweeping Cenozoic magmatic front acted as the trigger for main-stage gold mineralization at 40 to 39 Ma. All these factors contributed to the exceptional size and grade of Goldstrike.

A Nanoscale Investigation of Carlin-Type Gold Deposits: An Atom-Scale Elemental and Isotopic Perspective

Carlin-type gold deposits are one of the most important gold mineralization styles in the world. Despite their economic importance and the large volume of work that has been published, there remain crucial questions regarding their metallogenesis. Much of this uncertainty is due to the cryptic nature of the gold occurrence, with gold occurring as dispersed nanoscale inclusions within host pyrite rims that formed on earlier formed barren pyrite cores. The small size of the gold inclusions has made determining their nature within the host sulfides and the mechanisms by which they precipitated from the ore fluids particularly problematic. This study combines high-resolution electron probe microanalysis (EPMA) with atom probe tomography (APT) to constrain whether the gold occurs as nanospheres or is dispersed within the Carlin pyrites. APT offers the unique capability of obtaining major, minor, trace, and isotopic chemical information at near-atomic spatial resolution. We use this capability to investigate the atomic-scale distribution of trace elements within Carlin-type pyrite rims, as well as the relative differences of sulfur isotopes within the rim and core of gold-hosting pyrite. We show that gold within a sample from the Turquoise Ridge deposit (Nevada) occurs within arsenian pyrite overgrowth (rims) that formed on a pyrite core. Furthermore, this As-rich rim does not contain nanonuggets of gold and instead contains dispersed lattice-bound Au within the pyrite crystal structure. The spatial correlation of gold and arsenic within our samples is consistent with increased local arsenic concentrations that enhanced the ability of arsenian pyrite to host dispersed gold (Kusebauch et al., 2019). We hypothesize that point defects in the lattice induced by the addition of arsenic to the pyrite structure facilitate the dissemination of gold. The lack of gold nanospheres in our study is consistent with previous work showing that dispersed gold in arsenian pyrite can occur in concentrations up to ~1:200 (gold/arsenic). We also report a method for determining the sulfur isotope ratios from atom probe data sets of pyrite (±As) that illustrates a relative change between the pyrite core and its Au and arsenian pyrite rim. This spatial variation confirms that the observed pyrite core-rim structure is due to two-stage growth involving a sedimentary or magmatic-hydrothermal core and hydrothermal rim, as opposed to precipitation from an evolving hydrothermal fluid.