“Invisible gold” in pyrite is defined as an Au solid solution of the pyrite lattice, sub-microscopic Au nanoparticles (NPs) in the pyrite, or other chemisorption complexes of Au. Because the relationship between the Au and As concentrations in pyrite could indicate the genesis of the deposit, the purpose of this study is to assess the micro-analytical characteristics of the Au–As relationship in pyrite from epithermal and hydrothermally affected sedimentary Au deposits by secondary ion mass spectrometry. The Au and As concentrations in pyrite vary from 0.04 to 30 ppm and from 1 to 1000 ppm, respectively, in the high-sulfidation Nansatsu-type epithermal deposits; these concentrations are both lower than those of the low-sulfidation epithermal Hishikari deposit. The Au concentrations in pyrrhotite and pyrite reach 6 and 0.3 ppm, respectively, in the Kalahari Goldridge banded-iron-formation-hosted gold deposit, and Au in pyrrhotite may sometimes exist as NPs, whereas As concentrations in pyrrhotite and pyrite are both low and lie in a narrow range from 6 to 22 ppm. Whether Au is present as NPs is important in ore dressing. The Au and As concentrations in pyrite from the Witwatersrand gold field range from 0.02 to 1.1 ppm and from 8 to 4000 ppm, respectively. The shape of the pyrite grains might prove to be an indicator of the hydrothermal influence on deposits of sedimentary origin, which implies the genesis of the deposits.

The Takatori hypothermal tin–tungsten vein deposit is composed of wolframite-bearing quartz veins with minor cassiterite, chalcopyrite, pyrite, and lithium-bearing muscovite and sericite. Several wolframite rims show replacement textures, which are assumed to form by iron replacement with manganese postdating the wolframite precipitation. Lithium isotope ratios (δ⁷Li) of Li-bearing muscovite from the Takatori veins range from −3.1‰ to −2.1‰, and such Li-bearing muscovites are proven to occur at the early stage of mineralization. Fine-grained sericite with lower Li content shows relatively higher δ⁷Li values, and might have precipitated after the main ore forming event. The maximum oxygen isotope equilibrium temperature of quartz–muscovite pairs is 460 °C, and it is inferred that the fluids might be in equilibrium with ilmenite series granitic rocks. Oxygen isotope ratios (δ¹⁸O) of the Takatori ore-forming fluid range from +10‰ to +8‰. The δ¹⁸O values of the fluid decreased with decreasing temperature probably because the fluid was mixed with surrounding pore water and meteoric water. The formation pressure for the Takatori deposit is calculated to be 160 MPa on the basis of the difference between the pressure-independent oxygen isotope equilibrium temperature and pressure-dependent homogenization fluid inclusions temperature. The ore-formation depth is calculated to be around 6 km. These lines of evidence suggest that a granitic magma beneath the deposit played a crucial role in the Takatori deposit formation.

The Hishikari low-sulfidation epithermal gold (Au) deposit in Kyushu, Japan, is world-famous for its premium ore. It has been hypothesized that magmatic contributions to the hydrothermal fluid during early stages of mineralization is possible, even if the hydrothermal fluids for many Au occurrences near the Hishikari deposit are of meteoric origin and are influenced by basement sedimentary rocks. The purpose of this study is to obtain constraints on the genesis and evolution of hydrothermal fluids in the formation of the high-grade Hishikari Au deposit by carbon and oxygen isotope ratios of calcite-bearing samples. Since the microanalysis of carbon and oxygen isotope ratios in every 12 μm of the calcite-bearing sample along the growth direction (corresponding to 10 years of the Hishikari mineralization) scatter in a particular range, the fluid evolution might not be a gradual change from a magmatic to a meteoric origin. Alternatively, a rapid turnover of two fluids might be happening locally. The average sulfur isotope ratio of hydrothermal pyrite is similar to that of the adjacent magma. However, according to the secondary ion mass spectrometry (SIMS) microanalysis, local pyrite with extremely low sulfur isotope ratios may interact with basement sedimentary rocks. Unlike other epithermal Au deposits in the vicinity, rapid local mixing of the magmatic-origin deep fluid and meteoric-origin fluid reacted with organic matter containing basement sedimentary rocks might cause gold precipitation at the Hishikari deposit.