The nature and origin of pigments in black opal from Lightning Ridge, New South Wales, Australia

Black opal (opal-AG) owes its dark coloration to a fine-grained pigment commonly inferred to be mainly carbon, yet chemical compositions for black opals suggest there may be additional components. Here we search for such components in pigment concentrates prepared by dissolving black opal nodules (nobbies) from Lightning Ridge (NSW) in hydrofluoric acid, using electron microscopy (scanning electron microscopy, transmission electron microscopy), X-ray diffraction and laser-ablation ICP-MS. The results demonstrate the presence of sulfides-predominantly pyrite and chalcopyrite, with minor galena and Ti-oxide phases, as additional components of the pigment. ATR-FTIR analysis indicates the presence of C=O and C-H groups, consistent with an organic origin. Transmission electron microscopy images of pigment show variously deformed, originally spherical similar to 100 nm particles rich in sulfide and carbon, which are interpreted as thin coatings of pigment on now dissolved opaline silica spheres. Laser-ablation ICP-MS analysis identifies remnant silica in pigment concentrates, which may be interpreted as opaline silica surviving HF treatment protected as inclusions in sulfides. When examined within the context of petrographic observations from more than 1000 opal nodules (nobbies) at Lightning Ridge, these new results suggest that pigment carbon and sulfides in the nodules formed microbially under initially anoxic groundwater conditions, within pre-existing cavities concurrently being filled with silica sol ultimately derived from chemical weathering of feldspar-rich volcaniclastic sediment. Intensely black pigment layers observed at the floor of many nodules indicate settling of dark, high-density (sulfide-Ti-oxide-rich) pigment within cavities, with the implication that sulfate-reducing bacterial (SRB) activity commences early during the silica sol-gel ripening process. Microbial activity may persist until after the cavity has completely filled with the silica sol, as illustrated by abundant black opals with uniformly distributed pigment. Pigment formed at this stage may no longer be able to settle out within the ripening and increasingly viscous silica gel, thus forming pigmentation throughout the opal cavity. The existence of 'amber', pigment-poor opal with intensely black basal pigment layers is interpreted as signalling a lack of sulfate to sustain further SRB activity, or a change to more oxidising conditions, possibly related to interaction with surface waters within a downward-penetrating weathering front. A change in redox conditions would shut off activity of SRB and thus sulfide pigment production and allow development of aerobic microbial activity as described by others.