Gallium-aluminum systematics of marine hydrogenetic ferromanganese crusts: Inter-oceanic differences and fractionation during scavenging

Despite its status as a critical metal in the EU and the U.S., the geochemical behavior of gallium (Ga) in the Earth’s surface environment is not yet well constrained, which is in marked contrast to its geochemical partner aluminum (Al). Especially hydrogenetic ferromanganese crusts which may represent a potential future unconventional resource of critical metals, are surprisingly underexplored with regard to their Ga-Al systematics. This study presents the first data on the Ga-Al pair in hydrogenetic Fe-Mn crusts from various locations in the Pacific Ocean and from the Rio Grande Rise in the SW Atlantic. We also provide Ga-Al data for certified reference materials for Fe-Mn nodules NOD-P-1, NOD-A-1, and JMn-1. Our results also show that marine hydrogenetic Fe-Mn crusts cannot be considered an unconventional Ga resource, in marked contrast to several other critical metals. Aluminum and Ga concentrations in these precipitates are not controlled by detrital components. Both elements show a geochemical behavior comparable to that of the hydroxide-dominated elements Zr and Hf during scavenging from ambient seawater by hydrogenetic Fe-Mn crusts. The Ga/Al mass ratios of Atlantic (0.10–0.16 g/kg) and Pacific crusts (0.18–1.2 g/kg) are about one and a half orders of magnitude lower than those of respective ambient seawater and mimic the inter-oceanic fractionation of the Ga-Al pair between these two ocean basins. Without exception, the Atlantic Fe-Mn crusts show lower Ga/Al ratios than the Pacific crusts. The systematically lower Ga/Al ratios of the crusts relative to those of seawater reveal preferential scavenging of Al relative to Ga during the formation of Fe-Mn crusts. This is in line with previous studies that reported a higher particle reactivity of Al compared to Ga in the marine environment. However, this fractionation trend contradicts predictions based on a simplified model commonly used to approximate trace element scavenging by marine metal (hydr)oxides based on hydrolysis constants, which favors Ga enrichment relative to Al as the hydrolysis constant of Ga is higher than that of Al. The observed Ga-Al fractionation may be related to the preferential retention of Al compared to Ga on the surface of the Fe-Mn (oxyhydr)oxides because in contrast to Ga, desorption of Al is characterized by very slow reaction kinetics or is even irreversible. Alternatively, stronger organic complexation of dissolved Ga than Al in seawater (which is supported by the stability constants of various organic Ga and Al complexes) and the resulting preferential retention of Ga over Al in solution by dissolved organic ligands may be another viable mechanism to explain the observed Ga-Al fractionation between hydrogenetic Fe-Mn crusts and seawater. While more experimentally determined thermodynamic data are necessary, the rather consistent difference between hydrogenetic Fe-Mn crusts and ambient seawater supports an important role of organic ligands in the chemical speciation of Ga in seawater.