Image analysis from TEM and AFM micrograph, Table S1, S2, S3, Figure S1, Figure S2

We report on metal enrichment along a natural pH gradient owing to increased CO2 degassing at cold, shal- low seeps of Vulcano Island in the Mediterranean Sea, off Sicily. We assessed composition of unfiltered and filtered seawater (b100 nm) along acidic zones ranging between ambient and pH 5, and showed that most seep derived elements are present as nanoclusters which then aggregate into larger colloids while mixing with ambient seawater along a pH gradient. Size and elemental composition of such naturally occurring nanoparticles assessed by modern characterisation methods were in good agreement with the results from conventional analytical methods. We provide analytical evidence for the presence in the water column of a large fraction of seep derived ele- ments (e.g. approximately 50% of iron, over 80% of Mn, 100% of Cr, S and Zn) in the form of nano sized par- ticles (e.g. b100 nm) even at typical open ocean pHs. We launch in situ sampling protocols and sample preparation procedures for multi-method suitable to obtain accurate measurements on nanoparticles from environmental samples. Based on our results a first insight to the formation of natural nanoparticles at cold CO2 seeps is presented and the persistence of such nano-clusters in the surrounding seawater is stipulated.

Description of manganese nodules collected in a metamorphic limestone Cambrian formation near Philipsburg, Montana

In the Philipsburg district, in western Montana a low arch of a Paleozoic limestones has been cut and deformed on the east and a south sides by a small batholith of Tertiary granodiorite. The manganese deposits are confined to an area of about 2 square miles underlain by sedimentary rocks and adjacent to the granodiorite body. The ore, chiefly pyrolusite, was apparently derived from rhodochrosite that was abundant in the veins and had replaced the adjacent limestones. The oxide ore is found chiefly within 600 feet of the surface, though one small body was mined at a depth of 700 feet. Commonly these bodies are aggregates of nodules or spheroids that range in size from that of an egg to that of a coconut or larger. In some places they show an irregular texture somewhat like that of a sponge, and in others the material composing them is loose and friable and apparently structureless. Psilomelane is the principal constituent of many of the nodules, in which it forms layers that alternate with softer oxides.