Natural phosphides - the minerals containing phosphorus in a redox state lower than zero – are common constituents of meteorites but virtually unknown on the Earth. Herein we present the first rich occurrence of iron-nickel phosphides of terrestrial origin. Phosphide-bearing rocks are exposed in three localities in the surroundings of the Dead Sea, Levant: in the northern Negev Desert, Israel and Transjordan Plateau, south of Amman, Jordan. Seven minerals from the ternary Fe-Ni-P system have been identified with five of them, NiP2, Ni5P4, Ni2P, FeP and FeP2, previously unknown in nature. The results of the present study could provide a new insight on the terrestrial origin of natural phosphides – the most likely source of reactive prebiotic phosphorus at the times of the early Earth.

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Cyclophosphates are a class of energy-rich compounds whose hydrolytic decomposition (ring opening) liberates energy that is sufficient for initiation of biomimetic phosphorylation reactions. Because of that, cyclophosphates might be considered as a likely source of reactive prebiotic phosphorus on early Earth. A major obstacle toward adoption of this hypothesis is that cyclophosphates have so far not been encountered in nature. We herein report on the discovery of these minerals in the terrestrial environment, at the Dead Sea basin in Israel. Cyclophosphates represent the most condensed phosphate species known in nature. A pathway for cyclophosphate geosynthesis is herein proposed, involving simple pyrolytic oxidation of terrestrial phosphides. Discovery of natural cyclophosphates opens new opportunities for modeling prebiotic phosphorylation reactions that resulted in the emergence of primordial life on our planet.

Negevite, ideally NiP2, is a new phosphide mineral from pyrometamorphic complex of the Hatrurim Formation (the Mottled Zone), Southern Levant. It is found in phosphide assemblages of the Hatrurim Basin, south Negev Desert, Israel, and Daba-Siwaqa complex, Jordan. The mineral occurs as tiny isometric grains reaching 15 μm in size and forms intimate intergrowths with other phosphides related to the Fe-Ni-P system. In reflected light, negevite is white with yellowish tint and isotropic. Reflectance values for COM recommended wavelengths [R (%), λ (nm)] are as follows: 54.6 (470), 55.0 (546), 55.3 (589), 55.6 (650). Chemical composition of the holotype specimen (electron micro-probe, wt%): Ni 42.57, Co 3.40, Fe 2.87, P 42.93, S 8.33, total 100.10, corresponding to the empirical formula (Ni0.88Co0.07Fe0.06)Σ1.01(P1.68S0.31)Σ1.99. The crystal structure of negevite was solved and refined to R1 = 1.73% based on 52 independent observed [I >2σ(I)] reflections. The mineral is cubic, space group Pa3, a = 5.4816(5) Å, V = 164.71(3) Å3, and Z = 4. Dx = 4.881(1) g/cm3 calculated on the basis of the empirical formula. Negevite is a first natural phosphide belonging to the pyrite structure type. It is a chemical and structural analog of vaesite, NiS2, krutovite, NiAs2, and penroseite, NiSe2. The well-explored catalytic and photocatalytic properties of a synthetic counterpart of negevite could provide new insights into the possible role of higher phosphides as a source of low-valent phosphorus in prebiotic phosphorylation processes.

This paper is a first detailed report of natural hexagonal solid solutions along the join Fe2P–Ni2P. Transjordanite, Ni2P, a Ni-dominant counterpart of barringerite (a low-pressure polymorph of Fe2P), is a new mineral. It was discovered in the pyrometamorphic phosphide assemblages of the Hatrurim Formation (the Dead Sea area, Southern Levant) and was named for the occurrence on the Transjordan Plateau, West Jordan. Later on, the mineral was confirmed in the Cambria meteorite (iron ungrouped, fine octahedrite), and it likely occurs in CM2 carbonaceous chondrites (Mighei group). Under reflected light, transjordanite is white with a beige tint. It is non-pleochroic and weakly anisotropic. Reflectance values for four COM recommended wavelengths are [Rmax/Rmin, % (λ, nm)]: 45.1/44.2 (470), 49.9/48.5 (546), 52.1/50.3 (589), 54.3/52.1 (650). Transjordanite is hexagonal, space group P62m; unit-cell parameters for the holotype specimen, (Ni1.72Fe0.27)1.99P1.02, are: a = 5.8897(3), c = 3.3547(2) Å, V = 100.78(1) Å3, Z = 3. Dcalc = 7.30 g/cm3. The crystal structure of holotype transjordanite was solved and refined to R1 = 0.013 based on 190 independent observed [I > 2σ(I)] reflections. The crystal structure represents a framework composed of two types of infinite rods propagated along the c-axis: (1) edge-sharing tetrahedra [M(1)P4] and (2) edge-sharing [M(2)P5] square pyramids. Determination of unit-cell parameters for 12 members of the Fe2P–Ni2P solid-solution series demonstrates that substitution of Ni for Fe in transjordanite and vice versa in barringerite does not obey Vegard’s law, indicative of preferential incorporation of minor substituent into M(1) position. Terrestrial transjordanite may contain up to 3 wt% Mo, whereas meteoritic mineral bears up to 0.2 wt% S.