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Chemical Diversity of Metal Sulfide Minerals and Its Implications for Origin of Life

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Chemical Diversity of Metal Sulfide Minerals and Its Implications for Origin of Life Chemical Diversity of Metal Sulfide Minerals and its Implications for Origin of Life Yamei Li 1*, Norio Kitadai 1 and Ryuhei Nakamura 1,2* 1 Earth-Life Science Institute, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro-ku, Tokyo 152-8550, Japan; 2 Biofunctional Catalyst Research Team, RIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako, Saitama 351-0198, Japan; * Correspondence: [email protected]; [email protected]; Tel.: +81-3-5734-3414 60000 55000 50000 45000 2 40000 FeS 35000 2 30000 CuFeS 25000 Locality counts 20000 12 S 4 15000 8 4 S Sb 7 ] 14 4 2 8 2 S FeAsS Fe S (x = 0-0.07) 6 FeS S 10000 3 5 Fe 9 4 4 S 4 1+x S 2 FeS 2 Cu S Cu 2 FeSnS [ FeSb 2 6 5000 4 (Ni,Fe) FeS CuFe Cu Ag Pb FeSb (Fe,Ni) 0 FeNi Pyrite Idaite Bornite Troilite CubaniteStannite Violarite Valleriite Pyrrhotite Marcasite Berthierite Pentlandite Jamesonite Freibergite Isocubanite Daubréelite Chalcopyrite Arsenopyrite Mackinawite Gudmundite Figure S1. Species-locality distribution of Fe-containing sulfides (top 20). 1800 8 S 1600 9 1400 (Ni,Fe) 1200 1000 NiS 800 S NiAsS Locality counts 1-1.07 4 600 Cl S 26 2 S 4 (Fe,Ni) 25 8 S 2 2 FeNi S 400 S 8 2 2 NiSbS S 4 3 CoNi S 2 Ni 200 3 (Bi,Pb) (Fe,Cu,Ni) Ni 3 NiS 6 Ag(Fe,Ni) K Ni 0 Millerite Violarite Vaesite Siegenite Parkerite Pentlandite Ullmannite Polydymite Mackinawite Djerfisherite Heazlewoodite Gersdorffite-Pa3 Argentopentlandite Figure S2. Species-locality distribution of Ni-containing sulfides (top 12). Figure S Figure S 3 Locality Counts 10000 15000 20000 25000 30000 . 5000 Locality Counts Species 1000 1200 200 400 600 800 0 4 Chalcopyrite . 0 Species Cobaltite CuFeS2 CoAsS - Linnaeite distribution locality Chalcocite Siegenite Co S - 2 4 locality distribution of locality Cu2S Carrollite CoNi2S4 Bornite Cu5FeS4 Glaucodot CuCo2S4 Tetrahedrite Cobaltpentlandite CoFe(AsS)2 Cu12Sb4S13 Alloclasite Co9S8 Covellite CuS Cattierite CoAsS of Cu Tennantite Willyamite CoS2 Cu12As4S13 Bournonite - Costibite CoSbS containing Co Paracostibite CuPbSbS3 - CoSbS containing containing Digenite CoSbS Jaipurite Cu1.8S CoS Enargite Julienite sulfide Cu3AsS Na2Co(SCN)4.8H2O 4 Cubanite sulfide CuFe2S3 s (top 10) (top s s . Figure S Figure S Locality Counts 1000 2000 3000 4000 5000 6000 Locality Count 0 100 150 200 250 300 350 50 Molybdenite 0 Alabandite 5602 6 5 . MoS Species MnS Species 2 Helvine Be3Mn4(SiO4)3S Jordisite Hauerite 101 Benavidesite MnS Low crystallinity MoS2 - 2 - locality distribution of locality locality distribution of locality Pb MnSb S Hemusite Samsonite 4 6 14 7 Cu6SnMoS8 Rambergite Ag4MnSb2S6 Uchucchacuaite Tarkianite MnS 6 (Cu,Fe)(Re,Mo)4S8 AgMnPb3Sb5S12 Clerite Maikainite Gravegliaite MnSb2S4 2 Joegoldsteinite Cu10Fe3MoGe3S16 MnS4O3.3H2O Ekplexite Agmantinite Mn MnCr2S4 Mo 1 (Nb,Mo)S2.(Mg1-xAlx)(OH)2+x - - Browneite Ag2MnSnS4 containing containing containing containing Kaskasite MnS Buseckite 1 Manganokaskasite (Mo,Nb)S2.(Mg1-xAlx)(OH)2+x (Fe,Zn,Mn)S ManganokaskasiteGraţianite Manganoquadratite MnBi2S4 1 sulfide sulfides (Mo,Nb)S2.(Mn1-xAlx)(OH)2+x (Mo,Nb)S2(Mn1-xAlx)(OH)2+x Merelaniite Pb5Mn3Ag2Sb6As4S24 1 Pb Mo VSbS s 4 4 15 . Figure S Figure S Locality Counts 10 15 20 25 30 Locality Counts 0 5 100 120 140 7 20 40 60 80 8 0 . Tungstenite . Species Species Colusite WS Cu12VAs3S16 2 Sulvanite - - locality distribution of W locality locality distribution of V locality Cu3VS4 Nekrasovite Kiddcreekite Cu13VSn3S16 Cu6WSnS8 Patrónite Germanocolusite VS4 Catamarcaite Cu VGe S Stibiocolusite 13 3 16 Cu6GeWS8 Cu13V(Sb,Sn,As)3S16 Colimaite Ekplexite - K VS 3 4 - containing sulfides containing Merelaniite sulfides containing (Nb,Mo,W)S2.(Mg1-xAlx)(OH)2+x Pb4Mo4VSbS15 Yushkinite (Mg,Al)(OH)2VS2 Ovamboite Cu10Fe3WGe3S16 . (b) Valence Crystal Symmetry Chemical State Mineral Name Locality Distribution Composition Crystal Space Cu S System Group Chalcocite Cu2S +1 -2 Monoclinic P21/b +1,+ Tetrahedrite Cu12Sb4S13 -2 Cubic I4 3m 2 Covellite CuS +1 -1 Hexagonal P6�3/mmc +1,+ Tennantite Cu12As4S13 -2 Cubic I4 3m 2 Bournonite CuPbSbS3 Orthorhombic Pmn2� 1 Digenite Cu1.8S Trigonal R3m Enargite Cu3AsS4 Orthorhombic Pmn21 � Polybasite-M2a2b2c Monoclinic B2/b Cu(Ag,Cu)6A Polybasite-T2ac Trigonal P321 g9Sb2S11 Polybasite-Tac Trigonal P3m1 Stromeyerite CuAgS Orthorhombic mmm � Figure S9. (a) Locality-mineral distribution of Cu mono-metal sulfide species and chemical diversity with regards to chemical composition, Cu/S valence states and crystal symmetry; (b) plots of the distribution of species type and locality counts for species containing Cu(I), Cu(II) and Cu(I,II) valence states. (b) Valence Crystal Symmetry Chemical State Mineral Name Composition Crystal Space Ni S Locality Distribution System Group Millerite NiS +2 -2 Trigonal R3m Gersdorffite-Pa3 Ni(As,S)2 2 -2 cubic Ullmannite NiSbS cubic P213 Heazlewoodite Ni3S2 trigonal R32 Polydymite Ni3S4 +2,+3 -2 cubic Va e s ite NiS 2 +2 -1 cubic Pa3 Parkerite Ni3(Bi,Pb)2S2 monoclinic Vysotskite (Pd,Ni)S +2 -2 Tetragonal Figure S10. (a) Locality-mineral distribution of Ni mono-metal sulfide species and chemical diversity with regards to chemical composition, Ni/S valence states and crystal symmetry; (b) plots of the distribution of species type and locality counts for species containing Ni(II), Ni(III) and Ni(II,III) valence states. Valence ) Crystal Symmetry Chemical State Mineral Name Composition Crystal Space Co S Locality Distribution System Group Cobaltite CoAsS +3 Orthorhombic Pca21 Linnaeite Co3S4 +2,+3 -2 Cubic Cobaltpentlandite Co9S8 Cubic Fm3m Alloclasite CoAsS Monoclinic P21 Cattierite CoS2 +2 -1 Cubic Pa3 Willyamite Cubic Costibite CoSbS +3 Orthorhombic Pmn21 Paracostibite Orthorhombic Jaipurite CoS +2 -2 Hexagonal Na2Co(SCN)4 Julienite +2 -2 Monoclinic P21/n .8H2O Figure S11. (a) Locality-mineral distribution of Co mono-metal sulfide species and chemical diversity with regards to chemical composition, Co/S valence states and crystal symmetry; (b) plots of the distribution of species type and locality counts for species containing Co(II), Co(III) and Co(II,III) valence states. Table S1. Chemical properties of Fe-Cu and Fe-Ni binary metal sulfide minerals. Fe, Cu Locality Chemical Valence State Crystal Symmetry Mineral Name Counts Composition Cu Fe S Crystal System Space Group Chalcopyrite 26279 CuFeS2 +1 +3 -2 Tetragonal I42d Bornite 5293 Cu5FeS4 +1 +3 -2 Orthorhombic Pbca Cubanite 748 CuFe2S3 +1 +2,+3 -2 Orthorhombic 2/m2/m2/m Stannite 632 Cu2FeSn4S4 +1 +2 -2 Tetragonal I42m Freibergite 630 Ag6Cu4Fe2Sb4S12 +1 +2 -2 Tetragonal I43m 2[(Fe,Cu)S]·1.53[( Valleriite 229 +2 +2 -2 Hexagonal Mg,Al)(OH)2] Isocubanite 184 CuFe2S3 +1 +2,+3 -2 Cubic Fm3m Idaite 133 Cu3FeS4 +2 +2 -2 Hexagonal Fe, Ni Valence State Crystal Symmetry Locality Mineral Name Chemical Composition Crystal Space Counts Fe Ni S System Group Pentlandite 1392 (Ni,Fe)9S8 Cubic Fm3m Mackinawite 424 (Fe,Ni)1+xS (x = 0-0.07) +2 +2 -2 Tetragonal P4/nmm Violarite 361 FeNi2S4 +2 +3 -2 Cubic Smythite 71 (Fe,Ni)3+xS4 (x ≈ 0-0.3) Trigonal R3m Argentopentlandite 63 Ag(Fe,Ni)8S8 Cubic Fm3m� Godlevskite 32 (Ni,Fe)9S8 Orthorhombic C222 Table S2. Sulfide minerals with ternary metal compositions. Mineral Name Locality Counts Chemical Composition Djerfisherite 57 K6(Fe,Cu,Ni)25S26Cl Sugakiite 3 Cu(Fe,Ni)8S8 Kharaelakhite 2 (Cu,Pt,Pb,Fe,Ni)9S8 Owensite 2 (Ba,Pb2+)6(Cu1+,Fe2+,Ni2+)25S2-27 Samaniite 2 Cu2Fe5Ni2S8 Ferhodsite 1 (Fe,Rh,Ni,Ir,Cu,Pt)9S8 Zoharite 1 (Ba,K)6(Fe,Cu,Ni)25S27 Tarkianite 6 (Cu,Fe)(Re,Mo)4S8 Maikainite 2 Cu1+10Fe2+3Mo4+Ge4+3S2-16 Ovamboite 1 Cu1+10Fe2+3W4+Ge4+3S2-16 Table S3. X-ray amorphous mineral species in the RRUFF database. Mineral Name Chemical Composition Delvauxite CaFe3+4(P5+O4)2(OH)8. 4-5H2O Diadochite Fe3+2(PO4)(SO4)(OH). 6H2O Ekanite Ca2ThSi8O20 Evansite Al3PO4(OH)6. 8H2O Georgeite Cu2+2CO3(OH)2 Ice H2O Jordisite Mo4+S2-2 Zaratite Ni2+3C4+O3(OH)4. 4H2O .
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