Chemistry and Sulfur Isotopes of the Chert-Clastic Sequence Surrounding the Kajika Massive Sulfide Ores at the Ashio Copper Mine, Ashio Terrane, Central Japan

Abstract. Chemical and sulfur isotopic compositions were obtained for a series of rocks within the chert‐clastic sequence surrounding the Kajika massive sulfide ore horizon at Shibukawasawa in the Ashio copper‐mining district, Ashio Terrane, central Japan. The sequence is lithologically classified into three units: chert, siliceous shale with basic volcanics, and sandstone‐shale, in ascending stratigraphic order. The Kajika ore horizon corresponds to the lowermost part of the unit that contains siliceous shale with basic volcanics. The rocks around the Kajika ore horizon are enriched in P₂O₅ (max. 0.22 %), Ba (max. 2400 ppm), Cu (595 ppm), V (323 ppm), Pb (168 ppm), Zn (124 ppm), and Mo (24 ppm) in siliceous shale; and Ba (4220 ppm), Zr (974 ppm), Cr (718 ppm), Ni (492 ppm), V (362 ppm), Zn (232 ppm), Nb (231 ppm), and Co (71 ppm) in the basic volcanics. The siliceous shale is enriched in a number of redox‐sensitive elements such as Cu, V, Pb, Zn, and Mo, which are known to be enriched in black shale and anoxic and hydrothermal sediments. The δ³⁴S values of sulfides in the chert and sandstone‐shale lie in the range of 0±2 %, and those in the siliceous shale range from ‐5 to ‐14 %. The measured δ³⁴S values in the basic volcanics are ‐0.3, ‐2.7, and ‐31.5 %. These heavier δ³⁴S signatures (around 0 %) recorded throughout the sequence indicate that the rocks formed under anoxic bottom‐water conditions. Slightly lighter δ³⁴S values recorded in siliceous shale might reflect significant mixing of sulfides that formed by sulfate‐reducing bacteria in an overlying oxic environment. The long‐term duration of anoxic conditions indicated by the heavier δ³⁴S signature is considered to have played an important role in protecting the Kajika sulfide ores from oxidative decomposition and preserving the ores in sedimentary accumulations.