From around 1889, Edward Barnard pioneered deep photography of the sky, finding many 'holes in the Milky Way'. At first he compared them to sunspots, but by 1899 was prepared to write: "One can scarcely conceive a vacancy with holes in it, unless there is nebulous matter covering these apparently vacant places in which holes might occur". These holes are now known as dark nebulae, dusty molecular clouds silhouetted against the background star field of the galaxy; the most prominent are listed in his Barnard Catalogue. The first direct detection of cold diffuse matter in interstellar space came in 1904, when Johannes Hartmann observed the binary star Mintaka (Delta Orionis) with the Potsdam Great Refractor. Hartmann reported that absorption from the "K" line of calcium appeared "extraordinarily weak, but almost perfectly sharp" and also reported the "quite surprising result that the calcium line at 393.4 nanometres does not share in the periodic displacements of the lines caused by the orbital motion of the spectroscopic binary star". The stationary nature of the line led Hartmann to conclude that the gas responsible for the absorption was not present in the atmosphere of the star, but was instead located within an isolated cloud of matter residing somewhere along the line of sight to this star. This discovery launched the study of the interstellar medium.