The weathering of limestones containing minor percentages of iron minerals originally deposited with the limestones may result in the residual concentration of bodies of limonite or "brown ores" associated with clays near the surface. This process is similar in all essential respects to the concentration of the Lake Superior ores. Such limonitic ores are found rather widely distributed through the Appalachian region and in many other parts of the world. Because of the ease with which they can be mined and smelted on a small scale they have been used since early times, but have furnished only a very small fraction of the world's iron.
3. In a third class of sedimentary ores, the iron minerals are supposed to have been introduced as replacements of limestones subsequent to sedimentation. Such ores are not always easy to discriminate from ores resulting primarily from sedimentation. This class is represented by the high-grade deposits of Bilbao, Spain, Austrian deposits, and by smaller deposits in other countries. The Bilbao ores consist mainly of siderite, which near the surface has altered to large bodies of oxide minerals. They occur in limestones and shales and are not associated with igneous rocks. The deposits are believed to have been formed by ordinary surface waters carrying iron in solution, and depositing it in the form of iron carbonate as replacements of the limestones. The original source of the iron is believed to have been small quantities of iron minerals disseminated through the ordinary country rocks of the district. The action of surface waters, in thus concentrating the iron in certain localities which are favorable for precipitation, is similar to the formation of the lead and zinc ores of the Mississippi valley, referred to in the next chapter. Deposits formed in this manner may be roughly tabular and resemble bedded deposits, or they may be of very irregular shapes.
The sedimentary iron ores in general evidently represent an advanced stage of katamorphism, and illustrate the tendency of this phase of the metamorphic cycle toward simplification and segregation of certain materials. The exact conditions of original sedimentation present one of the great unsolved problems of geology, referred to in Chapter III.