Earth’s secondary atmosphere began to develop at the time of planetary differentiation, probably in connection with volcanic activity. Its component gases, however, were most likely very different from those emitted by modern volcanoes. Accordingly, the composition of the early secondary atmosphere was quite distinct from that of today’s atmosphere. Carbon monoxide, carbon dioxide, water vapour, and methane predominated; however, free oxygen could not have been present, since even modern volcanic gases contain no oxygen. It is therefore assumed that the secondary atmosphere during the Archean Eon (4 billion to 2.5 billion years ago) was anoxygenic. The free oxygen that makes up the bulk of the present atmosphere evolved over geologic time by two possible processes. First, solar ultraviolet radiation (the short-wavelength component of sunlight) would have provided the energy needed to break up water vapour into hydrogen, which escaped into space, and free oxygen, which remained in the atmosphere. This process was in all likelihood important before the appearance of the oldest extant rocks, but after that time the second process, organic photosynthesis, became predominant. Primitive organisms, such as blue-green algae (or cyanobacteria), cause carbon dioxide and water to react by photosynthesis to produce carbohydrates, which they need for growth, repair, and other vital functions, and this reaction releases free oxygen. The discovery of stromatolites (layered or conical sedimentary structures formed by sediment-binding marine algae) in 3.5-billion-year-old limestones in several parts of the world indicates that blue-green algae existed by that time. The presence of such early carbonate sediments is evidence that carbon dioxide was present in the atmosphere, and it has been calculated that it was at least 100 times greater than the amount in the present-day atmosphere. It can be assumed that such abundant carbon dioxide would have caused retention of heat, resulting in a greenhouse effect and a hot atmosphere.What happened to all the oxygen that was released? It might be surprising to learn that it took at least 1 billion years before there was sufficient oxygen in the atmosphere for oxidative diagenesis to give rise to red beds (sandstones that are predominantly red in colour due to fully oxidized iron coating individual grains) and that 2.2 billion years passed before a large number of life-forms could evolve. An idea formulated by the American paleontologist Preston Cloud has been widely accepted as an answer to this question. The earliest primitive organisms produced free oxygen as a by-product, and in the absence of oxygen-mediating enzymes it was harmful to their living cells and had to be removed. Fortunately for the development of life on the early Earth there was extensive volcanic activity, which resulted in the deposition of much lava, the erosion of which released enormous quantities of iron into the oceans. This ferrous iron is water-soluble and therefore could be easily transported, but it had to be converted to ferric iron, which is highly insoluble, before it could be precipitated as iron formations. In short, the organisms produced the oxygen and the iron formations accepted it. Iron formations can be found in the earliest sediments (those deposited 3.8 billion years ago) at Isua in West Greenland, and thus this process must have been operative by this time. Iron formations dating to early Precambrian time (4.6 billion to 541 million years ago) are so thick and common that they provide the major source of the world’s iron. Large quantities of iron continued to be deposited until about 2 billion years ago, after which time the formations decreased and disappeared from the sedimentary record. Sulfides also accepted oxygen in the early oceans to be deposited as sulfates in evaporites, but such rocks are easily destroyed. One finds, nonetheless, 3.5-billion-year-old barite/gypsum-bearing evaporites up to 15 metres (about 49 feet) thick and at least 25 km (15.5 miles) in extent in the Pilbara region of Western Australia. It seems likely that the excess iron in the early oceans was finally cleared out by about 1.7 billion years ago, and this decrease in the deposition of iron formations resulted in an appreciable rise in the oxygen content of the atmosphere, which in turn enabled more eolian red beds to form. Further evidence of the lack of oxygen in the early atmosphere is provided by detrital uraninite and pyrite and by paleosols—i.e., fossil soils. Detrital uraninite and pyrite are readily oxidized in the presence of oxygen and thus do not survive weathering processes during erosion, transport, and deposition in an oxygenous atmosphere. Yet, these minerals are well preserved in their original unoxidized state in conglomerates that have been dated to be more than 2.2 billion years old on several continents. Paleosols also provide valuable clues, as they were in equilibrium with the prevailing atmosphere. From analyses of early Precambrian paleosols it has been determined that the oxygen content of the atmosphere 2.2 billion years ago was one hundredth of the present atmospheric level (PAL).Fossils of eukaryotes, which are organisms that require an oxygen content of about 0.02 PAL, bear witness to the beginning of oxidative metabolism. The first microscopic eukaryotes appeared about 1.4 billion years ago. Life-forms with soft parts, such as jellyfish and worms, developed in profusion, albeit locally, toward the end of the Precambrian about 650 million years ago, and it is estimated that this corresponds to an oxygen level of 0.1 PAL. By the time land plants first appeared, roughly 400 million years ago, atmospheric oxygen levels had reached their present values.
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