SEDIMENTARY OR-FORMING PROCESS CHAPTERS 269 ‘Superior ‘Tons (:10" of BIF Oceanic cust Continental 2 cast plato Figure 5.16 Tectonicand environmental model showing the depositional settings for Algoma, Superior, and Rapitan type BIFs after Clemmey, 1985, Maynard, 191]. The inset histogram illustrates the approximate tonnages Of BIF resource fr each ofthe three major types as function of time [after Holland, 1984) ‘occurrence of iron ores associated with glacio- genic sediments formed during the major Neo- proterozoie ice ages. The type occurrence is the Rapitan Group in the McKenzie Mountains of northwest Canada, In addition to the above tectonic classification, BIFs have also been categorized in terms of the mineralogy of the associated iron phases. Although in most BIFs the iron mineral is an oxide phase (hematite or magnetitel, carbonate (siderite), silicate (greenalite and minnesotaite), and sulfide (pyrite) iron minerals also occur, together with chert or carbonaceous shale. This observation led James (1954) to suggest a facies concept for BIF formation whereby the progres- sion from oxide through carbonate to sulfide phases was considered to reflect precipitation of the relevant iron minerals in successively more reducing envizonments (iron silicate phases are stable over a wide range of Eh and do not, there: fore, conform to this simple progression). A con- sideration of the stability of the main iron phases ‘asa function of Eh and pH confirms that the redox state of the depositional environment plays an important role in determining the mineralogy of BIFs, although the situation is undoubtedly more ‘complex than the facies concept would suggest. Figure 5.17a shows that ferrous iron is stable in solutions that are acidic and redueing, but that for ‘2 given pH, oxidation (or an increase in the Eh) will stabilize hematite (Fe,O, or ferric oxidel, which is the principal iron phase over a wide270 pasts seonwenraty/suanicia mRoCISEs @ En (vote) ® Prodechrasite Eh (vot) HNO, Figure 5.17 (a) Eh-pH diagram showing the stabilities of common iron minerals. The conditions that apply to this particular phase diagram are: That, molarities of Fe, , and CO, ae, respectively, 10°, 1 and 1 [b] Eh-pH diagram showing the stabilities of common manganese minerals Identical conditions apply, but withthe ‘molarity of Min = 10-* diagrams modified after Garrels and Christ, 1965, Krauskopf and | 1995}. Note that the ‘manganese oxides (MnO, and MoO, ae stable at higher Eh than the equivalent ferric oxide (hematite, and would only form, therefore, undsr more oxidizing conditions. range of geologically pertinent conditions. Siderite and pyrite are only stable under reducing con- ditions although these fields would obviously expand if the activities of total carbonate or sulphur in solution were increased, Similarly, the phase diagram indicates that magnetite is only stable under reducing and alkaline conditions, but this field expands well into the range of neutral pH if the activities of carbonate and sulphur are lower than the prevailing conditions for this diagram, Banded iron-formations ate chemical sediments in which the major components, Fe and Si, appear to have been derived from the ocean itself, rather than from a continental source, as in the case for izonstones. This is evident from the lack of alum- inous and silicate mineral particulate matter in BIFs. Models for the formation of these rocks are controversial and hampered by a lack of modem analogues. Features which need to be explained include the origin of the Fe and Si, their transport and precipitation mechanisms, the cause of the delicate silica- and iron-rich banding at various seales, and their formation during certain time periods, in particular between around 2500 and 2000 Ma. The source of iron is dominantly from the ocean itself, through either direct introduction of Fe* from hydrothermal exhalations [black smokers; see Chapter 3) on the sea floor or dis- solution of oceanic crust. Rare earth element pat- terns of BIFs suggest that hydrothermal venting and volcanic activity are likely to have contrib: uted significantly to the source of Fe in AlgomaSEDIMENTARY ORE-FORMING PROCESS cHAPHERS 271 sutace i =m ye Eb petit 50m 3 aT e é Aetoxinerace 190 m— =| oo 3 s |tnydroxides)| 4 é| nystetnenal 2, CUT td J input re PRY ae 4 ‘Carbon > Le [Fe-poor chen] Black Figure 5.18 Model invoking upwelling and oxidation of ferrous iron from an oceanic source to explain the depositional environment for BIFs. Oxidation of ferrous iron and precipitation of feric iron compounds occurs ata diffuse redox interface formed by the production of oxygen inthe upper water levels, either by photosynchesizing organisms or by ultraviolet radiation induced photo-oxidation, or oth. The lateral zonation of BIF facies (Le siderite-magnetite-hematite| shown here difters from the simple scheme envisaged by James (1954), Diagram ‘modified after Klein and Beukes (1993). type BIFs, but that this influence diminished with time such that Rapitan ores reflect a direct ocean water character (Misra, 2000), However, the enormous volumes of iron required to form the Lake Superior type BIES, given that they appear to be spatially unrelated to voleanie or exhalative sea-floor activity, remains something of a prob- Jem. The oceans themselves ate likely to represent an adequate source of Si since the solubility of amorphous silica (as Si(OH,) is relatively high {about 120 mgI} Te seems likely that the Archean-Paleoproterozoic oceans would have been saturated with respect to silica, ensuring a steady precipitation and accumulation of siliceous ‘matter on the ocean floor during this early stage of Earth history. This pattem is likely to have changed in later geological times when the organ. jsms that use silica to build an exoskeleton (Le siliceous protozoans such as radilaria) evolved and the element was extracted from the water col: ‘umn, The modem oceans, for example, typically contain <10mg I! dissolved silica and are sarkedly undersaturated (MacKenzie, 1975]. The decrease of available Si in the oceans asa function of biological evolution contributes to an explana tion for the changing character of iron ores, from BIFs to ironstones, with time. ‘The transport and precipitation mechanisms involved in BIF genesis have traditionally been explained in terms of the Fe2* upwelling model, analogous to the observations of phosphorus “upwelling onto the continental shelves (see sec- tion 5.3.3 below]. Figure 5.18 illustrates the main elements of the model, after Klein and Beukes (1993). Ferrous izon from deep, reduced ocean levels is introduced to shallower shelf environ. ments by upwelling currents similiar to those seen along the western coastlines of continents such as Africa and the Americas today. These currents interact with the shallower waters and Fe. is oxidized, with subsequent hydrolysis and precipitation of ferric hydroxide (Fe(OH) In marine environments where CO, activities are sufficiently high, FeCO, would precipitate Oxidation takes place at shallow water levels ‘where sunlight can penetrate and is due either to production of oxygen by photosynthesizing ‘organisms living inthe photic zone, orto photons of ultraviolet and blue light, which induce photo- ‘oxidation of ferrous to ferric ions (Cairns Smith,