Geochemistry of manganese nodules from a British Columbia fjord

Concretions of iron and manganese oxides and hydrous oxidesóobjects commonly called manganese nodulesóare widely distributed not only on the deep-sea floor but also in shallow marine environments1. Such concretions were not known to occur north of Cape Mendocino in the shallow water zones bordering the North-East Pacific Ocean until the summer of 1966 when they were recovered by one of us (J. W. M.) in dredge samples from Jervis Inlet, a fjord approximately 50 miles north-west of Vancouver, British Columbia.

The amount of water loss was determined by drying at 110°C

Deep-sea deposits, which resemble in nearly every respect the deep-sea oozes have been observed in many islands of the East-Indian Archipelago, notably the islands of Borneo, Rotti and Timor. Manganese nodules are found in equivalents of deeep-sea red clays on Timor and Rotti island. In this paper, those relative to red clay deposits dating from a Cretaceous ocean are analysed in detail in the vicinity of the town of Niki Niki in Western Timor.

Analysis of Mn-nodules from the Indian Ocean

This report studies the principal paramters governing the distribution of iron-manganese concretions on the sea floor of the Indian Ocean, as well as their petrography and mineralogy. The results are mainly based on the recoveries made during voyages 31, 33 and 35 of the "Vityaz"' (1959-1962) and partly during voyages 36 and 41 (1964-1966). During these voyages samples of Mn concretions and Mn crust were collected (by bottom grabs, cores, trawlings, and dredgings) at 39 stations. The following account is devoted to the problems concerning the geochemistry of these concretions.

Geochemistry of felsic rocks and minerals of ODP Hole 135-841B

A felsic volcanic series (605-825 mbsf) overlain by upper Eocene shallow-water sediments (500-605 mbsf) and basalticandesitic sills that intruded into sediments of Holocene to Miocene age (0-500 mbsf) was drilled in the forearc region of the Lau Basin at a water depth of 4810 m. The volcanic sequence at Site 841 includes altered and mineralized calc-alkaline rhyolites and dacites, dacitic tuffs, lapilli tuffs, flow breccias, and welded tuffs. These rocks formed subaerially or in a very shallow-water environment suffering a subsidence of >5000 m since Eocene times. Calculations of gains and losses of the major components during alteration show most pronounced changes in the uppermost 70 m of the volcanic sequence. Here, Al, Fe, Mg, and K are enriched, whereas Si and Na are strongly depleted. Illite, vermiculite, chlorite, and hematite predominate in this part of the hole. Throughout the section, quartz, plagioclase, kaolinite, and calcite are present. Sulfide mineralization (up to 10 vol%) consisting mainly of disseminated pyrite (with minor pyrrhotite inclusions) and marcasite together with minor amounts of chalcopyrite is pervasive throughout. Locally, a few sulfide-bearing quartz-carbonate veins as well as Ti-amphibole replacement by rutile and then by pyrite were observed. Strong variations in the As content of sulfides (from 0 to 0.69 wt%) from the same depth interval and local enrichments of Co, Ni, and Cu in pyrite are interpreted to result from fluctuations in fluid composition. Calculations of oxygen and sulfur fugacities indicate that fO2 and fS2 were high at the top and lower at the bottom of the sequence. Sulfur isotope determinations on separated pyrite grains from two samples give d34S values of +6.4ë and +8.4ë, which are close to those reported from Kuroko and Okinawa Trough massive sulfide deposits and calc-alkaline volcanic rocks of the Japanese Ryukyu Island Arc. Calculated chlorite formation temperatures of 265°-290°C at the top of the sequence are consistent with minimum formation temperatures of fluid inclusions in secondary quartz, revealing a narrow range of 270°-297°C. Chlorite formation temperatures are constant downhole and do not exceed 300°C. The presence of marcasite and 4C-type pyrrhotite indicates a formation temperature of <= 250°C. At a later stage, illite was formed at the top of the volcanic series at temperatures well below 200°C.

Documentation of manganese nodules form the northwest Indian Ocean

Microscopic and electron probe examination of some manganese nodules show that they consist of segregations of manganese-iron oxides in an interstitial material almost free of manganese but rich in iron and silicates. The segregations are widely spaced in the volcanic cores of the nodules but become more abundant towards their outer crusts where they form the centres of linked polygons of interstitial materials. Most of the minor elements are concentrated in the segregations compared to the interstitial materials. It is suggested that the structures observed result partly from solution and reprecipitation of elements in the original volcanic cores of the nodules and partly from the replacement and coating of these cores by manganese-iron oxides precipitated from sea water.

Description and chemical composition of manganese nodules sampled during the R/V "Vityaz" Expedition Vityaz-35

This paper presents data on the chemical composition of iron-manganese nodules and associated sediments collected during the 35th voyage of the R/V "Vityaz" in 1962. The samples were made available to the author by Prof, P. L. Bezrukov. Data on the general distribution of manganese nodules at the bottom of the Indian Ocean were already given by P. L. Bezrukov (1962, 1963). Here the author analyzed the geochemistry of nodules samples from seven stations and four samples from the associated sediments. The analysis separates the outer layer of nodules from their apparent internal core.

Chemistry on manganese nodules from the Pacific Ocean

Three manganese nodules from the Pacific Ocean have been analysed for 35 elements by using mainly spectrophotometric and spectrographic methods. Cu, Co, Ni, Zn, and Pb were found in amounts approaching 1 %, which far exceeds their average concentrations in igneous rocks. On the other hand, elements having readily hydrolysable ions, such as Ga, Sc, Zr, Y, La and Ti, are present only in amounts comparable with their concentrations in igneous rocks. Sb, Bit Be, and Cr were not detected. The hydrochloric acid-insoluble fraction of nodules is practically free of the heavy metals that are characteristic of the acid-soluble fraction; it consists principally of clay minerals, together with lesser amounts of quartz, apatite, biotite and sodium and potassium felspars.

Geochemistry of primary and secondary mineral phases in ODP Leg 209 sediments

Primary and secondary mineral phases from Holes 1268A (11 samples), 1272A (9 samples), and 1274A (12 samples) were analyzed by electron microprobe in Bonn and Cologne (Germany). Bulk rock powders of these samples were also analyzed geochemically, including major and trace elements (Paulick et al., 2006, doi:10.1016/j.chemgeo.2006.04.011). Ocean Drilling Program (ODP) Leg 209 Holes 1268A, 1272A, and 1274A differ remarkably in alteration intensity and mineralogy, and details regarding their lithologic characteristics are presented in Bach et al. (2004, doi:10.1029/2004GC000744) and Shipboard Scientific Party (2004, doi:10.2973/odp.proc.ir.209.101.2004). Because of the least altered character of peridotite in Hole 1274A, abundant clinopyroxene, orthopyroxene, olivine, and spinel were analyzed at this site. In Hole 1272A, primary silicates are rare and analyses were restricted to some samples that contain traces of olivine and orthopyroxene. Because of the intensity of alteration, Hole 1268A is devoid of primary phases except spinel. Commonly, alteration is pseudomorphic and serpentinization of olivine and orthopyroxene can be distinguished. Accordingly, compositional variations of the alteration minerals with regard to the precursor minerals are one of the issues investigated in this data report.

Chemistry of secondary minerals from the deep sheeted dike complex of ODP Holes 137-504B and 140-504B

Dolerites sampled from the lower sheeted dikes from Hole 504B during Ocean Drilling Program Legs 137 and 140, between 1562.4 and 2000.4 mbsf, were examined to document the mineralogy, petrography, and mineral parageneses associated with secondary alteration, to constrain the thermal history and composition of hydrothermal fluids. The main methods used were mineral chemical analyses by electron microprobe, X-ray diffraction, and cathodoluminescence microscopy. Temperatures of alteration were estimated on the basis of single and/or coexisting mineral chemistry. Permeability is important in controlling the type and extent of alteration in the studied dike section. At the meter-scale, intervals of weakly altered dolerites containing fresh olivine are interpreted as having experienced restricted exposure to hydrothermal fluids. At the centimeter- or millimeter-scale, alteration patches and extensively altered halos adjacent to veins reflect the permeability related to intergranular primary porosity and cracks. Most of the sheeted dike alteration in this case resulted from non-focused, pervasive fluid-rock interaction. This study confirms and extends the previous model for hydrothermal alteration at Hole 504B: hydrothermal alteration at the ridge axis followed by seawater recharge and off-axis alteration. The major new discoveries, all related to higher temperatures of alteration, are: (1) the presence of hydrothermal plagioclase (An80-95), (2) the presence of deuteric and/or hydrothermal diopside, and (3) the general increasing proportion of amphiboles, and particularly magnesio-hornblende with depth. We propose that the dolerites at Hole 504B were altered in five stages. Stage 1 occurred at high temperatures (less than 500° to 700°C) and involved late-magmatic formation of Na- and Ti-rich diopside, the hydrothermal formation of Na, Ti-poor diopside and the hydrothermal formation of an assemblage of An-rich plagioclase + hornblende. Stage 2 occurred at lower temperatures (250°-320°C) and is characterized by the appearance of actinolite, chlorite, chlorite-smectite, and/or talc (in low permeability zones) and albite. During Stage 3, quartz and epidote precipitated from evolved hydrothermal fluids at temperatures between 310° and 320°C. Anhydrite appeared during Stage 4 and likely precipitated directly from heated seawater. Stage 5 occurred off-axis at low temperatures (250°C) with laumontite and prehnite from evolved fluids.

(Table 1, page 220), Spot chemical analyses of a section of nodule 5133.7

Microscopic and electron probe examination of some manganese nodules show that they consist of segregations of manganese-iron oxides in an interstitial material almost free of manganese but rich in iron and silicates. The segregations are widely spaced in the volcanic cores of the nodules but become more abundant towards their outer crusts where they form the centres of linked polygons of interstitial materials. Most of the minor elements are concentrated in the segregations compared to the interstitial materials. It is suggested that the structures observed result partly from solution and reprecipitation of elements in the original volcanic cores of the nodules and partly from the replacement and coating of these cores by manganese-iron oxides precipitated from sea water.