Sulfur isotopic variations in nodular and disseminated pyrite at DSDP Hole 93-603B

Analyses of modern marine sediments have suggested that availability and type of organic matter, sedimentation rate, and openness of the sulfate system influence the degree of isotopic fractionation between seawater sulfate and sedimentary iron sulfides. Isotopic studies of ancient sulfides should, therefore, provide insights into conditions of deposition and early diagenesis. Analysis of d34S of disseminated pyrite from Cretaceous sediments of Hole 603B yielded fractionations relative to coeval seawater sulfate ranging from 40 to 55 per mil, which are within the range for modern oxic marine sediments reported by others. Sulfur/carbon ratios are similar to those found from modern marine sediments and suggest that disseminated pyrite formation was dependent upon available organic carbon. These results imply that depositional and early diagenetic conditions during the Cretaceous in Hole 603B were similar to those occurring in initially oxic marine environments today. Macroscopic (nodular) pyrite from Hole 603B is isotopically variable (d34S values = - 48 to + 33 per mil), but generally more positive than disseminated pyrite. The isotopic evidence suggests that macroscopic pyrite formed during late stages of sulfate reduction in a system closed with respect to sulfate. However, detailed analyses of large pyrite nodules did not yield a consistent pattern of isotopic variation from center to rim.

Mineral resources in Lower Brule Indian Reservation

On the Lower Brule Indian Reservation in South Dakota, about 3 million tons of metallic manganese are in low-grade deposits in the DeGrey Member of the Pierre Shale on the reservation. The geology and methods of mining and processing this sub-economic mineral resource have been studied extensively; technologically, extraction of manganese is possible. However, an efficient, economical method to separate manganese-bearing nodules from the shale host rocks has yet to be found. The manganiferous nodules occur in the Oacoma zone of the Sully shale member (De-Grey Member) which is a subdivision of the South Dakota Pierre Shale formation. These nodular deposits have an interesting similarity in stratigraphical position, lithology and manganese content to those of the Porcupine Mountain area in Manitoba.

Description and chemical and mineral composition of iron oxide samples from two Finnish lakes

Fifteen iron oxide accumulations from the bottoms of two Finnish lakes ("lake ores") were found to contain as much as 50% Fe. Differential X-ray powder diffraction and selective dissolution by oxalate showed that the samples consisted of poorly crystallized goethite and ferrihydrite. The crust ores of one lake had higher ferrihydrite to goethite ratios than the nodular ores of the other lake. The higher ferrihydrite proportion was attributed to a higher rate of Fe2+ supply from the ground water and/or a higher rate of oxidation as a function of water depth and bottom-sediment permeability. Values of Al-for-Fe substitution of the goethites determined from unit-cell dimensions agreed with those obtained from chemical extraction if the unit-cell volume rather than the c dimension was used. In very small goethite crystals a slight expansion of the a unit-cell dimension is probaby compensated by a corresponding contraction of the c dimension, so that a contraction of the c dimension need not necessarily be caused by Al substitution. The goethites of the two lakes differed significantly in their Al-for-Fe substitutions and hence in their unit-cell sizes, OH-bending characteristics, dehydroxylation temperatures, dissolution kinetics, and Mössbauer parameters. The difference in Al substitution (0 vs. 7 mole %) is attributed to the Al-supplying power of the bottom sediments: the silty-clayey sediments in one lake appear to have supplied A1 during goethite formation, whereas the gravelly-sandy sediments in the other lake did not. The compositions of the goethites thus reflect their environments of formation.

Late Cenozoic silicoflagellate biostratigraphy, relative paleotemperature, and distribution of various genera and morphologic subgroups with remarks on noteworthy occurrences at DSDP Leg 86 Holes

A quantitative study of late Cenozoic silicoflagellates from the northwestern Pacific sites of Deep Sea Drilling Project Leg 86 shows a relative paleotemperature (Ts) gradient with lowest values (Ts = 30) in the north. Some new ecostratigraphic relations for the region are indicated, such as the last common occurrence of Dictyocha brevispina at 2.6 - 3.0 m.y. ago during a cool interval. Elements of North Pacific and low-latitude biostratigraphic zonations can be identified, but the mixing of cool- and warm-indicator taxa prompted the definition of the new Miocene Mesocena hexalitha Subzone and Pliocene Distephanus jimlingii Subzone. Scanning-electron microscope study of Leg 86 silicoflagellates was done to determine whether various types of skeletal surface texture are temperature dependent. To conduct the study we organized a new surface-texture descriptive code, which characterizes the apical structure/basal ring/spine sequence using new definitions of the terms crenulate (C), linear (L), nodular (N), reticulate (R), and smooth (S). One new silicoflagellate genus, Caryocha Bukry et Monechi, n. gen., is described and several new combinations are made.

Lithofacies, chronostratigraphy, minerals and diagenetic silica facies at DSDP Leg 80 Holes

X-ray powder diffraction and optical and scanning-electron microscope analyses of sediment samples taken from four sites drilled in the Goban Spur area of the northeast Atlantic show variable diagenetic silicification of sediments at several stratigraphic horizons. The results are as follows: 1. The silicified sediments are middle Eocene at Site 548, Paleocene to lower Albian at Site 549, upper to lower Paleocene at Site 550, and lower Turanian at Site 551. 2. There are three types of these silicified sediments: nodular type in carbonate-rich host sediments, bedded type in clayey host sediments, and a type transitional between the other two. 3. Silica diagenesis is considered to progress as follows: dissolution of siliceous fossils; precipitation of opal CT in pore spaces and transformation of biogenic silica (opal A) to opal CT, development of opal CT cement; chalcedonic quartz precipitation in pore spaces and replacement of foraminiferal tests by chalcedonic quartz; and finally, transformation of opal CT to quartz, and cementation. But the strong influence of host-sediment types on diagenetic silica fades is recognized. Bedded-type silicified sediments in a clayey environment indicate a lower grade of silica diagenesis. Only very weak chalcedonic quartz formation is recognized, and there is no opal CT cementation, even in Lower Cretaceous bedded-type clayey silicified sediments. 4. The rf(101) spacing of opal CT shows two distinct trends of ordering or decrease with burial depth; one is a rapid change, in the case of nodular silicified sediments, and the other is a more gentle shift, found in bedded silicified sediments. 5. Diagenetic silica facies of the nodular type develop as irregular concentric zones around some nodule nuclei. Also, quartz-chert nodule formation occurs at rather shallower horizons, and is discordant with the trend of decreasing d(101) spacing in opal CT. 6. Silicified sediments at Site 551 are shallower than at the other sites. The diagenetic silica facies suggest the probable erosion of 300 m or more of sediment at this site. 7. The zeolites clinoptilolite and phillipsite were found in the sediment samples recovered on Leg 80. Clinoptilolite occurs from the shallower levels to the deepest horizons of diagenetically silicified zones, suggesting that clinoptilolite formation is related to diagenesis of biogenic silica. Phillipsite at Site 551 (Section 551-5-2) may originate from volcanogenie material.

Miozene larger foraminifera in ODP Leg 133 holes

The Marion Plateau is a large carbonate platform off northeastern Queensland. Three sites (815, 816, and 826) were drilled on this platform and form the basis for this study. Larger benthic foraminifers, together with rare planktonic forms from the shallow-water carbonates that form the main part of the platform sequence, were studied to establish a biostratigraphy. The presence of Lepidocyclina (Nephrolepidiná) howchini sensu lato and Ladoronia vermicularis, together with Globorotalia (Globorotalia) praemenardii and Orbulina, indicate an early middle Miocene (N9-N12) age (i.e., lower Tf stage) for these carbonates. Dolomitization has destroyed much of the original fabric of these carbonates, making study of the larger foraminifers difficult. Sites 815 (forereef location) and 826 (backreef, lagoonal setting) provide the best faunas. However, at all sites nodular coralline algae and Halimeda are the major bioclasts; coral fragments form a major component at Sites 816 and 826. The middle Miocene neritic sequence is separated from the overlying hemipelagic sequence by an unconformity that spans much of the middle and late Miocene. At Site 815, which is in a forereef situation, the overlying hemipelagic sequence contains a Zone N17A fauna, but at Site 816, higher on the platform, a similar sequence contains a Zone N19 fauna. The faunas indicate that the platform was built up during the early middle Miocene and remained at fairly constant water depths and temperatures during this period. It was then exposed prior to subsiding rapidly during the late Miocene and Pliocene to depths similar to those of the present day.

Chemostratigraphy (CaCO3, TOC, d13Corg) of Sinemurian black shales

The Shales-with-'Beef' and Black Ven Marls of the Charmouth Mudstone Formation (Sinemurian) exposed on the Dorset Coast in southern England (Wessex Basin) show stratigraphic variation in carbonate, organic carbon and organic-carbon isotopes. Little environmental significance is attached to the variation of carbonate except in the case of the tabular and nodular limestones interrupting the sequence that probably record stratigraphic condensation and/or sedimentary stillstands that, in an extreme case, were accompanied by sea-floor erosion to produce the bored and encrusted 'Coinstone'. Relatively high total organiccarbon (TOC) contents are present in the laminated mudstones of the lower turneri Zone (upper brooki and lower birch Subzones) and the obtusum Zone (obtusum and stellare Subzones). Basin stratification related to fresh-water influx was the most likely aid to deoxygenation and enhanced preservation of organic matter. The organic-carbon isotope curve (d13Corg), which shows positive excursions in the upper turneri Zone (upper birchi Subzone) and highest obtusum - raricostatum Zones (highest stellare Subzone, densinodulum and lower raricostatoides Subzones), does not correlate with the TOC stratigraphy and was clearly not controlled by local patterns of organic-matter burial. Long-term (hundreds-of-thousands of years) variations in the carbon-isotope (d13Corg) curve are interpreted as reflecting changing seawater isotopic composition and, in the case of the stratigraphically higher interval, may be related to marine organic-carbon burial on the margins of the proto-Atlantic, as exemplified by the Lusitanian Basin in Portugal. Correlation of the carbon-isotope profile with putative sea-level curves is problematic in detail, although significant local transgressive pulses in the turneri and late raricostatum Zones are approximately coincident with positive d13Corg excursions.

Contents and stable carbon isotope compositions of biomarkers indicative for AOM-communities dominated by different ANME groups in two carbonate samples from Hydrate Hole pockmark

Different types of seep carbonates were recovered from the 'Kouilou pockmarks' on the Congo deep-sea fan in approximately 3100 m water depth. The carbonate aggregates are represented by pyritiferous nodules, crusts and slabs, tubes, and filled molds. The latter are interpreted to represent casts of former burrows of bivalves and holothurians. The nodules consisting of high-Mg-calcite apparently formed deeper within the sediments than the predominantly aragonitic crusts and slabs. Nodule formation was caused by anaerobic oxidation of methane dominantly involving archaea of the phylogenetic ANME-1 group, whereas aragonitic crusts resulted from the activity of archaea of the ANME-2 cluster. Evidence for this correlation is based on the distribution of specific biomarkers in the two types of carbonate aggregates, showing higher hydroxyarchaeol to archaeol ratios in the crusts as opposed to nodules. Formation of crusts closer to the seafloor than nodules is indicated by higher carbonate contents of crusts, probably reflecting higher porosities of the host sediment during carbonate formation. This finding is supported by lower d18O values of crusts, agreeing with precipitation from pore waters similar in composition to seawater. The aragonitic mineralogy of the crusts is also in accord with precipitation from sulfate-rich pore waters similar to seawater. Moreover, the interpretation regarding the relative depth of formation of crusts and nodules agrees with the commonly observed pattern that ANME-1 archaea tend to occur deeper in the sediment than members of the ANME-2 group. Methane represents the predominant carbon source of all carbonates (d13C values as low as -58.9 per mil V-PDB) and the encrusted archaeal biomarkers (d13C values as low as -140 per mil V-PDB). Oxygen isotope values of some nodular carbonates, ranging from + 3.9 to + 5.1per mil V-PDB, are too high for precipitation in equilibrium with seawater, probably reflecting the destabilization of gas hydrates, which are particularly abundant at the Kouilou pockmarks.

Geochemistry of some manganese nodules

The manganese nodules occur in greater or less quantity all over the ocean-bed, and most abundantly in the Pacific. They occur in all sizes, from minute grains to masses of a pound weight, and even greater, and form nodular concretions of concentric shells, round a nucleus, which is very frequently a piece of pumice or a shark's tooth. Their outside has a peculiar and very characteristic mammillated surface, which enables them to be identified at a glance. When freshly brought up they are very soft, being easily scraped to powder with a knife. They gradually get harder on exposure to the air. The powder, heated in a closed tube, gives out water which re-acts alkaline, and has an empyreumatic odour. Heated with strong hydrochloric acid, it liberates abundance of chlorine, and the residue which remains is white, consisting of silica, clay, and sand, the sand being the same as is found in the bottom mud from the same locality. Their composition varies greatly, different nodules containing different quantities of mechanically admixed mud, and the number of different elements found in them is very large. Copper, iron, cobalt, nickel, manganese, alumina, lime, magnesia, silica, and phosphoric acid have been detected in a large number; but I have not as yet been able to make a complete analysis of any of them. I have, however, made a few determinations of the most important component substances. For this purpose the outside and densest layers of the nodules were selected, and portions of them were pulverised and dried for ten or twelve hours at 140° C. The amount of chlorine liberated on treatment with hydrochloric acid was determined by Bunsen's method, and the iron was determined by titration with stannous chloride. The samples analysed were from four different localities.

Chemical composition of DSDP and ODP cherts

Rare earth element (REE), major, and trace element abundances and relative fractionations in forty nodular cherts sampled by the Deep Sea Drilling Project (DSDP) and Ocean Drilling Program (ODP) indicate that the REE composition of chert records the interplay between terrigenous sources and scavenging from the local seawater. Major and (non-REE) trace element ratios indicate that the aluminosilicate fraction within the chert is similar to NASC (North American Shale Composite), with average Pacific chert including ~7% NASC-like particles, Indian chert ~11% NASC, Atlantic chert ~17% NASC, and southern high latitude (SHL) chert 53% NASC. Using La as a proxy for sum REE, approximations of excessive La (the amount of La in excess of that supplied by the detrital aluminosilicate fraction) indicate that Pacific chert contains the greatest excessive La (85% of total La) and SHL chert the least (38% of total La). As shown by interelement associations, this excessive La is most likely an adsorbed component onto aluminosilicate and phosphatic phases. Accordingly, chert from the large Pacific Ocean, where deposition occurs relatively removed from significant terrigenous input, records a depositional REE signal dominated by adsorption of dissolved REEs from seawater. Pacific chert Ce/Ce* <<1 and normative La/Yb ~ 0.8-1, resulting from adsorption of local Ce-depleted seawater and preferential adsorption of LREEs from seawater (e.g., normative La/Yb ~0.4), which increases the normative La/Yb ratio recorded in chert. Chert from the Atlantic basin, a moderately sized ocean basin lined by passive margins and with more terrigenous input than the Pacific, records a mix of adsorptive and terrigenous REE signals, with moderately negative Ce anomalies and normative La/Yb ratios intermediate to those of the Pacific and those of terrigenous input. Chert from the SHL region is dominated by the large terrigenous input on the Antarctic passive margin, with inherited Ce/Ce* ~1 and inherited normative La/Yb values of ~1.2-1.4. Ce/Ce* does not vary with age, either throughout the entire data base or within a particular basin. Overall, Ce/Ce* does not correlate with P2O5 concentrations, even though phosphatic phases may be an important REE carrier.

Oxygen isotopes and hydrocarbon composition of gas hydrate and hydrate water from ODP Leg 165 sites

Ocean Drilling Program (ODP) Leg 164 recovered a number of large solid gas hydrate from Sites 994, 996, and 997 on the Blake Ridge. Sites 994 and 997 samples, either nodular or thick massive pieces, were subjected to laboratory analysis and measurements to determine the structure, molecular and isotopic composition, thermal conductivity, and equilibrium dissociation conditions. X-ray computed tomography (CT) imagery, X-ray diffraction, nuclear magnetic resonance (NMR), and Raman spectroscopy have revealed that the gas hydrates recovered from the Blake Ridge are nearly 100% methane gas hydrate of Structure I, cubic with a lattice constant of a = 11.95 ± 0.05 angström, and a molar ratio of water to gas (hydration number) of 6.2. The d18O of water is 2.67 per mil to 3.51 per mil SMOW, which is 3.5-4.0 heavier than the ambient interstitial waters. The d13C and dD of methane are -66 per mil to -70 per mil and -201 per mil to -206 per mil, respectively, suggesting that the methane was generated through bacterial CO2 reduction. Thermal conductivity values of the Blake Ridge hydrates range from 0.3 to 0.5 W/(m K). Equilibrium dissociation experiments indicate that the three-phase equilibrium for the specimen is 3.27 MPa at 274.7 K. This is almost identical to that of synthetic pure methane hydrate in freshwater.

(Table 1, page 400) Metal content of different manganese nodules from cruise VA-04 (R/V Valdivia) in the Pacific Ocean

Deep sea manganese nodules are considered as important natural resources for the future because of their Ni, Cu and Co contents. Their different shapes cannot be correlated clearly with their chemical composition. Surface constitution, however, can be associated with the metal contents. A classification of the nodules is suggested on the basis of these results. The iron content of the nodules strikingly shows relations to the physical properties (e.g. density and porosity). The method of density-measurement is the reason for this covariance. The investigation of freeze-dried nodular substance does not give this result. The Fe-rich nodules lose more hydration water than the Fe-poor ones during heat drying. The reason for this effect is the different crystallinity, respectively the particle size. The mean particle size is calculated on the basis of geometrical models. The X-ray-diffraction analysis proves the variation of crystallinity in connection with the Fe-content, too. The internal nodular textures also show characteristic distinctions.

Annotated record of the detailed examination of ferromanganese concretions from the Gulf of Bothnia in the Baltic Sea

Ferromanganese concretions cover large areas of the Gulf of Bothnia. They are flat to well-rounded, the rounded ones being richer in oxyhydroxides of iron and manganese. Rounded and ellipsoidal nodules, particularly those in the northern Gulf of Bothnia, are richest in Mn, Ni, Ba and Cu, which probably coexist in a Mn oxyhydroxide phase. Flat nodules are enriched in Fe, P, rare earths and As, probably associated with an Fe oxy-hydroxide component. Aluminum, V, Cr and Ti occur in still another phase. The sediments of the gulf generally consist of a 10-50 mm-thick layer of oxidized surface sediment, enriched in Mn, Ba, P and Ni lying on top of reduced sediments which are diagenetically depleted in these elements. The remobilized elements have redeposited in the nodules, but this process cannot explain the origin of all the nodular material. Some released Mn, Ba and Ni furthermore enter into suspended phases, which eventually leave the Baltic Sea. The economic value of the nodules in the Gulf of Bothnia is probably limited at present.