Carbon isotopic composition and lattice-bound carbonate of Peru-Chile margin phosphorites

New light-stable carbonate-carbon isotope and lattice-bound CO₂ data from Quaternary Peru-Chile margin phosphatic nodules, crusts and pelletal grains, and from associated dolomicritic concretions, are presented, which provide constraints on the timing and mechanisms of growth of these phases in organic carbon-rich sediments. Comparison of δ¹³C values from carbonate fluorapatite (CFA) nodules and pelletal grains (−4.8 to 0.0‰ and −2.9 to +1.0‰ PDB, respectively) with pore-water total dissolved δ¹³C values from these sediments suggests early authigenic CFA precipitation from pore waters within a few centimeters of the sediment-water interface in association with suboxic to perhaps anoxic microbial degradation of organic matter. In contrast, the dolomicritic cores of nodules recovered from about 12°S display both strongly negative to positive δ¹³C values (−10.8 to +6.1‰) characteristic of formation deeper in the sediments in association with methanogenic and perhaps sulfate reduction microbial processes.

The amount of structural carbonate in CFA suggests that carbonate substitution generally increases as δ¹³C in CFA decreases, a probable consequence of increasing carbonate and accompanying charge-balancing substitutions in the CFA lattice in response to increasing pore-water carbonate ion concentrations with depth below the sediment-water interface. In one buried upward-growing nodule, decreasing CFA δ¹³C and increasing structural CO₂ also correspond to decreasing CFA growth rates. These data suggest that in addition to other constraints such as pore-water phosphorus and fluoride availability, the lower limit of CFA precipitation in suboxic to anoxic sediments may be controlled by lattice poisoning due to excessive dissolved carbonate ion concentrations. In organic-rich Peru-Chile margin sediments this depth threshold appears to be at approximately 5–10 cm below the sediment-water interface where maximum CFA CO₂ contents of about 6 Wt.% occur; in less organic-rich settings, greater depths of precipitation of CFA may be anticipated. Below this relatively shallow depth of CFA precipitation on the Peru shelf, high pore-water alkalinity and associated elevated total dissolved carbon and carbonate ion concentration apparently favor the precipitation of authigenic carbonates.     

Rare earth elements in the phosphatic-enriched sediment of the Peru shelf

Apatite-enriched materials from the Peru shelf have been analyzed for their major oxide and rare earth element (REE) concentrations. The samples consist of (1) the fine fraction of sediment, mostly clay material, (2) phosphatic pellets and fish debris, which are dispersed throughout the fine-grained sediment, (3) tabular-shaped phosphatic crusts, which occur within the uppermost few centimeters of sediment, and (4) phosphatic nodules, which occur on the seafloor. The bulk REE concentrations of the concretions suggest that these elements are partitioned between the enclosed detrital material and the apatite fraction. Analysis of the fine-grained sediment with which the samples are associated suggested that this detrital fraction in the concretions should have shale REE values; the analysis of the fish debris suggested that the apatite fraction might have seawater values. The seawater contribution of REE's is negligible in the nodules and crust, in which the apatite occurs as a fine-grained interstitial cement. That is, the concentration of REE's and the REE patterns are predominantly a function of the amount of enclosed fine-grained sediment. By contrast, the REE pattern of the pelletal apatite suggests a seawater source and the absolute REE concentrations are relatively high. The REE/P₂O₅ ratios of the apatite fraction of these samples thus vary from approximately zero (in the case of the crust and nodules) to as much as approximately 1.2 × 10⁻³ (in the case of the pellets). The range of this ratio suggests that rather subtle variations in the depositional environment might cause a significant variation in the REE content of this authigenic fraction of the sediment.

Pelletal glauconite was also recovered from one sediment core. Its REE concentrations closely resemble those of the fish debris.     

Minor and rare elements in manganese crusts and nodules and sediments from the Manihiki plateau and adjacent areas: Results of HMNZS Tui cruises

Six manganese crusts, 13 manganese nodules, and 16 sediments were analyzed by instrumental neutron activation analysis. Data were generated on selected major and minor elements but geochemical evaluations are based only on Fe, Sc, U, Th, and the rare earth elements (REE). Manganese crusts and manganese nodules have comparable trivalent REE contents and show a shale‐like distribution pattern. Both crusts and nodules are characterized by a positive Ce anomaly but the anomaly is higher in nodules. REE contents in manganese nodules show a linear dependence on the Fe content, and it is concluded that these elements are incorporated in the Fe‐rich (δ‐MnO₂) phase. In the crusts, the REE correlate with Sc and are therefore assumed to be associated with the clay minerals. Uranium contents are significantly higher in the crusts than in nodules whereas Th is slightly higher in the nodules. There is a clear positive correlation between U and Th in nodules but there are too few data to make a similar conclusion for crusts. Compositional data suggest a division of the sediments into two groups. The carbonate sediments have much lower REE contents and a more pronounced negative Ce anomaly than the clays, while both show a lithogenous component as indicated by a slight negative Eu anomaly.     

Apatite and associated minerals in ferromanganese crusts from the Magellan Seamounts

The phosphate fraction extracted from a combined technological sample of ferromanganese crusts obtained from the Magellan Seamounts (Northwest Pacific) was studied with analytical electron microscopic methods. The material examined is represented by small rock fragments composed of well crystallized calcium phosphate with pores filled in with Mn oxides consisting largely of vernadite. The rock hosts crystallized barite aggregates, disseminated ultramicroscopic cubic pyrite crystals, filamentous halloysite aggregates, and assemblages of finely dispersed REE minerals represented by cerianite and parisite, which incrust the surface of apatite or are dispersed in the phosphatic matrix. The presence of the latter minerals shows that some REE related to the phosphatic phase do not enter the apatite lattice, which might influence the general pattern of the REE distribution in bulk samples     

南海多金属结壳(核)铁锰矿物/海水界面效应与成矿元素的富集

海底铁锰结壳和结核是重要的海底矿产资源,蕴含着丰富的金属元素并且具有巨大的经济价值。本文主要以南海多金属结壳（核）为研究对象,采用X射线粉晶衍射（XRD）、激光拉曼光谱、红外光谱分析（FTIR）以及X射线光电子能谱对铁锰矿物的矿物学和谱学特征进行了系统的分析和研究。粉晶衍射和拉曼光谱分析结果表明,南海多金属结壳的矿物组成为水羟锰矿、石英和长石,结核的矿物组成为钡镁锰矿、水羟锰矿、石英和长石,铁相矿物均为无定形铁氧化物/氢氧化物,并且锰相矿物和铁相矿物的结晶程度均较差。红外光谱分析结果显示多金属结核和结壳中的铁锰矿物具有大量表面羟基,这些含质子表面羟基官能团,可为海水中各成矿元素的络合提供丰富的活性位点。XPS分析表明多金属结核和结壳中铁锰矿物表面以Fe、Mn和O元素为主,其中Fe呈正三价态,Mn以正四、正三价为主,可能还含有少部分正二价态。对比南海多金属结壳（核）与太平海山结壳,南海多金属结壳（核）具有更为显著的表面羟基氧（-OH）含量,而太平洋海山结壳则以晶格氧（O^2-）为主,表明太平洋海山结壳铁锰矿物结晶程度较南海多金属结壳（核）高。综合研究表明,在海底铁锰结壳和结核中（氢）氧化锰/铁矿物与海水之间界面效应对金属离子的富集机理主要有：（1）金属离子与矿物表面羟基进行络合反应,形成以配位键相连的羟基络合物,或与表面的质子交换生成稳定的内层络合物;（2）矿物的带电表面与金属离子通过静电作用形成双电层,生成外层络合物;（3）金属离子与矿物结构中的Mn、Fe离子同晶置换而成为结构阳离子。     

Phosphorite from the Continental Margin off Madras, Bay of Bengal

A recent survey reveals that phosphorites occur over an area of 800 km2 between 100 and 500 m depths on the outer continental shelf and upper slope ESE off Madras. Appreciable subsurface continuity of phosphorites is not indicated. They mostly occur over two terraces recorded between the 100 and 200, and 350 and 400m isobaths. Sampled phosphorites may be classified under four types: (1) dense conglomeratic phosphorites in the size range 2 5 cm, (2) dark gray phosphatic nodules in the size range 1 3 cm, (3) creamy white calcareous algal nodules with phosphatic laminations in the size range 0.5 3 cm, and (4) recent gastropod shells with phosphatic studs. Conglomeratic phosphorites confined mostly to the upper terrace were recov ered along with calcareous pelecypod and gastropod fossils belonging to Cretaceous to Oligocene age. Gray phosphatic nodules occur over upper as well as lower terraces. The algal nodules are mostly confined to the upper terrace and are less abundant. Acoustic profiles (3.5 kHz) and the recovery of fossils indicate that the upper terrace is a karstic surface of a carbonate platform, probably of Cretaceous to Oligocene age. Petrographic study of the conglomeratic phosphorite shows skeletal matter set in phosphatic matrix and what appears to be the phosphatized limestone. Selective phosphatization of foraminiferal tests is common. Dark gray phosphatic nodules show brownish-gray laminations containing phosphatized skeletal fragments set in phosphatic matrix. Creamy white calcareous algal nodules exhibit alternate gray phosphatic and white calcitic laminations. All the phosphorite types are composed of carbonate fluorapatite and calcite as major minerals, followed by quartz and aragonite. Phosphorous pentoxide content of conglomeratic type varies from 15% to 20%, dark gray nodules from 16% to 19.98%, and calcareous algal nodules from 8.10% to 17.54%. The significant enrichment of Mo and Pb in phosphorites is attributed to their fixation in organic matter under reduced condition. SEM studies indicate a microbial origin for the gray phosphatic and algal nodules. Studies suggest four episodes of phosphatization with intervening reworking and redoposition, probably commencing from the Eocene period. Phosphatization during the late Pleistocene and early Holocene period also can be ruled out.     

过渡金属元素Cu、Co、Ni在铁锰结核(壳)中富集的控制因素

在不同生成环境下生成的铁锰结核(壳)吸收不同的过渡金属元素。在成岩作用形成的铁锰结核中,Cu、Ni主要以锰相形式存在,而Co则以铁相的形式存在;在水成作用形成的铁锰结核(壳)中Cu、Co、Ni均以锰相的形式存在。这些过渡金属元素在成岩作用形成的结核中的存在与铁锰结核(壳)中锰矿物和铁的氧化物、氢氧化物的晶体化学特征密切相关,而在水成作用形成的铁锰结核(壳)中的富集与锰矿物和铁的氧化物、氢氧化物的晶体化。学特征关系不大。同时铁锰结核(壳)中锰矿物和铁的氧化物、氢氧化物又严格地受结核(壳)的生成环境的制约,因此,过渡金属元素Cu、Co、Ni在铁锰结核(壳)中的富集在一定程度上受结核(壳)生成环境的控制。     

南海神狐海域沉积物自生黄铁矿和石膏S同位素特征及对甲烷渗漏强度的示踪

The northern slope of the South China Sea is a gas-hydrate-bearing region related to a high deposition rate of organic-rich sediments co-occurring with intense methanogenesis in subseafloor environments.Anaerobic oxidation of methane(AOM) coupled with bacterial sulfate reduction results in the precipitation of solid phase minerals in seepage sediment,including pyrite and gypsum.Abundant aggregates of pyrites and gypsums are observed between the depth of 667 and 850 cm below the seafloor(cmbsf) in the entire core sediment of HS328 from the northern South China Sea.Most pyrites are tubes consisting of framboidal cores and outer crusts.Gypsum aggregates occur as rosettes and spheroids consisting of plates.Some of them grow over pyrite,indicating that gypsum precipitation postdates pyrite formation.The sulfur isotopic values(δ~(34) S) of pyrite vary greatly(from –46.6‰ to –12.3‰ V-CDT) and increase with depth.Thus,the pyrite in the shallow sediments resulted from organoclastic sulfate reduction(OSR) and is influenced by AOM with depth.The relative high abundance and δ~(34) S values of pyrite in sediments at depths from 580 to 810 cmbsf indicate that this interval is the location of a paleo-sulfate methane transition zone(SMTZ).The sulfur isotopic composition of gypsum(from–25‰ to –20.7‰) is much lower than that of the seawater sulfate,indicating the existence of a 34 S-depletion source of sulfur species that most likely are products of the oxidation of pyrites formed in OSR.Pyrite oxidation is controlled by ambient electron acceptors such as MnO_2,iron(Ⅲ) and oxygen driven by the SMTZ location shift to great depths.The δ~(34) S values of gypsum at greater depth are lower than those of the associated pyrite,revealing downward diffusion of 34 S-depleted sulfate from the mixture of oxidation of pyrite derived by OSR and the seawater sulfate.These sulfates also lead to an increase of calcium ions from the dissolution of calcium carbonate mineral,which will be favor to the formation of gypsum.Overall,the mineralogy and sulfur isotopic composition of the pyrite and gypsum suggest variable redox conditions caused by reduced seepage intensities,and the pyrite and gypsum can be a recorder of the intensity evolution of methane seepage.     

Deformation bands evolving from dilation to cementation bands in a hydrocarbon reservoir (Vienna Basin,Austria)

In this study we analyzed five core samples from a hydrocarbon reservoir, the Matzen Field in the Vienna Basin (Austria). Deformation bands occur as single bands or as strands of several bands. In contrast to most published examples of deformation bands in terrigeneous sandstones, the reduction of porosity is predominantly caused by the precipitation of Fe-rich dolomite cement within the bands, and only subordinately by cataclasis of detrital grains. The chemical composition of this dolomite cement (10–12 wt% FeO) differs from detrital dolomite grains in the host rock (<2 wt% FeO). This observation in combination with stable isotope data suggests that the cement is not derived from the detrital grains, but precipitated from a fluid from an external, non-meteoric source. After an initial increase of porosity by dilation, disaggregation and fragmentation of detrital grains, a Fe-rich carbonate fluid crystallized within the bands, thereby reducing the porosity relative to the host sediment. The retention of pyrite cement by these cementation bands as well as the different degree of oil staining on either side of the bands demonstrate that these cementation bands act as effective barriers to the migration of fluids and should be considered in reservoir models.     

黄河与长江入海沉积物中碳酸盐含量和矿物颗粒形态特征及影响因素

利用X射线物相分析、扫描电镜及能谱分析等方法分析了长江和黄河入海沉积物矿物颗粒形态特征及不同粒级的碳酸盐矿物百分含量分布。结果表明,长江和黄河入海沉积物的碳酸盐矿物含量均在9%左右,差异不大。长江碳酸盐矿物含量在粗粒级较高,随着粒度变细波动式降低,黄河碳酸盐矿物含量则随粒度变细而逐步增加;黄河方解石含量高而白云石低,长江的情况正好相反。长江和黄河入海沉积物中的白云石颗粒大多比较完整,侵蚀沿完全解理面发生,菱面体形态明显。长江白云石上可以见到大量的磨蚀和溶蚀形态。黄河白云石保存较好,侵蚀程度较低,磨蚀和碰撞形态明显,溶蚀形态很少,发现典型的马鞍状白云石颗粒。长江和黄河的方解石均遭受强烈侵蚀。长江方解石溶蚀特征特别明显,深入矿物颗粒内部。黄河方解石侵蚀深度相对浅表,侵蚀形态多为磨蚀、碰撞和溶蚀等物理和化学综合侵蚀特征。长江某些方解石表面布满细小鲕状方解石颗粒,似为局部自由空间的胶体-陈化成因特征。黄河方解石呈现多个次生微晶集合体,显示其黄土粘粒空隙胶结物成因形态。碳酸盐矿物的菱面体形态和菱面体完全解理所特有的60°和120°交角,是其电镜下的最佳识别特征。长江和黄河沉积物物源、流域风化强度以及矿物晶体结构本身的特...     

珠江口淇澳岛海岸带沉积物中硫酸盐还原和不同形态硫的分布

对珠江口淇澳岛海岸带3个站位(QA-11,QA-9和QA-14)的沉积物中不同形态的还原硫(酸可挥发性硫,黄铁矿和有机硫)、总有机碳(TOC)和孔隙水中SO42-,甲烷浓度进行了测定,并且利用稳态扩散模型计算其中2个站位(QA-9和QA-14)硫酸盐还原通量[1.74和1.14 mmol/(m2.d)]和甲烷厌氧氧化通量[0.34和0.29 mmol/(m2.d)]。研究结果表明由于潮间带沉积物受到SO42-供给的限制,因此位于潮间带的QA-11站位硫酸盐还原带较浅(约16 cm);在潮下带的QA-9和QA-14站位,随离海岸距离和水深的增加,硫酸盐还原通量呈现减小的趋势,并且硫酸还原逐渐受到可利用活性有机质的限制;甲烷厌氧氧化对硫酸盐还原的贡献表现出增加的趋势,由19.2%增加至25.5%。三个站位沉积物中按不同形态还原硫含量由大到小列出,它们是有机硫(OS)、黄铁矿(DS)、酸可挥发性硫(AVS)。沉积物中AVS的空间分布与硫酸盐还原通量有正相关性。QA-11和QA-14站位的黄铁矿与AVS硫的含量比值大于3,分别为7.9和3.6,表明两个站位的黄铁矿形成可能受硫酸盐还原作用的控制;QA-9站位黄铁矿与AVS硫的含量比值为2.2,暗示AVS向黄铁矿转化受到可利用活性铁的限制。     

Authigenic carbonates related to active seepage of methane-rich hot brines at the Cheops mud volcano,Menes caldera (Nile deep-sea fan,eastern Mediterranean Sea)

On the passive margin of the Nile deep-sea fan, the active Cheops mud volcano (MV; ca. 1,500 m diameter, ~20–30 m above seafloor, 3,010–3,020 m water depth) comprises a crater lake with hot (up to ca. 42 °C) methane-rich muddy brines in places overflowing down the MV flanks. During the Medeco2 cruise in fall 2007, ROV dives enabled detailed sampling of the brine fluid, bottom lake sediments at ca. 450 m lake depth, sub-surface sediments from the MV flanks, and carbonate crusts at the MV foot. Based on mineralogical, elemental and stable isotope analyses, this study aims at exploring the origin of the brine fluid and the key biogeochemical processes controlling the formation of these deep-sea authigenic carbonates. In addition to their patchy occurrence in crusts outcropping at the seafloor, authigenic carbonates occur as small concretions disseminated within sub-seafloor sediments, as well as in the bottom sediments and muddy brine of the crater lake. Aragonite and Mg-calcite dominate in the carbonate crusts and in sub-seafloor concretions at the MV foot, whereas Mg-calcite, dolomite and ankerite dominate in the muddy brine lake and in sub-seafloor concretions near the crater rim. The carbonate crusts and sub-seafloor concretions at the MV foot precipitated in isotopic equilibrium with bottom seawater temperature; their low δ¹³C values (–42.6 to –24.5‰) indicate that anaerobic oxidation of methane was the main driver of carbonate precipitation. By contrast, carbonates from the muddy lake brine, bottom lake concretions and crater rim concretions display much higher δ¹³C (up to –5.2‰) and low δ¹⁸O values (down to –2.8‰); this is consistent with their formation in warm fluids of deep origin characterized by ¹³C-rich CO₂ and, as confirmed by independent evidence, slightly higher heavy rare earth element signatures, the main driver of carbonate precipitation being methanogenesis. Moreover, the benthic activity within the seafloor sediment enhances aerobic oxidation of methane and of sulphide that promotes carbonate dissolution and gypsum precipitation. These findings imply that the coupling of carbon and sulphur microbial reactions represents the major link for the transfer of elements and for carbon isotope fractionation between fluids and authigenic minerals. A new challenge awaiting future studies in cold seep environments is to expand this work to oxidized and reduced sulphur authigenic minerals.     

A comparative analysis of compositional variations in and between marine ferromanganese nodules and crusts in the South Pacific and their environmental controls

Regional variation of Mn, Fe, Co, Ni and Cu in ferromanganese oxides (nodules and crusts) in the central south Pacific is related to primary productivity, oxygen minimum layer, and calcium carbonate compensation depth. The largely latitudinal influence of these environmental parameters on nodule and crust composition reflects their predominantly latitudinal variation. Primary productivity is the principal regional environmental control, influencing diagenetic enrichment of these elements in nodules through its effect, mediated by the CCD, on supply and concentration of labile organic matter vs. carbonate remains to the sediments. It influences hydrogenetic enrichment of these elements in nodules and crusts through its effect, mediated by the oxygen minimum layer (mainly in the case of crusts), on their export from surface waters.The elements’ varying susceptibility to being scavenged or organically bound influences the contrasting composition of diagenetic vs. hydrogenetic ferromanganese oxides, which is further influenced by depth. Hydrogenesis is the fundamental process governing nodule and crust formation, superimposed on which is diagenesis under specific circumstances; both are subject to intermittent interruption, diminution and augmentation by changes in environmental parameters. Application of regionally operative environmental controls locally explains local compositional variations and helps refine exploration criteria for economically viable nodules and crusts.     

Morphological Features of Co-Rich Manganese Deposits and Their Relation to Seabed Slopes

The morphological features associated with Co-rich manganese deposits, the size variations of nodules, and the occurrence of different substrates have been analyzed, to evaluate the influence of various seabed slope angles on the distribution of these features. The coverage and size of the crusts depend on their surface morphology and seabed topography, resulting in cobble-type, lineated, or step-like outcrops. Small nodules (1 - 4 cm in diameter) dominate all seabed slopes, with a few locations having nodules ranging from 1 to 8 or 1 to 10 cm. Sediments invariably occur as substrates for nodules and as cover for crusts, their coverage being inversely proportional to that of the nodules and crust outcrops. Steeper seafloor areas have large crust outcrops exposed with no or few nodules and sediments associated with them. The intermediate slopes have a combination of nodules, sediments, and crusts in various proportions, depending on topography and gradient. Large-scale nodule occurrences, followed by sediment fields and crust outcrops on seabed slopes of greater than 3 degrees, 3 - 7 degreees, and less than 15 degrees, respectively, represent typical morphological distribution zones of the Co-rich manganese deposits on a seamount in the central Pacific Ocean. A transition zone between nodule-dominated fields and large crust outcrops occurs for slopes from 7 degrees to 15 degrees. This detailed study on distribution of Co-rich deposits gives a better understanding for purposes of their exploitation.     

Modes of iron-manganese mineralization on the bottom of Lake Baikal

The investigation of the bottom of Lake Baikal carried out during the 2008 summer season by means of Mir manned deep-submergence vehicles resulted in the recovery of a series of sediments, ferruginous crusts, and peculiar mineralized tubes several centimeters high and up to 2–6 cm in diameter. According to the scanning electron investigation, these formations consist mainly of the enclosing sediment particles and biogcnie silica cemented by iron and minor manganese hydroxides. The chemical composition of the tubes is similar to both that of the enclosing sediments and slightly ferruginous crusts and nodules, but the tubes and crusts are somewhat richer relative to the sediments in some microelements, namely, arsenic, cadmium, and uranium. In general, the structure and composition of these tubes reminds one of the worm tubes common in the sediments of a number of seas. The investigation of the rare earth elements in some samples or ferruginous formations and sediments revealed a positive europium anomaly, which might be related to either the composition of the surrounding continental magmatic rocks or to the influence of hypothetical hydrothermal solutions.     

琼东南盆地与甲烷渗漏有关的早期成岩作用和孔隙水化学组分异常

X-射线衍射和扫描电镜观察表明,采自南海北部琼东南盆地的沉积物样品中有天然气水合物和甲烷渗漏指示意义的自生碳酸盐、硫酸盐和草莓状framboids黄铁矿,自生矿物组合和显微结构特征与冷泉沉积物类似,属微生物成因。沉积物孔隙水化学组分分析结果显示,随着埋藏深度加深,SO₄2-,Ca2+,Mg2+和Sr2+浓度明显降低,Mg2+浓度与Ca2+浓度和Sr2+浓度与Ca2+浓度的比值急剧增加,这些地球化学特征与世界上天然气水合物产区的浅表层沉积物孔隙水中离子浓度异常吻合较好,暗示采样站位深部可能有油气或天然气水合物藏。     

Authigenic barite nodules and carbonate concretions in the Upper Devonian shale succession of western New York – A record of variable methane flux during burial

Authigenic barite nodules associated with modestly ¹³C-depleted calcium carbonate concretions and ³⁴S-enriched pyrite at the bottom of the Upper Devonian Hanover Shale of western New York provide evidence of sulfate reduction coupled with anaerobic oxidation of methane (AOM). The methane, much of it biogenic in origin, may have diffused upward from Middle Devonian Marcellus Shale and perhaps the Upper Ordovician Utica Shale. Strong ³⁴S enrichment and high δ³⁴S/δ¹⁸O values of the barite nodules reflect: (1) substantial kinetic fractionation induced by microbial sulfate reduction perhaps intensified by a low seawater sulfate recharge rate and (2) upward delivery of Ba²⁺- and CH₄- bearing pore fluid sourced within underlying sulfate-depleted deposits. However, the association of authigenic calcium carbonate and barite in the same stratigraphic interval, especially the presence of barite overgrowths on carbonate concretions, is not consistent with what is known of AOM-related mineralization of a sediment column passing downward through the sulfate–methane transition (SMT). The documented early formation of authigenic carbonate followed by barite observed relations may reflect a diminished rate of methanogenesis and/or CH₄ supply. The tempered methane flux would have induced the SMT to descend the sediment column enabling barite to form within the same stratigraphic horizon that ¹³C-depleted calcium carbonate had most recently precipitated. Diminished methane flux may have been caused by burial-related passage of the organic-rich Marcellus Shale below the depth of peak biogenic methane generation and its replacement at that depth interval by organic-lean deposits of the upper part of the Hamilton Group. Subsidence of the SMT would have increased the preservation potential of authigenic barite. However, continued survival of the labile barite as it eventually moved through the SMT suggests that the underlying sulfate-depleted zone was strongly enriched in Ba²⁺.     

Hardground formation in the Bannock Basin, Eastern Mediterranean

Twenty kilogrammes of crusts and slabs of indurated carbonate sediment, usually referred to as hardgrounds, were dredged along the eastern steep wall of the Bannock Basin during the 1984 cruise of R.V. Bannock.

The crusts range in thickness from one to a few centimetres and the fragments of these crusts are irregular in shape. Their surface is always uneven and their colour ranges from white to brownish dark grey. Some slabs are impregnated along one side by ferromanganese sesquioxides, and borings occur in several samples. Serpulid tubes have been observed in one instance. The borings and serpulids suggest formation of the hardgrounds at or close to the sediment/water interface and exposure at the seafloor.

The degree of lithification is generally different on the inferred upper and lower sides of the slabs. An upward increase of lithification across the slabs is reflected by mineralogy, ultrastructure and stable isotope composition of the carbonate. X-ray diffraction analyses indicate high-magnesian calcite as the predominant carbonate with minor amounts of low-magnesian calcite and dolomite. Occasionally, large gypsum crystals are attached to the hardgrounds and sometimes smaller ones are dispersed through the carbonate matrix.

An increase in diagenesis is reflected by the passage from friable, nodular nannofossil chalk to nannofossil limestone and hard xenotopic calcite micrite. Overgrowth of coccoliths and internal cementation of the tests of planktonic foraminifera by high-Mg calcite increase from chalk to limestone. In the hard, fully cemented micrites, coccoliths can no longer be recognised in the xenotopic fabric. Pteropods occur as dissolution moulds with aragonite preserved as only tiny relics.

Carbon and oxygen isotope analyses were performed on different samples. The progressive lithification to chalk and limestone is marked by a shift in the δ¹⁸O values from +1.2‰ to +5.4‰ (PDB). This change indicates that precipitation of high-Mg calcite and possibly also recrystallisation of the original biogenic carbonate took place within cold and hypersaline brines which were enriched in ¹⁸O. The oxygen isotope data suggest that lithification and gypsum precipitation occurred under identical conditions. The carbon isotope data show progressive diagenetic change from values near +1‰ to values of +3‰. This change may reflect a contribution of methanogenetic CO₂ to the hypersaline brine.     

Mineralogy and composition of manganese crusts and nodules and sediments from the Manihiki plateau and adjacent areas: Results of HMNZS Tui Cruises

Forty‐four sediment samples and 23 Mn crusts and Mn nodules have been analyzed for several elements in order to characterize their geochemical nature. Most of the Mn crusts and Mn nodules are of hydrogenous origin, although one crust (U375) from the flanks of the Rarotonga volcano is thought to be of hydrothermal origin. δ‐MnO₂ is the principal Mn mineral in the crusts, whereas todorokite and birnessite occur in addition to δ‐MnO₂ in the nodules. The sediments can be divided into carbonates, with calcite as the dominant phase, and deep‐sea clay, consisting mainly of illite and smectite.     

Distribution, texture and composition of modern phosphate pellets in Peru shelf muds

Textural analysis, including estimates of concentrations of authigenic phosphate pellets, were made for eight sediment cores from the Peru continental margin. Phosphatic pellets separated from these modern organic-rich sediments are black, spherical-ovoidal in shape, and in thin section often display a concentric structure around a nucleus consisting of inorganic mineral grains. Some pellets have a gray-white exterior coating which appears to be secondary diagenetic calcite. Phosphatic pellets account for upwards of 80% of the sediment mass in some cores. Pellets concentrate in specific size classes, generally between 125 and 500 μm in diameter, and occur within a poorly sorted sediment.