Petrology and major element geochemistry of Peru margin phosphorites and associated diagenetic minerals: Authigenesis in modern organic-rich sediments

New petrographic and major element geochemical data from modern Peru margin upper slope-outer shelf phosphorites are presented, which provide insight into their origin and paragenetic relationship with other authigenic minerals (glauconite, pyrite and dolomite) occurring in organic-rich sediments. Glauconites are precipitated relatively early following the partial reduction of ferric iron and, following this process, phosphate, pyrite, and then dolomite precipitation take place at progressively deeper levels in the sediment in association with microbial reduction of sulfate. As in many ancient economic phosphorite deposits, the phosphatic facies here consist of nodules, crusts, coatings and strata composed of phosphatic pelletal grains (ooids, structureless grains, intraclasts, clumps and biogenic grains) in association with organic-rich biosiliceous sediments. All are considered to have formed within a few centimeters or within a few tens of centimeters below the sediment-water interface. Important factors that influence which morphology will tend to develop include the amount of available pore space, the presence of suitable nucleation sites, the amount and size of siliciclastic detritus incorporated as inclusions and the relative solution chemistries of the precipitating solutions. Bacterial mediation may play an important, but as yet unspecified role in the precipitation process. Textural data and factor analysis of chemical data suggest that structureless pellets are relatively inclusion-free Na-F-Mg-CO₃-substituted pore-water precipitates whereas ooids are inclusion-rich pore-water precipitates poor in lattice-substituted components. Variations in nodular cement birefringence and crystallinity are suggested to have been produced by similar lattice substitutions that directly reflect pore-water carbonate ion concentrations and thus relative degrees of organic-matter degradation. Phosphate and dolomite are intimately mixed, yet mineralogically distinct phases in phosphatized dolomicrites.

Depth-stratified threshold carbonate ion concentrations may control the lower limit at which phosphatic minerals may precipitate. Below depths of a few centimeters, excessive carbonate ion concentrations and diminished reactive iron and sulfate concentrations favor the development of dolomite while precluding further development of phosphatic minerals and pyrite. Periodic sediment reorganization (bioturbation, current winnowing and erosion, mass wasting, etc.) plays an important role in both concentrating pelletal grains and maintaining nodules and crusts at critical depth levels in the sediment, as well as mixing ordered mineral parageneses into complicated sequences.     

Guest editorial

Surficial sediments rich in apatite pellets were recovered from an 80‐m‐deep area that runs parallel to the eastern coast of Vizcaino Bay, Baja California. This area is subject to intense seasonal upwelling, the sediments presenting elevated phosphate (P₂O₅), organic carbon (C_org), and carbonate concentrations. The pellets are moderately well sorted, concentrated mainly in the 3ø size class within a poorly sorted sediment matrix. Abundant nodular apatite and phosphatized bone fragments were found in only one of the pellet‐bearing samples. This sample has a P₂O₅concentration of over 20%, the ≥ — 2.5ø to 0.5ø grain size classes alone being formed of up to 32% P₂O₅. The high proportion of fragmented nodules and the presence of volcanic rock pebbles indicate that at least part of this deposit is allochthonous. The apatite pellets have a flat to concave‐downward heavy rare earth (HREE) shale normalized pattern and, except for La, are depleted in light rare earth elements (LREE). The close resemblance between the HREE patterns and the relatively high La concentration in the pellets of Vizcaino Bay, and the onland phosphorites of the southern Baja California Peninsula, suggest similar depositional histories for these deposits. No significant Ce anomalies were observed, but a negative Eu deviation is common in all of the pellet‐bearing sediments. The depletion of LREE in the pellets of Vizcaino Bay may indicate the preferential removal of these elements by weathering processes.     

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     

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.     

Phosphate inclusions in tuffites from the Krishtofovich Rise (Sea of Japan)

Tuffites of the core taken from the underwater Krishtofovich Rise in the southeastern Sea of Japan contain phosphate inclusions that were studied by scanning electron microscopy and chemical methods. The tuffites relatively enriched in phosphorus represent products of Miocene alkaline volcanism and are overlain by a thin layer of sediments partly transformed into smectites and containing microfossils presumably of the Late Miocene age. The phosphate inclusions variable in shapes and consistency are largely confined to the lower sedimentary layer, although occurring as single fragments of compact rock and nonlithified small inclusions in voids of altered tuffs as well. By their structure, microtextures, and main chemical composition, the phosphate inclusions are similar to the phosphorites from other areas of the ocean, which indicates their similar biogenic-diagenetic origin. Judging from the REE composition in the most phosphatized matter, they originate largely from seawater and, to a lesser extent, from tuffites. The redistribution of mobile phosphorus enclosed in the tuffites results in a small-scale phosphatization insufficient for ore formation.     

河口潮滩沉积物磷的季节性累积和生物有效性

对长江口潮滩表层沉积生磷的赋存形态和含量的研究表明,碎屑态磷为沉积物中磷的主要形态,约占总磷的62.52%;铁结合态磷和有机磷次之,分别占总磷的18.06%和14.69%;自生磷灰石加钙结合态磷和吸附态磷最少。综合研究区内的各种理化条件,指出弱吸附态磷、铁结合态磷和有机磷是长江口潮滩潜在生物可利用磷,约占总磷的33.16%,是导致水体富营养化的潜在因素。上覆水的盐度效应是影响沉积物铁结合态磷含量的关键性因子;而自生磷灰石加钙结合态磷的含量变化则与上覆水的温度、溶氧量及沉积物有机质的分解有关;有机磷在时间和空间尺度上都存在较大变化,主要与潮滩生物动态过程,即磷的再矿化有关。     

Microstructures of Agulhas Bank phosphorites

Electron microscopic study of Agulhas Bank phosphorites has revealed a large variety in their microstructures, including gel-like, fibrous, ultramicrogranular, ultramicrocrystallic and microcrystallic as well as microstructures of intermediate types. The crystallisation is mostly developed on carbonate-phosphate contacts and in free spaces between mineral grains and does not depend on absolute age of the phosphorite.     

Phosphorites of the Sea of Japan

The lithology and geochemistry of the Miocene concretional phosphorites recovered from four submarine rises in the Sea of Japan (the North and South Yamato, the East Korean, and the Krishtofovich) were examined by means of analytical electron microscopy and ICP-MS chemical and microchemical elemental analysis. The microstructural studies and the data on the distributions of the 57 major and trace elements in these phosphorites revealed their close similarities to the Late Quaternary nodular phosphorites from the Namibian shelf, as well as phosphorites from other parts of the world, thus suggesting a common genetic affinity. Unlike the Namibian phosphorites, our samples collected from the Sea of Japan display a number of geochemical signatures indicative of volcanic and hydrothermal activity. This is supported by the presence of positive Ce and Eu anomalies in some samples and the Ga enrichment in a sample from the Chentsov Volcano.     

渤海主要汇入河流碎屑磷灰石地球化学特征及成因

渤海的碎屑物质详细记录了源区的地质信息,对其进行物源示踪研究有助于提高我们对周围造山带及黄河的演化、中国东部陆架海碎屑物质扩散等的认识。本文利用激光剥蚀电感耦合等离子质谱分别对辽东湾、渤海湾及莱州湾周围主要汇入河流的碎屑磷灰石进行原位微量元素分析,结合Kolmogorov-Smirnov统计方法的多维判别图与反向传播神经网络等方法,分析渤海主要汇入河流碎屑磷灰石的微量元素与稀土元素。结果表明在汇入渤海的主要河流中,碎屑磷灰石的微量元素主要以Sr元素与Y元素为主,且都出现较为明显的HREE富集,但在不同河流之间的碎屑磷灰石Sr元素与REE也存在一定差异,这可能与其母岩不同相关。     

On the origin of phosphorites from Christmas Island in the Indian Ocean

A detailed investigation of microstructures of the phosphorites from Christmas Island under a scanning electron microscope coupled with an analysis of their chemical composition revealed that both their structure and composition are quite similar to those of the granular and microgranular phosphorites on present-day continents, as well as those of the phosphorites on some of the Pacific guyots. Their composition, together with their geological position and interrelationships with the surrounding rocks, proves that the ornitogenic hypothesis based on the presumed guano accumulation followed by its transformation into phosphatic rock is not compatible with the field observations. Meanwhile, the problem of the source of the Fe and Mn impregnation in the phosphorites remains unresolved and needs further investigations.     

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.     

Rare Earth and Metal Geochemistry of Land and Submarine Phosphorites in the Baja California Peninsula,Mexico

The geochemical composition of phosphorites and phosphatic sediments in the Baja California peninsula is studied and used to assess the environment in which phosphogenesis took place. The deposits are classified in three groups: (1) stratified phosphorites, (2) phosphatic sandy sediments from beaches and dunes, and (3) submarine sediments. Some of the elements that might have substituted Ca and PO₄ during francolite mineralization were studied by means of ICP-AES. Significant differences are seen in the concentration of these metals (e.g., Cr = 72-406 μg g^?1 and V = 17-198 μg g^?1), indicating that their concentration is not only controlled by the P₂O₅ concentration, but also by paleo-environmental conditions existing during francolite precipitation. Shale normalized REE patterns suggest two main environments of formation: (1) a strong negative Ce anomaly (< ? 0.3) and La enrichment (La/Nd ≥ 1) enrichment, suggesting well oxygenated shelf environments and probably lower light REE weathering, and (2) a weak negative Ce anomaly (> ? 0.3) and La depletion (La/Nd ≤ 1) suggesting shallower waters or restricted circulation and probably LREE weathering.     

Phosphorus regeneration vs. burial in sediments of the Arabian Sea

Solid-phase phosphorus (P) speciation and benthic phosphate fluxes have been determined in Arabian Sea sediments. Benthic phosphate fluxes are highest in the continental slope sediments, underlying bottom waters with low oxygen concentrations. Organic matter degradation and phosphate desorption from iron oxides do not produce sufficient phosphate to explain these high phosphate fluxes. The potentially high deposition of P associated with fish debris (P_fish) in the Arabian Sea, and a good correlation between benthic phosphate fluxes and P_fish accumulation rates suggest that benthic phosphate fluxes in these sediments are to a large extent governed by dissolution of biogenic apatite. Factors controlling dissolution and preservation of fish debris, therefore, may play an important role in the burial and regeneration of P in continental margin sediments. A sharp decrease of the reactive P accumulation rate with increasing water depth, in combination with rather constant primary productivity rates throughout the northern Arabian Sea, indicates that P burial in continental margin sediments located within the OMZ is more efficient than in deep basin sediments. The effectiveness of P burial is to a large extent regulated by P regeneration occurring in the water column and redeposition processes. Sedimentary phosphorus burial efficiencies, thus, should be interpreted with caution in terms of the environmental conditions.     

The occurrence of gold in hydrothermal sulfide at Southwest Indian Ridge 49.6°E

Massive sulfide precipitates found in the Southwest Indian Ridge(SWIR) 49.6°E hydrothermal field are enriched in gold.Here,the mineralogy and mineral chemistry of these massive sulfides to constrain the process of gold precipitation were studied.Sulfide samples in this field include lowertemperature Zn-rich sulfides and relative higher-temperature Fe-rich sulfides.Zn-rich sulfides are dominated by sphalerite-pyrite-chalcopyrite assemblages,with concentrations of gold ranging from 9.08 to 17.0 μg/g.Fe-rich sulfides consist mainly of pyrite-marcasite-isocubanite assemblages,with gold concentrations from 2.17 to 3.79 μg/g.The significant enrichment in gold within the lowertemperature Zn-rich sulfides and the effective separation of Zn and Fe in hydrothermal precipitates at the surface of this field are here interpreted to reflect the strong temperature dependence of gold transportation and deposition within the sulfides.In Zn-rich samples,large amounts of isolated native gold grains were identified.They were found mainly as inclusions up to 8 μm in diameter,occupying porous cavities in sphalerite or in the elevated iron content rim of sphalerite.The fineness of the gold ranged from 810 to 830.Unlike previously published results on other hydrothermal fields,these data show a low gold fineness values in SWIR 49.6°E.The FeS content of sphalerite associated with gold grains ranged from 3.2 mole % to 18.9 mole %.This was higher than in other fields,indicating that the sulfur activity is relatively low during the gold precipitation process and that sulfur activity may be one of the main factors affecting gold fineness in the SWIR 49.6°E hydrothermal field.Evidence regarding gold fineness and sulfur activity suggests that gold was quite likely transported as AuHS0 rather than as a Au(HS)-2 complex.     

Phosphogenesis on selected low atolls in the near-equatorial part of the Western Indian Ocean

The compositions, structures, and microstructures of different types of phosphorites and poorly phosphatized rocks from low atolls in the near-equatorial part of the Western Indian Ocean are described. The rocks were examined under optical and scanning microscopes using microprobing techniques and etching of selected samples with weak solvents as well as with the help of chemical analyses. It is proved that phosphorites have been formed owing to the uneven phosphatization of the primary carbonate rocks; the degree of their phosphatization ranges from traces to 40% P₂O₅. In the phosphorites, numerous organic remains were encountered; they included fragments of plankton, debris of tortoise shells, and coccoidal and filamentous bacteria-like formations. It is suggested that the phosphorites were formed due to the high local biological productivity over the outer edges of coral reefs and are not related to guano accumulation or to endoupwelling.     

Early diagenesis of organic matter in Peru continental margin sediments: Phosphorite precipitation

Pore water chemistry (total dissolved CO₂, NH₄, NO₃, NO₂, PO₄, Si(OH)₄, Ca, Mg, Fe, Mn, SO₄, H₂S and F, and titration alkalinity), solid phase chemistry (C_org, P_org, C_TOT, N_TOT, F, Si_OPAL and S_II), and sediment characteristics (porosity, dry bulk density and formation factors) were determined on a centimeter-scale spacing in the upper 20–40 cm of sediments under intense upwelling areas on the Peru continental shelf. These data demonstrate that carbonate fluorapatite (CFA) is precipitating from pore waters in the upper few centimeters of a gelatinous mud with high organic carbon content (up to 20% C_org), very high porosity ( > 0.96 ml cm⁻³) and very low dry bulk density (< 0.1 g cm⁻³). Dissolved phosphate concentrations at the sediment-water interface range from 20 to 100 μM, orders of magnitude higher than bottom-water concentrations, and much higher than predicted from regeneration of organic matter. The mechanism of this interfacial phosphate release is unclear, but is apparently uncoupled from carbon and nitrogen metabolism and thus may be linked either to dissolution of fish debris or to the presence of a microbial mat in surficial sediments. Fluoride is incorporated into CFA by diffusion from the overlying seawater, and carbonate ions are provided from pore-water alkalinity. Magnesium concentrations in this reaction zone are not significantly different from those of seawater, suggesting that magnesium depletion is not a necessary prerequisite for CFA precipitation.

The environment of precipitation is interface-linked rather than driven by organic diagenesis of phosphorus deeper in the sediment. Most of the cores display a wide range of diagenetic characteristics below the immediate interfacial region, but almost all show the precipitation signature near the interface. This interface-linked early diagenetic porewater environment for the precipitation of CFA explains many of the geochemical characteristics of phosphorites and provides a “testable” model to compare the modern phosphogenic analog with ancient phosphorite deposits. Two of the cores display very high solid phase phosphorus and fluoride contents reflecting the presence of apparently modern pelletal apatites.     

Marine Minerals in the Mexican Pacific: Toward Efficient Resource Management

Vast reserves of marine minerals are known to occur within the Mexican Exclusive Economic Zone. These reserves include: (1) heavy mineral placers rich in titanium and iron along the coast of San Antonio del Mar, Baja California and the southern States of Oaxaca and Guerrero; (2) phosphorites, which represent the only source for superphosphate fertilizers along the Pacific coast off the Baja California peninsula and the Gulf of Tehuantepec; and (3) manganese oxide deposits in nodule and crusts located adjacent to the Clarion-Clipperton Zone and containing high concentrations of Cu + Ni + Co (up to 1.9%), which are essential for the steel and super-alloy industries. Few but important efforts toward surveying these deposits have been carried out by Mexican and international researchers. Relevant data generated by these investigations are reviewed here and put together in a single document. Adequate knowledge of Mexican mineral resources is essential for the development of management strategies when offshore mining starts during this century. Thus, the review discusses the economics inherent to ocean mining in Mexico, setting baselines for future exploration and development activities in the Mexican Exclusive Economic Zone.     

Marine Minerals in the Mexican Pacific: Toward Efficient Resource Management

Abstract

Vast reserves of marine minerals are known to occur within the Mexican Exclusive Economic Zone. These reserves include: (1) heavy mineral placers rich in titanium and iron along the coast of San Antonio del Mar, Baja California and the southern States of Oaxaca and Guerrero; (2) phosphorites, which represent the only source for superphosphate fertilizers along the Pacific coast off the Baja California peninsula and the Gulf of Tehuantepec; and (3) manganese oxide deposits in nodule and crusts located adjacent to the Clarion-Clipperton Zone and containing high concentrations of Cu + Ni + Co (up to 1.9%), which are essential for the steel and super-alloy industries. Few but important efforts toward surveying these deposits have been carried out by Mexican and international researchers. Relevant data generated by these investigations are reviewed here and put together in a single document. Adequate knowledge of Mexican mineral resources is essential for the development of management strategies when offshore mining starts during this century. Thus, the review discusses the economics inherent to ocean mining in Mexico, setting baselines for future exploration and development activities in the Mexican Exclusive Economic Zone.     

Linking pollution induced community tolerance (PICT) and microbial community structure in chronically metal polluted estuarine sediments

We tested the ability of pollution induced community tolerance (PICT) to detect the effects of chronic metal pollution on estuarine sediment microbial communities, along a gradient spanning two orders of magnitude in metal concentrations. In tandem, we investigated the associated microbial community structure using terminal restriction fragment length polymorphism (T-RFLP). Tolerance of microbes to Cu, measured as IC50 (inhibitory concentration 50%), was strongly correlated with pore water Cu concentration (r(2)=0.842). No strong correlation existed for other metals tested, highlighting the ability of PICT to identify the pollutant causing a toxic effect. There was no correlation between microbial community structure and community tolerance to metals tested, but analysis of community structure did provide some information on reasons for observed PICT response. PICT methodology used here provided a greater strength and consistency of association with pollutant concentration compared to microbial community structure and can be recommended as a sensitive indicator of metal pollution on estuarine sediment microbial communities.