Marine Phosphorites Research Articles

Fe-(oxyhydr)oxide participation in REE enrichment in early Cambrian phosphorites from South China: Evidence from in-situ geochemical analysis

Marine phosphorites have shown extraordinary REE potential. Enrichment mechanisms have been investigated as yet, however, the roles of Fe/Mn (oxyhydr)oxides in REE enrichment were poorly known. In this paper, we report new data for early Cambrian phosphorites in South China with a particular focus on REE enrichment and Fe-redox cycling. Phosphorites from the Cambrian Gezhongwu occur in the upper and lower units. The phosphorites contain a large number of of Fe (oxyhydr)oxides, especially those in the upper unit. SEM and laser Raman show that Fe (oxyhydr)oxides have a gray rim and a bright core, attributed to transformation from hematite to goethite during the weathering. In-situ elemental analyses show Fe (oxyhydr)oxides have PAAS-normalized REE patterns depleted in LREE and enriched in HREE with negative to positive Eu anomalies and positive Y anomalies. However, two patterns are clearly distinguished according to Ce anomalies and these are related to the origins of Fe-(oxyhydr)oxides: hydrothermal Fe (oxyhydr)oxides with negative Ce anomalies and hydrogenic ones with positive Ce anomalies. The role of Fe (oxyhydr)oxides played in REE enrichment was controlled by Fe-redox pumping. In this process, Fe (oxyhydr)oxides adsorbed REEs in oxic water columns; after precipitating to suboxic/anoxic conditions, the absorbed REEs were released into porewater. Francolites subsequently formed and captured REEs during early diagenesis. Even though additional evidence is required, our investigations were significant in conforming the origins of Fe/Mn (oxyhydr)oxides and their role in REE enrichment in marine phosphorites.

Phosphorite occurrences on the western continental margin of India: An update

Marine phosphorites are well known from the tropical upwelling zones along the west coast of North America, South America, and African continents. Despite having similar oceanographic and topographic set-ups, comparable scales of phosphorite occurrences have not been reported from the western margin of the Indian subcontinent. However, Seabed surveys carried out by the Geological Survey of India during the last decade unearthed phosphatic crusts and nodules from several elevated topographic domains off the west coast of India. These new findings necessitate an update to the phosphorite zone map of the present-day Ocean. On the seamounts and spurs off the west coast of India, ferruginous and non-ferruginous phosphorites occur in the form of crusts and nodules within the water depth range of 300 to 800 m. Geochemical evidence and concurrent occurrences of varied types of phosphorites within the same topographic domain point to the prevalence of multiple episodes of short-duration phosphogenesis along the western margin of India.

Distinct REY sources recorded in the Doushantuo phosphorite

During the Ediacaran period, massive marine phosphorites were deposited worldwide, which could represent a global sink of rare earth elements and yttrium (REY) in oceans. In the Doushantuo Formation of South China, the REY source has been preliminarily constrained as the mixed sources of seawater and terrigenous matter in these phosphorites. However, the REY composition of both seawater and terrigenous endmembers is still unclear; therefore, it’s difficult to identify the contributions of seawater and terrigenous sourced REY. In this work, REY and other trace elements of bulk phosphorites, in situ carbonates, and apatite grains were analyzed from a drill core (Fangmashan) of the Doushantuo Formation in South China. Combined with mineralogical observations, the REY composition of seawater and terrigenous endmembers is well-constrained. Along the investigated Fangmashan drill core, all in situ carbonates (calcites and dolomites) show a modern seawater-like REY pattern, indicating that the REY characteristics of the Doushantuo seawater could be similar to those of modern oxic seawater without significant changes. Alternatively, apatites from the lower and upper phosphorites showed distinct REY patterns. One type of apatite in the upper phosphorites showed a modern seawater-like REY pattern, indicating authigenic REE enrichment from the seawater column. However, another type of apatite in the upper phosphorites with an REE pattern that deviated from seawater showed high ΣREY (∼691.16 ± 309.78) and low Y/Ho (∼40.52 ± 4.05), probably reflecting mixed REY sources and/or the effects of early diagenesis. It is noted that most apatites in the lower phosphorites are obviously enriched in light REY (LREY: La - Nd) compared to heavy REY (HREY: Ho - Lu and Y), which may represent a significant contribution of the terrestrial REY source. This study reveals that the REY composition of paleo-seawater could be similar to modern seawater as early as the Neoproterozoic and supports a significant contribution to understanding the difference in the REY composition of phosphorites in geological history.

Enrichment and sources of REY in phosphate fractions: Constraints from the leaching of REY-rich deep-sea sediments

Rare earth elements and yttrium (REY)-rich deep-sea sediments, regarded as a potential resource, have triggered extensive investigations over the last decade. The conclusion that the REY enrichment is closely related to the phosphate components contradicts the low REY content (ΣREY) of marine phosphorites, leading to questions about the control of deep-sea phosphate on the enrichment and cycling of REY. Herein, we performed a series of chemical leaching experiments on a group of REY-rich samples (up to 5983 ppm) from two sediment cores obtained from the Pigafetta Basin in the western Pacific to investigate the phosphate and non-phosphate fractions. We found that phosphate components in deep-sea sediments, termed REY-rich phosphates, contain a mean ΣREY of 27,635 ppm and ΣREY/P2O5 of >0.75, which are 1–2 orders of magnitude higher than that of marine phosphorites. The 87Sr/86Sr (0.7083–0.7092) and εNd (–6.41 to –5.15) of the phosphate fractions exhibited strong terrigenous attributes and fell within the range of that of bottom water since 25 Ma. Notably, the non-phosphate components, primarily phillipsite and clay, exhibited stronger terrigenous attributes, confirming extremely low sedimentation rate in the study area. The development and accumulation of REY-rich phosphate, as a consequence of low sedimentation rate in deep water together with erosion and sorting by bottom current, control the content and patterns of REY in deep-sea sediments. Fe-Mn oxides that migrated to the seafloor from the water column were limited and consumed less REY, although their strong Ce enrichment led to the loss of Ce in seawater. The phosphate components in sediments inherited the primary REY pattern of seawater and became the major REY budget on the seabed. In this study, we propose that the mineralization during the sinking of biological particles not only controls the REY distribution in the water column but also becomes an important REY source migration to the seabed and rapidly releases at the sediment–water interface. Consequently, REY can be effectively concentrated by the phosphate components under low sedimentation rates, yielding weak fractionated seawater REY patterns with lower Y/Ho ratios.

Seabed mining and blue growth: exploring the potential of marine mineral deposits as a sustainable source of rare earth elements (MaREEs) (IUPAC Technical Report)

Abstract The expected growth of the global economy and the projected rise in world population call for a greatly increased supply of materials critical for implementing clean technologies, such as rare earth elements (REEs) and other rare metals. Because the demand for critical metals is increasing and land-based mineral deposits are being depleted, seafloor resources are seen as the next frontier for mineral exploration and extraction. Marine mineral deposits with a great resource potential for transition, rare, and critical metals include mainly deep-sea mineral deposits, such as polymetallic sulfides, polymetallic nodules, cobalt-rich crusts, phosphorites, and rare earth element-rich muds. Major areas with economic interest for seabed mineral exploration and mining are the following: nodules in the Penrhyn Basin-Cook Islands Exclusive Economic Zone (EEZ), the Clarion–Clipperton nodule Zone, Peru Basin nodules, and the Central Indian Ocean Basin; seafloor massive sulfide deposits in the exclusive economic zones of Papua New Guinea, Japan, and New Zealand as well as the Mid-Atlantic Ridge and the three Indian Ocean spreading ridges; cobalt-rich crusts in the Pacific Prime Crust Zone and the Canary Islands Seamounts and the Rio Grande Rise in the Atlantic Ocean; and the rare earth element-rich deep-sea muds around Minamitorishima Island in the equatorial North Pacific. In addition, zones for marine phosphorites exploration are located in Chatham Rise, offshore Baja California, and on the shelf off Namibia. Moreover, shallow-water resources, like placer deposits, represent another marine source for many critical minerals, metals, and gems. The main concerns of deep-sea mining are related to its environmental impacts. Ecological impacts of rare earth element mining on deep-sea ecosystems are still poorly evaluated. Furthermore, marine mining may cause conflicts with various stakeholders such as fisheries, communications cable owners, offshore wind farms, and tourism. The global ocean is an immense source of food, energy, raw materials, clean water, and ecosystem services and suffers seriously by multiple stressors from anthropogenic sources. The development of a blue economy strategy needs a better knowledge of the environmental impacts. By protecting vulnerable areas, applying new technologies for deep-sea mineral exploration and mining, marine spatial planning, and a regulatory framework for minerals extraction, we may achieve sustainable management and use of our oceans.

Effect of Carbonate Alkalinity on the Solubility of Modern Marine Phosphorite

Effect of Carbonate Alkalinity on the Solubility of Modern Marine Phosphorite

REY enrichment mechanisms in the early Cambrian phosphorite from South China

Worldwide phosphogenesis during the early Cambrian occurred coevally with localized Rare Earth Element plus Y (REY)-rich phosphorite in Zhijin, South China. Although characteristics of the Zhijin phosphorite have been well constrained, the major factors controlling REY enrichment remain unknown. To address this, the research studied the REY occurrence forms and enrichment mechanisms. Accordingly, carbonate C and O isotopes, micropetrographic, and in situ geochemical analyses of Zhijin phosphorites were conducted. Results show that the phosphates are composed of closely-packed nano to μm-scale apatites, which were spherulitic and short cylindrical, comprising mainly fluorapatites and minor francolites. Element mapping verifies that REYs were hosted in apatites by isomorphous substitution, with minor REY being adsorbed by clay minerals. Further, REY was incorporated into apatite crystals during the early diagenesis according to LaN/SmN vs. LaN/YbN plots. Apatites show Medium REE (MREE)-rich post-Archean Australian shale-normalized distribution patterns, attributed to selective adsorption of MREEs by Fe-/Mn oxides/hydroxides or organic matters. Plots of Nd and Ceanom manifest lower sedimentation rates of REY, providing adequate time for REY absorption in the seawater. Excluding secular variations of REEs in the ocean chemistry, we suggest that constrained paleogeography provided a suitable space for REEs entering apatite crystals during early diagenesis. This is possibly the primary cause for the vast REE reserves of the Zhijin phosphorite deposit. In addition, redox conditions, temperature, biological activities, and weathering played non-critical roles in REY enrichment in apatites. Our findings can inform on multi-factor constraints of REY-rich marine phosphorites in the early Cambrian and provide a further understanding of REY enrichment in worldwide sedimentary marine phosphorites.

Mechanism and Influencing Factors of REY Enrichment in Deep-Sea Sediments

Deep-sea sediments with high contents of rare-earth elements and yttrium (REY) are expected to serve as a potential resource for REY, which have recently been proved to be mainly contributed by phosphate component. Studies have shown that the carriers of REY in deep-sea sediments include aluminosilicate, Fe-Mn oxyhydroxides, and phosphate components. The ∑REY of the phosphate component is 1–2 orders of magnitude higher than those of the other two carriers, expressed as ∑REY = 0.001 × [Al2O3] − 0.002 × [MnO] + 0.056 × [P2O5] − 32. The sediment P2O5 content of 1.5% explains 89.1% of the total variance of the sediment ∑REY content. According to global data, P has a stronger positive correlation with ∑REY compared with Mn, Fe, Al, etc.; 45.5% of samples have a P2O5 content of less than 0.25%, and ∑REY of not higher than 400 ppm. The ∑REY of the phosphate component reaches n × 104 ppm, much higher than that of marine phosphorites and lower than that of REY-phosphate minerals, which are called REY-rich phosphates in this study. The results of microscopic observation and separation by grain size indicate that the REY-rich phosphate component is mainly composed of bioapatite. When ∑REY > 2000 ppm, the average CaO/P2O5 ratio of the samples is 1.55, indicating that the phosphate composition is between carbonate fluoroapatite and hydroxyfluorapatite. According to a knowledge map of sediment elements, the phosphate component is mainly composed of P, Ca, Sr, REY, Sc, U, and Th, and its chemical composition is relatively stable. The phosphate component has a negative Ce anomaly and positive Y anomaly, and a REY pattern similar to that of marine phosphorites and seawater. After the early diagenesis process (biogeochemistry, adsorption, desorption, transformation, and migration), the REY enrichment in the phosphate component is completed near the seawater/sediment interface. In the process of REY enrichment, the precipitation and enrichment of P is critical. According to current research progress, the REY enrichment is the result of comprehensive factors, including low sedimentation rate, high ∑REY of the bottom seawater, a non-carbonate depositional environment, oxidation conditions, and certain bottom current conditions.

The origin and composition of carbonatite-derived carbonate-bearing fluorapatite deposits

Carbonate-bearing fluorapatite rocks occur at over 30 globally distributed carbonatite complexes and represent a substantial potential supply of phosphorus for the fertiliser industry. However, the process(es) involved in forming carbonate-bearing fluorapatite at some carbonatites remain equivocal, with both hydrothermal and weathering mechanisms inferred. In this contribution, we compare the paragenesis and trace element contents of carbonate-bearing fluorapatite rocks from the Kovdor, Sokli, Bukusu, Catalão I and Glenover carbonatites in order to further understand their origin, as well as to comment upon the concentration of elements that may be deleterious to fertiliser production. The paragenesis of apatite from each deposit is broadly equivalent, comprising residual magmatic grains overgrown by several different stages of carbonate-bearing fluorapatite. The first forms epitactic overgrowths on residual magmatic grains, followed by the formation of massive apatite which, in turn, is cross-cut by late euhedral and colloform apatite generations. Compositionally, the paragenetic sequence corresponds to a substantial decrease in the concentration of rare earth elements (REE), Sr, Na and Th, with an increase in U and Cd. The carbonate-bearing fluorapatite exhibits a negative Ce anomaly, attributed to oxic conditions in a surficial environment and, in combination with the textural and compositional commonality, supports a weathering origin for these rocks. Carbonate-bearing fluorapatite has Th contents which are several orders of magnitude lower than magmatic apatite grains, potentially making such apatite a more environmentally attractive feedstock for the fertiliser industry. Uranium and cadmium contents are higher in carbonate-bearing fluorapatite than magmatic carbonatite apatite, but are much lower than most marine phosphorites.

Marine Phosphorites as Potential Resources for Heavy Rare Earth Elements and Yttrium

Marine phosphorites are known to concentrate rare earth elements and yttrium (REY) during early diagenetic formation. Much of the REY data available are decades old and incomplete, and there has not been a systematic study of REY distributions in marine phosphorite deposits that formed over a range of oceanic environments. Consequently, we initiated this study to determine if marine phosphorite deposits found in the global ocean host REY concentrations of high enough grade to be of economic interest. This paper addresses continental-margin (CM) and open-ocean seamount phosphorites. All 75 samples analyzed are composed predominantly of carbonate fluorapatite and minor detrital and authigenic minerals. CM phosphorites have low total REY contents (mean 161 ppm) and high heavy REY (HREY) complements (mean 49%), while seamount phosphorites have 4–6 times higher individual REY contents (except for Ce, which is subequal; mean ΣREY 727 ppm), and very high HREY complements (mean 60%). The predominant causes of higher concentrations and larger HREY complements in seamount phosphorites compared to CM phosphorites are age, changes in seawater REY concentrations over time, water depth of formation, changes in pH and complexing ligands, and differences in organic carbon content in the depositional environments. Potential ore deposits with high HREY complements, like the marine phosphorites analyzed here, could help supply the HREY needed for high-tech and green-tech applications without creating an oversupply of the LREY.

Calcium-Phosphate Biomineralization Induced by Alkaline Phosphatase Activity in Escherichia coli: Localization, Kinetics, and Potential Signatures in the Fossil Record

Bacteria are thought to play an important role in the formation of calcium-phosphate minerals composing marine phosphorites, as supported by the common occurrence of fossil microbes in these rocks. Phosphatase enzymes may play a key role in this process. Indeed, they may increase the supersaturation with respect to Ca-phosphates by releasing orthophosphate ions following hydrolysis of organic phosphorus. However, several questions remain unanswered about the cellular-level mechanisms involved in this model, and its potential signatures in the mineral products. We studied Ca-phosphate precipitation by different strains of Escherichia coli which were genetically modified to differ in the abundance and cellular localization of the alkaline phosphatase (PHO A) produced. The mineral precipitated by either E. coli or purified PHO A was invariably identified as a carbonate-free non-stoichiometric hydroxyapatite. However, the bacterial precipitates could be discriminated from the ones formed by purified PHO A at the nano-scale. PHO A localization was shown to influence the pattern of Ca-phosphate nucleation and growth. Finally, the rate of calcification was proved to be consistent with the PHO A enzyme kinetics. Overall, this study provides mechanistic keys to better understand phosphogenesis in the environment, and experimental references to better interpret the microbial fossil record in phosphorites.

Gradual changes in upwelled seawater conditions (redox, pH) from the late Cretaceous through early Paleogene at the northwest coast of Africa: Negative Ce anomaly trend recorded in fossil bio-apatite

Marine vertebrate fossils from late Cretaceous–early Paleogene shallow marine phosphorites of Morocco were investigated for their trace element compositions and neodymium isotopic ratios in order to constrain marine and depositional conditions. The various analyzed fossils are separated into two groups with different geochemical compositions: (1) shark tooth enameloid with generally lower Cu, Ba, rare earth elements (REEs) and U, and higher Na, Zn and Sr concentrations than (2) dentine, bone, and coprolites. These differences are related to the originally different structures of these fossils.All the fossils revealed very similar shale-normalized REE patterns, with negative Ce anomaly and heavy REE enrichment mimicking the REE pattern of modern oxic-seawater. The results therefore suggest REE uptake by the fossils from an early diagenetic pore fluid that was dominated by seawater. Importantly, the Ce anomaly does not vary among the different types of fossil remains and the values are very similar in a given layer. Moreover, a step-wise shift towards lower Ce/Ce* values from older to younger beds is apparent. Nd isotope analyses across the phosphorite succession yielded minor variation with an average εNd(t) value of −6.2±0.4 (n=12) indicating no major changes in the REE source during the studied interval. The relatively radiogenic values reflect Tethyan connection and/or important contribution of a mafic Nd source from weathering in the region.The age-related trend in the Ce anomaly is interpreted to be due to changes in redox and/or pH conditions of the upwelling seawater on the shallow shelf areas. The driving force of these changes was probably an extended global oceanic circulation, especially enhanced connection and water exchange between the North and South Atlantic.

The role of symbiosis in the transition of some eukaryotes from aquatic to terrestrial environments

Symbiosis may have played a far greater role in biological evolution than was previously thought. The symbiosis that made the colonization of land by plants possible was as a consequence of the development of arbuscular mycorrhizae. However, the present review draws attention to the role of lichens in assisting in this transition and to the phenomenon of lichenization. The recent discovery of lichen fossils in marine phosphorites in China and molecular clock estimates indicate that lichenized fungi were already present in Precambrian seas and, like contemporary species, played a role as pioneers in occupying new habitats. There is evidence that the holistic properties of associations between fungi and cyanobacteria and/or green algae facilitated the transition onto land and the subsequent colonization of terrestrial habitats. A key role in this process was played by poikilohydry. The algal components of delichenized fungi, along with lichens and photosynthetic aquatic organisms all contributed to the increase in atmospheric oxygen. Lichens, fungi and cyanobacteria settling on land were undoubtedly important in the formation of soils and thereafter enhancing their fertility. It is suggested that vascular and other green plants were able grow on these primitive soils that were stabilized by the growth of lichens, algae and cyanobacteria in a similar way to those which play a role in desert crusts at the present time.

A Review of Phosphate Mineral Nucleation in Biology and Geobiology

Relationships between geological phosphorite deposition and biological apatite nucleation have often been overlooked. However, similarities in biological apatite and phosphorite mineralogy suggest that their chemical formation mechanisms may be similar. This review serves to draw parallels between two newly described phosphorite mineralization processes, and proposes a similar novel mechanism for biologically controlled apatite mineral nucleation. This mechanism integrates polyphosphate biochemistry with crystal nucleation theory. Recently, the roles of polyphosphates in the nucleation of marine phosphorites were discovered. Marine bacteria and diatoms have been shown to store and concentrate inorganic phosphate (Pi) as amorphous, polyphosphate granules. Subsequent release of these P reserves into the local marine environment as Pi results in biologically induced phosphorite nucleation. Pi storage and release through an intracellular polyphosphate intermediate may also occur in mineralizing oral bacteria. Polyphosphates may be associated with biologically controlled apatite nucleation within vertebrates and invertebrates. Historically, biological apatite nucleation has been attributed to either a biochemical increase in local Pi concentration or matrix-mediated apatite nucleation control. This review proposes a mechanism that integrates both theories. Intracellular and extracellular amorphous granules, rich in both calcium and phosphorus, have been observed in apatite-biomineralizing vertebrates, protists, and atremate brachiopods. These granules may represent stores of calcium-polyphosphate. Not unlike phosphorite nucleation by bacteria and diatoms, polyphosphate depolymerization to Pi would be controlled by phosphatase activity. Enzymatic polyphosphate depolymerization would increase apatite saturation to the level required for mineral nucleation, while matrix proteins would simultaneously control the progression of new biological apatite formation.

Filamentous sulfur bacteria preserved in modern and ancient phosphatic sediments: implications for the role of oxygen and bacteria in phosphogenesis

Marine phosphate-rich sedimentary deposits (phosphorites) are important geological reservoirs for the biologically essential nutrient phosphorous. Phosphorites first appear in abundance approximately 600 million years ago, but their proliferation at that time is poorly understood. Recent marine phosphorites spatially correlate with the habitats of vacuolated sulfide-oxidizing bacteria that store polyphosphates under oxic conditions to be utilized under sulfidic conditions. Hydrolysis of the stored polyphosphate results in the rapid precipitation of the phosphate-rich mineral apatite-providing a mechanism to explain the association between modern phosphorites and these bacteria. Whether sulfur bacteria were important to the formation of ancient phosphorites has been unresolved. Here, we present the remains of modern sulfide-oxidizing bacteria that are partially encrusted in apatite, providing evidence that bacterially mediated phosphogenesis can rapidly permineralize sulfide-oxidizing bacteria and perhaps other types of organic remains. We also describe filamentous microfossils that resemble modern sulfide-oxidizing bacteria from two major phosphogenic episodes in the geologic record. These microfossils contain sulfur-rich inclusions that may represent relict sulfur globules, a diagnostic feature of modern sulfide-oxidizing bacteria. These findings suggest that sulfur bacteria, which are known to mediate the precipitation of apatite in modern sediments, were also present in certain phosphogenic settings for at least the last 600 million years. If polyphosphate-utilizing sulfide-oxidizing bacteria also played a role in the formation of ancient phosphorites, their requirements for oxygen, or oxygen-requiring metabolites such as nitrate, might explain the temporal correlation between the first appearance of globally distributed marine phosphorites and increasing oxygenation of Neoproterozoic oceans.

Geochemistry of organic matter in natural apatites of phosphorites according to EPR spectra of free radicals

The following organic radicals were identified by EPR spectroscopy in apatite from marine phosphorites (granular, nodular, shelly, and microcrystalline), supergene phosphorites (from ocean islands only), and modern and fossil biological materials (human dental enamel, fossil shark teeth, and pathogenic cardioliths): ĊH3, ĊH2-R, HOĊHR,(CH3)2-ĊR,3org, PO32−, P(OR)3, and perinaphtðenyl. Each textural and petrographic type of apatite corresponds to a specific model of organic radicals, which correlates with the type of organic matter (sapropelic, humic, guano, or collagen). The latter is controlled by the conditions of mineral formation, including climatic ones, and postdiagenetic (catagenetic) processes. A relationship was established between the EPR spectra of observed organic radicals and the valence state and structural position of impurity ions: (1) vanadium: V4+ (VO2+) in the Ca2+ II site or V5+ (VO4)3− → (PO4)3− and (2) uranium: U4+(UO2) in the Ca2+ II site or U6+ chemisorbed on the surface as UO22+

Chemotrophic Microbial Mats and Their Potential for Preservation in the Rock Record

Putative microbialites are commonly regarded to have formed in association with photosynthetic microorganisms, such as cyanobacteria. However, many modern microbial mat ecosystems are dominated by chemotrophic bacteria and archaea. Like phototrophs, filamentous sulfur-oxidizing bacteria form large mats at the sediment/water interface that can act to stabilize sediments, and their metabolic activities may mediate the formation of marine phosphorites. Similarly, bacteria and archaea associated with the anaerobic oxidation of methane (AOM) catalyze the precipitation of seafloor authigenic carbonates. When preserved, lipid biomarkers, isotopic signatures, body fossils, and lithological indicators of the local depositional environment may be used to identify chemotrophic mats in the rock record. The recognition of chemotrophic communities in the rock record has the potential to transform our understanding of ancient microbial ecologies, evolution, and geochemical conditions. Chemotrophic microbes on Earth occupy naturally occurring interfaces between oxidized and reduced chemical species and thus may provide a new set of search criteria to target life-detection efforts on other planets.

Rare earth elements in supergene phosphorites

An analysis of rare earth elements in various types of supergene phosphorites established the following sequence of increasing average total contents (ppm): phosphorite from Christmas Island in the Indian Ocean, 3.89; spelean coprolitic phosphorite, 21.98; phosphorite from the weathering zone of sedimentary rocks, 27.41; phosphorite from the weathering zone of endogenous rocks, 372.32; and lacustrine coprolitic phosphorite, 461.59. Supergene phosphorites, especially the most common among them from the weathering zone of sedimentary rocks, are significantly depleted relative to marine phosphorites both in average and maximum REE contents. The REE contents of supergene phosphorites are controlled by several factors, including the REE contents in the primary rocks affected by weathering, the physicochemical conditions of phosphorite formation, the presence of a biogenic component in the phosphatogenetic system, and the structural type of the phosphorites. There is a strong positive correlation within the group of light and, in part, middle REEs (La, Ce, Nd, Sm, and Eu) and between the heavy REEs Yb and Lu, whereas the correlation between these two groups is weaker or insignificant. Gd and Tb are well correlated with the elements of both groups.

Sedimentology of Bahía Sebastián Vizcaíno, Baja California, México.

With support from the Oceanographic Ships H05 “Altair” and H03 “Alexander von Humboldt” of the Mexican Navy, 37 samples were collected using a Van Veen sediment dredge in Ranger Bank, Sebastian Vizcaino Bay, and around Punta Canoas of Cedros Island, on the west coast of Baja California. The distribution of sediments, grain size,composition of organic carbon and carbonatecontent, and phosphates were determined.Two major areas of sedimentation were identified: (a) the Ranger Bank, where oxidative anddynamical processes occur within a limestonedominated environment, and coal with highconcentrations of organic matter with mediumsize sand (f = 1.0 to 2.1); b) the northeast portion of Sebastian Vizcaino Bay where the size of the sediments range from very fine to coarse grain (f = 0.2 to 3.7); there a high concentration of phosphates (maximum 22.3 %) occurs, with biogenic material consisting mainly of organic detritus, such as diatomaceous material, phosphorite from fish and other organisms. This can be considered a zone where incipient formation of phophoritic material is generated and formation of future marine phosphorite occurs. The prevailing material in Keller Canal, located between Cedros and Nativity islands consists of coarse grains because of the strong currents that remove the finematerial, whereas in the central-western portion of the bay abundant and very fine sand and mud occur, which are associated with low speed near the center of rotation of an anticyclonic semipermanent flow that characterizes water movement in the Bay.

Authigenic dolomite cementation in the Upper Cretaceous Phosphate Formation, Western Desert, Egypt

The Upper Cretaceous Phosphate Formation in the Western Desert of Egypt displays a characteristic facies association that includes marine phosphorites interbedded with black shales and glauconitic sandstones. The upper part of the formation is characterized by the presence of thin phosphatic beds, which are filled-extensively-with disordered and non stoichiometric (mean MgCO 3 = 41.4 ± 0.34 mol%) authigenic dolomite cement. SEM and the back scattered images of these coarse crystalline dolomite cements reveal that they display planar euhedral crystal boundaries, polymodal crystal size distribution and variable inclusion pattern. The relatively low and wide ranged δ 18O (− 0.87 to − 4.15‰ VPDB) values of the dolomite cements coupled with their depleted Sr (mean = 187 ± 26 ppm) and high iron and manganese values (mean = 6851 ± 554 ppm and 11599 ± 229 ppm respectively) invoke that they were formed from mixed hypo-saline fluids within a mixing marine–meteoric zone probably during a low stand period at the vicinity of the Maastrichtian/Early Tertiary unconformity. Meanwhile, their negative δ 13C (− 1.31 to − 3.56‰ VPDB) values argue for a possible involvement of isotopically light carbon, derived from degradation of organic matter, during their precipitation.