The aluminosilicate fraction of North Pacific manganese nodules

Nine nodules collected from throughout the deep North Pacific were analyzed for their mineralogy and major-element composition before and after leaching with Chester-Hughes solution. Data indicate that the mineral phillipsite accounts for the major part (> 75%) of the aluminosilicate fraction of all nodules. It is suggested that formation of phillipsite takes place on growing nodule surfaces coupled with the oxidation of absorbed manganous ion. All the nodules could be described as ternary mixtures of amorphous iron fraction (Fe-Ti-P), manganese oxide fraction (Mn-Mg Cu-Ni), and phillipsite fraction (Al-Si-K-Na), these fractions accounting for 96% of the variability of the chemical composition.     

The use of phillipsite in test construction of agglutinated deep-sea benthonic foraminifera*

Agglutinated deep-sea benthonic foraminifera with tests composed of phillipsite are documented and illustrated from a red clay sequence in a Giant Piston Core from the central North Pacific. Associated with the benthonic foraminifera are phillipsite crystal rosettes and aggregates of phiilipsite crystals. The benthonic foraminifera and phillipsite crystals constitute most of the > 38 μm fraction, but have little effect upon the mean size of the red clay sediments.     

大洋多金属结核中铁锰质矿物拉曼光谱特征初探

拉曼光谱是一种快速无损的分析手段,它既可观察样品的显微结构构造,也可分析样品的成分和结构。为了丰富多金属结核的岩石矿物学特征,文章对西太平洋某海山区的多金属结核样品进行了X射线粉末衍射分析和拉曼光谱分析。X射线分析结果显示该区域样品主要含有水羟锰矿、钡镁锰矿、斜长石、钙十字沸石和石英,显微构造主要有纹层状构造、柱状构造、树枝状构造、充填构造等。通过分析对比潮湿样品和烘干样品铁锰质矿物的拉曼特征谱峰,得出结核中水羟锰矿的特征谱峰位于490 cm~(-1)、570 cm~(-1)和626 cm~(-1)附近,钡镁锰矿的特征谱峰则位于640 cm~(-1)附近,与陆地上对应矿物的特征拉曼谱峰不同。结核中的钡镁锰矿结构不稳定,经过风干或者抛磨后部分产生相变,不同显微结构中,相变情况不同。经与RRUFF数据库比对,识别出钙十字沸石、斜长石等自形晶,多分布于结核最内层,往结核外层总体减少。矿物微晶多见铁锰质矿物微晶和钙十字沸石微晶,铁锰质矿物绕其向外生长。     

Rare earth elements in ferromanganese nodules and other marine phases

The concentrations of rare-earth elements (REE) have been measured in 31 ferromanganese nodules from the Pacific and Indian Oceans and vary by almost a factor of 5. Too few nodules have been analyzed to define possible regional trends. The shale-normalized patterns, however, permit division of nodules into two groups: those from depth greater than 3000–3500 m and those from less depth. The factors that determine this change in the relative concentration of REE may be related to the mineralogy of manganese phases and/or the transport of REE to the deep ocean by particulate matter.Comparison of the REE patterns of nodules with those of phillipsite, phosphorite, clays, CaCO₃ and seawater suggests that the patterns of these phases reflect fractionation from an initial pattern closely resembling that of shale. By assuming that the accumulation rate of REE in clays, CaCO₃ and nodules is represented by that for surface sediments, it has been possible to estimate an accumulation rate of phillipsite in pelagic sediments of the Pacific of 0.02 mg/cm²/yr.     

Composition and Genesis of Zeolitic Claystones from the Central Indian Ocean Basin

We examined more than fifty indurated sediments recovered from the Central Indian Ocean Basin （CIOB） during the course of collection for manganese nodules and crusts. The samples occur as slabs either over which ferromanganese oxides are present or over a substrate of altered oceanic basalt in conjunction with palagonite or within the nucleus of manganese nodules. Mineralogically and compositionally, the samples show a mixture of phillipsite, palagonite and montmorillonite. We suggest that the volcanogenic precursors occurring in the CIOB were subjected to varying degrees of alteration under the influence of low temperature conditions, resulting in the formation of zeolitic claystones. The CIOB samples have similarities to those reported from various sites in the world oceans.     

Crystal chemistry of diagenetic zeolites in volcanoclastic deposits of Italy

Zeolites from the most important volcanoclastic deposits of Italy include: (1) phillipsite and heulandite from the cinerite of the central northern Apennines; (2) chabazite and phillipsite from the phonolitic tephritic ignimbrite with black pumices; (3) phillipsite from the “tufo lionato” of Vulcano Laziale; (4) chabazite and phillipsite from the Campanian ignimbrite; (5) phillipsite from the Neapolitan yellow tuff; and (6) chabazite and phillipsite from the pyroclastics of Monte Vulture. Compared with sedimentary phillipsites and chabazites described in the literature, the chabazites and phillipsites studied here have lower Si/Al ratios and higher K contents. These chemical peculiarities are correlated with both the K-rich vesuvitic-leucititic, latitic-phonolitic, and potassic alkali-trachytic chemistry of the ash from which they were derived and, very likely, with the character of the hydrologically open system environment in which they formed. The zeolite of the heulandite-clinoptilolite group from the cinerite of the central northern Apennines is classified as a true heulandite on the basis of its chemical composition and thermal behavior.     

Geochemistry of rare earth elements in oceanic phillipsites

The behavior of rare earth elements (REE) was examined in oceanic phillipsites collected from four horizons of eupelagic clay in the Southern Basin of the Pacific. The REE concentrations were determined in the >50-μm-fraction phillipsite samples by the ICP-MS method. The composition of separate phillipsite accretions was studied using the electron microprobe and secondary ion mass-spectrometry. Rare earth elements in phillipsite-only samples are related to the admixture of ferrocalcium hydroxophosphates. The analysis of separate phillipsite accretions reveals low (<0.1–18.1 ppm) REE (III) concentrations. The Ce concentration varies between 2.7 and 140 ppm. The correlation analysis shows that REE (III) are present as an admixture of iron oxyhydroxides in separate phillipsite accretions. Based on the REE (III) concentration in iron oxyhydroxides, we can identify two generations of phillipsite accretions. Massive rounded accretions (phillipsite I) are depleted in REE, while pseudorhombic (phillipsite II) accretions are enriched in REE and marked by a positive Ce anomaly. Oceanic phillipsites do not accumulate REE or inherit the REE signature of the volcaniclastic material and oceanic deep water. Hence, the REE distribution in phillipsites does not depend on the sedimentation rate and host sediment composition.     

铀系不平衡测年法在我国秦岭南麓黄土钙结核中的应用

秦岭南麓汉江流域上游地区分布着厚达二、三十米的黄土堆积,与秦岭以北地区黄土相比差异明显。汉江流域黄土中的钙结核分布十分广泛,钙结核内壁附着纯净致密的碳酸盐晶体,而秦岭以北黄土钙结核中却少有碳酸盐晶体析出。铀系不平衡测年是一门发展成熟、测年精度高、测年范围相对较广的第四纪重要测年方法,本文尝试利用铀系测年法对汉江流域上游柳陂黄土剖面钙结核样品内的碳酸盐晶体进行了铀系测年分析。柳陂剖面厚约17 m,可辨认出多层古土壤与黄土地层。自柳陂剖面中下部获取的4件钙结核样品测年结果分别为距今115.57±0.66 ka、130.15±0.65 ka、303.97±14.47 ka和356.40±11.60 ka,随着地层深度增加,^230Th年代增长,且与磁化率揭示的土壤地层序列基本一致。所以初步推断柳陂黄土剖面的地层序列为S1、L2、S2-I、S2-II、L3和S3。研究表明,秦岭南麓钙结核的^230Th年龄可为黄土地层的独立定年提供重要参考。根据碳酸盐钙结核形成机制,认为钙结核中碳酸盐晶体的^230Th年代能够指示相应黄土地层的最小年龄。     

Melilitite-carbonatite tuffs in the Laetolil Beds of Tanzania

The upper unit of the Laetolil Beds, 45 to 60 m thick, is about 80% wind worked or eolian tuff and 20% air-fall tuff. The air-fall tuffs comprise a phonolitic tuff and numerous thin tuffs of original melilitite-carbonatite composition. Most of the melilitite-carbonatite tuffs consist largely of sand-sized lava globules and crystals cemented by calcite. Evidence of former carbonatite ash is provided by calcite globules, fenestral textures, and high contents of Ba and Sr in early-deposited calcite. These air-fall tuffs were produced by volatile-rich eruptions of highly fluid magma. In a typical eruptive cycle, lava droplets were followed by crystals which increased in size during the eruption. Commonly the final event was an eruption of fine ash and carbonatite globules. Particularly violent explosions ejected blocks of lava and plutonic rock 10 to 15 cm in diameter for distances of 20 km.The climate was semiarid, and melilitite-carbonatite ash layers were first cemented by soluble salts such as trona resulting from incongruent solution of the carbonatite ash by rainfall. Repeated solution and crystallization of salts resulted in a polygonal fracture pattern in the thinner tuffs. Ash layers not cemented by soluble salts were eroded and redeposited by wind to form eolian tuffs. Subsequently both the air-fall and eolian tuffs were modified by several diagenetic stages, mostly in the vadose zone, to form rocks consisting principally of montmorillonite, phillipsite, and calcite. At an early stage calcium carbonate derived from carbonatite ash was precipitated as micrite both as a cement and replacement of organic matter. Glass, nepheline, and melilite were now weathered to clay, releasing components to form phillipsite. Calcite spar was precipitated last, as a replacement, cement, and pore filling. Unaltered glass, preserved in some of the eolian tuffs, has an unusually high content of Na, K, and Fe for a melilitite composition.These beds contain a rich fauna, notable for the excellent preservation of delicate fossils such as bovid dung, land snails, and bird eggs. This preservation is attributed, at least in part, to carbonatite ash. Carbonatite ash was also responsible for the preservation of footprints in one of the tuffs.     

Phillipsite formation in nephelinitic rocks in response to hydrothermal alteration at Mount Etinde,Cameroon

Fresh nephelinitic rocks and hydrothermally altered rocks at Mount Etinde (Cameroon Volcanic Line, West Africa) have been studied by combined whole rock geochemistry (ICP-MS), mineralogy and mineral chemistry (SEM-EDS, WDS, XRD) techniques. The nephelinites have feldspathoids, clinopyroxene, perovskite and titanomagnetite as the principal minerals in the mode with subsidiary apatite and sphene. The mineralogy of their hydrothermally altered counterparts includes phillipsite, calcite and analcime which are secondary phases developed in response to hydrothermal fluid events. Correspondingly, the bulk rock geochemical data show elevated SiO₂, CaO, Na₂O and K₂O concentrations with increasing alteration and Al₂O₃ and Fe₂O₃ depletion while MgO, MnO and TiO₂ concentrations are largely unaffected. The nephelinites also have high concentrations of LILLE, HFSE and REE and upon hydrothermal alteration they show an enrichment of LREE and MREE over HREE. Phillipsite is the principal alteration mineral in the rocks and it occurs along cracks, vesicles and also forms alteromorphs after feldspathoids. The Ce content of these categories of phillipsite varies. Phillipsite along cracks is richer in Ce while phillipsite associated with calcite has lower Ce concentration and the phillipsite alteromorphs very little or no Ce. Various stages of fluid circulation are proposed hereby to explain the variations in phillipsite generation and composition.     

Geochemistry of Rare Earth Elements in the Ocean

This work briefly outlines modern ideas on geochemistry of rare earth elements (REE) in the ocean. Sources of REE and chemical properties of these elements, which govern their migration ability in natural processes, are considered. The REE behavior in the river water–seawater mixing zone is analyzed. The fractionation of dissolved and suspended REE in oceanic water in both aerobic and anaerobic conditions is also considered. It is shown that the variability of REE composition in pelagic sediments reflects the fractionation of these elements in the oceanic water as a consequence of material differentiation in the ocean. The REE distribution in terrigenous, authigenic, hydrothermal, and biogenic constituents of sediments, such as clay, bone debris, barite, phillipsite, Fe–Mn oxyhydroxides (ferromanganese nodules and micronodules), Fe–Ca hydroxo-phosphate, diatoms, and foraminifers, is considered.     

Petrology of ultrabasic inclusions from basalts of Minusa and Transbaikalian regions (Siberia,USSR)

The paper presents a detailed study of the ultrabasic nodules in alkali basalts of the Minusa and Transbaikalian regions (Siberia, USSR), represented by spinel lherzolites, websterites, clinopyroxenites, plagioclase-clinopyroxene rocks, as well as fragments of large augite crystals and sanidine crystals. In the course of this study 8 new chemical analyses of inclusions and 23 chemical analyses of minerals from them have been performed. The results of the investigations imply that lherzolites and websterites are xenoliths from the upper mantle, fragments of large augite and sanidine crystals are high-pressure phenocrysts, while clinopyroxenites are cognate nodules.In the process of transportation to the surface ultrabasic nodules are subjected to strong corrosion by the basalt magma. It is noteworthy that pyroxenes and spinel are least resistant to this aggressive action, while olivine is much more stable. Because of this fact, pyroxenites have less chance of remaining intact and being found by investigators than dunites and peridotites. Therefore it is quite probable that in the upper mantle, besides spinel and garnet lherzolites, there may be present large amounts of pyroxenites, which become rather rare among the ultrabasic inclusions because they disintegrate during transportation to the surface.     

Experimente zur Zeolithbildung durch hydrothermale Umwandlung

The formation of zeolites by hydrothermal alteration has been investigated by taking trass from the Laach volcanic area as a sample. Zeolites to be found are chabazite, phillipsite and analcime, all of which originated from the same phonolitic glass. This paper aims at explaining the formation of zeolites by means of experimental alteration of the pumice with various solutions. NaOH and KOH solutions were used in the experiments, these limited the formation conditions of chabazite, phillipsite, analcime in alkaline environments. Moreover, experiments were carried out with H₂O dist and with solutions that formed during the alteration of pumice by reacting with H₂O. These experiments were conducted to supply clues concerning the formation of zeolites in the Laach volcanic area. With NaOH solutions zeolites were formed from pumice within a temperature range of 70 to 250° C and a concentration range of 0.001 to 1.0 n; with KOH solutions they were formed in the same concentration range within a temperature range of 100 to 250° C. The formation of zeolites proved to depend much on temperature and concentration: At low temperatures high concentrations are necessary, higher temperatures need lower concentrations. With NaOH solutions the zeolites are formed in the succession, chabazite, phillipsite, analcime at increasing temperatures and increasing concentrations. With KOH solutions the same succession is to be found with rising temperature. With rising concentration, however, this succession is changed at higher temperatures: Phillipsite appears in place of analcime at high temperatures and concentrations. By the alteration of pumice with H₂O, zeolites are formed from 200° C onward. With solutions that had been formed during the alteration of pumice by reacting with H₂O, the minimum temperature for the formation of zeolites was 180° C. Concerning the genesis of zeolites in the Laach volcanic area, the experiments showed that the temperature for the formation of analcime was about 250° C; for the formation of chabazite and phillipsite it was between 150 and 190° C. The pH of the reacting solutions may have been between 7 and 8. Thus the experiments proved that from the same material different zeolites, chabazite, phillipsite, analcime may be formed by temperature change of the reacting solutions (H₂O to slightly alkaline solutions).     

Evaluation of Jordanian zeolite tuff as a controlled slow-release fertilizer for NH4 +

 The exchange and release properties of the natural phillipsite tuff from the Aritain area in Jordan were evaluated by studying the exchange properties of this natural zeolite in the NH₄ ⁺–Na⁺ system. Exchange isotherms at 18, 35, and 50  °C showed that phillipsite exchanged NH₄ ⁺ preferably over Na⁺ at all temperatures. However, the selectivity coefficient for NH₄ ⁺ decreased with decreasing temperature. The release of NH₄ ⁺ from phillipsite saturated with ammonium sulfate took place in two stages characterized by different SO₄ ^2– : NH₄ ⁺ ratios. Aritain phillipsite from NE Jordan could be processed and used as NH₄ ⁺ slow-release fertilizers. The use of NH₄ ⁺-phillipsite tuff offers an option to the widely used soluble NH₄-fertilizers in agciculture to avoid environmental problems associated with nitrogen contamination of surface water and groundwater. Received: 19 December 1996 · Accepted: 13 May 1997     

Influence of hydrodynamic regime on the mineral composition of deep-sea sediments

The composition of sand-silt and pelite fractions of deep-sea sediments deposited under different hydrodynamic conditions was studied. Assemblages of clastic, clayey, biogenic, and authigenic minerals formed under the influence of surface and bottom currents were traced. It is shown that biogenic opal, fine-dispersed celestobarite, and authigenic protosyngenetic ferromanganese micronodules, which are composed of only manganese phases, represent indicators of cyclonic gyres characterized by enhanced bioproductivity. Collophane (bone detritus), phillipsite, palagonite, and large celestobarite crystals prevail in mineral assemblages below the anticyclonic gyres, whereas ore micronodules are depleted in manganese. Surface and bottom currents control the distribution of clastic (terrigenous edaphogenic, terrestrial-volcanogenic) and clay minerals, as well as biogenic opal in the form of Ethmodiscus frustules in sediments. Edaphogenic mineral assemblages represent the reliable indicators of bottom currents.     

AUTHIGENIC CEMENTATION OF SCORIACEOUS DEEP-SEA SEDIMENTS WEST OF THE SOCIETY RIDGE,SOUTH PACIFIC1

Harmotome-rich scorias and indurated tuffaceous mudstones occur in sediments west of the Society Ridge, South Pacific. Diagenetic alteration of mafic palagonite produces the following authigenic minerals: harmotome, phillipsite, goethite, limonite and montmorillonite. A major mode of induration of pyroclastic-rich marine sediments is the devitrification of mafic palagonite producing the following diagenetic cementing minerals: phillipsite, harmotome, limonite, and to some extent, manganese and ferromanganese oxides.     

Renewable, controlled and environmentally safe phosphorus release in soils from mixtures of NH4 +-phillipsite tuff and phosphate rocks

 The renewable and controlled-release fertilization system investigated here uses NH₄ ⁺-exchanged phillipsite tuff, from Jordan, to help in the dissolution of phosphate rock. Accordingly, controlled and renewable soluble nitrogen, phosphate and Ca are released as nutrients for plants. NH₄ ⁺ phillipsite can sequester Ca ions released by the dissolution of phosphate rock, therefore, leading to further phosphate rock dissolution. In this study the results show that the amount of phosphate released is more than that released by phosphate rock alone. This method offers an alternative to the use of highly soluble fertilizers and may avoid environmental problems associated with their extensive use in agriculture. Received: 22 May 1997 · Accepted: 12 August 1997     

Authigenie gypsum in deep-sea manganese nodules

Gypsum crystals of authigenic origin have been found in manganese nodules of the deep-sea sediment surface (4500-5500 m water depth) from the Central Pacific Ocean.     

Zeolite studies III: On natural phillipsite,gismondite, harmotome,chabazite, and gmelinite

Part I: Chemical and structural effects of cation-exchange Attempts were made to prepare, by appropriate exchange methods, homoionic samples of phillipsite, gismondite, harmotome, chabazite and gmelinite containing Ba, Ca, K, Na or Li-ions. Powdered natural samples were used as starting material. All samples were analysed chemically before and after the cation exchange. The results of the analyses demonstrated clearly that the „exchange capacity“ depends on the method used, the structure of the zeolite and the nature of the cation involved in the exchange. The analyses also disclosed the important fact that the ratio in Mole % of the sum of exchangeable cations: Al₂O₃ of the natural and of the exchanged samples is generally <1, and can be as low as 0.74. Examples are presented where cation exchange results in a substantial change in the framework structure. Part II: Dehydration behavior and structural changes at elevated temperatures Samples of the natural zeolites mentioned above, and of some of their cation exchange products were dehydrated in air of controlled humidity up to 600° C. The slopes of the weight loss curves of chabazite and gmelinite are continuous, whereas those of phillipsite, gismondite, and harmotome show a discontinuity between 90–190° C, indicating the existence of two discrete hydrated phases for each of these zeolites. High temperature x-ray studies of powdered samples confirmed this result. The high temperature hydrates of phillipsite, gismondite, and harmotome persist reversibly up to approximately 230° C. At higher temperatures, new probably anhydrous phases form. Gmelinite, at 240° C, transforms irreversibly to anhydrous gmelinite which is stable up to >700° C. The transition was studied by single crystal techniques. The chabazite structure remains intact up to >700° C. The absolute water content and the dehydration behavoir of the zeolites investigated are primarily dependent on the nature of the exchange cation. The structural changes at elevated temperatures are determined by the silica alumina framework. Part III: Hydrothermal stability* and interconversions The stability of phillipsite, gismondite, harmotome, chabazite, gmelinite, their exchange products, and of the synthetic Linde zeolites Faujasite and Type A was studied in the temperature range between 150° and 350° C at a constant pressure of 1000 atm of H₂O. Between 180° and 260° C all examined Sodium and Calcium zeolites were metastable with respect to analcite (wairakite**). Phillipsite and sodium-rich zeolites generally converted to analcite (wairakite) directly. Ca^ex-chabazite and Ca^ex-gmelinite formed phillipsite, whereas Ca-gismondite and Ca-Type A formed natrolite as intermediate phases. Li-gmelinite converted to bikitaite***. (This represents the first successful preparation of natrolite and bikitaite. Attempts starting from gels or glasses have been unsuccessful so far.) Ba-gmelinite converted to harmotome at 250° C. This transformation was studied microscopically and by single crystal x-ray techniques. The transformations that take place on hydrothermal treatment as well as on low temperature cation exchange of zeolites (see Part I) indicate that, unlike the conditions prevailing in clays, the type of cation and the ratio of cations in the exchange positions have an important influence on the structure of the silicaalumina-oxygen framework. This explains two phenomena: The lack of solid solution between two potential end members of a solid solution series (for instance phillipsite-gismondite), and the large number of different zeolites in nature, where a great variety in the ratios of available alkali and alkaline earths ions must be expected. Any classification of zeolites becomes still more difficult in view of the fact that conversions among different groups (chabazite → phillipsite) and different structures (three-dimensional framework → fibre) take place relatively easily. Contribution No. 59–92, College of Mineral Industries, The Pennsylvania State University, University Park, Pennsylvania.     

Samples from the crystallising boundary layer of a zoned magma chamber

The spatial and chemical relationships between the melt occupying the reservoir and the mineral assemblages crystallising at the margins are reconstructed for the magma chamber which produced the 11000 yr.B.P. tephra deposit of Laacher See Volcano. The melt showed vertical chemical zonation immediately prior to eruption, and throughout most of the magma volume only a small fraction of crystals were present. The eruption also ejected crystal-rich nodules, ranging from mafic to felsic in composition, which are samples of the materials crystallising at the boundaries of the chamber. New data on nodule petrography and chemical compositions of whole-rocks, minerals and interstitial glasses are presented. Volume fraction of interstitial glass is not systematically related to mineral assemblage and varies typically between 1 and 20 vol%, i.e. the crystals interlock. One exception is a group of mafic nodules with glass volume fractions between 25 and 40 vol%. Bulk compositions of mafic nodules show strong enrichments or depletions in all major elements relative to the mafic phonolite interstitial melt. Felsic nodules show much less pronounced differences with their interstitial melt. Felsic nodules contain interstitial glasses with a range of compositions similar to that in the zoned bulk of the chamber and were probably derived from different heights on the walls. Mafic nodules have glass compositions similar to those at the base of the zoned liquid column and were probably derived from the floor. Modal mineralogy, glass composition and mineral composition are systematically related in the nodules whereas in individual pumices samples derived from the main body of the chamber, a broader range of mineral compositions are often found. Mineral assemblages were especially diverse in the upper part of the chamber. It is deduced that the whole of the essentially liquid part of the chamber was emptied by the eruption, that strongly contrasting mineral assemblages were forming simultaneously on the walls and floor, that the gradient in crystal content in the crystallisation boundary layer was more gradual at the floor than at the walls, and that the pumice mineralogy is not a simple phenocryst assemblage but is a mixture of crystals which grew from melts separated in space and/or time.