963 resultados para Ni-Co mixed oxides


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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

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Selective oxidation is one of the simplest functionalization methods and essentially all monomers used in manufacturing artificial fibers and plastics are obtained by catalytic oxidation processes. Formally, oxidation is considered as an increase in the oxidation number of the carbon atoms, then reactions such as dehydrogenation, ammoxidation, cyclization or chlorination are all oxidation reactions. In this field, most of processes for the synthesis of important chemicals used vanadium oxide-based catalysts. These catalytic systems are used either in the form of multicomponent mixed oxides and oxysalts, e.g., in the oxidation of n-butane (V/P/O) and of benzene (supported V/Mo/O) to maleic anhydride, or in the form of supported metal oxide, e.g., in the manufacture of phthalic anhydride by o-xylene oxidation, of sulphuric acid by oxidation of SO2, in the reduction of NOx with ammonia and in the ammoxidation of alkyl aromatics. In addition, supported vanadia catalysts have also been investigated for the oxidative dehydrogenation of alkanes to olefins , oxidation of pentane to maleic anhydride and the selective oxidation of methanol to formaldehyde or methyl formate [1]. During my PhD I focused my work on two gas phase selective oxidation reactions. The work was done at the Department of Industrial Chemistry and Materials (University of Bologna) in collaboration with Polynt SpA. Polynt is a leader company in the development, production and marketing of catalysts for gas-phase oxidation. In particular, I studied the catalytic system for n-butane oxidation to maleic anhydride (fluid bed technology) and for o-xylene oxidation to phthalic anhydride. Both reactions are catalyzed by systems based on vanadium, but catalysts are completely different. Part A is dedicated to the study of V/P/O catalyst for n-butane selective oxidation, while in the Part B the results of an investigation on TiO2-supported V2O5, catalyst for o-xylene oxidation are showed. In Part A, a general introduction about the importance of maleic anhydride, its uses, the industrial processes and the catalytic system are reported. The reaction is the only industrial direct oxidation of paraffins to a chemical intermediate. It is produced by n-butane oxidation either using fixed bed and fluid bed technology; in both cases the catalyst is the vanadyl pyrophosphate (VPP). Notwithstanding the good performances, the yield value didn’t exceed 60% and the system is continuously studied to improve activity and selectivity. The main open problem is the understanding of the real active phase working under reaction conditions. Several articles deal with the role of different crystalline and/or amorphous vanadium/phosphorous (VPO) compounds. In all cases, bulk VPP is assumed to constitute the core of the active phase, while two different hypotheses have been formulated concerning the catalytic surface. In one case the development of surface amorphous layers that play a direct role in the reaction is described, in the second case specific planes of crystalline VPP are assumed to contribute to the reaction pattern, and the redox process occurs reversibly between VPP and VOPO4. Both hypotheses are supported also by in-situ characterization techniques, but the experiments were performed with different catalysts and probably under slightly different working conditions. Due to complexity of the system, these differences could be the cause of the contradictions present in literature. Supposing that a key role could be played by P/V ratio, I prepared, characterized and tested two samples with different P/V ratio. Transformation occurring on catalytic surfaces under different conditions of temperature and gas-phase composition were studied by means of in-situ Raman spectroscopy, trying to investigate the changes that VPP undergoes during reaction. The goal is to understand which kind of compound constituting the catalyst surface is the most active and selective for butane oxidation reaction, and also which features the catalyst should possess to ensure the development of this surface (e.g. catalyst composition). On the basis of results from this study, it could be possible to project a new catalyst more active and selective with respect to the present ones. In fact, the second topic investigated is the possibility to reproduce the surface active layer of VPP onto a support. In general, supportation is a way to improve mechanical features of the catalysts and to overcome problems such as possible development of local hot spot temperatures, which could cause a decrease of selectivity at high conversion, and high costs of catalyst. In literature it is possible to find different works dealing with the development of supported catalysts, but in general intrinsic characteristics of VPP are worsened due to the chemical interaction between active phase and support. Moreover all these works deal with the supportation of VPP; on the contrary, my work is an attempt to build-up a V/P/O active layer on the surface of a zirconia support by thermal treatment of a precursor obtained by impregnation of a V5+ salt and of H3PO4. In-situ Raman analysis during the thermal treatment, as well as reactivity tests are used to investigate the parameters that may influence the generation of the active phase. Part B is devoted to the study of o-xylene oxidation of phthalic anhydride; industrially, the reaction is carried out in gas-phase using as catalysts a supported system formed by V2O5 on TiO2. The V/Ti/O system is quite complex; different vanadium species could be present on the titania surface, as a function of the vanadium content and of the titania surface area: (i) V species which is chemically bound to the support via oxo bridges (isolated V in octahedral or tetrahedral coordination, depending on the hydration degree), (ii) a polymeric species spread over titania, and (iii) bulk vanadium oxide, either amorphous or crystalline. The different species could have different catalytic properties therefore changing the relative amount of V species can be a way to optimize the catalytic performances of the system. For this reason, samples containing increasing amount of vanadium were prepared and tested in the oxidation of o-xylene, with the aim of find a correlations between V/Ti/O catalytic activity and the amount of the different vanadium species. The second part deals with the role of a gas-phase promoter. Catalytic surface can change under working conditions; the high temperatures and a different gas-phase composition could have an effect also on the formation of different V species. Furthermore, in the industrial practice, the vanadium oxide-based catalysts need the addition of gas-phase promoters in the feed stream, that although do not have a direct role in the reaction stoichiometry, when present leads to considerable improvement of catalytic performance. Starting point of my investigation is the possibility that steam, a component always present in oxidation reactions environment, could cause changes in the nature of catalytic surface under reaction conditions. For this reason, the dynamic phenomena occurring at the surface of a 7wt% V2O5 on TiO2 catalyst in the presence of steam is investigated by means of Raman spectroscopy. Moreover a correlation between the amount of the different vanadium species and catalytic performances have been searched. Finally, the role of dopants has been studied. The industrial V/Ti/O system contains several dopants; the nature and the relative amount of promoters may vary depending on catalyst supplier and on the technology employed for the process, either a single-bed or a multi-layer catalytic fixed-bed. Promoters have a quite remarkable effect on both activity and selectivity to phthalic anhydride. Their role is crucial, and the proper control of the relative amount of each component is fundamental for the process performance. Furthermore, it can not be excluded that the same promoter may play different role depending on reaction conditions (T, composition of gas phase..). The reaction network of phthalic anhydride formation is very complex and includes several parallel and consecutive reactions; for this reason a proper understanding of the role of each dopant cannot be separated from the analysis of the reaction scheme. One of the most important promoters at industrial level, which is always present in the catalytic formulations is Cs. It is known that Cs plays an important role on selectivity to phthalic anhydride, but the reasons of this phenomenon are not really clear. Therefore the effect of Cs on the reaction scheme has been investigated at two different temperature with the aim of evidencing in which step of the reaction network this promoter plays its role.

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n this work, three Cypraea species (C. talpa, C. tigris and C. zebra) were exhaustively studied. The shells have been separated in the structural layers. The mineralogy, ultra- and micro-structure of each layer were analyzed by Confocal Laser Scanning Microscopy (CLSM), Scanning Electron Microscopy (SEM), X-Ray Diffractometry (XRD) and Raman Spectroscopy (RS). The presence of biologically relevant trace metals (Mn, Co, Fe, Zn, Cr, etc.) has been investigated using Instrumental Neutron Activation Analysis (INAA) and Inductively Coupled Plasma – Mass Spectrometry (ICP-MS) as detection tool. A new method has been developed and optimized to extract and analyze the soluble organic matrix (SOM) of the shell. Although the molecular nature of the SOM is not really known, it contains at least large protein fraction, if not only consists of proteins. The extracted matrices were compared between layers and species using Size Exclusion High Performance Liquid Chromatography coupled with Ultra Violet Spectrometry (SE-HPLC-UV), Gel electrophoresis (GE) and protein quantification tests. For the first time to our knowledge the association of trace elements to the protein in the SOM of the shell was studied using hyphenated on line as well as combined off line techniques and validated through inter-comparison tests between the different methods applied. Interesting correlations between the trace element concentration, the microstructure and the protein content were directly and indirectly detected. The metals Cu, Ni, Co and Zn have shown to bind to the SOM extracted from C. talpa, C. tigris and C. zebra shells. Within the conclusions of this work it was demonstrated that these protein-metal-complexes (or metal containing proteins) change from one layer to the other and are different between the three snails analyzed. In addition, the complexes are clearly related only to certain protein fractions of the SOM, and not to the whole SOM observed. These fractions and show not to be very metal-specific (i.e. some of these fractions bind two or three different metals).

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Le biomasse sono attualmente la più promettente alternativa ai combustibili fossili per la produzione di sostanze chimiche e fuels. A causa di problematiche di natura etica la ricerca oggi si sta muovendo verso l'uso delle biomasse che sfruttano terreni non coltivabili e materie prime non commestibili, quali la lignocellulosa. Attualmente sono state identificate diverse molecole piattaforma derivanti da biomasse lignocellulosiche. Tra queste ha suscitato grande interesse la 2-furaldeide o furfurale (FU). Tale molecola può essere ottenuta mediante disidratazione di monosaccaridi pentosi e possiede elevate potenzialità; è infatti considerata un intermedio chiave per la sintesi di un’ampia varietà di combustibili alternativi come il metilfurano (MFU) e prodotti ad elevato valore aggiunto per l’industria polimerica e la chimica fine come l’alcol furfurilico (FAL). In letteratura tali prodotti vengono principalmente ottenuti in processi condotti in fase liquida mediante l’utilizzo di catalizzatori eterogenei a base di metalli nobili come: Ni-Co-Ru-Pd, Pt/C o Pt/Al2O3, NiMoB/γ-Al2O3, in presenza di idrogeno molecolare come agente riducente. La riduzione del gruppo carbonilico mediante l’utilizzo di alcoli come fonti di idrogeno e catalizzatori a base di metalli non nobili tramite la reazione di Meerwein–Ponndorf–Verley (MPV), rappresenta un approccio alternativo che limita il consumo di H2 e permette di utilizzare bio-alcoli come donatori di idrogeno. Lo scopo di questo lavoro di tesi è stato quello di mettere a punto un processo continuo, in fase gas, di riduzione della FU a FAL e MFU, utilizzando metanolo come fonte di idrogeno tramite un meccanismo di H-transfer. In dettaglio il lavoro svolto può essere così riassunto: Sintesi dei sistemi catalitici MgO e Mg/Fe/O e loro caratterizzazione mediante analisi XRD, BET, TGA/DTA, spettroscopia RAMAN. Studio dell’attività catalitica dei catalizzatori preparati nella reazione di riduzione in fase gas di FU a FAL e MFU utilizzando metanolo come fonte di idrogeno.

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The aim of this master’s research thesis was the employment of an enantiopure 1,3-aminoalcohol, the 1-(α-aminobenzyl)-2-naphthol, known as Betti base, for the synthesis of some novel compounds which show a C2 symmetry. Some of these compounds, after derivatization, were used as ligands in association with transition metals to prepare some catalysts for enantioselective catalytic reactions. Some aminoalcohol (Salan-type) derivatives of these compounds were obtained upon reduction and in some cases it was possible to obtain complexes with transition metals such as Mn, Ni, Co and Cu. Furthermore a novel 6-membered analogue bisoxazoline ligand, 2,6-bis((R)-1-Phenyl-1H-naphtho[1,2-e][1,3]oxazin-3-yl)pyridine, was obtained and from it two Cu-complexes were prepared. The metal complexes were employed in some reactions to test the asymmetric induction, which was in some cases up to discrete values.

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Global warming issue becomes more significant to human beings and other organisms on the earth. Among many greenhouse gases, carbon dioxide (CO2) has the largest contribution to global warming. To find an effective way to utilize the greenhouse gas is urgent. It is the best way to convert CO2 to useful compounds. CO2 reforming of methane is an attractive process to convert CO2 and methane into synthesis gas (CO/H2), which can be used as a feedstock for gasoline, methanol, and other hydrocarbons. Nickel and cobalt were found to have good activity for CO2 reforming. However, they have a poor stability due to carbon deposition. This research developed efficient Ni-Co solid solution catalysts with excellent activities and high stability for CO2 reforming of methane. First, the structure of binary oxide solid solution of nickel and cobalt was investigated. It was found that while the calcination of Ni(NO3)2 and Co(NO3)2 mixture with 1:1 molar ratio at a high temperature above 800 oC generated NiO-CoO solid solution, only Ni3O4-Co3O4 solid solution was observed after the calcination at a low temperature of 500 oC. Furthermore, if the calcination was carried out at a medium temperature arranged from 600 to 700 oC, both NiO-CoO and Ni3O4-Co3O4 solid solutions can be formed. This occurred because Co3O4 can induce the formation of Ni3O4, whereas NiO can stabilize CoO. In addition, the lattice parameter of Ni3O4, which was predicted by using Vegard’s Law, is 8.2054 Å. As a very important part of this dissertation, Ni-Co solid solution was evaluated as catalysts for CO2 reforming of methane. It was revealed that nickel-cobalt solid solution showed excellent catalytic performance and high stability for CO2 reforming of methane. However, the stability of Ni-Co solid solution catalysts is strongly dependent on their composition and preparation condition. The optimum composition is 50%Ni-50%Co. Furthermore, the structure of Ni-Co catalysts was characterized by XRD, Vvis, TPR, TPD, BET, AES, TEM, XANES and EXAFS. The relationship between the structure and the catalytic performance was established: (1) The reduced NiO-CoO solid solution possesses better catalytic performance and stability than the reduced Ni3O4-Co3O4 solid solution. (2) Ni is richer on surface in Ni-Co catalysts. And (3) the reduction of Ni-Co-O solid solution generated two types of particles, small and large particles. The small ones are dispersed on large ones as catalytic component.

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Thirty sediment cores (30-40 cm in length), 47 Ekman dredge sediments, and Mn concretions were collected from Lake Biwa. The concentrations of 36 elements in the samples were determined by instrumental neutron activation, X-ray fluorescence, atomic absorption, and colorimetric analyses. The elements determined included Mn, P, As, Sb, Fe, Ni, Co, Zn, Cu, Pb, Hg, Cr, Ti, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sc, Hf, La, Ce, Sm, Eu, Yb, Lu, U, Th, Au, Ta, Nd, Br and N. Based on statistical considerations and calculation of the concentration factors of the elements, the features of the elemental distribution in Lake Biwa sediment were determined. The main results are summarized as follows : (1) Concentrations of Mn and As were very high in the uppermost oxidized layer of the offshore sediment and Mn concretions. This resulted from the dissolution-deposition cycles of these elements within the sedimentary column and the bottom water. The fixation of As at the sediment surface is mainly attributed to the adsorption of arsenate onto Mn (II) -rich hydrous Mn (IV) oxide. (2) There were high concentrations of Zn, Cu, Pb and Hg in the recent sediments. Although the source of these elements is attributed to human activities, the individual distributions of Zn and Cu in the sediment may result from the deposition of metal-rich planktonic debris and subsequent degradation of the debris. (3) The orders of increasing concentrations of alkali metals and lanthanides in the sediment from the central region compared with the nearshore pediment were identical to the orders of increasing atomic numbers from Na to Cs and from La to Lu, respectively.

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In September-October 1998, during Cruise 14 of R/V Akademik Fedorov to the Barents Sea, in the region of 82° N between the Spitsbergen and Novaya Zemlya archipelagos samples of snow and ice were collected within four polygons. By means of atomic absorption with an electothermal atomizer (onboard the ship) in filtered (dissolved form) and unfiltered (sum of dissolved and particulate forms) samples of snow melt and ice melt concentrations of Fe, Mn, Cu, Cr, Ni, Co, Pb, and Cd were determined in order to estimate level of potential contamination of snow and ice with these metals. Excluding data on Ni, Cd (and probably Cu) in ice that were regarded to be unsatisfactory because of probable contamination of the ice samples during drilling concentrations of all the elements in snow and ice of the northern part of the Barents Sea appeared to be close to their background values or below. An attempt to identify the main sources of metal supply to snow from the atmosphere by comparison of ratios of metal particulate form to total content in snow of the Barents Sea and the same ratios in snow samples from clean regions of Finland and from contaminated areas of the Kola Peninsula showed that aerosols in the area of the expedition were supplied into the Barents Sea atmosphere from different sources, both natural and anthropogenic.

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Serpentinization of abyssal peridotites is known to produce extremely reducing conditions as a result of dihydrogen (H2,aq) release upon oxidation of ferrous iron in primary phases to ferric iron in secondary minerals by H2O.We have compiled and evaluated thermodynamic data for Fe-Ni-Co-O-S phases and computed phase relations in fO2,g-fS2,g and aH2,aq-aH2S,aq diagrams for temperatures between 150 and 400°C at 50MPa.We use the relations and compositions of Fe-Ni-Co-O-S phases to trace changes in oxygen and sulfur fugacities during progressive serpentinization and steatitization of peridotites from the Mid-Atlantic Ridge in the 15°20'N Fracture Zone area (Ocean Drilling Program Leg 209). Petrographic observations suggest a systematic change from awaruite- magnetite-pentlandite and heazlewoodite-magnetite-pentlandite assemblages forming in the early stages of serpentinization to millerite-pyrite-polydymite-dominated assemblages in steatized rocks. Awaruite is observed in all brucite-bearing partly serpentinized rocks. Apparently, buffering of silica activities to low values by the presence of brucite facilitates the formation of large amounts of hydrogen, which leads to the formation of awaruite. Associated with the prominent desulfurization of pentlandite, sulfide is removed from the rock during the initial stage of serpentinization. In contrast, steatitization indicates increased silica activities and that highsulfur-fugacity sulfides, such as polydymite and pyrite-vaesite solid solution, form as the reducing capacity of the peridotite is exhausted and H2 activities drop. Under these conditions, sulfides will not desulfurize but precipitate and the sulfur content of the rock increases. The co-evolution of fO2,g-fS2,g in the system follows an isopotential of H2S,aq, indicating that H2S in vent fluids is buffered. In contrast, H2 in vent fluids is not buffered by Fe-Ni-Co-O-S phases, which merely monitor the evolution of H2 activities in the fluids in the course of progressive rock alteration.The co-occurrence of pentlandite- awaruite-magnetite indicates H2,aq activities in the interacting fluids near the stability limit of water. The presence of a hydrogen gas phase would add to the catalyzing capacity of awaruite and would facilitate the abiotic formation of organic compounds.

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From the south-eastern Tyrrhenian deep-sea floor, four sediment cores of "Meteor" cruise 22 (1971) are described. These cores were taken in the basin between the Aeolian Islands and the Marsili Seamount, an elevation of more tha 3000 m above the sea floor. The sedimentation of the deep-sea basin is distinguished by a sequence of turbidites with a high sedimentation rate. The composition of the clastic material and the position of the cores in the mouth area of the morphologically very pronounced Stromboli Canyon suggest an interpretation of the turbidite sequence as fan of this canyon onto the deep-sea floor. A white rhyolitic pumice-tephra at the base of the 4 m thick sequence of turbidites in core M22-102 has been correlated with the Pelato eruption of the island of Liparo in the 6th century A.D. At the foot of the Marsili Seamount - apparently in morphologically elevated positions - the influence of the turbidite sedimentation increases, the rate of sedimentation is lower and stratigraphic omissions are probable. Here, rather compacted globigerina marls have been found in only 15 -25 cm depth. In addition, volcanic material in the form of lapilli layers, palagonitized ashes and detrital volcanic sands of the Marsili Seamount have been encountered in this area. An up to 3 cm thick layer of completely palagonitized basaltic ash intercalates with the marls at the base of two cores. Layers of very fresh olivine basaltic lapilli in core 103 and palagonitized lapilli of latitic composition in core 104 testify to an explosive submarine volcanism of the Marsili Seamount. According to the stratigraphy of core 103, the latest manifestations of this basaltic volcanism belong to the late Pleistocene (Emiliana huxleyi-zone of Nannoplankton stratigraphy) The basaltic lapilli are glassy to perhyaline with phenocrysts or microphenocrysts predominantely of olivine. The petrological character of the basaltic volcanites with high MgO, Ni, Cr and high MgO/FeO- and Ni/Co-ratios exhibits primitive basaltic features. These basalts clearly differ from basalts of the ocean floors, mid-ocean ridges and marginal basins. Prominent features are a missing iron-enrichment trend and low TiO2. Al2O3 tends to be high, as well as K2O and related trace elements (Ba, Sr). In spite of silica undrsaturation and high color index, the Marsili basalt exhibit some analogies with the calcalkaline basalts of the Aeolian arc, as well as the undersaturated basalts of some other circumoceanic areas.

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Thirty-eight samples from DSDP Sites 549 to 551 were analyzed for major and minor components and trace element abundances. Multivariate statistical analysis of geochemical data groups the samples into two major classes: an organic-carbon- rich group (> 1% TOC) containing high levels of marine organic matter and certain trace elements (Cu, Zn, V, Ni, Co, Ba, and Cr) and an organic-carbon-lean group depleted in these components. The greatest organic and trace metal enrichments occur in the uppermost Albian to Turanian sections of Sites 549 to 551. Carbon-isotopic values of bulk carbonate for the middle Cenomanian section of Site 550 (2.35 to 2.70 per mil) and the upper Cenomanian-Turonian sections of Sites 549 (3.35 to 4.47 per mil) and 551 (3.13 to 3.72 per mil) are similar to coeval values reported elsewhere in the region. The relatively heavy d13C values from Sites 549 and 551 indicate that this interval was deposited during the global "oceanic anoxic event" that occurred at the Cenomanian/Turonian boundary. Variation in the d18O of bulk carbonate for Section 550B-18-1 of middle Cenomanian age suggests that paleosalinity and/or paleotemperature variations may have occurred concurrently with periodic anoxia at this site. Climatically controlled increases in surface-water runoff may have caused surface waters to periodically freshen, resulting in stable salinity stratification

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This paper reports data including new analyses of contents of Ni, Co, V, Mo, Fe, Mn, Zn, Ba, Sc, Y, Cd, Rb, Cs, and W in bottom sediments of the Deryugin Basin. Features of chemical element distribution in the bottom area were identified and zones of maximum accumulation of major and trace elements were allocated. A correlation between the elements was shown.

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Distribution of Fe, Mn, Ti, Cu, Ni, Co, V, Cr, Mo, As in bottom sediments of a section from the Hawaiian Islands to the coast of Mexico. In the surface layer and isochronic layers of sediments from biogenic-terrigenous sediments of the Mexico coast to pelagic red clays of the Northeast Basin contents of all studied elements increase, and more sharply for mobile ones - Mn, Mo, Cu, Ni, Co, As. In near Hawaii sediments rich in coarsely fragmented volcanic-terrigenous and pyroclastic material of basalt composition enriched in Ti, Fe, Cr, V, P contents of these elements in surface sediments and in sediment mass increase and contents of Mn, Mo, Ni, Co, Cu, As (for the same reason) decrease compared to red clays. An area of hemipelagic and transition sediments is identified; these sediments have much higher contents of Mn, Fe, Cu, Ni, Mo, As, (Ba) than red clays and similar sediments of the Northwest Pacific Ocean. This is due to hydrothermal activity in the tectonically active zone at the northern extension of the East Pacific Rise. Similar character of distribution of the elements in the surface layer and in the isochrone layers of bottom sediments along the most part of the section is shown. Similarity between distribution of the elements in sediments of the western and the eastern parts of the Transpacific section is established.