Studies on diffusion and profiles of elements in deep-sea manganese nodules

Elemental compositions are measured in manganese nodules collected from the Northern Mid-Pacific floor by inductively-coupled plasma atomic emission spectrometry (1CP-AES) and their growth rates are determined by radiometric methods. The result shows that depth distributions of elements in nodules vary with depth as follows; (i) increase, (ii) decrease and (iii) fluctuation. These internodule variations in elemental compositions are considered to be caused by diffusion and migration of elements in nodules and heterogeneities in textures of nodules. In the present paper, a diffusive model is used to elucidate the inward-increase profile of some elements in nodules. The effective diffusive coefficients are estimated to be of the order of 10-9 cm2/a for Ni, V and Zn in the nodules, which is less than the value reported for radionuclides.

Detrital and authigenic(?) baddeleyite(ZrO_2) in ferromanganese nodules of Central Indian Ocean Basin

Occurrence of baddeleyite（ZrO_2） which is a rare mineral has been recorded in ferromanganese nodules of Central Indian Ocean Basin（CIOB）.The mineral occurs either as independent isolated sub-rounded to elliptical grains or in clusters forming fine subhedral crystals（〈3μm） within ferromanganese concretionary growth bands.The mode of occurrence,texturai features and chemistry of the mineral suggest detrital and possibly an authigenic origin for baddeleyite.For authigenic origin it is proposed that zirconium might have got released either from the terrigenous sediments or the altered seafloor rocks forming halogen complexes and subsequently it has re-precipitated in me form of baddeleyite within manganese nodules under oxic to sub-oxic conditions.

Geochemistry and Origin of Layers in Single Manganese Nodule from the Philippine Sea and Manganese Nodules from Offshore Minami-Torishima, Western Pacific

Layers from one manganese nodule dredged from the Philippine Sea（16°56＇N, 129°48＇E; water depth, 5700 m） and 45 bulk nodules from offshore Minami-Torishima Island, Japan（23°3＇N, 153°22＇E; water depth, 1200 m） were analyzed chemically and their origin is discussed based on geochemical constraints. In general, Cu, Ni, Zn and Mo tend to increase with increasing Mn content, while Co, Pb, Ba, V, Sc, Th, and the rare earth elements（REEs） show less variation with increasing Mn content. Nodule 42 H from the Philippine Sea has an average Mn/Fe ratio close to 1 and shows a positive Ce anomaly, suggesting a predominant hydrogenous origin. Profiles of 230Th230 ex and Thex/232 Th ratios in the outer ~0.3 mm of nodule 42 H indicate a steady growth rate of ~1.7 mm/Myr. Nodule E30 from offshore Minami-Torishima is characterized by lower Mn, Fe, Mn/Fe（0.53） and Mo/V（0.2） ratios but higher P and Cu/Ni（0.31） ratio relative to other nodules from that area. The Ce content of E30 is unusually low（82 ppm） when compared with other nodules from the area and it is the only nodule analyzed with a negative Ce anomaly（-0.64）. Based on the geochemical data we suggest that most nodules from offshore Minami-Torishima are primarily of hydrogenous origin except E30, which is dominated by hydrothermal input, and E45, which has about a 35% hydrothermal contribution.

Growth Rate Estimates of Supergene Manganese Nodule by ^(40)Ar/^( 39)Ar Isotopic Dating

Increasing world-class, high-grade, and metals-enriched supergene manganese ore deposits have been discovered in the last two decades, making them more and more economically important. However, data on the timing and duration of their formation are sparse, mainly due to the difficulties extracting datable minerals suited to traditional radiometric dating methods. Hollandite, cryptomelane, coronadite, todorokite, and manjiroite are common manganese oxide minerals in supergene environments. These minerals host potassium of variable amounts from 0.1 wt% to 5.0 wt% in their structural sites. This geochemical property provides possibility to date supergene manganese ores by using K-Ar and 40Ar/ 39Ar methods. In this study, we perform 40Ar/ 39Ar dating on a 7.1-cm-thick botryoidal manganese nodule from an ancient weathering profile at Mount Tabor, central Queensland, Australia. Laser microprobe incremental analyses of distinct growth bands, from the inner core through the intermediate bands to the outermost crusts of the nodule, have yielded high quality 40Ar/ 39Ar ages at 27.3 Ma, 20.9 Ma, 19.2 Ma, and 16.1 Ma, respectively. The age results permit preliminary estimates on the average growth rates of the nodule varying from 4.7×10 -3 mm/ka to 7.6×10 -3 mm/ka to 9.0×10 -3 mm/ka, from the core to the rim. Results of this study are of significance in our understanding of the mode, mechanism, process, and climatic conditions in the formation of supergene manganese ore deposits.

Pelagic Manganese Nodules--A New Type of Oncolites

Pelagic manganese nodules from the East Pacific Ocean have been studied using polarizing,scanning electron and transmission electron microscopes. It has been revealed that the manganesenodules are composed of cores and stromatolite coatings. The structures and textures of thesenodules are peculiar to oncolite. Consequently, the pelagic manganese nodules are manganeseoncolites. Based on the stromatolites in the coatings, the manganese oncolites from the East Paci-fic Ocean can be divided into two types. One is smooth on surface and dense inside. Its coatingsare composed mainly of Minima. The other has a knobby surface and is loose internally. Itscoatings consist mainly of Admirabilis. The TEM investigation has also revealed that the con-structors of the manganese oncolites are ultra-microbes. The Minima is constructed byMiniactinomyces chinensis sp. nov. and the Admirabilis is built by Spirisosphaerospora pacifica sp.nov.

Image Processing of Manganese Nodules Based on Background Gray Value Calculation

To troubleshoot two problems arising from the segmentation of manganese nodule images-uneven illumination and morphological defects caused by white sand coverage,we propose,with reference to features of manganese nodules,a method called“background gray value calculation”.As the result of the image procession with the aid this method,the two problems above are solved eventually,together with acquisition of a segmentable image of manganese nodules.As a result,its comparison with other segmentation methods justifies its feasibility and stability.Judging from simulation results,it is indicated that this method is applicable to repair the target shape in the image,and segment the manganese nodule image in a short time.Also,it could be used to synchronously process a large number of manganese nodules on different conditions in an image,laying a good foundation for automatic underwater manganese nodule survey.Even if the target in the image is slightly distorted,the statistical data of manganese nodules are still accurate.Moreover,other methods cannot be fully applied to the segmentation of manganese nodule images;in another word,the effectiveness and stability of this method are proved.

Recovery of Mn^(2+), Co^(2+) and Ni^(2+) from manganese nodules by redox leaching and solvent extraction

The recovery of Mn, Co and Ni from deep-sea manganese nodules was conducted by acid oxidative leaching and solvent extraction. The results indicate that pyrrhotite used during leaching can effectively facilitate the leaching out of manganese, cobalt and nickel. The leaching behaviors of Mn, Ni and Co were determined and the influences of temperature, leaching time and sulphuric acid concentration on leaching rate were also investigated. Co and Ni are precipitated from the leaching liquor by adding sodium sulfide into solution with agitation for 2 h at 50 ℃, and the manganese sulphate is obtained by concentrating the resulting solution. By re-dissolving the precipitates of cobalt and nickel, the separation of cobalt and nickel is performed using di(2-ethylhexyl) phosphoric acid (D2EHPA) for impurities elimination with 8 stages at organic-to-aqueous(O/A) volume ratio of 3:5, and 2- ethylhexyl phosphonic acid mono-2-ethylhexyl ester (known as PC88A or P507) for cobalt extraction with 3 stages counter-current operations at O/A volume ratio of 2:3 followed by their scrubbings and strippings, respectively. The final maximum recovery rates for manganese, cobalt and nickel are 85%, 75% and 78%, respectively.

Radiochemical studies of deep - sea manganese nodules

Five manganese nodules collected from the Northern Mid - Pacific have been analysed for their U and Th isotopes.lt is found that the enrichment of thorium compared to uranium is universal in deep- sea manganese, nodules and in the top sides of the nodules there are large excesses of Th and Pa decreasing exponentially with depth. For each of the nodules, the concordant growth rates are obtained from three different methods: 230Thex 230Thex/232Th and 231Paex.The growth rates of manganese nodules are closely related to the chemical compositions of the nodules and the types of the underlying sediments. The growth rates of five nodules are determined to be in the range of 0.79-7.4 mm/106a, in agreement with those predicted from the chemical compositions of the nodules. By the comparison of the extrapolated 230Thex,230Thex/232 Th and 231PaeX data from the top and bottom surfaces of the nodule from Site M21 yields, the nodule turnover time is (9.83-13.7)×104a.

Implications of REE incorporation and host sediment influence on the origin and growth processes of ferromanganese nodules from Central Indian Ocean Basin

This study presents new major,trace and REE data for thirty-five ferromanganese nodules recovered from areas representing three different sediment types(siliceous,red clay and their transition zone)in the Central Indian Ocean Basin(CIOB)to address their genetic aspects,classification,growth rate,nature of host sediments and influence of REE in the processes of nodule formation.The nodules from CIOB are mostly either hydrogenetic(metals coming from oxygenated bottom water)and diagenetic(metals coming from suboxic sediment pore water)or a combination of both,depending on the source of supply of metal.However,a number of biogeochemical processes mediate this supply of metals which again changes from time to time,making the nodule growth process highly dynamic.This study suggests that at the initial stage of nodule growth,host sediments do not play much role in controlling the growth processes for which REEs can enter both Mn and Fe oxyhydroxide phases equally.Thus,the bottom water signature is imprinted in these early formed nodules irrespective of their host sediment substrate but with gradual growth and burial in the sediment,the main mode of metal enrichment becomes diagenetic through sediment pore water.This tends to increase the concentration of Mn,Ni and Cu over other elements which are retained in the sediment fraction.Among the REEs,Ce concentration of the nodules shows significant positive anomaly due to variation in redox potential and hence its magnitude can be used to get an idea about the metal enrichment procedure and the genetic type of the nodules.However,based on host sediment only,not much difference is found in the magnitude of Ce anomaly in these nodules.On the other hand,discrimination diagram,based on HFSE and REY chemistry,indicates that most of these nodules are of diagenetic origin under oxic condition with a trend towards hydrogenetic field.Further,the genetic type of the ferromanganese nodules from the CIOB are more effectively differentiated by a combination of their major and trace element concentrations rather than solely based on their REE or HFSE chemistry or host sediment substrate.

Preparation and Characterization of La Doped Ferrite Using Marine Manganese Nodules as Raw Materials

A kind of La doped ferrite was prepared with marine manganese nodules derived from East Pacific sea-bottom as raw material, NaOH as fluxing reagent, La(NO3)3 as doping agent, by calcination at 1000 ℃ for 5 h. XRD analysis showed that the ferrite products were of a spinel structure, and that its molecular formula could be expressed as MnFe2-xRxO4. SEM images proved that these ferrites showed octahedral and cubic aspects. It was found that there is some relationship between the La doping amount and the magnetic property of the ferrite. When the La doping amount was 0.03, the susceptibility of the ferrite was maximal. The as-prepared La doped ferrite is a kind of soft magnetic material that is easy to be magnetized with rather weak coercive force.

Rare Earth Elements in Manganese Nodules from the Central Pacific Ocean

Manganese nodules in areas CP and CC of the central Pacific are rich in REE. Comparatively speaking,the REE contents of nodules in area CP are hihger than those in area CC; and the REE contents of nodulesfrom seamounts are higher than those of nodules from sea-floor plains and hills. Within the nodules, the REEshow a zonal distribution. The REE distribution patterns of the nodules are similar to those of the sedimentsand have a mirror image relationship with those of the sea water. Trivalent REE were not obviously differenti-ated when they entered into the nodules from the sea water.A major factor causing the difference of REE abundances between nodules and sediments is the redoxconditions. The redox intensity of the ocean floor of the Pacific is controlled mainly by Antarctic Bottom Wat-er(AABW), The iron-bearing facies in the nodules is the main carrier of REE.

REDUCTIVE LEACHING OF MANGANESE NODULE BY CHALCOPYRITE INDILUTE HCL SOLUTION

ＲＥＤＵＣＴＩＶＥＬＥＡＣＨＩＮＧＯＦＭＡＮＧＡＮＥＳＥＮＯＤＵＬＥＢＹＣＨＡＬＣＯＰＹＲＩＴＥＩＮＤＩＬＵＴＥＨＣＬＳＯＬＵＴＩＯＮＧｕｏ；Ｘｕｅｙｉ（ＤｅｐａｒｔｍｅｎｔｏｆＮｏｎｆｅｒｒｏｕｓＭｅｔａｌｌｕｒｇｙ，ＣｅｎｔｒａｌＳｏｕｔｈＵｎｉ...

COMPOSITIONAL VARIATIONS IN MANGANESE NODULES COLLECTED FROM THE NORTH PENRHYN BASIN

Manganese nodules collected from the North Penrhyn Basin are characterized by low content of Mn and Fe, medium content of Ni and Cu , and medium Mn / Fe ratios . The average content of Ni plus Co is 1.11% , maximum 1.89% . Ni content slightly exceeds the Cu content in the nodules. Ni and Cu are strongly correlated with Mn , whereas Co is strongly correlated with Fe . Nodules containing Ni+Cu+Co near or in excess of 1% are rich in Mn and have a high Mn/Fe ratio. Those with highest content of Ni+Cu+Co are concentrated at or near the carbonate compensation depth . Nodules metal contents vary with latitude and have a reciprocal relationship with abundance. Contents of Mn, Ni, Cu and Ni+Cu+Co are high in nodules found at 2 - 6°S and vary decreasingly toward 1°N and 12°S , whereas Co content varies increasingly from 2°S towards 12°S. Nodule compositional variations with latitude are controlled by biological productivity, carbonate compensation depth , sedimentation rate, and bottom current.

Abundance of total bacteria, ATP and manganese-oxidating bacteria in the sediments and manganese nodules of the Northwestern Pacific Ocean

In the seawater and sediments of the ocean, there exist huge quantities of bacteria whose living activities cause various chemical reaction processes. It is demonstrated that microorganisms play a fundamental role on chemical changes of the sediments and diageneses. Over the last twenty years, great interest has been increased about the role of deep-sea bacteria in the ferromanganese sedimentary process. Much work has been done on this aspect in the Atlantic Ocean, the Baltic Sea and the Pacific O-

Metallic Reserves of Submarine Manganese Nodules to be Estimated and Harnessed Prudently: Evidence from China's Jiaolong Manned Submersible

Since the discovery of oceanic manganese nodules during the expedition of the British ocean-going ship Challenger from 1872 to 1876, research and development for seabed manganese nodules have never ceased owing to the huge economic inducements. Manganese nodules are the black or dark brown, spherical or massive Mn-bearing ores, deposits of which are found on the sea bottom. The nodules are a mixture of silicate and insoluble potassium permanganates （also with sub-Ti, Fe and Na permanganates） that contain more than 30 kinds of metallic elements, among which those of greatest economic interest are Mn （27-30%）, Ni（1.25-1.5%）, Cu（1- 1.4%）, Co（0.2- 0.25 %）, Fe, Si, and AI, with minor amounts of Ca, Na, K, Ti, B, H and O.

Review of Nodule Mineral Image Segmentation Algorithms for Deep-Sea Mineral Resource Assessment

A large number of nodule minerals exist in the deep sea.Based on the factors of difficulty in shooting,high economic cost and high accuracy of resource assessment,large-scale planned commercial mining has not yet been conducted.Only experimental mining has been carried out in areas with high mineral density and obvious benefits after mineral resource assessment.As an efficient method for deep-sea mineral resource assessment,the deep towing system is equipped with a visual system for mineral resource analysis using collected images and videos,which has become a key component of resource assessment.Therefore,high accuracy in deep-sea mineral image segmentation is the primary goal of the segmentation algorithm.In this paper,the existing deep-sea nodule mineral image segmentation algorithms are studied in depth and divided into traditional and deep learning-based segmentation methods,and the advantages and disadvantages of each are compared and summarized.The deep learning methods show great advantages in deep-sea mineral image segmentation,and there is a great improvement in segmentation accuracy and efficiency compared with the traditional methods.Then,the mineral image dataset and segmentation evaluation metrics are listed.Finally,possible future research topics and improvement measures are discussed for the reference of other researchers.

A STUDY OF IRON AND MANGANESE IN THE WESTERN MID-PACIFIC

Our study on the horizontal and vertical distribution , change pattern , and migration form origin of iron and manganese and the factors affecting them in surface sediment in the western Mid-Pacific and in columnar sediment of station L 2032 is introduced . The author inferred the lysocline and compensation depth of the ocean by using the content changes of Fe and Mn ;differentiated rapidly sedimentation types by using the difference of Fe and Mn contents , estimated tentatively their contents in different sediments by using the dyeability of Fe and Mn . The author notes that the economically valuable Fe-Mn nodules can be formed during Fe-Mn deposition in the ocean and that in studies on Fe and Mn deposition , the affecting factors should be analyzed comprehensively .

Experimental investigation of the inhibition of deep-sea mining sediment plumes by polyaluminum chloride

Deep-sea sediment disturbance may occur when collecting polymetallic nodules,resulting in the creation of plumes that could have a negative impact on the ecological environment.This study aims to investigate the potential solution of using polyaluminum chloride(PAC)in the water jet.The effects of PAC are examined through a self-designed simulation system for deep-sea polymetallic nodule collection and sediment samples from a potential deep-sea mining area.The experimental results showed that the optimal PAC dose was found to be 0.75 g/L.Compared with the test conditions without the addition of PAC,the presence of PAC leads to a reduction in volume,lower characteristic turbidity,smaller diffusion velocity,and shorter settling time of the plume.This indicates that PAC inhibits the entire development process of the plume.The addition of PAC leads to the flocculation of mm-sized particles,resulting in the formation of cm-sized flocs.The flocculation of particles decreases the rate of erosion on the seabed by around 30%.This reduction in erosion helps to decrease the formation of plumes.Additionally,when the size of suspended particles increases,it reduces the scale at which they diffuse.Furthermore,the settling velocity of flocs(around 10^(-2) m/s)is much higher that of compared to sediment particles(around 10^(-5) m/s),which effectively reduces the amount of time the plume remains in suspension.

DETERMINATION OF GROWTH RATE OF MANGANESE NODULE AND SEDIMENTATION RATE OF DEEP-SEA SEDIMENT VIA ^(10)Be-DATING

Manganese nodules are deposit rich in manganese and other metals which "grow" on the ocean floor. The study of manganese nodule growth rate and deep sea sediment has both scientific and economic significance. Natural 10Be （half-life= 1.5 Ma ）is produced from spallations of atmospheric nitrogen and oxygen induced by cosmic ray in the stratosphere. After several years of residence in the atmosphere, the 10Be falls on the earth or deposits in the ocean, accumulating in marine

Discovery of low-mature hydrocarbon in manganese nodules and ooze from the Central Pacific deep sea floor

Extracts from manganese nodules and ooze from the Central Pacific deep sea floor were analyzed using the chromatogram-mass spectrum, and it was found that most of the biomarker molecules are of the low-mature type (some have characteristics of mature): the ratio of 'A'/C is high between 11.4%-19.75%; CPI is 1.22-1.23; C31-22S/ (22S+22R) hopane is 0.59-0.60, Tm/Ts is 0.99-1.99; pa moretane/(αβ+βα) hopane is 0.12-0.14; C29 sterane 20S/(20S+20R) is 0.35-0.41; ββ/(ββ+αα) is 0.38-0.45; arene TA(I)/TA(I+Ⅱ) is 0.16-0.21; methyl-phenanthrene index (MPI1) is 0.35-0.67. According to the geological settings of the sampling area and its organic geochemical characteristics, it is considered that the hydrothermal activities on the ocean floor facilitate the decomposition of organic matter in the sediment, which leads to the generation and migration of hydrocarbon into manganese nodules and ooze. This discovery is important for understanding the mechanisms of hydrocarbon generation in the ocean floor and