Determination of Platinum‐Group Elements and Gold in Ferromanganese Nodule Reference Samples

A measurement procedure for determining of Ru, Pd, Ir, Pt and Au mass fractions in ferromanganese deposits by inductively coupled plasma‐mass spectrometry after acid digestion and anion exchange preconcentration is presented. To eliminate incomplete recovery after sorption preconcentration of the platinum‐group elements (PGE) and Au, a standard addition method was used. Detection limits ranged from 0.02 ng (Pd, Ir) to 0.19 ng (Ru). The measurement results for ferromanganese nodule reference material NOD‐A‐1 and NOD‐P‐1 agree with earlier reported values. Intermediate precision of PGE concentration data for nodule reference materials in this work was 5–24% (1s) and could reflect sample heterogeneity.     

Role of the biogenic factor in platinum accumulation by oceanic ferromanganese nodules

A complex study of oceanic ferromanganese nodules (FMN) from the abyssal Clarion-Clipperton Fracture Zone and Lamont Guyot (Pacific Ocean) is performed. The concentrations of noble and trace elements are determined by AAS, INAA, and RFA-SR. Furthermore, SEM, and activation autoradiography are applied. Experiments are carried out using Pt, Au, and Ir radionuclides (radioisotope indicator method).     

广西贵港岩溶地质高背景区富含铁锰结核土壤的矿物学与重金属地球化学特征

岩溶地质高背景区土壤中普遍存在的铁锰结核对重金属的赋存状态和有效性有重要影响。选择广西贵港覃塘岩溶地质高背景区富含铁锰结核的表层土壤(0~20 cm)为研究对象,筛分出不同粒径的铁锰结核(10~120目)和细粒径土壤(<120目)样品进行化学分析,针对以下三个方面开展研究:(1)重金属(As、Cd、Cr、Cu、Hg、Ni、Pb和Zn)在铁锰结核和细粒径土壤中的分布分配规律和铁氧化物矿物的组成;(2)铁氧化物矿物对富含铁锰结核的土壤中Cd等重金属富集的影响;(3)重金属在富含铁锰结核的土壤中的赋存机制。研究发现,铁锰结核中的Fe和Mn以及Cd等重金属含量随着粒径的增大而不断增加,说明Cd等重金属元素更倾向于在大粒径铁锰结核中富集;土壤中Cd等重金属总量的约90%赋存在结核中,表明研究区土壤中重金属主要以结核形式赋存;富含铁锰结核的土壤中赤铁矿和针铁矿的平均含量分别为0.61%和4.94%,且结核粒径越大,针铁矿和赤铁矿含量越高;除Hg外,Cd等重金属含量与针铁矿和赤铁矿的含量均呈现极显著正相关,与赤铁矿的相关性稍优于针铁矿,表明铁氧化物矿物与富含铁锰结核土壤中的Cd等重金属元素富集密切相关。铁锰结核的存在既能促进Cd等重金属在土壤中的富集,又能降低土壤中重金属的生物有效性,研究结果为解释岩溶地质高背景区土壤Cd等重金属元素高含量、低生物有效性提供了理论依据。     

Effect of hydrochloric acid on grain size analysis of the Quaternary red clay rich in tiny ferromanganese nodules,Jiangxi province,southern China

There are many tiny ferromanganese nodules that cannot be found and eliminated easily in Quaternary red clay in southern China. The existence of these tiny ferromanganese nodules may influence grain size analysis results. Therefore, this paper focuses on the effects of the ferromanganese nodules on the grain size analysis and the effects of hydrochloric acid (HCl) on removing these nodules. The experimental results showed that the nodules clearly influenced the results of grain size analysis. The tiny ferromanganese nodules increased the coarse fraction and show a low peak in the coarse fraction of >100 μm on the frequency curves. The addition of HCl in the pretreatment process of grain size analysis can eliminate the effects of these tiny nodules effectively. Additionally, the HCl reacts with clay minerals and causes a reduction of the <4 μm fraction.     

富钴结壳中贵金属元素的特征

对太平洋CL、CM海山调查时获取9个富钴结壳样品,采用化学处理及ICP-MS法进行分析。对贵金属元素含量分布特征、富集因子、标准化模式以及来源进行探讨和研究。结果表明：海山结壳中贵金属元素Ag、Au、Ru、Rh、Pd、Pt等的平均含量分别为： 1.05×10^-6、2.3×10^-6、15.6×10^-9、22.3×10^-9、2.39×10^-9和432×10^-9。与结核、洋壳及陆地矿石的Pd/（Pt+Pd）、Pt/（Pt+Pd）和Pd/Pt等贵金属元素的比值相比,大洋富钴结壳的 Pd/（Pt+Pd） 比值最低,为0.006;其次是结核,为0.06;洋壳为0.08;陆地矿石的Pd/（Pt+Pd）比值较大,为0.35～0.65。结壳的Pt/（Pt+Pd）比值最高,为0.99;其次是结核,为0.95;洋壳为0.93;陆地矿石的Pt/（Pt+Pd）比值相对较低,为0.33～0.65。统计分析显示了不同区域、不同环境中贵金属元素的特征参数变化,并且说明富钴结壳中富铂、金、钌、铑,而贫钯。贵金属元素标准化显示,海山富钴结壳均存在着Pt、Au正异常和Pd的负异常,其中Au异常幅度与结核的Au异常一致。     

Geochemical features and genesis of continental cobalt-rich ferromanganese crusts

Mass cobalt-rich ferromanganese microcrusts and nodules similar in morphology and chemical composition to cobalt-rich ferromanganese deep-ocean crusts were found in Cenozoic volcanic rocks in southern Primorye. Research has shown that ore genesis of this type is genetically related to argillization and destruction of siliceous rocks by CO₂-rich fluids, which is confirmed by experimental data on carbon erosion of iron-containing materials. Two types of this fluid ore genesis are recognized: (1) relatively high-temperature (vapor-condensate), related to late volcanic processes and fracture gas infiltration, and (2) low-temperature (vapor-liquid-condensate), controlled by degassing followed by carbon mobilization (gasification). Primarily colloidal ferromanganese segregations have high contents of Co, Ni, Pb, Cu, and Ce, typical of oceanic ore genesis. Regardless of the concentrations of these metals in the protoliths, their contents in microcrusts are similar (n-10n wt.%). This indicates the same ore genesis mechanism and similar sorption properties of the colloidal ferromanganese material formed. Barium- and cerium-rich ferromanganese microcrusts and nodules are abundant. Condensed drops of iron-containing platinum were found in apobasaltic nickel-rich ferromanganese segregations. There is a cerium paradox expressed as a minimum or a total lack of cerium among rare-earth phosphates associated with ferromanganese microcrusts. Fluid destruction and oxide metallization of ocean-floor basalts are assumed to be the main source of metals for oceanic ferromanganese crusts and nodules.     

Geochemistry of the Manganese Ore Process in the Ocean: Evidence from Rare Earth Elements

Processes governing the formation of rare earth elements (REE) composition are considered for ferromanganese deposits (nodules, separate parts of nodules, and micronodules of different fractions) within the Clarion–Clipperton ore province in the Pacific Ocean. It is shown that ferromanganese oxyhydroxide deposits with different chemical compositions can be produced in sediments under similar sedimentation conditions. In areas with high bioproductivity, the size of micronodules has a positive correlation with the Mn content and Mn/Fe and P/Fe ratios and a negative correlation with Fe, P, REE, and Ce anomaly. The behavior of REE in micronodules from sediments within bioproductive zones is related to increase of the influence of diagenetic processes in sediments as a response to the growth of the size of micronodules. Distinctions in the chemical composition of micronodules and nodules are related to their interrelations with associated sediments. Micronodules grow in sediments using hydrogenous ferromanganese oxyhydroxides. As they grow, micronodules are enriched in the labile fraction of sediments reworked during diagenesis. Sources of the material of ferromanganese nodules are governed by their formation at the water bottom interface. Their upper part is formed by direct settling of iron oxyhydroxides from the bottom water, whereas the lower part is accumulated due to diagenetic processes in sediments. Differences of REE compositions in ferromanganese deposits are caused by the reduction of manganese during diagenesis and its separation from iron. Iron oxyhydroxides form a sorption complex due to the sorption of phosphate-ion from bottom and pore waters. The sorption of phosphate-ion results in an additional sorption of REE.     

海底金属矿产资源的开发--回顾与未来展望

占地球面积70％的海洋蕴藏着巨量的矿产资源。文章简要回顾了铁锰结核、富钴结壳及热液硫化物等海底金属矿产资源开发研究的进展、经验和挫折,并通过综合分析指出,海洋矿产资源的开发是新世纪的必然趋势,而新近在西南太平洋发现的浅成低温热液金矿可能成为海洋金属矿产开发研究的热点。     

Nodules in sediments of an artificial reservoir in the Altai Territory

Nodules of various compositions, including ferromanganese nodules, have been found in bottom sediments of an artificial reservoir in the central Altai Territory. The nodules were formed in the alkaline environment against the background of a high carbonate content and saturation with oxygen. The rate of nodule growth is no less than 1.7–1.8 mm/yr and the pH value of water varies from 8.0 to 9.7. Fe and Mn contents in soil and loam of the drainage area are lower than the global clarke value, whereas Ca, K, and Na contents are much higher. The main mass of bottom sediments in the reservoir is markedly enriched in Cd, Mg, Mn, Sr, Ni, Cr, Sb, V, and Pb, but they are depleted in Cu, Mo, Zn, and Li, relative to the soil and loam. Elements in ferromanganese nodules are arranged in the following way in terms of the decreasing concentration coefficient: Mn (27) > Ba (13.4) > Co (10.7) > Mo (9.2) > Cd (5.35) > Ni (3.88) > V (3.52) > Cu (3.3) > Fe (3.2) > Sb (2.17) > Sr (2.04) > Pb (1.5) > Zn (1.43) > Cr (1.1) > Li (0.78) > Mg (0.75) > Na (0.69) > K (0.67) > Ca (0.51). The microelemental composition of nodules in the reservoir qualitatively fits the composition of ferromanganese nodules in seas and oceans. However, the contents of major ore elements (Ni, Cu, Co, Zn, Pb, Mo, and V) in ferromanganese nodules from the World Ocean are much higher than in nodules from the examined reservoir.     

Comparison of elemental accumulation rates between ferromanganese deposits and sediments in the South Pacific Ocean

Rates of accumulation of Fe and Mn, as well as Cu, Ni, Co, Pb, Zn, Hg, U and Th have been determined for five ferromanganese deposits from four localities in the South Pacific Ocean.Manganese is accumulating in nodules and crusts at a rate roughly equivalent to that found to be accumulating in sediments in the same area. Iron shows a deficiency in accumulation in nodules and crusts with respect to sediments, especially near the continents, but also in the central and south-central Pacific. Copper is accumulating in nodules and crusts at a rate one order of magnitude less than the surrounding sediments.This is interpreted as meaning that most of the Mn is supplied as an authigenic phase to both sediments and nodules while Fe is supplied mostly by ferromanganese micro-nodules and by detrital and adsorbed components of sediments; and Cu is enriched in sediments relative to nodules and crusts most probably through biological activity.     

Detrital and authigenic(?) baddeleyite (ZrO2) in ferromanganese nodules of Central Indian Ocean Basin

Occurrence of baddeleyite (ZrO2) 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 (<3 mm) within ferromanganese concretionary growth bands. The mode of occurrence, textural 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 the form of baddeleyite within manganese nodules under oxic to sub-oxic conditions.     

Mineral resources of the ocean

Major data concerning the history of investigation, distribution, mineral and chemical composition, and formation processes of mineral resources of the ocean, namely ferromanganese nodules, ore crusts, phosphorites, and hydrothermal mineral formations, including ore-bearing and metalliferous sediments, massive sulfides, and hydrothermal ferromanganese crusts are reviewed. The problem of the scale of mineral accumulations in the ocean and their quality, along with prospects of their future recovery, is discussed.     

Accumulation and fractionation of trace elements in soil ferromanganese nodules of different size

The concentrations and distribution of bulk and mobile species of trace elements were investigated in various size fractions of ferromanganese nodules from bleached meadow-brown soils. It was shown that the enrichment factor of trace elements increases during the growth of nodules; however, the character of element accumulation appeared to depend on the nature of the element. The nodules intensely accumulate Mn, Co, Ni, and Pb and, to a lesser extent, Cu and Mo. The process of trace element uptake by the nodules is most contrasting in the middle part of the soil profile. The nature of trace element concentration by soil nodules is rather complex and requires further special investigations.     

Mineralogy of morphogenetic types of ferromanganese deposits in the world ocean

The mineralogy and structural features of the main types of ferromanganese deposits—nodules, micronodules, Co-bearing crusts, crustlike nodules, and low-temperature hydrothermal manganese crusts and ferruginous ochers—are considered. The correlation between their mineral composition and structure is shown. The proposed classification of mineral types is based on characteristic assemblages of Fe and Mn minerals.     

New Data on Ferromanganese Crusts of Mendeleev Rise,Arctic Ocean

Doklady Earth Sciences - This paper considers the compositions of ferromanganese crusts and nodules (FMCNs) growing on bedrock of Mendeleev Rise, collected in 2016 using a research submarine. The...     

Ferromanganese oxide deposits from the Central Pacific Ocean,II. Nodules and associated sediments

Bulk chemical, mineralogical and selective leach analyses have been made on a suite of abyssal ferromanganese nodules and associated sediments from the S.W. equatorial Pacific Ocean. Compositional relations between nodules, sediment oxyhydroxides and nearby ferromanganese encrustations are drawn assuming that the crusts represent purely hydrogenetic ferromanganese material. Crusts, δMnO₂-rich nodules and sediment oxyhydroxides are compositionally similar and distinct from diagenetic todorokitebearing nodules. Compared to Fe-Mn crusts, sediment oxyhydroxides are however slightly enriched, relative to Mn and Ni, in Fe, Cu, Zn, Ti and Al, and depleted in Co and Pb, reflecting processes of non-hydrogenous element supply and diagenesis. δMnO₂ nodules exhibit compositions intermediate between Fe-Mn crusts and sediment oxyhydroxides and thus are considered to accrete oxides from both the water column and associated sediments.Deep ocean vertical element fluxes associated with large organic aggregates, biogenic calcite, silica and soft parts have been calculated for the study area. Fluxes associated with organic aggregates are one to three orders of magnitude greater than those associated with the other phases considered, are in good agreement with element accumulation rates in sediments, and are up to four orders of magnitude greater than element accumulation rates in nodules. Metal release from labile biogenic material in surface sediments can qualitatively explain the differences between the composition of Fe-Mn crusts and sediment oxyhydroxides.Todorokite-rich diagenetic nodules are confined to an eastwards widening equatorial wedge. It is proposed that todorokite precipitates directly from interstitial waters. Since the transition metal chemistry of interstitial waters is controlled dominantly by reactions involving the breakdown of organic carbon, the supply and degradation rate of organic material is a critical factor in the formation of diagenetic nodules. The wide range of (trace metal/Mn) ratios observed in marine todorokite reflects a balance between the release of trace metals from labile biogenic phases and the reductive remobilisation of Mn oxide, both of which are related to the breakdown of organic carbon.     

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 (silic...     

A new concept of pedogenic nodule formation in landscapes of the Russian Far East

The typification of ferromanganese nodules (FMN) formed in subaqueous and subaerial settings and in residual materials, as well as FMN localization in various sediments and soils, is discussed. The genetic diversity of morphologically similar FMN and the transformation of FMN-bearing complexes with changes in landscapes have been established.     

Specific chemical and mineral composition of ferromanganese nodules from the Chukchi Sea

The specific chemical and mineral composition of discoid, cake-shaped, and platy ferromanganese nodules (FMNs) from the Chukchi Sea are considered. The main ore components of these FMNs are Fe, Mn, and P. The contents of trace elements (except for Ba and Sr) do not exceed hundredths of percent. Maximum concentrations of most of these elements are specific for the cake-shaped nodules. In general, Mn accumulates most intensely in FMNs. Next (in order of decrease) are Ag(?), Co, and Pb; Sr, Fe, P, Y, and Ca; and Ni, La, Zn, and Cu. As for Ba, Cr, Mg, and K, they do not accumulate in the FMNs. “Dilution” is typical of Si, Al, Na, and Ti. The main ore phases are strengite and amorphous Mn hydroxides. It has been revealed for the first time for the Chukchi Sea that Cu, Zn, Sn, Ni, Pb, W, Bi, Cr, Fe, Ti, Ag, Au, Y, Zr, and La–Nd lanthanides form individual mineral microphases in FMNs: native elements, intermetallic compounds, oxides, and, much more seldom, tungstates, silicates, and phosphates. Accessory ore mineralization is the best pronounced and most diverse in the platy nodules. Though the FMNs from the Chukchi Sea are diagenetic, high-temperature fluids are, most likely, the source of microinclusions of various accessory ore minerals.