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1.
Manganese at equilibrium in seawater occurs dominantly as Mn2+ and inorganic complexes at a concentration ratio of about 1:0.72; solubility decreases exponentially with increasing pH or Eh. However, the nodule oxides birnessite and todorokite are at least four orders of magnitude undersaturated relative to the Mn concentrations of seawater, and are metastable relative to hausmannite and manganite. This apparent lack of equilibrium is explicable by the mechanism of precipitation.Surfaces assist Mn precipitation by catalyzing equilibration between dissolved and reactive O2 and simultaneously also by adsorbing ionic Mn species. The effective Eh at the surface becomes 200–400 mV above that of seawater; the oxidation rate of Mn increases about 108 ×, and the activation energies for Mn oxidation decrease ~ 11.5 kcal/mole. Consequently, marine Mn nodules and crusts form by adsorption and catalytic oxidation of Mn2+ and ferrous ions at nucleating surfaces such as sea-floor silicates, oxyhydroxides, carbonates, phosphates and biogenic debris. The resulting ferromanganese surfaces autocatalyze further growth. In addition, Mn-fixing bacteria may also significantly accelerate accretion rates on these surfaces.Mn which accumulates in submarine sediments may be diagenetically recycled in response to steep solubility gradients causing upward migration from more acidic and reducing horizons toward the sea floor. In contrast, the concentrations of the predominant ferric complexes, Fe(OH)30 and Fe(OH)4?, are relatively less sensitive to the Eh's and pH's found in this environment; Fe is therefore not as readily recycled within buried sediments. Consequently, Fe is not so effectively enriched on the sea floor, although it precipitates more readily than Mn because seawater is saturated in amorphous Fe(OH)3.The metastable, perhaps kinetically-related, Mn oxides of nodules have a characteristic distribution: birnessite predominates in oxidizing environments of low sedimentation rate and todorokite where sedimentation rates and diagenetic Mn mobility are higher. Surface adsorption and cation substitution within the disordered birnessite-todorokite structure account for the high trace element content of Mn nodules.  相似文献   

2.
The Mn distribution in Panama Basin area sediments and interstitial waters is discussed. Striking surficial Mn enrichments produced by a well-known diagenetic recycling process characterize the sediments of the region. Thermodynamic solubility calculations indicate that in at least one core interstitial waters approach saturation with respect to MnCO3. A mixed carbonate phase of composition (Mn48 Ca47 Mg5)CO3 was recovered from an ash band in the same core. The association of this material with the coarse volcaniclastic debris is thought to result from facile manganous carbonate precipitation in sediment horizons of coarser mean grain size. Since sulphate reduction in the upper two metres of Panama Basin sediments is fairly minor, little increase in alkalinity is observed, and it is postulated that significant production of carbonate alkalinity is not a prerequisite for manganous carbonate generation in hemipelagic sediments. A more important factor appears to be the availability of Mn oxides for solution during early diagenesis. Stable C isotopic analyses indicate that little C of organic origin is used in the precipitation reaction in either Panama Basin or Loch Fyne (Scotland) sediments.  相似文献   

3.
Processes of authigenic manganese ore formation in sediments of the northern equatorial Pacific are considered on the basis of study of the surface layer (<2 mm) of ferromanganese nodule and four micronodule size fractions from the associated surface sediment (0–7 cm). Inhomogeneity of the nodule composition is shown. The Mn/Fe ratio is maximal in samples taken from the lateral sectors of nodule at the water-sediment interface. Compositional differences of nodules are related to the preferential accumulation of microelements in iron oxyhydroxides (P, Sr, Pb, U, Bi, Th, Y, and REE), manganese hydroxides (Co, Ni, Cu, Zn, Cd, Mo, Tl, W), and lithogenous component trapped during nodule growth (Ga, Rb, Ba, and Cs). The Ce accumulation in the REE composition is maximal in the upper and lower parts of the nodule characterized by the minimal Mn/Fe values. The compositional comparison of manganese micronodules and surface layers of the nodule demonstrated that the micronodule material was subjected to a more intense reworking during the diagenesis of sediments. The micronodules are characterized by higher Mn/Fe and P/Fe ratios but lower Ni/Cu and Co/Ni ratios. The micronodules and nodules do not differ in terms of contents of Ce and Th that are least mobile elements during the diagenesis of elements. Differences in the chemical composition of micronodules and nodules are related not only to the additional input of Mn in the process of diagenesis, but also to the transformation of iron oxyhydroxides after the removal of Mn from the close association with Fe formed in the suspended matter at the stage of sedimentation.  相似文献   

4.
Abstract. The occurrence, lithology, and stratigraphic setting of buried manganese deposits and associated host sediments in cores obtained on Legs 123–210 of the Ocean Drilling Program (ODP) are examined in order to establish the formative environment and conditions of preservation. Fossil manganese nodule and crusts are found to have formed or deposited throughout the period from 100 Ma to the present, with an additional example of formation near 137 Ma, suggesting that the deep-sea environment has been oxic and suitable for the formation of manganese nodules and crusts since the Cretaceous. Many manganese nodules and crusts occur on horizons corresponding to hiatuses in sedimentation or periods of slow sedimentation, consistent with the environment in which modern nodules form (sedimentation rate less than 10 m/m.y.). Sediments overlying the fossil nodules and crusts are oozes or biogenic sediments with sedimentation rates of 1–18 m/m.y. Low total organic carbon (<0.1 wt%) in the overlying sediments and high sulfate content (>25 mM) in interstitial water around the manganese horizon suggest that no strong reduction occurred within the overlying sediments. Coverage by biogenic sediments containing only small amounts of organic matter is therefore considered important for the preservation of manganese nodules and crusts. Manganese carbonate occurs sporadically as nodules, concretions or thin layers in various host sediments, including clay, calcareous ooze and siliceous ooze with sedimentation rates of 6–125 m/m.y. Hiatuses are rare around the host sediments of manganese carbonate. Higher total organic carbon (0.2–1.8 wt%) in the host sediments and lower sulfate content (0–25 mM) in interstitial water around the manganese carbonate horizon suggest that reduction in association with decomposition of organic matter would have proceeded in the host sediments.  相似文献   

5.
Iron and manganese redox cycling in the sediment — water interface region in the Kalix River estuary was investigated by using sediment trap data, pore-water and solid-phase sediment data. Nondetrital phases (presumably reactive Fe and Mn oxides) form substantial fractions of the total settling flux of Fe and Mn (51% of Fetotal and 84% of Mntotal). A steady-state box model reveals that nondetrital Fe and Mn differ considerably in reactivity during post-depositional redox cycling in the sediment. The production rate of dissolved Mn (1.6 mmol m–2 d–1) exceeded the depositional flux of nondetrital Mn (0.27 mmol m–2 d–1) by a factor of about 6. In contrast, the production rate of upwardly diffusing pore-water Fe (0.77 mmol m–2 d–1) amounted to only 22% of the depositional flux of nondetrital Fe (3.5 mmol m–2 d–1). Upwardly diffusing pore-water Fe and Mn are effectively oxidized and trapped in the oxic surface layer of the sediment, resulting in negligible benthic effluxes of Fe and Mn. Consequently, the concentrations of nondetrital Fe and Mn in permanently deposited, anoxic sediment are similar to those in the settling material. Reactive Fe oxides appear to form a substantial fraction of this buried, non-detrital Fe. The in-situ oxidation rates of Fe and Mn are tentatively estimated to be 0.51 and 0.16–1.7 mol cm–3 d–1, respectively.  相似文献   

6.
A total of 1344 manganese nodules and 187 pelagic sediments from 9 areas in the North and the South Pacific were analyzed for U by the delayed-neutron counting technique. A strong positive correlation between U and Fe in nodules and sediments suggests a co-precipitative removal from sea water into the Fe-rich ferromanganese mineral phase δ -MnO2. Enrichment of U and Fe in nodules from the northwestern slopes of two submarine hills (U between 6 and 9 ppm) in the equatorial nodule belt is thought to be caused by directional bottom water flow creating elevated oxygenized conditions in areas opposed to the flow. Economically important nodule deposits from the nodule belt and the Peru Basin have generally low U contents, between 3 and 5 ppm. Insignificant resources of U of about 4 × 105 in the Pacific manganese nodules are estimated.  相似文献   

7.
Under and climate conditions the chemical weathering of manganese ores is govermed by the fugacities of O2,CO2 and S2 in the atmosphere and soils.Manganese minerals exhibit solid phase transformations without migration of Fe and Mn.Under tropical and subtropical humid climate condi-tions low-valent Mn is instable and apt to be oxidized into high valency state.High-valent Mn miner-als are stable and easy to form secondary high-grade Mn ores.Secondary concentration is possible for Mn ores in carbonate formations,while those in clastic rocks tend to migrate and may be washed away.Such differences are the main obstacles in prospecting Mn ore deposits.  相似文献   

8.
在甘孜—理塘结合带内理塘县中木拉乡附近发现锰结核。通过地质填图和综合研究,该锰结核产于结合带内瓦能蛇绿混杂岩组中的黑色粉砂质板岩中。其沉积层序为玄武岩→硅质岩→含锰结核粉砂质板岩。锰结核主量元素具有高Mn、低Fe、Si、Ca的特点,其中Mn含量为42.19%,高出大洋锰结核平均值1.83倍,Mn/Fe值较高,达8.1。锰结核中除Cr高于大洋锰结核平均值2～7倍外,多数微量元素低于大洋锰结核平均值。稀土元素具有较明显的Ce正异常,稀土总量、轻重稀土分异程度、Eu异常特征与混杂岩中的砂岩、硅质岩近似,而与玄武岩差别较大。该锰结核产出于大陆边缘构造环境,火山活动微弱,代表甘孜—理塘洋扩张到最大程度时的沉积。其时甘孜—理塘洋规模仍是有限的。  相似文献   

9.
Manganese carbonate can be converted to many kinds of manganese oxides when it is aerated in air and oxygen.Pure manganese carbonate can be changed into Mn3O4 and γ-MnOOH,and manganese carbonate ore can be converted to MnO2 under the air-aerating and oxygen-aerating circumstances.The oxidation process of manganese carbonate is a changing process of mineral association,and is also a converting process of valence of manganese itself.Not only equilibrium stat,but also nonequilibrium state are involved in this whole process,This process is an irreversible heterogeneous complex reaction,and oberys the nonequilibrium thermodynamic model,The oxidation rate of manganese cabonate is controlled by many factors,especially nonmanganese metallic ions which play an important role in the oxidation process of manganese carbonate.  相似文献   

10.
The Mn contents and sedimentation rates of two cores from different areas of the Peru Basin have been determined. The southern core is associated with Mn nodules of conventional slow accretion rates (~ mm/106 yr) while the northern one accompanies nodules with very high growth rates (~102 mm/106 yr). The depletion of Mn observed within the top 40 cm of the cores is interpreted as resulting from a diagenetic remobilization of Mn+2 due to the oxidative characteristics of the sedimentary column. In both cores, the calculated flux of Mn provided by the sediment is higher than the total Mn recovered in the overlying nodules. This indicates that the Mn content of the Peru Basin nodules can be supplied by diagenetic processes from the sediment, not only for the slowly growing nodules but also for the extremely fast growing concretions found in the north of the basin.  相似文献   

11.
Supergene manganese oxides, occurring in shales, breccias and dolomites of Proterozoic Age, in the Western Australian Pilbara Manganese Group, have Mn/Fe ranging from 1.9 to 254 and Mn4+ to Mn (Total) of 0.49–0.94. The manganese mineralogy is dominated by tetravalent manganese oxides, especially by cryptomelane, with lesser amounts of pyrolusite, nsutite, manjiroite, romanechite and other manganese oxide minerals. The manganese minerals are commonly associated with iron oxides, chiefly goethite, indicating incomplete separation of Mn from Fe during Tertiary Age arid climate weathering of older, manganiferous formations. These manganese oxides also contain variable amounts of braunite and very minor hausmannite and bixbyite. The braunite occurs in three generations: sedimentary-diagenetic, recrystallised sedimentary-diagenetic, and supergene. The mode of origin of the hausmannite and bixbyite is uncertain but it is possible that they resulted from diagenesis and/or low-grade regional metamorphism. The supergene manganese deposits appear to have been derived from manganiferous Lower Proterozoic banded iron formations and dolomites of the Hamersley Basin and overlying Middle Proterozoic Bangemali Basin braunite-containing sediments.  相似文献   

12.
Fifty buried manganese nodules at different depth intervals were recovered in 12 sediment cores from the Central Indian Ocean Basin (CIOB). A maximum of 15 buried nodules were encountered in one sediment core (AAS-22/GC-07) and the deepest nodule was recovered at 5.50 m below seafloor in core AAS-04/GC-5A. Approximately 80% of the buried nodules are small in size (2 cm diameter) in contrast to the Atlantic Ocean and Peru Basin (Pacific Ocean) where the majority of the buried nodules are large, 8 cm and >6 cm, respectively. Buried nodule size decreases with core depth and this distribution appears to be similar to the phenomenon of “Brazil Nut Effect”. Buried nodules exhibit both smooth and rough surface textures and are ellipsoidal, elongated, rounded, sub rounded, irregular and polynucleated. Buried nodules from siliceous ooze are enriched in Mn, Cu, Ni, Zn, Mo, Ga, V and Rb whereas those from red clay are enriched in Fe, Co, Ti, U, Th, Y, Cr, Nb and Rare Earth Elements (REE). Buried nodules from siliceous ooze suggest their formation under hydrogenetic, early digenetic and diagenetic processes whereas those from red clay are of hydrogenetic origin.REE are enriched more than 1.5 times in buried nodules from red clay compared to siliceous ooze. However, the mode of incorporation of REE into buried nodules from both sedimentary environments is by a single authigenic phase consisting of Fe–Ti–P. Shale-normalized REE patterns and Ce anomalies suggest that nodules from siliceous ooze formed under more oxidizing conditions than those from red clay. Nodules buried at depths between 1.5 and 2.5 m are diagenetic (Mn/Fe ratio 10–15), formed in highly oxic environments (large positive Ce anomalies) and record aeolian dust (high Eu anomalies). Chemical composition, surface texture and morphology of buried nodules are similar to those of surface nodules from the same basin. Furthermore, buried nodule compositions do not exhibit any distinct patterns within the core depth, suggesting that buried nodules neither grow nor dissolve after their burial in the sediment column.  相似文献   

13.
The uptake of Ni and Co in the hydrous Mn oxide or the amorphous Fe-oxide phases of ferromanganese deposits in the oceans was studied by electron-microprobe analyses of 17 natural manganese nodules and by experiments on desorption-dissolution of these metals from synthetic Fe oxide or Mn oxides and natural nodule material. Ni was found to occur nearly always in the Mn-oxide phases of natural nodules, while Co occurs both in the Mn-oxide and Fe-oxide phases, with a slight preference for the latter. The solubility of Ni and Co (from coprecipitates of these metals with Fe hydroxides after aging) in seawater was found to depend strongly on the crystallinity of the host phase. The adsorption of Co by the synthetic Mn oxides from seawater was higher than that of Ni. The experimentally determined solubility of Ni and Co in seawater from natural nodule material is extremely low and matches the concentration range of these metals in ocean water.  相似文献   

14.
Horizons of several types of Upper Jurassic to Lower Cretaceous manganese nodules occur locally in sequences of radiolarian cherts within the Nicoya Ophiolite Complex (NW Costa Rica). Field studies, X-ray diffraction analysis, petrographic, chemical and experimental studies give evidence of a sedimentary, early diagenetic origin of the nodules, in contrast to earlier suggestions. Smooth, discoidal, compact and very dense nodules with diameters of some mm to 9 cm dominate. They are characterized by braunite, hollandite, pyrolusite and quartz as well as 39–61% Mn, 0.9–1.6% Fe, 5–26% SiO2, 1.3–1.9% A12O3, 1.5–3.0% Ba, 460–5400 ppm Cu, 85–340 ppm Ni and 40–130 ppm Co, among others. It is suggested that the original mineralogy (todorokite?) was altered during thermometamorphic (braunite) and hydrothermal (hollandite, pyrolusite) events. Petrographic similarities between the fossil nodules and modern deep-sea nodules are striking. Using standard hydrothermal techniques in an experimental study it is shown that under special conditions, braunite can be produced from modern nodule material.  相似文献   

15.

Arsenic (As), iron (Fe), and manganese (Mn) contents were measured in sediment nodules and associated pore waters obtained from sediment cores collected from a salt marsh on Pólvora Island (southern Brazil). Sediment cores were obtained when brackish water dominated the estuary, at two different environments: an unvegetated mudflat colonized by crabs (Neohelice granulata), and a low intertidal stand vegetated by Spartina alterniflora. We determined the percentage of nodules in each depth interval of the cores, along with redox potential, and As, Fe, and Mn contents of the nodules. The mineralogy of the nodules was investigated, and results showed they are mainly composed by quartz, phyllosilicates, and amorphous Fe–Mn oxides/oxyhydroxides. Pore water results showed that bioturbation by local crabs supports oxygen penetration to depths of ca. 25 cm below the salt marsh surface, with lower Fe contents in pore water associated with the brackish period. However, S. alterniflora growth appears to have a greater impact on sediment geochemistry of Fe, Mn, and possibly As due to sulfate reduction and the associated decrease in pore water pH. Higher Fe concentrations were observed in the pore waters during the period of brackish water dominance, which also corresponded to the S. alterniflora growth season. The study demonstrates that differences in geochemical conditions (e.g., Fe content) that can develop in salt marsh sediments owing to different types of bioirrigation processes (i.e., bioirrigation driven by crabs versus that related to the growth of S. alterniflora) play important roles in the biogeochemical cycling of As.

  相似文献   

16.
Manganese mineralisation in the Oakover Basin is associated with Mesoproterozoic extension, basin formation and deposition of the Manganese Group. The underlying basement architecture of the Oakover Basin (a local half-graben geometry), inherited from the Neoarchean rifting event, plays an important role on the distribution, style and timing of manganese deposits. Fault-hosted manganese deposits are dominant along the ‘active’ faulted eastern margin, whereas flat-lying sedimentary deposits are dominant along the western ‘passive’ margin reflecting differences in ore-forming processes. The large number of significant manganese deposits in the Oakover Basin, previously thought to reflect a spatial association with Carawine Dolomite, more likely reflects the restricted nature of the Mesoproterozoic basin and development of a large reservoir of Mn2+ and Fe2+ in an anoxic zone of a stratified basin. Low O2 conditions in the basin were caused by a paleotopographic high forming a barrier to open ocean circulation. The western margin sedimentary deposits formed later than the fault-hosted hydrothermal deposits along the eastern margin, once a significant reservoir of Mn2+ and Fe2+ had developed, and when there was sufficient subsidence to allow migration of the redox front onto the shallow shelf, with Mn precipitation on and within the seafloor sediments. The sedimentary manganese deposits are not uniformly distributed along the western edge of the basin; instead they are concentrated into discrete areas (e.g. Mt Cooke–Utah–Mt Rove, Bee Hill, Skull Springs and the Ripon Hills districts), suggesting a degree of structural control on their distribution. Fault-hosted manganese is observed beneath and adjacent to many of the sedimentary deposits. Marked geochemical differences are observed between the Woodie Woodie hydrothermal deposits and the sedimentary deposits. Woodie Woodie deposits display higher Ba, U, Mo, As, Sn, Bi, Pb, S and Cu than the sedimentary deposits, reflecting the composition of the hydrothermal fluids. The Al2O3 values of the Ripon Hills and Mt Cooke deposits are much higher than the Woodie Woodie deposits, reflecting the composition of the dominant host rock, as Al2O3 is typically <5 wt% in the Carawine Dolomite, but is >10 wt% in basal shale units of the Manganese Group. Highly variable Mn:Fe ratios (?5:1) in the hydrothermal manganese at Woodie Woodie reflects rapid deposition of Mn in and around fault zones. In contrast, slower accumulation of Mn oxides on and within the seafloor to form the large sedimentary deposits results in Mn:Fe ratios closer to 1:1 and elevated Co + Ni and REE values.  相似文献   

17.
Ferruginate shells and tubular worm burrows from the oxygenated zone of the Black Sea (Kalamit Bay and Danube River mouth) are studied using transmission and scanning electron microscopy combined with analyses of elemental composition. Iron and manganese hydroxide nodules considered here are enriched in phosphorus. They contain variable amounts of terrigenous and biogenic material derived from host sediments. The hydroxides are mainly characterized by colloform structure, whereas globular and crystalline structures are less common. The dominating iron phase is represented by ferroxyhite and protoferroxyhite, whereas the manganese phase is composed of Fe-free vernadite. Relative to sediments, concentrations of Mn, As, and Mo increase 12–18 times, while concentrations of Fe, P, Ni, and Co increase 5–7 times during the nodule formation.  相似文献   

18.
Thorium- and uranium isotopes were measured in a diagenetic manganese nodule from the Peru basin applying alpha- and thermal ionization mass spectrometry (TIMS). Alpha-counting of 62 samples was carried out with a depth resolution of 0.4 mm to gain a high-resolution230Thexcess profile. In addition, 17 samples were measured with TIMS to obtain precise isotope concentrations and isotope ratios. We got values of 0.06–0.59 ppb (230Th), 0.43–1.40 ppm (232Th), 0.09–0.49 ppb (234U) and 1.66–8.24 ppm (238U). The uranium activity ratio in the uppermost samples (1–6 mm) and in two further sections in the nodule at 12.5±1.0 mm and 27.3–33.5 mm comes close to the present ocean water value of 1.144±0.004. In two other sections of the nodule, this ratio is significantly higher, probably reflecting incorporation of diagenetic uranium. The upper 25 mm section of the Mn nodule shows a relatively smooth exponential decrease in the230Thexcess concentration (TIMS). The slope of the best fit yields a growth rate of 110 mm/Ma up to 24.5 mm depth. The section from 25 to 30.3 mm depth shows constant230Thexcess concentrations probably due to growth rates even faster than those in the top section of the nodule. From 33 to 50 mm depth, the growth rate is approximately 60 mm/Ma. Two layers in the nodule with distinct laminations (11–15 and 28–33 mm depth) probably formed during the transition from isotopic stage 8 to 7 and in stage 5e, respectively. The Mn/Fe ratio shows higher values during interglacials 5 and 7, and lower ones during glacials 4 and 6. A comparison of our data with data from adjacent sediment cores suggests (a) a variable supply of hydrothermal Mn to sediments and Mn nodules of the Peru basin or (b) suboxic conditions at the water sediment interface during periods with lower Mn/Fe ratios.  相似文献   

19.
Indicator role of trace elements in sedimentation and ore formation is considered for sediments from Station 2182 in the Angola Basin. It is shown that pelagic sediments were formed from two main sources: biogenic calcium carbonate and lithogenic sediment component compositionally similar to the miopelagic clay. Increase of the Mn/Al ratio, Ce anomaly in the REE composition, Co/Ni and Mo/W ratios, and anomalous accumulation of Tl, Pb, Bi and other microelements indicate that sediments from horizons 15–20 and 30–35 cm contain significant amounts of hydrogenic material as Fe-Mn oxyhydroxides. Manganese micronodules (MN) were extracted from different horizons (10–15, 15–20, and 30–35 cm) and analyzed to study the hydrogenic component. Their development is related to retardation of biogenic and lithogenic sedimentation. The studied manganese micronodules are represented by the hydrogenic-diagenetic formations >100 μm in size with Mn/Fe = 2.0–2.8, Co/Ni = 0.2–0.4, Ce an = 4.2–5.7, and Mo/W = 5.2–7.9. The MN content is too low to affect the major and trace element composition of sediments. The main part of Fe and Mn is confined to fraction <10 μm.  相似文献   

20.
Four cores of anoxic sediments were collected from the Seine estuary to assess the early diagenesis pathways leading to the formation of previously reactive phase. Pore waters were analyzed for dissolved iron (Fe) and manganese (Mn) and different ligands (e.g., sulfate, chloride, total inorganic carbon). The anoxic zone is present up to the first centimeter depth, in these conditions the reduction of Mn and Fe oxides and SO4 2− was verified. The sulfate reduction was well established with a subsequent carbon mineralization in the NORMAI94 core. The chemical speciation of Mn and Fe in the dissolved and solid phases was determined. For the dissolved phase, thermodynamic calculations were used to characterize and illustrate the importance of carbonate and phosphate phases as sinks for Fe and Mn. The ion activity product (IAP) of Fe and Mn species was compared to the solubility products (Ks) of these species. In the solid phase, the presence of higher concentration of calcium carbonate in the Seine sediments is an important factor controlling Mn cycle. The carbonate-bound Mn can reach more than 75% of the total concentration. This result is confirmed by the use of electron spin resonance (ESR) spectroscopy. The reduction of Fe is closely coupled to the sulfate reduction by the formation of new solid phases such as FeS and FeS2, which can be regarded as temporal sinks for sulfides. These forms were quantified in all cores as acid volatile sulfide (AVS: FeS+ free sulfide) and chromium reducible sulfide (CRS: FeS2+elemental sulfur S0).  相似文献   

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