Phase associations and potential selective extraction methods for selected high-tech metals from ferromanganese nodules and crusts with siderophores

Deep-sea ferromanganese deposits contain a wide range of economically important metals. Ferromanganese crusts and nodules represent an important future resource, since they not only contain base metals such as Mn, Ni, Co, Cu and Zn, but are also enriched in critical or rare high-technology elements such as Li, Mo, Nb, W, the rare earth elements and yttrium (REY). These metals could be extracted from nodules and crusts as a by-product to the base metal production. However, there are no proper separation techniques available that selectively extract certain metals out of the carrier phases. By sequential leaching, we demonstrated that, except for Li, which is present in an easily soluble form, all other high-tech metals enriched in ferromanganese nodules and crusts are largely associated with the Fe-oxyhydroxide phases and only to subordinate extents with Mn-oxide phases. Based on this fact, we conducted selective leaching experiments with the Fe-specific organic ligand desferrioxamine-B, a naturally occurring and ubiquitous siderophore. We showed by leaching of ferromanganese nodules and crusts with desferrioxamine-B that a significant and selective extraction of high-tech metals such as Li, Mo, Zr, Hf and Ta is possible, while other elements like Fe and the base metals Mn, Ni, Cu, Co and Zn are not extracted to large extents. The set of selectively extracted elements can be extended to Nb and W if Mn and carbonate phases are stripped from the bulk nodule or crust prior to the siderophore leach by e.g. a sequential leaching technique. This combination of sequential leaches with a siderophore leach enhanced the extraction to 30–50% of each Mo, Nb, W and Ta from a mixed type Clarion-Clipperton Zone (CCZ) nodule and 40–80% from a diagenetic Peru Basin nodule, whilst only 5–10% Fe and even less Mn are extracted from the nodules. Li is extracted to about 60% from the CCZ nodule and a maximum of 80% Li is extracted from the Peru Basin nodule.Our pilot work on selective extraction of high-tech metals from marine ferromanganese nodules and crusts showed that specific metal-binding organic ligands may have promising potential in future processing technologies of these oxide deposits.     

Tidal river sediments in the Washington,D.C. area. I. Distribution and sources of trace metals

Thirty-three bottom sediments were collected from the Potomac and Anacostia rivers, Tidal Basin, and Washington Ship Channel in June 1991 to define the extent of trace metal contamination and to elucidate source areas of sediment contaminants. In addition, twenty-three sediment samples were collected directly in front of and within major storm and combined sewers that discharge directly to these areas. Trace metals (e.g., Cu, Cr, Cd, Hg, Pb, and Zn) exhibited a wide range in values throughout the study area. Sediment concentrations of Pb ranged from 32.0 μg Pb g^?1 to 3,630 μg Pb g^?1, Cd from 0.24 μg Cd g^?1 to 4.1 μg Cd g^?1, and Hg from 0.13 μg Hg g^?1 to 9.2 μg Hg g^?1, with generally higher concentrations in either outfall or sewer sediments compared to river bottom-sediments. In the Anacostia River, concentration differences among sewer, outfall, and river sediments, along with downriver spatial trends in trace metals suggest that numerous storm and combined swers are major sources of trace metals. Similar results were observed in both the Tidal Basin and Washington Ship Channel. Cadminum and Pb concentrations are higher in specific sewers and outfalls, whereas the distribution of other metals suggests a more diffuse source to the rivers and basins of the area. Cadmium and Pb also exhibited the greatest enrichment throughout the study area, with peak values located in the Anacostia River, near the Washington Navy Yard. Enrichment factors decrease in the order: Cd>Pb>Zn>Hg>Cu>Cr. Between 70% and 96% of sediment-bound Pb and Cd was released from a N₂-purged IN HCl leach. On average, ≤40% of total sedimentary Cu was liberated, possibly due to the partial attack of organic components of the sediment. Sediments of the tidal freshwater portion of the Potomac estuary reflect a moderate to highly components area with substantial enrichments of sedimentary Pb, Cd, and Zn. The sediment phase that contains these metals indicates the potential mobility of the sediment-bound metals if they are reworked during either storm events or dredging.     

P204萃淋树脂反相萃取色谱分离富集光度法测定岩石矿物中痕量铍

研究了国产P204萃淋树脂反相萃取色谱分离富集岩石矿物中的痕量铍。在EDTA-Zn和H_2O_2存在下,上柱分离Fe、Ti、Al以及大量其它常见元素,再用5mol/L HCl洗脱Be后进行测定。方法用地质标准物质分析验证,其结果与推荐值吻合,对含Be为0.0092％的硅酸盐岩石样品进行7次平行分析,(?)=0.0091％,RSD=5.4％。     

Non-destructive alpha-spectrometry and radiochemical studies of deep-sea manganese nodules

A deep-sea Mn nodule handpicked from top of a 20 cm diameter North Pacific tripod core was directly counted by an α-spectrometer with a silicon surface barrier detector. A distinct ²¹⁰Po peak was recorded for the nodule upper side in contact with bottom seawater. Based on the spectrum, the ²¹⁰Po (supported by ²¹⁰Pb with 22 year half life) is thought to be confined in the top few microns of the nodule. Since the ²¹⁰Po peak diminishes considerably for the bottom side resting on sediment, nondestructive α-spectrometry is useful for determining the sea floor orientation of nodules. This method was tested for a western North Pacific dredged Mn nodule, and was successful in identifying the orientation (and also surface loss of the nodule by dredging).Radiochemical analysis was also carried out for carefully scraped samples from the top and bottom of the two nodules. The growth rates of the hand-picked nodule based on excess ²³⁰Th and ²³¹Pa profiles were 1 to 4 mm/10⁶ y and apparently varied with time. The dredged sample has grown at 2 to 6 mm/ 10⁶ y and the growth has likely been episodic. The radionuclide composition was significantly different between the top and bottom. Evidence was found that the radionuclide fluxes of ²³⁰Th and ²³¹Pa into the nodules considerably changed during the growing histories. The ²³⁰Th/²³²Th activity ratios in the nodule tops are comparable with those in bottom seawater suggesting that the top is growing with metals of seawater origin. However it remains unresolved whether the nodule bottoms are growing by utilizing metals in the sediment pore water.     

覆盖区勘查地球化学理论研究进展与案例

覆盖区勘查地球化学近年在迁移机理研究上最显著的进展是在矿体上方覆盖层土壤中直接观测到Cu、Au等纳米金属微粒和植物细胞中的成矿元素,从纳米尺度和分子水平直接观测到的微观迁移证据使得覆盖区勘查地球化学迁移机理研究从描述性模型向实证性模型实现了质的飞跃.通过对北方干旱沙漠覆盖区金矿、中部湿润农田覆盖区铜镍矿、南方植被红土覆盖区的铜金银矿研究表明,Cu、Au元素主要以纳米微粒形式穿透火山岩、变质岩和土壤覆盖层,用深穿透地球化学的微粒分离和铁锰氧化物提取技术可以有效指示隐伏矿体.干旱盆地砂岩型铀矿的研究表明,铀在氧化条件下以铀酰络阳离子(UO₂2+) 形式迁移到地表,并被土壤中粘土所吸附,吸附相中的铀占全部的铀比例最高(17%~40%),使用物理分离粘土或化学提取粘土吸附相铀可以有效地指示深部铀矿体.      

Removal of Lead,Copper, Zinc and Cadmium from Water Using Phosphate Rock

Removal of Pb^2＋, Cu^2＋, Zn^2＋ and Cd^2＋ from aqueous solutions by sorption on a natural phosphate rock （FAP） was investigated. The effects of the contact time and initial metal concentration were examined in the batch method. The percentage sorption of heavy metals from solution ranges generally between 50% and 99%. The amount of sorbed metal ions follows the order Cu〉Pb〉Cd〉Zn. Heavy metal immobilization was attributed to both surface complexation of metal ions on the surface of FAP grains and partial dissolution and precipitation of a heavy metal-containing phosphate. The very low desorption ratio of heavy metals further supports the effectiveness of FAP as an alternative and low-cost material to remove toxic Pb^2＋, Cu^2＋, Zn^2＋ and Cd^2＋ from polluted waters.     

Phosphorus speciation and availability in intertidal sediments of the Yangtze Estuary,China

In order to better understand P cycling and bioavailability in the intertidal system of the Yangtze Estuary, both surface (0–5 cm) and core (30 cm long) sediments were collected and sequentially extracted to analyze the solid-phase reservoirs of sedimentary P: loosely sorbed P; Fe-bound P; authigenic P; detrital P; and organic P. The total sedimentary P in surface and core sediments ranged from 14.58–36.81 μmol g⁻¹ and 17.11–24.55 μmol g⁻¹, respectively, and was dominated by inorganic P. The average percentage of each fraction of P in surface sediments followed the sequence: detrital P (54.9%) > Fe-bound P (23.7%) > organic P (14.3%) > authigenic P (6.3%) > loosely sorbed P (0.8%), whereas in core sediments it followed the sequence: detrital P (61.7%) > Fe-bound P (17.0%) > authigenic P (13.1%) > organic P (7.5%) > loosely sorbed P (0.7%). Post-depositional reorganization of P was observed in both surface and core sediments, converting organic P and Fe-bound P to authigenic P. The accumulation rates and burial efficiencies of the total P in the intertidal area ranged from 118.70–904.98 μmol cm⁻² a⁻¹ and 80.29–88.11%, respectively. High burial efficiency of the total P is likely related to the high percentage of detrital P and the high sediment accumulation rate. In addition, the bioavailable P represented a significant proportion of the sedimentary P pool, which on average accounted for 37.4% and 25.1% of the total P in surface and core sediments, respectively. This result indicates that the tidal sediment is a potential internal source of P for this P-limiting estuarine ecosystem.     

Characteristics of the tight sand reservoirs in the delta front in the Xu-2 Member of the Upper Triassic Xujiahe Formation (Hechuan area of the central Sichuan Basin,SW China)

The Xu-2 Member of the Upper Triassic Xujiahe Formation (Hechuan area, southwestern China) is an important potential sedimentary sequence for gas exploration in the central Sichuan Basin. Thus, we performed a comprehensive study of drilling parameters, sedimentary cores, well logging, and core test data and combined our results with previous research and the geological background of the basin. We found that the Hechuan area was a delta front that included underwater distributary channels, interchannels, and mouth and distal bars during deposition of the Xu-2 Member. The sand body genetic types were divided into three categories based on where they developed: an underwater distributary channel, a mouth bar, or a distal bar. The lithology of the Xu-2 reservoirs is mainly feldspathic litharenite, lithic arkose, subarkose, litharenite, and sublitharenite. Residual intergranular pores and intergranular dissolution pores are the major pore types in the reservoirs. Reservoirs with porosities of 0.18–15.84% and permeabilities of 0.001–8.72?×?10^?3 μm² showed a correlation coefficient of 0.7592. The reservoir throats are mainly tubular and constricted. Overall, the sedimentary environment and diagenesis are the major controlling factors for reservoir formation in the study area. The reservoir zones with relatively high porosity and permeability mainly developed in a delta front with underwater distributary channels and mouth bars. Chlorite growth preserved the primary pores during early diagenesis stage B, and intergranular dissolution pores resulted from contact with organic acids derived from source rocks during middle diagenesis stage A₁. Compaction and cementation significantly decreased porosity during middle diagenesis stage A₂. These important factors influenced reservoir quality.     

Zinc speciation in mining and smelter contaminated overbank sediments by EXAFS spectroscopy

Overbank sediments contaminated with metalliferous minerals are a source of toxic metals that pose risks to living organisms. The overbank sediments from the Geul river in Belgium contain 4000-69,000 mg/kg Zn as a result of mining and smelting activities, principally during the 19th century. Three main Zn species were identified by powder Zn K-edge EXAFS spectroscopy: smithsonite (ZnCO₃), tetrahedrally coordinated sorbed Zn (sorbed ^IVZn) and Zn-containing trioctahedral phyllosilicate. Smithsonite is a primary mineral, which accounts for approximately 20-60% of the Zn in sediments affected by mining and smelting of oxidized Zn ores (mostly carbonates and silicates). This species is almost absent in sediments affected by mining and smelting of both sulphidic (ZnS, PbS) and oxidized ores, presumably because of acidic dissolution associated with the oxidation of sulphides, as suggested by the lower pH of this second type of sediment (pH(CaCl₂) <7.0 vs. pH(CaCl₂) >7.0 for the first type). Thus, sulphide minerals in sediment deposits can act as a secondary source of dissolved metals by a chemical process analogous to acid mine drainage. The sorbed ^IVZn component ranges up to approximately 30%, with the highest proportion occurring at pH(CaCl₂) <7.0 as a result of the readsorption of dissolved Zn²⁺ on sediments constituents. Kerolite-like Zn-rich phyllosilicate is the major secondary species in all samples, and in some the only detected species, thus providing the first evidence for pervasive sequestration of Zn into this newly formed precipitate at the field scale.     

Rare earth elements and strontium isotopes of polymetallic nodules from southeastern Pacific Ocean

Rare earth element (REE) distributions and ⁸⁷Sr/⁸⁶Sr ratios were determined for nodule crusts and associated surface sediments collected in the southeastern Pacific Ocean between South America and the Tuamotu archipelago. The shale-normalized patterns of the REE from the surface sediments show pronounced negative anomalies in Ce which indicate a marine origin. One ⁸⁷Sr/⁸⁶Sr ratio also has a value characteristic for seawater strontium. REE patterns from the nodule crusts, when normalized to shales, seawater or associated surface sediment, show that a marine origin can also be proposed for the oxy-hydroxides. Only the Ce shows a systematic scatter, which could be the result of fluctuations in the oxidation-reduction conditions during nodule growth. The marine origin for REE is corroborated by the ⁸⁷Sr/⁸⁶Sr ratios which average 0 · 70905 ± 0 · 00019 (2σ), a value close to the seawater ⁸⁷Sr/⁸⁶Sr ratio of 0·70910 ± 0 · 00035. If the major metals of the polymetallic nodules have the same origin as these trace elements, then a direct precipitation from seawater can be postulated for the crusts studied here.     

Mn, Fe, Zn and As speciation in a fast-growing ferromanganese marine nodule

The speciation of Mn, Fe, As, and Zn in a fast-growing (0.02mm/yr), shallow-marine, ferromanganese nodule has been examined by micro X-ray fluorescence, micro X-ray diffraction, and micro X-ray absorption spectroscopy. This nodule exhibits alternating Fe-rich and Mn-rich layers reflecting redox variations in water chemistry. Fe occurs as two-line ferrihydrite. The As is strictly associated with Fe and is mostly pentavalent, with an environment similar to that of As sorbed on or coprecipitated with synthetic ferrihydrite. The Mn is in the form of turbostratic birnessite with ∼10% trivalent manganese in the layers and probably ∼8% corner-sharing metal octahedra in the interlayers. The Zn is enriched on the rim of the nodule, associated with Mn. The Zn is completely (>90%) tetrahedrally coordinated and sorbed in the interlayers of birnessite on vacant layer Mn sites. The Zn and Mn species are similar to ones found in soils, suggesting common structural principles despite the differing formation conditions in these systems.     

Ferromanganese nodules of the Baltic Sea: Composition,helium isotopes,and growth rate

Results of the study of shallow-water ferromanganese nodules in the Gulf of Finland of the Baltic Sea, which are of practical interest for metallurgical and chemical industries, are discussed. The nodules contain the following elements: Mn, Fe, Si, Al, Na, Mg, Ti, K, V, Cu, Ni, Zn, P, and Ba. Contents of Mn (～30%) and Fe (～10%) are virtually similar to those in deep-sea oceanic nodules. However, concentrations of Ti, Cu, and Ni are notably lower than average values in oceanic nodules. The helium isotopic composition was studied to reveal cosmic dust in the nodule substance. The measured ³He and ⁴He concentrations are ～10^?12 and ～10^?5 cm³/g, respectively. The isotope ratio ³He/⁴He is approximately 10^?7. More than 60% ³He is of cosmic (solar) origin, whereas ⁴He is of terrigenous (radiogenic) origin. Based on the cosmic duct concentration and the space tracer method, the FMN growth rate is estimated at 8–9 mm/ka at the nodule age varying from ～800 to 1500 yr. The growth rate of nodule has negative correlation with its size. Based on literature data, the growth rate of FMN from the western Baltic Sea is twice as high. An independent calculation of the FMN growth rate based on the diffusion-sorption mechanism (DSM) yielded 8.1 mm/ka, which is very close to the result based on the space tracer method. This value is proposed as the average growth rate of the studied nodules. Comparison with our previous measurements of growth rates for oceanic nodules showed that these values differ only slightly and are equal to n mm/ka, where n < 10. It is inferred that the formation mechanism of both marine and oceanic nodules is based on the same principles that control the generation of mobile forms of Mn in the bottom layer of sediments, i.e., principles related to bioproductivity of sea and ocean basins. Fluxes of lithogenic forms of Mn are of minor importance.     

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.     

Critical metals in manganese nodules from the Cook Islands EEZ,abundances and distributions

The Cook Islands (CIs) Exclusive Economic Zone (EEZ) encompasses 1,977,000 km² and includes the Penrhyn and Samoa basins abyssal plains where manganese nodules flourish due to the availability of prolific nucleus material, slow sedimentation rates, and strong bottom currents. A group of CIs nodules was analyzed for mineralogical and chemical composition, which include many critical metals not before analyzed for CIs nodules. These nodules have varying sizes and nuclei material; however all are composed predominantly of δ-MnO₂ and X-ray amorphous iron oxyhydroxide. The mineralogy, Fe/Mn ratios, rare earth element contents, and slow growth rates (mean 1.9 mm/10⁶ years) reflect formation primarily by hydrogenetic precipitation. The paucity of diagenetic input can be explained by low primary productivity at the surface and resultant low organic matter content in seafloor sediment, producing oxic seafloor and sub-seafloor environments. The nodules contain high mean contents of Co (0.41%), Ni (0.38%), Ti (1.20%), and total rare earth elements plus yttrium (REY; 0.167%), and also high contents of Mo, Nb, V, W, and Zr.Compiled data from a series of four cruises by the Japan International Cooperation Agency and the Mining agency of Japan from 1985 to 2000 were used to generate a map that defines the statistical distribution of nodule abundance throughout the EEZ, except the Manihiki Plateau. The abundance distribution map shows a belt of high nodule abundance (19–45 kg/m²) that starts in the southeast corner of the EEZ, runs northwest, and also bifurcates into a SW trending branch. Small, isolated areas contain abundances of nodules of up to 58 kg/m². Six ~ 20,000 km² areas of particularly high abundance were chosen to represent potential exploration areas, and maps for metal concentration were generated to visualize metal distribution and to extrapolate estimated metal tonnages within the six sites and the EEZ as a whole. Grades for Mn, Cu, and Ni are low in CIs nodules in areas of high abundance; however, Ti, Co, and REY show high contents where nodule abundances are high. Of the six areas identified to represent a range of metal contents, one at the northern end of the N-S abundance main belt optimizes the most metals and would yield the highest dry metric tons for Mn (61,002,292), Ni (1,247,834), Mo (186,166), V (356,247), W (30,215), and Zr (195,323). When compared with the Clarion–Clipperton Zone, the CIs nodules show higher nodule abundances (> 25 kg/m² over ~ 123,844 km²), and are more enriched in the green-tech, high-tech, and energy metals Co, Ti, Te, Nb, REY, Pt, and Zr. The CIs EEZ shows a significant resource potential for these critical metals due to their high prices, high demand, and the high nodule abundance, which will allow for a smaller footprint for a 20-year mine site and therefore smaller environmental impact.     

变质改造型关键金属矿——富集Li-Rb-Cs-Tl-Ga的云母片岩

关键金属矿产是国际上最近提出的资源概念,对战略性新兴产业的发展至关重要,但认知程度较低。洛扎岩浆-变质杂岩体位于喜马拉雅带东部,侵位于藏南拆离系内。在岩体东北侧,云母片岩被含电气石淡色花岗岩捕虏。云母片岩主要由金云母、绿泥石和少量黑云母组成。从全岩地球化学成分来看,云母片岩具有含量较高的Al₂O₃(13.38%～14.32%)、K₂O(6.09%～9.66%)、FeO^*(27.11%～30.09%)、MgO(15.25%～17.21%)、TiO₂(0.09%～0.26%),富集关键金属Li(650×10^-6～1 031×10^-6)、Rb(1 649×10^-6～2 773×10^-6)、Cs(98×10^-6～229×10^-6)、Tl(5.7×10^-6～12.1×10^-6)、Ga(121×10^-6     

Experimental study of the selective adsorption of heavy metals onto clay minerals

The interaction between minerals and heavy metals has been a hot object of study in environmental science,mineralogy and soil science,Through the selective adsorption experiment of Ca-montomorillonite,illite and kaolinite to Cu2 ,Pb^2 ,Zn^2 ,Cd^2 ,and Cr^3 ions at certain conditions,it could be concluded that Cr^3 is most effectively sorbed by all the three minerals.Also,it can be found that Pb^2 shows a strong affinity for illite and kaolinite while cu^2 for montmorillonite .Based on the adsorption experiment at varying pH of solution,it can be found that the amount of heavy etals sorbed by minerals increases with increasing pH of the solution.     

Interaction of organic compounds with calcium carbonate—III. Amino acid composition of sorbed layers

Nitrogenous organic compounds in sorbed surface layers and in calcified organic matter associated with calcium carbonate sediment particles consist of 40–50% amino acids, 2% amino sugars and 25% ammonia. In grain size classes > 20 μm these compounds are mainly contained in the calcified protein of carbonate secreting organisms but with smaller grain sizes—and consequently increased specific surface area—they are contained in sorbed layers at the mineral surface. The composition of the sorbed layer is characterized by a predominance of neutral amino acids, a relative enrichment of basic and weakly polar amino acids, and a deficiency of acidic amino acids in comparison with the proteinaceous matter of calcifying organisms. The respective abundances for sorbed and calcified matter are: 505 and 380 Res./ of neutral amino acids, 262 and 450 Res./1000 of acidic amino acids, 92 and 51 Res./l000 of basic amino acids, and 141 and 129 Res./1000 of weakly polar amino acids.The composition of the sorbed layer appears to be the result of sorption of proteinaceous matter from solution since it reflects the free and peptide-bound amino acid composition of seawater. The characteristic amino acid assemblage could also be the result of preferential decomposition of protein and subsequent enrichment of neutral and basic amino acids; however, sorption from solution appears more likely since the total amount of amino acids sorbed to calcium carbonate (0.58 mg m ^?2) corresponds closely to the amount of protein known to cover one m² of aqueous substrate in monolayer arrangement. Sorption from solution is further supported by the low arginine/ornithine ratios in both the sorbed layer and the natural dissolved organic matter. This process might lead to a characteristic amino acid spectrum in fine grained calcareous sediments that reflects the composition of the dissolved organic matter in seawater rather than that of the carbonate secreting proteinaceous matter.     

Natural speciation of Ni, Zn, Ba, and As in ferromanganese coatings on quartz using X-ray fluorescence, absorption, and diffraction

The mineralogy of natural ferromanganese coatings on quartz grains and the crystal chemistry of associated trace elements Ni, Zn, Ba, and As were characterized by X-ray microfluorescence, X-ray diffraction, and EXAFS spectroscopy. Fe is speciated as ferrihydrite and Mn as vernadite. The two oxides form alternating Fe- and Mn-rich layers that are irregularly distributed and not always continuous. Unlike naturally abundant Fe-vernadite, in which Fe and Mn are mixed at the nanoscale, the ferrihydrite and vernadite are physically segregated and the trace elements clearly partitioned at the microscopic scale. Vernadite consists of two populations of interstratified one-water layer (7 Å phyllomanganate) and two-water layer (10 Å phyllomanganate) crystallites. In one population, 7 Å layers dominate, and in the other 10 Å layers dominate. The three trace metals Ni, Zn, and Ba are associated with vernadite and the metalloid As with ferrihydrite. In vernadite, nickel is both substituted isomorphically for Mn in the manganese layer and sorbed at vacant Mn layer sites in the interlayer. The partitioning of Ni is pH-dependent, with a strong preference for the first site at circumneutral pH and for the second at acidic pH. Thus, the site occupancy of Ni in vernadite may be an indicator of marine vs. continental origin, and in the latter, of the acidity of streams, lakes, or soil pore waters in which the vernadite formed. Zinc is sorbed only in the interlayer at vacant Mn layer sites. It is fully tetrahedral at a Zn/Mn molar ratio of 0.0138, and partly octahedral at a Zn/Mn ratio of 0.1036 consistent with experimental studies showing that the ^VIZn/^IVZn ratio increases with Zn loading. Barium is sorbed in a slightly offset position above empty tetrahedral cavities in the interlayer. Arsenic tetrahedra are retained at the ferrihydrite surface by a bidentate-binuclear attachment to two adjacent iron octahedra, as commonly observed. Trace elements in ferromanganese precipitates are partitioned at a few, well-defined, crystallographic sites that have some elemental specificity, and thus selectivity. The relative diversity of sorption sites contrasts with the simplicity of the layer structure of vernadite, in which charge deficit arises only from Mn⁴⁺ vacancies (i.e., no Mn³⁺ for Mn⁴⁺ substitution). Therefore, sorption mechanisms primarily depend on physical and chemical properties of the sorbate and competition with other ions in solution, such as protons at low pH for Ni sorption.     

Mechanism of arsenic release to groundwater,Bangladesh and West Bengal

In some areas of Bangladesh and West Bengal, concentrations of As in groundwater exceed guide concentrations, set internationally and nationally at 10 to 50 μg l⁻¹ and may reach levels in the mg l⁻¹ range. The As derives from reductive dissolution of Fe oxyhydroxide and release of its sorbed As. The Fe oxyhydroxide exists in the aquifer as dispersed phases, such as coatings on sedimentary grains. Recalculated to pure FeOOH, As concentrations in this phase reach 517 ppm. Reduction of the Fe is driven by microbial metabolism of sedimentary organic matter, which is present in concentrations as high as 6% C. Arsenic released by oxidation of pyrite, as water levels are drawn down and air enters the aquifer, contributes negligibly to the problem of As pollution. Identification of the mechanism of As release to groundwater helps to provide a framework to guide the placement of new water wells so that they will have acceptable concentrations of As.     

Iron and Trace Metals in Microbial Mats and Underlying Sediments: Results From Guerrero Negro Saltern, Baja California Sur, Mexico

Total trace metals (Cd, Co, Cu, Fe, Mn, Ni, Pb, Zn), Al, and pyrite- and reactive-associated metals were measured for the first time in a microbial mat and its underlying anoxic-sulfidic sediment collected in the saltern of Guerrero Negro (GN), Baja California Sur, Mexico. It is postulated that the formation of acid volatile sulfide (AVS) and pyrite in the area of GN could be limited by the availability of reactive Fe, as suggested by its limited abundance (mat and sediment combined average value of only 19 ± 10 ??mol g^?1; n = 22) as well as the low pyrite (0.89?C7.9 ??mol g^?1) and AVS (0.19?C21 ??mol g^?1) concentrations (for anoxic-sulfidic sediments), intermediate degrees of pyritization (12?C50%), high degrees of sulfidization (14?C100%), generally low degrees of trace metal pyritization, and slight impoverishment in total Fe. This is a surprising result considering the large potential reservoir of available Fe in the surrounding desert. Our findings suggest that pyrite formation in the cycling of trace metals in the saltern of GN is not very important and that other sedimentary phases (e.g., organic matter, carbonates) may be more important reservoirs of trace elements. Enrichment factors [EF_Me = (Me/Al)_sample/(Me/Al)_background] of Co, Pb, and Cd were high in the mat (EF_Me = 2.2 ± 0.4, 2.8 ± 1.6 and 34.5 ± 9.8, respectively) and even higher in the underlying sediment (EF_Me = 4.7 ± 1.5, 14.5 ± 6.2 and 89 ± 27, respectively), but Fe was slightly impoverished (average EF_Fe of 0.49 ± 0.13 and 0.50 ± 0.27 in both mat and sediment). Organic carbon to pyrite-sulfur (C/S) molar ratios measured in the mat (2.9 × 10²?C27 × 10²) and sediment (0.81 × 10²?C6.6 × 10²) were, on average, approximately 77 times higher than those typically found in marine sediments (7.5 ± 2.1). These results may indicate that ancient evaporation basins or hypersaline sedimentary environments could be identified on the basis of extremely high C/S ratios (e.g., >100) and low reactive Fe.