Transport and sediment–water partitioning of trace metals in acid mine drainage: an example from the abandoned Kwangyang Au–Ag mine area, South Korea

Transport and sediment–water partitioning of trace metals (Cr, Co, Fe, Pb, Cu, Ni, Zn, Cd) in acid mine drainage were studied in two creeks in the Kwangyang Au–Ag mine area, southern part of Korea. Chemical analysis of stream waters and the weak acid (0.1 N HCl) extraction, strong acid (HF–HNO₃–HClO₄) extraction, and sequential extraction of stream sediments were performed. Heavy metal pollution of sediments was higher in Chonam-ri creek than in Sagok-ri creek, because there is a larger source of base metal sulfides in the ores and waste dump upstream of Chonam-ri creek. The sediment–water distribution coefficients (K _d) for metals in both creeks were dependent on the water pH and decreased in the order Pb ≈ Al > Cu > Mn > Zn > Co > Ni ≈ Cd. K _d values for Al, Cu and Zn were very sensitive to changes in pH. The results of sequential extraction indicated that among non-residual fractions, Fe–Mn oxides are most important for retaining trace metals in the sediments. Therefore, the precipitation of Fe(–Mn) oxides due to pH increase in downstream sites plays an important role in regulating the concentrations of dissolved trace metals in both creeks. For Al, Co, Cu, Mn, Pb and Zn, the metal concentrations determined by 0.1 N HCl extraction (Korean Standard Method for Soil Pollution) were almost identical to the cumulative concentrations determined for the first three weakly-bound fractions (exchangeable + bound to carbonates + bound to Fe–Mn oxides) in the sequential extraction procedure. This suggests that 0.1 N HCl extraction can be effectively used to assess the environmentally available and/or bioavailable forms of trace metals in natural stream sediments.     

Distribution and immobilization of heavy metals in Pliocene aquifer sediments in Wadi El Natrun depression, Western Desert

The Pliocene aquifer receives inflow of Miocene and Pleistocene aquifer waters in Wadi El Natrun depression. The aquifer also receives inflow from the agricultural activity and septic tanks. Nine sediment samples were collected from the Pliocene aquifer in Wadi E1 Natrun. Heavy metal (Cu, Sr, Zn, Mn, Fe, Al, Ba, Cr, Ni, V, Cd, Co, Mo, and Pb) concentrations of Pliocene aquifer sediments were investigated in bulk, sand, and mud fractions. The determination of extractable trace metals (Cu, Zn, Fe, Mn, and Pb) in Pliocene aquifer sediments using sequential extraction procedure (four steps) has been performed in order to study environmental pathways (e.g., mobility of metals, bounding states). These employ a series of successively stronger chemical leaching reagents which nominally target the different compositional fractions. By analyzing the liquid leachates and the residual solid components, it is possible to determine not only the type and concentration of metals retained in each phase but also their potential ecological significance. Cu, Sr, Zn, Mn, Fe, and Al concentrations are higher in finer sediments than in coarser sediments, while Ba, Cr, Ni, V, Cd, Co, Mo, and Pb are enriched in the coarser fraction. The differences in relative concentrations are attributed to intense anthropogenic inputs from different sources. Heavy metal concentrations are higher than global average concentrations in sandstone, USEPA guidelines, and other local and international aquifer sediments. The order of trace elements in the bulk Pliocene aquifer sediments, from high to low concentrations, is Fe?>?Al?>?Mn?>?Cr?>?Zn?>?Cu?>?Ni?>?V?>?Sr?>?Ba?>?Pb?>?Mo?>?Cd?>?Co. The Pliocene aquifer sediments are highly contaminated for most toxic metals, except Pb and Co which have moderate contamination. The active soluble (F0) and exchangeable (F1) phases are represented by high concentrations of Cu, Zn, Fe, and Mn and relatively higher concentrations of Pb and Cd. This may be due to the increase of silt and clay fractions (mud) in sediments, which act as an adsorbent, retaining metals through ion exchange and other processes. The order of mobility of heavy metals in this phase is found to be Pb?>?Cd?>?Zn?>?Cu?>?Fe?>?Mn. The values of the active phase of most heavy metals are relatively high, indicating that Pliocene sediments are potentially a major sink for heavy metals characterized by high mobility and bioavailability. Fe–Mn oxyhydroxide phase is the most important fraction among labile fractions and represents 22% for Cd, 20% for Fe, 11% for Zn, 8% for Cu, 5% for Pb, and 3% for Mn. The organic matter-bound fraction contains 80% of Mn, 72% of Cu, 68% of Zn, 60% of Fe, 35% of Pb, and 30% of Cd (as mean). Summarizing the sequential extraction, a very good immobilization of the heavy metals by the organic matter-bound fraction is followed by the carbonate-exchangeable-bound fraction. The mobility of the Cd metal in the active and Fe–Mn oxyhydroxide phases is the highest, while the Mn metal had the lowest mobility.     

Contamination assessment and health risk of heavy metals in dust from Changqing industrial park of Baoji,NW China

The contents of Co, Cr, Cu, Mn, Ni, Pb and Zn in the dust samples collected from Changqing industrial park of Baoji city, NW China, were measured by XRF, while As and Hg in the dust samples were analyzed by AFS. Geo-accumulation index (I _geo), pollution index (PI) and integrated pollution index (IPI) were calculated to evaluate the heavy metal contamination level of dust. The health risk due to exposure to heavy metals in dust was analyzed by the Health Risk Assessment Model of US EPA. The results show that the arithmetic means of As, Co, Cr, Cu, Hg, Mn, Ni, Pb and Zn are 23.3, 16.4, 1591.8, 178.2, 0.243, 346.5, 40.2, 1,586.2 and 1,918.8 mg kg^?1, respectively, which are higher than the background values of Shaanxi soil, especially for Cr, Cu, Hg, Pb, and Zn. The mean values of I _geo reveal the order of Pb > Zn > Cr > Hg > Cu > As > Co > Ni > Mn. The high I _geo of Cr, Cu, Hg, Pb and Zn in dust indicates that there is considerable pollution from Cr, Cu, Hg, Pb and Zn, while the low I _geo of As, Co, Mn and Ni presents no pollution in dust. The assessment results of PI support the results of I _geo, and IPI indicates heavy metals in dust polluted seriously. The health risk assessment shows that ingestion of dust particles is the route for exposure to heavy metals from dust, followed by dermal adsorption. Exposure to As, Cr and Pb from dust may pose a potential health threat to children and adults. The risk of cancer from As, Co, Cr and Ni due to dust exposure is low.     

Mineralogy of manganese oxides from Groote Eylandt

The manganese ores on Groote Eylandt occur in a flat-lying horizon in a series of Lower Cretaceous sands and clays which overly unconformably the Middle Proterozoic sandstone basement. The ore horizon exhibits a variety of textural and compositional ore types. Textural types include pisolites and concretions, either free or cemented into massive, bouldery or pebbly horizons. Compositional variations result from varying degrees of admixture of the manganese materials with the sands and clays of the formation. — The ore minerals are pyrolusite and cryptomelane, with minor amounts of lithiophorite, psilomelane, nsutite and todorokite. Gangue minerals include kaolinite, quartz and goethite. — Mineralogical studies indicate that three microtypes of cryptomelane occur. Low levels of cobalt, nickel and zinc in certain of the ore types are associated with the mineral lithiophorite.     

Natural speciation of Mn, Ni, and Zn at the micrometer scale in a clayey paddy soil using X-ray fluorescence, absorption, and diffraction

The natural speciation of Mn (0.19 g/kg), Ni (46 mg/kg), and Zn (42 mg/kg) in the argillic horizon (120 cm depth, pH = 5.6) of an Ultisol from a paddy soil in northern Taiwan was investigated by advanced X-ray synchrotron techniques. Microchemical associations were imaged by synchrotron-based X-ray microfluorescence, host minerals were identified by standard and micrometer-resolved X-ray diffraction, and the local coordination environment of Mn, Ni, and Zn was probed using extended X-ray absorption fine structure (EXAFS) spectroscopy on a powdered sample and a soil thin section, and polarized EXAFS spectroscopy on a highly textured self-supporting clay film from the <2 μm fraction of the soil. Manganese was concentrated in Fe-Mn soft mottles (44.4 g/kg) as turbostratic hexagonal birnessite and lithiophorite having Mn³⁺/Mn⁴⁺ atomic ratios of ∼20% and 50%, respectively. Quantitative analysis of high-order scattering paths of the EXAFS spectrum for natural and synthetic lithiophorite revealed that Mn³⁺ and Mn⁴⁺ are ordered in the layer. A structural model is proposed, in which Mn⁴⁺ and Mn³⁺ are ordered similarly to Al and Li in the layer, with Mn³⁺ cations being surrounded by six Mn⁴⁺, and Mn⁴⁺ cations by three Mn³⁺ and three Mn⁴⁺. Similar cation ordering in the manganese and aluminum layers likely provides a more homogeneous local balance of the excess and deficit of charges in each layer and increases the stability of lithiophorite. Ni (r = 0.70 Å) substitutes for Mn (r(Mn⁴⁺) = 0.54 Å, r(Mn³⁺) = 0.65 Å) in the manganese layer in the natural lithiophorite. In contrast, Zn (r = 0.74 Å) fills vacant sites in the gibbsitic layer of natural lithiophorite, in a similar manner as lithium (r = 0.74 Å) in synthetic lithiophorite. The partitioning of Ni and Zn between the two layers is a result of the general preference of Ni, whose size is intermediate between those of Mn³⁺ and Li⁺, for slightly smaller sites. In contrast with nickel, which is detected only where there is lithiophorite, the Zn-lithiophorite association found in Fe-Mn mottles is not representative of the bulk soil. The combined use of X-ray diffraction, and powder and polarized EXAFS spectroscopy revealed that Zn is predominantly bound to hydroxy-Al interlayers sandwiched between 2:1 vermiculite layers in the fine soil matrix. The incorporation of Zn in the gibbsitic layer of both lithiophorite and vermiculite helps increase the stability of these minerals by providing positive charge to balance the negative charge from the 2:1 phyllosilicate layer and the layer of lithiophorite. This binding environment for zinc is probably the main mechanism by which zinc is sequestered in acidic to near-neutral aluminum-rich clayey soils.     

Sorption of metals on humic acid

The sorption on humic acid (HA) of metals from an aqueous solution containing Hg(II). Fe(III), Pb, Cu, Al, Ni, Cr(III), Cd, Zn, Co and Mn, was investigated with special emphasis on effects of pH, metal concentration and HA concentration. The sorption efficiency tended to increase with rise in pH, decrease in metal concentration and increase in HA concentration of the equilibrating solution. At pH 2.4. the order of sorption was: Hg? Fe? Pb? CuAl ? Ni ? CrZnCdCoMn. At pH 3.7. the order was: Hg and Fe were always most readily removed, while Co and Mn were sorbed least readily. There were indications of competition for active sites (CO₂H and phenolic OH groups) on the HA between the different metals. We were unable to find correlations between the affinities of the eleven metals to sorb on HA and their atomic weights, atomic numbers, valencies, and crystal and hydrated ionic radii. The sorption of the eleven metals on the HA could be described by the equation $\text{Y =}\text{100}\text{[1 + exp ? (A + BX)]}$, where Y = % metal removed by HA; X = mgHA; and A and B are empirical constants.     

Partitioning of divalent transition elements between octahedral sheets of trioctahedral smectites and water

Using trioctahedral smectites synthesized at low temperature (25 and 75°C). partition coefficients have been determined for M²⁺ transition metals (Mn, Fe, Co, Ni, Cu, Zn) between octahedral sheets of smectites and water. These coefficients D_(M²⁺?Mg) = (M²⁺)/(Mg) solid/(M²⁺)/(Mg) liquid have high values near 10⁴ for Cu, 1000 for Ni, Co, Zn, 300 for Fe and 30 for Mn. All transition metals are strongly stabilized in the magnesian solid phase, even Mn which leads to noncrystallized products. Within the range of experimental uncertainties, it is found that tetrahedral substitution of Si by Al and differences in temperature (from 25 to 75°C) have no influence on partition coefficients. Experimental data are closely related to thermodynamic properties of the cations and on this basis other partition coefficients can be calculated, for the (M²⁺ ? Fe²⁺) pair for instance. The behaviour of transition metals is explained using crystal field theory.     

Crystal chemistry of cobalt and nickel in lithiophorite and asbolane from New Caledonia

The crystal chemistry of Ni- and Co-bearing manganese oxides (lithiophorite and asbolane) has been investigated by X-ray Absorption Spectroscopy (XAS). The Mn oxides come from the lateritic weathering profiles of the ultrabasites of New Caledonia. The distinct behaviours of Ni and Co concern both oxidation states and local structures.The electronic structure and short range order around Co atoms do not depend on the nature of the Cocontaining phase. Co atoms are trivalent and 6-fold coordinated. Co-(O, OH) and Co-(Co, Mn) interatomic distances derived from EXAFS are equal to those found around Mn atoms which rules out the possibility of an adsorption of Co atoms directly above and below vacancies of MnO₂ layers. The high structural order around Co contrasts with the structural disorder observed around Mn. Cobalt atoms do not occupy specific Mn sites and are not randomly distributed within the octahedral Mn layers.Unlike Co, Ni exhibits distinct surroundings in both phases. In asbolane, Ni atoms build partial Ni(OH)₂ layers. Ni-OH distances are lower as compared with the free Ni hydroxide because of the formation of hydrogen bonds between Ni(OH)₂ and MnO₂ layers. In lithiophorite Ni atoms are located in the hydrargillite layer (Al(OH)₃). Both chemical composition and structural considerations militate for a Ni for Li substitution in lithiophorite. Finally, evidence is given for the existence of a mixed-layering between lithiophorite and asbolane and the chemical variations generally observed in these Mn oxides are interpreted as a variable proportion of (Mn, Co)(O, OH₂, Ni(OH)₂ and (Al, Li, Ni)(OH)₃ layers.     

Multivariate statistical techniques for evaluating and identifying the environmental significance of heavy metal contamination in sediments of the Yangtze River, China

The concentrations of heavy metals (Cr, Co, Ni, Cu, Zn, Pb, Cd, As, Hg, and Fe) in sediments of the Yangtze River, China, were investigated to evaluate levels of contamination and their potential sources. The lowest heavy metal concentrations were found in the source regions of the river basin. Relatively high concentrations of metals, except Cr, were found in the Sichuan Basin, and the highest concentrations were in the Xiangjiang and Shun’anhe rivers. All concentrations, except Ni, were higher than global averages. Principal component analysis and hierarchical cluster analysis showed that Zn, Pb, As, Hg, and Cd were derived mainly from the exploitation of various multi-metal minerals, industrial wastewater, and domestic sewage. Cu, Co, and Fe were derived mainly from natural weathering (erosion). Cr and Ni were derived mainly from agricultural activities, municipal and industrial wastewater. Sediment pollution was assessed using the geoaccumulation index (I _geo) and enrichment factor (EF). Among the ten heavy metals assessed, Cd and Pb had the highest I _geo values, followed by Cu, As, Zn, and Hg. The I _geo values of Fe, Cr, Co, and Ni were <0 in all sediments. EF provided similar information to I _geo: no enrichment was found for Cr, Co, and Ni. Cu, Zn, As, and Hg were relatively enriched at some sites while Cd and Pb showed significant enrichment.     

Experimental modeling of the immobilization of heavy metals at the carbonate adsorption–precipitation geochemical barrier

Experimental data obtained on the adsorption–precipitation immobilization of heavy metals (Cu, Zn, Pb, Cd, Co, and Ni) from acidic and neutral solutions by calcite and dolomite demonstrate that interaction of solutions of heavy metals with these minerals at pH > 7.8–8.1 leads to a significant decrease in the concentrations of the metals because of the crystallization of carbonates of these metals. Except Pb, which is equally removed from solutions by both minerals, the immobilization efficiency of the metals on dolomite is greater than on calculate at the same pH. Residual Zn, Cd, Co, and Ni concentrations are immobilized by chemosorption, which is the most efficient for Cd and less significant for Co, Ni, and Zn. It is proved that artificial geochemical barriers on the basis of carbonate rocks can be efficiently applied to protect environment from contamination with heavy metals.     

Mineralogy,composition and heavy metals’ concentration,distribution and source identification of surface sediments from the saline Maharlou Lake (Fars Province,Iran)

This study concerns the mineralogy, spatial distribution and sources of nine heavy metals in surface sediments of the Maharlou saline lake, close to the Shiraz metropolis in southern Iran. The sources for these sediments were studied by comparing the mineralogy and the distribution of heavy metals, using multivariate statistical analysis (correlation analysis and principal component analysis). The geochemical indices, including geo-accumulation index (Igeo), contamination factor (CF) and pollution load index (PLI), were used to assess the degree of heavy metal contamination in surface sediments. Sediment quality guidelines (SQGs) have also been applied to assess its toxicity. The XRD analysis shows that the main minerals of the surface sediments are aragonite, calcite, halite and quartz, with small amounts of montmorillonite, dolomite and sepiolite. The total heavy metal contents in surface sediments decrease in order of Sr?>?Ni?>?Cr?>?Zn?>?Cu?>?Co?>?Pb?>?As >?Cd and the average concentrations of Sr, Ni and As exceeded more than 10, 5 and 3 times, respectively, by comparing with the normalized upper continental crust (UCC) values. The results of pollution indices (Igeo, CF and PLI) revealed that strontium (Sr), nickel (Ni) and arsenic (As) were significantly enriched in those sediments. Based on the sediment quality guidelines (SQGs), Ni would infrequently cause toxicity. Multivariate statistical analysis indicated that the Ni, Co and Cr came mainly from natural geological background sources, while Cd, Cu, Pb, and Zn were derived from urban effluents (especially traffic emissions) and As originated from agriculture activities. Significant relationships of Sr with S, CaO and MgO in sediments suggest that Sr was derived from carbonate- and gypsum-bearing catchment source host rocks.     

Environmental contamination of trace elements in the vicinity of Okpara coal mine, Enugu, Southeastern Nigeria

Water, sediment, and mine spoil samples were collected within the vicinity of the Okpara coal mine in Enugu, Southeastern Nigeria, and analyzed for trace elements using ICP-MS to assess the level of environmental contamination by these elements. The results obtained show that the mine spoils and sediments are relatively enriched in Fe, with mean values of 1,307.8(mg/kg) for mine spoils and 94.15% for sediments. As, Cd, Cr, Mn,Ni, Pb, and Zn in the sediments were found to be enriched relative to the mean values obtained from the study area, showing contamination by these elements. The mean values of Fe, Mn, Cu, and Cr in the mine spoils and mean values of Fe, Cu, Pb, Zn, Ni, Cr, and Mn in sediments, respectively, are above the background values obtained from coal and shale in the study area, indicating enrichment with these elements. The water and sediments are moderately acidic, with mean pH values of 4.22?±?1.06 and 4.66?±?1.35, respectively. With the exception of Fe, Mn, and Ni, all other elements are within the Nigerian water quality standard and WHO limits for drinking water and other domestic purposes. The strong to moderate positive correlation between Fe and Cu (r?=?0.72), Fe and Zn (r?=?0.88), and Fe and As (r?=?0.60) at p?<?0.05 as obtained for the sediments depict the scavenging effect of Fe on these mobile elements. As also shows a strong positive correlation with Mn (r?=?≥ 0.70, p?<?0.05), indicating that Mn plays a major role in scavenging elements that are not co-precipitated with Fe. In water, the strong positive correlation observed between Cr and Cd (r?=?1.00), Cu and Ni (r?=?0.94), Pb and Cu (r?=?0.87) and Zn and Cu (r?=?0.99); Ni and Pb (r?=?0.83) and Zn and Ni (r?=?0.97); and between Pb and Zn (0.84) at p?<?0.05 may indicate similar element–water reaction control on the system due to similarities in chemical properties as well as a common source. Elevated levels of heavy metals in sediments relative to surface water probably imply that sorption and co-precipitation on Al and Fe oxides are more effective in the mobilization and attenuation of heavy metals in the mine area than acid-induced dissolution. The level of concentration of trace elements for the mine spoils will serve as baseline data for future reference in the study area.     

Comparison between non-residual Al,Co, Cu,Fe, Mn,Ni, Pb and Zn released by a three-step sequential extraction procedure and a dilute hydrochloric acid leach for soil and road deposited sediment

Surprisingly little is known about the relationship between the labile phases removed by sequential extraction procedures and those liberated by single leaches that minimally impact the alumino-silicate matrix of solids. This investigation examines the relationship between the summed concentrations of Al, Co, Cu, Fe, Mn, Ni, Pb and Zn released by an optimized 3-step standardized sequential extraction procedure and those released by a single 0.5 M HCl leach. Thirty-nine representative soil and road deposited sediment samples were examined from an urban watershed, in Honolulu, Hawaii, which has been shown to have a high degree of traffic-associated pollution. Properties of samples analyzed varied widely and exhibited a range in cation exchange capacities from 7 to 59 cmol_c/kg, pH values from 3.5 to 7.9, and organic C contents from 1 to 29%. Results indicate that the dilute HCl leach was slightly more aggressive than the sequential procedure as it removed significantly more Al, Cu, Fe, Mn and Ni; though no significant differences were observed between Co, Pb and Zn concentrations liberated by the two approaches. Both approaches showed limited dissolution of the crystal lattice with ⩽9% of the total Al liberated. Regardless of approach, element mobility was the same with the order being: Pb>Mn>Zn>Co≈Cu>Ni>Fe ∼ Al. Regression analysis indicated highly significant (P<0.0001) logarithmic relationships between the two digestion procedures, with coefficients of determination (r²) ⩾92% for all elements except Fe (54%) and Ni (64%). Further support for the strong relationships between elements liberated by both digestions was gained from geochemical contrasts between anomalous and background levels and concentration enrichment ratios. This was particularly true for Pb and Zn, the most anthropogenically enhanced trace metals in the watershed. All data indicated that a dilute HCl leach was a valuable, rapid, and cost-effective analytical tool in contamination assessment.     

Rate of deposition and quality of sedimentation dust in Al Ain and Ras Al Khaimah, United Arab Emirates

This study presents data on the mineralogy and the metal content of dust deposited in Al Ain and Ras Al Khaimah, United Arab Emirates. The mineralogical compositions of the dust were determined using X-ray diffraction, and the results revealed that quartz is the dominant mineral, whereas calcite, dolomite, plagioclase, and serpentine were minor minerals. Two sampling sites were chosen from both Al Ain and Ras Al Khaimah. The concentrations of Fe, Zn, Cu, Cr, Pb, Cd, Ni, and Co in the sedimentation dusts samples of these sites were determined using inductively coupled plasma. The levels of most of heavy metal were generally below those determined in the other cities in the Middle East. The air enrichment factors for all the samples were analyzed, and the results indicated that Cd, Zn, Co, and Ni were highly enriched relative to their crustal ratios (to Fe) and correspond to substantial contribution of anthropogenic source of these metals. These metals mainly originate from the traffic emissions and industrial activities with contribution from natural sources. The average rates of deposition in Al Ain and Ras Al Khaimah were 193 and 972 mg m^?2 day^?1, respectively. These rates were higher than those of other regions.     

Distribution and speciation of heavy metals in surface sediments from the Yangtze estuary and coastal areas

The concentrations and speciation of heavy metals (As, Cd, Cr, Cu, Hg, Ni, Pb and Zn) in the sediments of the nearshore area, river channel and coastal zones of the Yangtze estuary, China, were systematically investigated in this study. The concentrations of all heavy metals except Ni in the sediments of the nearshore area were higher than those of the river channel and coastal zones. In the nearshore area, the concentrations of most heavy metals except Hg in the sediments of the southern branch were higher than those of the northern branch because of the import of pollutants from the urban and industrial activities around. When compared with the threshold effect level (TEL) and geochemical background levels, Cr, Ni and As accumulated and posed potential adverse biological effects. The speciation analysis suggested that Cd, Pb and Zn in the sediments of the three zones showed higher bioavailability than the other heavy metals, and thus posed ecological risk. Significant correlations were observed among Cr, Cu, Ni and Zn (r > 0.77) in the nearshore area, Ni, Cu, Zn and Pb (r > 0.85) in the river channel and Ni, Cu, Cr, Pb and Zn (r > 0.75) in the coastal zone. Principal component analysis (PCA) indicated that the discharge of unban and industrial sewage, shipping pollution and the properties of the sediments (contents of Fe, Mn, Al, TOC, clay and silt) dominated the distribution of heavy metal in the nearshore area, river channel and coastal zones of the Yangtze estuary.     

Petrography,mineralogy and geochemistry of the Late Eocene oolitic ironstones of the Jebel Ank,Southern Tunisian Atlas

The oolitic ironstones ore deposit of Jebel Ank (central Tunisia), is a simply folded stratiform ore body of about 2.5–8 m thickness located in the upper part of the epicontinental Souar Formation (Late Eocene) and is covered by the continental Segui Formation (Mio-Pliocene). The deposit contains about 20 Mt of ore with an average grade of 50% Fe. Generally, oolitic iron deposition occurs in shallow water lagoonal environments. The Jebel Ank deposit lies between two regional disconformities (Late Eocene and Miocene), and is evidence of a transitional stage at the end of regional regression before renewed transgression. The footwall of the oolitic iron ore-bearing bed consists of a fine-grained sandstone bed (10–20 cm-thick) pinching out laterally westward into green clays. The hanging wall is composed of thin-bedded limestone and clay alternations (2–3.5 m-thick).Iron occurs in the form of cryptocrystalline goethite with limited Al-Fe substitution. The goethite contains around 48% Fe, 5% Al and up to 1.5% P. Jarosite, alunite and manganese minerals (cryptomelane, psilomelane and manjiorite) are supergene secondary minerals, probably related to descending surface fluids. These manganese minerals occur as accessory minerals with the goethite and are most abundant at the lowermost part of the succession showing varied morphologies (local cement, space filling and free centimeter sized nodules). Fe-oolites in the deposit are similar to those documented in many other oolitic ironstone deposits. The dominant Fe-oolite type (>90%) has a concentrically laminated cortex with no nucleus. The nuclei of the oolites that do have a nucleus are most commonly detrital quartz grains.Major elements in high grade samples (Fe₂O₃ > 65%) vary within a limited range and show higher concentrations of SiO₂ (average 7.85%) and Al₂O₃ (average 5.1%), with minor TiO₂, MnO, MgO, Na₂O, K₂O, and SO₃ (less than 1%). PAAS-normalized trace elements of bulk samples and Fe-oolite generally show similar behavior, both are enriched in V, Co, Ni, Mo, As, Zn, and Y and are depleted in Cu, Rb, Zr, Nb, Ba, and Hf. Anomalous V, Cr, Ni, Zn, and REE-Y are correlated with goethite. PAAS-normalized REE-Y patterns of both bulk samples and Fe-oolite show slight HREE enrichment, positive Ce with negative Y anomalies.The mineralogy (goethite and cryptomelane) along with the geochemistry (Si vs. Al; As + Cu + Mo + Pb + V + Zn vs. Ni + Co binary plots; Zn–Ni–Co triangular diagram, REE-Y content and patterns and Ce/Ce¹ vs. Nd and Ce/Ce¹ vs. Y_N/Ho_N binary plots) of the studied oolitic ironstone are congruent with a hydrogenetic type. While two possible sources of iron for Jebel Ank ironstone can be proposed: (i) submarine weathering of glauconite-rich sandstone and (ii) detrital iron from adjacent continental hinterland, the later is the more plausible source of iron, based on paleogeographic setting, the occurrence of fine sandstone underlying the iron level, occurrence of Mn-ores in the lower part of the Fe-ores succession, high phosphorous, zinc, ∑REE-Y concentrations and Y/Ho ratios, and low La/Ce ratios.     

The Occurrence of Sc,Co and Ni in Manganese Ore from Western China

China’s manganese resources are usually associated with the valuable elements such as silver, lead, zinc, cobalt, nickel, scandium, etc which should be comprehensively recovered during the manganese beneficiation. A manganese ore from western China contains Mn 23.18%, Co 0.073%, Ni 0.21% and Sc 0.013%. The mineralogy composition of ore and the occurrence of associated elements of Sc, Co as well as Ni are studied in this paper. According to the results, the manganese minerals in this ore are mainly lithiophorite and a little secondary pyrolusite. The lithiophorite in this ore is rich in aluminum and actually it is the generic name for the multi-mineral aggregates mixed by silicon, aluminum and iron, which is quite different with the ordinary psilomelane. There is not any Sc, Ni or Co mineral in this ore and more than 98% of Sc, Ni and Ni exists in lithiophorite and pyrolusite. The distribution of Sc, Co and Ni in lithiophorite is further studied by EPMA and the results indicate that Sc and Co in lithiophorite is sparse and dispersed distribution while Ni usually distributes in the argillaceous lithiophorite and is local enrichment. Reduction-sulfuric acid leaching tests show that the dissolution of Sc and Co happens before lithiophorite dissolves; the dissolution rate of Sc and Co is almost the same, which is significantly higher than the dissolution rate of manganese. However, the dissolution rate of Ni is extremely low with the dissolution of manganse, which indicates that Ni is hard to dissolve and its dissolution rate obviously lags behind that of Mn, Sc and Co. The conclusion can be drawn that Sc and Co exist in the lithiophorite crystals as interface adsorption while Ni exists in the clay (kaolinite) mixed up with lithiophorite as interface adsorption. The conclusion indicates that Sc and Co can dissolve before the dissolution of manganese at a high dissolution rate in the hydrometallurgical process while Ni is also into the solution through desorption from the interface of clay but its dissolution rate is rather slow because of the insoluble nature of clay.     

Manganese ore deposits in Koira-Noamundi province of Iron Ore Group, north Orissa, India: In the light of geochemical signature

Several small Mn–Fe oxide and Mn-oxide ore bodies associated with Precambrian Iron Ore Group of rocks are located within Koira-Noamundi province of north Orissa, India. These deposits are classified into in situ (stratiform), remobilized (stratabound) and reworked categories based on their field disposition. Volcaniclastic/terrigenous shale in large geographic extension is associated with these ore bodies.The in situ ore bodies are characterised by cryptomelane-, romanechite- and hematite-dominating minerals, low Mn/Fe ratio (1.1) and relatively lower abundance of trace (1500–2500 ppm) constituents. In such type of deposits the stratigraphic conformity of oxides with the tuffaceous shale suggests precipitation of Mn and Fe at a time of decreased volcaniclastic/terrigenous contribution. The minor and trace elements were removed from solution by adsorption rather than by precipitation. Both Mn and Fe oxides when precipitated adsorb trace elements strongly but the partitioning of elements takes place during diagenesis. The inter-elemental relationship reveals that Cu, Co, Ni, Pb and Zn were adsorbed on precipitating hydrous Mn oxides and form manganates. Some of these elements probably get desorbed from Fe oxide because of their inability to substitute for Fe³⁺ in the lattice of its oxide. However, P, V, As and Mo were less partitioned and retained in Fe-oxide phase. Positive correlation between Al₂O₃ and SiO₂, MgO, Na₂O, TiO₂ and some traces like Li, Nb, Sc, Y, Zr, Th and U points to their contribution through volcaniclastic/terrigenous detritus of both mafic and acidic composition.The remobilized ore bodies are developed in a later stage through dissolution, remobilization and reprecipitation of Mn oxides in favorable structural weak planes under supergene environment. Increase in average Mn/Fe ratio (8) and trace content (5000–8500 ppm) by 5–2.5 orders of magnitude, respectively, or more above its abundance in adjoining/underlying protore is characteristic of these deposits. The newly formed Mn ores constituting lithiophorite, cryptomelane/romanechite and goethite get quantitatively enriched in traces like Cu, Co, Ni, Pb and Zn. Positive correlation between Mn, Li, Co and Zn is due to the formation of mineral of lithiophorite–chalcophanite group during redistribution and reconcentration of Mn oxide. P and V, which were present in Fe oxide, also get dissolved and reprecipitate with Fe oxyhydroxide in these ores. Some other elements like Y, Th and U show positive relation with Fe. This is probably due to leaching of these elements during chemical weathering of associated shale and getting re-adsorbed in Fe-oxyhydroxide phase.However, under oxidizing environment selective cations like Ba, K, etc. resorb from Mn-structure, resulting in the development of pyrolusite (Mn/Fe>20). In such transformation, trace metals from pyrolusitic structure expels out, resulting thereby in a considerable reduction in total trace value (<3000 ppm).The reworked ore bodies are allochthonous in nature and developed through a number of stages during terrain evolution and lateritisation. Secondary processes such as reworking of pre-existing crust; solution and remobilization; precipitation and cementation and transport, etc. are responsible for their development. Such deposits are usually very low in Mn/Fe ratio (3) and trace content (<2000 ppm).     

Major ion chemistry and metal distribution in coal mine pit lake contaminated with industrial effluents: constraints of weathering and anthropogenic inputs

Ion chemistry of mine pit lake water reveals dominance of alkaline earths (Ca²⁺ and Mg²⁺) over total cation strength, while SO₄ ^2? and Cl^? constitute the majority of total anion load. Higher value of Ca²⁺?+?Mg²⁺/Na⁺?+?K⁺ (pre-monsoon 5.986, monsoon 8.866, post-monsoon 7.09) and Ca²⁺?+?Mg²⁺/HCO₃ ^??+?SO ₄ ² (pre-monsoon 7.14, monsoon 9.57, post-monsoon 8.29) is explained by weathering of Ca?CMg silicates and dissolution of Ca²⁺-bearing minerals present in parent rocks and overburden materials. Silicate weathering supposed to be the major geological contributor, in contrast to bicarbonate weathering does a little. Distribution coefficient for dissolved metals and sorbed to surface sediments is in the order of Cd?>?Pb?>?Fe?>?Zn?>?Cu?>?Cr?>?Mn. Speciation study of monitored metals in surface sediments shows that Fe and Mn are dominantly fractionated in exchangeable-acid reducible form, whereas rest of the metals (Cr, Pb, Cd, Zn, and Cu) mostly in residual form. Cd, Pb, and Zn show relatively higher recalcitrant factor that indicates their higher retention in lake sediments. Factor loading of monitored physico-chemical parameters resembles contribution/influences from geological weathering, anthropogenic inputs as well as natural temporal factors. Ionic load/strength of lake water accounted for geochemical process and natural factors, while pollutant load (viz BOD, COD and metals, etc.) is associated with anthropogenic inputs through industrial discharge.     

Metal geochemical and mineral magnetic characterization of the <2.5 μm fraction of urban soils in Xuzhou (China)

The concentrations of metals (Pb, Cu, Zn, Co, Ni, Fe and Mn) in the <2.5 μm fraction of surface soils (0–5 cm) from highly industrialized areas in Xuzhou (China) were determined. All analyzed metals with the exception of Mn and Co in the present study showed elevated concentrations in the <2.5 μm fraction of soils compared to background concentrations, particularly for Zn. Metal enrichment was positively correlated with carbonate complexation constants (but not bulk solubility products) as well as the first stability constants of metal-citrate, likely suggesting that both metal–organic complexation and/or precipitation of carbonate surfaces that subsequently adsorb metals are likely responsible for these metal enrichment on these samples. Sequential extraction analysis shows the metals Pb, Cu, Zn, Co and Mn were largely associated with the reducible fraction, whereas Ni was largely associated with the oxidisable fraction. Manganese is the only metal showing significant association with the exchangeable fraction (up to 33 %), suggesting that it may be the most susceptible metal to mobilization. Mineral magnetic analysis indicates that ferrimagnetic SSD + SP (stable single domain + superparamagnetic) minerals dominated the <2.5 μm fraction of Xuzhou surface soils. Lead, Cu and Zn were found to show significant correlations with χlf (p < 0.01), suggesting that magnetic technique might be beneficially used as a rapid and inexpensive method to estimate these metal contaminations in the <2.5 μm fraction of surface soils.