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1.
Deeply buried Mississippi Valley-type deposits that have been or are currently being mined in North America were initially discovered by drilling. Conventional geochemical methods are ineffective for detecting these ‘blind' deposits when they occur deep within sequences of stable-platform carbonates and shales. The ‘enzyme' leach is a selective analytical technique for determining trace elements associated with amorphous Mn oxide coatings in soils. In many areas of the world, the enzyme leach method is useful for detecting low-level geochemical anomalies in soils, which are associated with blind mineral deposits. Enzyme leach analysis of soils, collected at the Elmwood Mine, Tennessee, revealed high-contrast anomalies over ore bodies 370 m below the surface. In areas where the soils are in chemical equilibrium, ‘combination' anomalies occur over Zn ore bodies. These are characterized by asymmetrical halogen halos which occur around a halogen ‘central low'. Commodity metals (Zn and Pb) and trace elements associated with the ore (Cd, Ba, and Mn) form apical anomalies, which occur over the ore bodies and within the halogen halo. Under most circumstances, agricultural practices do not affect enzyme leach results. However, agricultural activity in central Tennessee appears to have altered the proportion of amorphous Mn oxides in the soils in some locations. Where the MnO2-form equilibrium of the soil has been disturbed, enzyme leach data are erratic. In the one instance where this was encountered, ratioing the data to Mn reveals anomalies which bracket the blind ore bodies.  相似文献   

2.
Organic-rich stream sediments, a widely used material in geochemical prospecting in Finland, were investigated by analyzing Mn, Fe, Co, Ni, Cu and Zn after a series of selective extractions.Forty-seven organic-rich stream-sediment samples were collected in the vicinity of a sulphide mineralization in Talvivaara, eastern Finland. Loss on ignition of the samples at 500°C was 20–95%. pH of the samples, measured in the water pressed from the samples, was 3.4–6.2 with a mean of 4.2.The < 0.5 mm grain-size fraction was subjected to a sequential extraction as follows: NH4-acetate for exchangeable cations; cold NH2OH·HCl for dissolution of Mn oxides; H2O2 for destruction of organic material; hot NH2OH·HCl for dissolution of Fe oxides; HF/HClO4/aqua regia for dissolving the residue. Each extraction was analyzed by flame AAS for Mn, Fe, Co, Ni, Cu and Zn.Manganese and Co are mostly in exchangeable form and in the residue, while the proportion complexed by the organic components is minimal. Iron and Ni own a lot of exchangeable character although a significant proportion of these elements is complexed by the organic components. Most of Cu is in organic form. Zinc is the element most evenly distributed between extractions.  相似文献   

3.
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   

4.
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).  相似文献   

5.
Manganese nodules and manganese carbonate concretions occur in the upper 10–15 cm of the Recent sediments of Loch Fyne, Argyllshire in water depths of 180–200 m. The nodules are spherical, a few mm to 3 cm in diameter, and consist of a black, Mn-rich core and a thin, red, Fe-rich rim. The carbonate occurs as irregular concretions, 0.5–8 cm in size, and as a cement in irregular nodule and shell fragment aggregates. It partially replaces some nodule material and clastic silicate inclusions, but does not affect aragonitic and calcitic shell fragments.The nodules are approximately 75% pure oxides and contain 30% Mn and 4% Fe. In the cores, the principal mineral phase is todorokite, with a Mn/Fe ratio of 17. The rim consists of X-ray amorphous Fe and Mn oxides with a Mn/Fe ratio of 0.66. The cores are enriched, relative to Al, in K, Ba, Co, Mo, Ni and Sr while the rims contain more P, Ti, As, Pb, Y and Zn.The manganese carbonate has the composition (Mn47.7 Ca45.1 Mg7.2) CO3. Apart from Cu, all minor elements are excluded from significant substitution in the carbonate lattice.Manganese nodules and carbonates form diagenetically within the Recent sediments of Loch Fyne. This accounts for the high Mn/Fe ratios in the oxide phases and the abundance of manganese carbonate concretions. Mn concentrations in the interstitial waters of sediment cores are high (ca. 10 ppm) as also, by inference, are the dissolved carbonate concentrations.  相似文献   

6.
《Applied Geochemistry》2004,19(6):973-979
The association of rare earth and other trace elements with Fe and Mn oxides was studied in Fe-Mn-nodules from a lateritic soil from Serra do Navio (Northern Brazil). Two improved methods of selective dissolution by hydroxylamine hydrochloride and acidified hydrogen peroxide along with a classical Na–citrate–bicarbonate–dithionite method were used. The two former reagents were used to dissolve Mn oxides without significant dissolution of Fe oxides, and the latter reagent was used to dissolve both Mn and Fe oxides. Soil nodules and matrix were separated by hand. Inductively coupled plasma atomic emission spectrometry and inductively coupled plasma mass spectrometry after fusion with lithium metaborate, and X-ray diffraction were used to determine the elemental and mineralogical composition of the nodules and soil matrix. The latter was composed of kaolinite, gibbsite, goethite, hematite, and quartz. In the nodules, lithiophorite LiAl2(MnIV2MnIII)O6(OH)6 was detected in addition to the above-mentioned minerals. The presence of hollandite (BaMn8O16) and/or coronadite (PbMn8O16) in the nodules is also possible. In comparison to the matrix, the nodules were enriched in Mn, Fe, K, and P, and relatively poor in Si, Al, and Ti. The nodules were also enriched in all trace elements determined. Phosphorus, As and Cr were associated mainly with Fe oxides; Cu, Ni, and V were associated with both Fe and Mn oxides; and Ba, Co, and Pb were associated mainly with Mn oxides. Distribution of rare earth elements indicated a strong positive Ce-anomaly in the nodules, compared to the absence of any anomaly in the matrix. Some of Ce was associated with Mn oxides. The improved methods achieved almost complete release of Mn from the sample without decreasing the selectivity of dissolution, i.e., without dissolving significant amounts of Fe oxides and other minerals, and provided reliable information on associations of trace elements with Mn oxides. These methods are thus proposed to be included in sequential extraction schemes for fractionation of trace elements in soils and sediments.  相似文献   

7.
A total of 64 sediment samples were collected along a stretch of about 988 km of the Trans-Amazonian Federal Highway, between Marabá and Itaituba, Pará State, in order to characterize the distribution of metals and trace elements. Due to the lithological and geological diversity along this stretch of the Amazon, the study region was divided in three distinct tracks. Statistical data analysis (Spearman correlation and Principal Factor Analysis) shows strong signature and predominance of regional rocks chemistry, such as mafic-ultramafic-bearing elements (Ni and Cr) and hydrothermalism-bearing elements such as Cu and Pb. Enrichment factors were calculated for three different normalizer agents: 1) Fe and Mn, representing the Fe and Mn (hydr)oxides, 2) Al representing clay minerals, and 3) organic matter (OM). The Fe and Mn (hydr)oxides showed to be the most proficient metal carrier among the geological matrices, likely due to the larger lithological diversity. On the other hand, OM positively correlated to trace element distribution.  相似文献   

8.
This paper describes a research program to determine if a geochemical signature is retained in surface and sub-surface soils over a well-contained underground nuclear explosion. Samples of soil at surface and about 10–15 cm below were collected on orthogonal traverses up to about 1 km from ground zero (GZ, surface projection of blast point) at three locations in central (Ville) and southern Yucca Flat (Laredo and Presidio) on the Nevada Test Site (NTS). They were analyzed for total element content by instrumental neutron activation (INAA) and, using selective leaches, for partial element content, namely that amount bound to amorphous Fe oxyhydroxide and that amount bound to Mn oxide. Forty-two elements were determined in these leaches of both surface and sub-surface soils, by inductively coupled plasma mass spectrometry (ICP-MS), ICP emission spectrometry (ICP-ES) and hydride generation quartz tube atomic absorption spectrometry (HG-QTAAS). These partial leaches were chosen on the premise that the extreme temperature and pressure conditions created by an underground blast would volatilize elements in the surrounding rock and transport them along with fission products to the surface where they would be trapped by these phases in the soil. The INAA data generally show consistent concentrations of major, minor and trace elements within each location. In contrast, the selective leach data show distinct geochemical anomalies in numerous elements. Iodine, As, Mo, and U demonstrate particularly consistent positive anomalies at and around GZ at all three locations by both leaches. The amplitudes of these anomalies can exceed two orders of magnitude over background, particularly for I. This positive response is shown by more elements associated with Mn oxide than associated with Fe oxyhydroxide at all three locations; furthermore these patterns are more coherent and intense for some elements. The Mn oxide phase itself is more consistently distributed than is the Fe oxyhydroxide phase at the sites within each location. In most cases, significant depletion of Fe as amorphous Fe oxyhydroxide coincides with the multiple positive anomalies in this phase. The number and group of elements displaying distinct patterns is dependent upon the location as well as on the leach. The concentration ranges of elements extracted from the Fe oxyhydroxide or Mn oxide phase are similar for sites at Laredo and Presidio but dissimilar from those at Ville, probably a reflection of the differing geological settings. Whereas some anomalies are spatially quite compact, extending only about 50 m from GZ (e.g. Rb, Cs, Th), others such as I and Sb extend up to 300 m. The geochemical behaviour of the surface soil samples, although slightly noisier, is similar to that of the sub-surface suite. These results indicate that analysis of specific geochemical phases in soils over a suspected underground nuclear test has an important role in the on-site inspection component of the verification of the Comprehensive Test Ban Treaty.  相似文献   

9.
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.  相似文献   

10.
Results of the study of contents and accumulation rates of Fe, Mn, and a number of trace elements in Upper Quaternary sediments of the Deryugin Basin are presented. Maps of the average contents and accumulation rates of excess Fe, Mn, Zn, Ba, Ni, Pb, Cu, and Mo in sediments of the first oxygen isotope stage (OIS) have been plotted. Anomalous contents and accumulation rates are confined to peripheral zones of the Deryugin sedimentary basin and large fracture zones. Different mechanisms of the influence of fluid-dynamic processes on the rate of hydrogenic and biogenic accumulation of ore elements are assumed.Translated from Litologiya i Poleznye Iskopaemye, No. 2, 2005, pp. 115–132.Original Russian Text Copyright © 2005 by Astakhov, Gorbarenko, Bakhareva, Gretskaya, Sattarova.  相似文献   

11.
In order to determine the metal-bearing phases with special emphasis on Cu, a sequential extraction has been carried out on seven soil samples from a sulphide-bearing spodosol profile in Liikavaara Östra, close to the Aitik Copper Mine in northern Sweden. A reference spodosol profile with very low abundances of sulphides located far from anthropogenic emissions was also studied. Five fractions were selected for the extraction: (I) CH3COONa-extractable (exchangeable/adsorbed/carbonate); (II) Na4P2O7-extractable (labile organics); (III) 0.25 M NH2OH·HCl-extractable (amorphous Fe oxyhydroxides/Mn oxides); (IV) 1 M NH2OH·HCl-extractable (crystalline Fe oxides); and (V) KClO3/HCl-extractable (organics and sulphides). The distribution of trace elements (Co, Cr, Cu, Ni, Pb and Zn) in the profile in Liikavaara Östra is different from that in the reference profile. Possible explanations for these differences are (i) the presence of sulphides in the soil, (ii) atmospheric deposition of dust derived from mining activities at the Aitik Copper Mine, and (iii) mineralogical heterogeneities inherited from the deposition of the till. There is no straightforward correlation between the amount of the extracted phases and the metal extractability in the soils. This fact indicates that other factors are important for the retention of trace metals as well. The data presented in this study suggest that Co, Cr and Ni, to a fairly large extent, are associated with the organic matter in the B-horizon in both profiles, while in the C-horizon in Liikavaara Östra, sulphides are probably the more important carriers of these elements. For Co and Ni, Fe oxyhydroxides seem to be important. Most of the Cr occurred in the residual remaining after the leaching procedure. Copper and Zn seem to be associated with the organic matter to some extent in the B-horizon. The concentration of Cu in the C-horizon in Liikavaara Östra is high (2310 ppm), but only a very small fraction is likely to be hosted by sulphides. It is concluded that the major part of Cu in the C-horizon and a prominent fraction in the B-horizon in Liikavaara Östra are associated with some secondary phase that is extractable during extractions III and IV. Possible candidates for this phase are goethite and inclusions of native Cu in weathered biotite.  相似文献   

12.
The behaviour of trace elements (Al, As, Cd, Co, Cr,Cu, Fe, Mn, Ni, V, Zn) was studied in five humus-richstreams (dissolved organic carbon = 14–40 mg/L)impacted by acid sulphate soils developed in marinesulphide-bearing fine-grained sediments. During heavyrainfalls in autumn, on which the study focusses, themetals Al, Cd, Co, Cu, Mn, Ni and Zn are extensivelyleached from these acidic soils (pH = 2.5–4.5), whileAs, Cr, Fe and V are not leached more strongly fromthis soil type than from areas of till and peat. Aspeciation experiment, based on anion and cationexchange of the stream waters in the field, showedthat (1) the metals Al, Cd, Co, Mn, Ni and Zn aretransported in the streams mainly as inorganiccations, (2) Cu exists mainly in cationic form but isalso to a significant extent associated with dissolvedhumic substances, (3) Fe occurs mainly in the anionicfraction explained by organic coating on colloidal Feoxyhydoxides and (4) the hydrochemistry of As, Cr andV is complex as these elements may exist in severalunquantified anionic fractions and to a minor extentin cationic species/forms. Whereas the proportion ofacid sulphate soils in the catchments had a largeimpact on concentrations levels of several elements inthe stream waters, these soils did not have a largeaffect on the speciation of elements in water.  相似文献   

13.
The Cr and Ni contents are high in the Eocene lignite of the Shenbei coalfield, which is a small intracontinental basin located in Liaoning Province, China. In this paper, we studied the distribution, origin and occurrence of Cr, Ni and other hazardous trace elements in the Shenbei lignite on the basis of coal petrology, and geochemistry of the lignite and combustion products. The following conclusions on the Shenbei lignite can be drawn: (1) The dominant maceral group in the Shenbei coal is huminite (humodetrinite), accounting for 96%–99% of the total maceral. Inertinite content is less than 1%. Liptinite content (sporinite and cutinite) is 0.2–1.6%. Common minerals in the Shenbei lignite include clay minerals (kaolinite), pyrite and quartz, and calcite and siderite. Chromite is not present in the lignite. (2) Potentially hazardous trace elements such as Co (22 μg/g), Cr (79 μg/g), Cu (63 μg/g), Zn (93 μg/g), V (88 μg/g) and Ni (75 μg/g) are strongly enriched in the Shenbei lignite compared with average concentration of trace elements in the Chinese coal and worldwide lignite. These elements are mainly associated with fulvic acid (FA) and/or coal organic macromolecular compounds in most of the studied lignite samples, indicating an organic association and enrichment of these elements in the Shenbei lignite. (3) Unusually high trace elements contents in the Shenbei lignite are derived mainly from the olivine basalt (country rock of coal basin) that consists of 52.7% plagioclase, 17.8% pyroxene, 14% olivine and 15.5% Ti–Fe oxide minerals. These olivine basalts have higher Cr, Ni, Pb and Zn contents than other types of rock and worldwide basalts do. (4) Fly ash of the Shenbei lignite, with 90% 1–50 μm amorphous particles and 8% 1–10 μm cenosphere, has high contents of Zn (23,707 μg/g), Be (12 μg/g), Sr (1574 μg/g), Pb (486 μg/g) and Cr (349 μg/g). In particular, the ferruginous micro-cenoshperes contain 1–12.79% Zn. Fine bottom ash (<0.031mm) of the Shenbei lignite has higher contents for most of the elements with the exception of Mo, Sn and Zn. Therefore, the potentially environmental and health impact of the fly ash and fine bottom ash should constitute a major concern.  相似文献   

14.
Incubation studies were carried out using 5 freshly collected sediments from shallow aquifers of the Hetao Basin, Inner Mongolia. The aquifer sediments covering a range of redox conditions, as indicated by their deep grey to yellow color were mixed with degassed artificial As solution or degassed deionized water at a ratio of solid to water of about 1:10 (wt./wt.). Suspensions which were either amended with glucose or autoclaved, were incubated in parallel with unamended suspensions. Five microcosm cultures of unamended sediments gradually release the equivalent of 0.03–0.30 μg/g As to the dissolved phase. The addition of glucose as a potential electron donor results in a marked stimulation in the mobilization of As (0.71–3.81 μg/g) in the amended incubations for all sediments. The quantity of As released accounts for 60–70% of As bound to Fe/Mn oxides in the original sediments. The microbially mediated mobilization of As with the organic nutrient as an electron donor is strongly associated with the As bound to Fe/Mn oxides, as well as the exchangeable As. During the incubations amended with glucose, 2–4% of the sediment Fe is released. The results suggest that the introduction of labile dissolved organic C into the yellowish sediment aquifers with As-free groundwater would reduce a significant proportion of the Fe(III) oxyhydroxides mediated by anaerobic bacteria respiration and increase groundwater As concentrations.  相似文献   

15.
Thirty-nine elements in humus and till matrix were compared at 109 sites overlying Ag–As–Cu–Mo–Pb–Zn mineralized occurrences in northeastern New Brunswick to assess humus for anomaly identification. Humus element concentrations were not consistently correlative with maximum or minimum concentrations found in the underlying till or bedrock. The humus demonstrated significantly higher mean elemental concentrations than the till for six specific elements: 9 times greater for Mn, 6 times greater for Cd, 5 times greater for Ag and Pb, 3 times greater for Hg, and double the concentration of Zn. Spatial dispersal patterns for these elements were much larger for humus content than that exhibited by the till matrix analysis, but did not delineate a point source. For elements in till, the highest concentrations were commonly found directly overlying the underlying mineralized bedrock source or within one km down-glacier of the source.The complexity of the humus geochemical patterns is attributed to the effects of post-glacial biogenic, down-slope hydrodynamic and solifluction modification of dispersed mineralization in the underlying till, and the greater capacity of humus to adsorb cations and form complexes with some elements, relative to the till matrix. Humus sampling in areas of glaciated terrain is considered to be mostly valuable for reconnaissance exploration as elements can be spatially dispersed over a much larger area than that found in the till or underlying bedrock.  相似文献   

16.
The Abrud–Arieş river system, western Romania, is subject to ongoing mining activity associated with Cu, Pb and Zn ore extraction. The catchment contains what is believed to be Europe's largest unutilized Au deposit at Roşia Montană that is planned to be exploited by open-cast mining techniques. The magnitude and environmental significance of metal (Cd, Cu, Pb, and Zn) concentrations in surface water and river channel sediment have been investigated along a 140 km reach of the Rivers Abrud and Arieş and 9 tributaries affected by mining. The speciation of sediment-bound metals was established using a 4-stage sequential extraction procedure (SEP) that identified four chemical phases: (1) exchangeable, (2) Fe/Mn oxides, (3) organic matter/sulphides and (4) residual. Peak solute and sediment-bound metal concentrations were found to occur in the River Abrud downstream of the EM Bucium mine and in mining-affected tributaries, with up to 71% of sites containing sediment metal concentrations in excess of Dutch intervention values. The River Arieş was found to be much less polluted than the River Abrud, with only Cu showing concentrations above guideline values, as a consequence of porphyry Cu mineralization in the catchment. The magnitude and spatial extent of metal pollution is influenced by local physico-chemical conditions and hydrological linkages between mining and local river systems. Sediment-bound Cd and Zn were found to be predominantly associated with the exchangeable phase of the sediment (9–74% and 6–65%, respectively), whilst Fe/Mn oxides (5–76%) and organic matter/sulphides (1–45%) generally accounted for a majority of Pb and Cu partitioning, respectively. Sites of environmentally significant sediment-metal pollution were identified in the Rivers Abrud and Arieş where exchangeable metal concentrations exceeded Dutch intervention values. The implications of metal contamination in the Arieş river basin to the proposed mining development at Roşia Montana are discussed in relation to other contaminated Romanian catchments and with the EU Water Framework Directive.  相似文献   

17.
The characterization of trace elements in terms of their apportionment among dissolved, macromolecular, nano- and micro-particulate phases in the water column of the Great Salt Lake carries implications for the potential entry of toxins into the food web of the lake. Samples from the anoxic deep and oxic shallow brine layers of the lake were fractionated using asymmetric flow field-flow fractionation (AF4). The associated trace elements were measured via online collision cell inductively-coupled plasma mass spectrometry (CC-ICP-MS). Results showed that of the total (dissolved + particulate) trace element mass, the percent associated with particulates varied from negligible (e.g. Sb), to greater than 50% (e.g. Al, Fe, Pb). Elements such as Cu, Zn, Mn, Co, Au, Hg, and U were associated with nanoparticles, as well as being present as dissolved species. Particulate-associated trace elements were predominantly associated with particulates larger than 450 nm in size. Among the smaller nanoparticulates (<450 nm), some trace elements (Ni, Zn, Au and Pb) showed higher percent mass (associated with nanoparticles) in the 0.9–7.5 nm size range relative to the 10–250 nm size range. The apparent nanoparticle size distributions were similar between the two brine layers; whereas, important differences in elemental associations to nanoparticles were discerned between the two layers. Elements such as Zn, Cu, Pb and Mo showed increasing signal intensities from oxic shallow to anoxic deep brine, suggesting the formation of sulfide nanoparticles, although this may also reflect association with dissolved organic matter. Aluminum and Fe showed greatly increased concentration with depth and equivalent size distributions that differed from those of Zn, Cu, Pb and Mo. Other elements (e.g. Mn, Ni, and Co) showed no significant change in signal intensity with depth. Arsenic was associated with <2 nm nanoparticles, and showed no increase in concentration with depth, possibly indicating dissolved arsenite. Mercury was associated with <2 nm nanoparticles, and showed greatly increased concentration with depth, possibly indicating association with dissolved organic matter.  相似文献   

18.
The clinopyroxenes and garnets from garnet lherzolite nodules in kimberlites were analyzed for the major and trace elements (Sc, Ti, V, Cr, Mn, Co, Sr, and Zr) with the secondary ion mass spectrometry (SIMS) techniques using an ion-microprobe. The concentration ranges for clinopyroxenes are: 12–90 ppm Sc, 60–2540 ppm Ti, 110–350 ppm V, 2400 ppm-1.68% Cr, 470–1100 ppm Mn, 18–70 ppm Co, 85–710 ppm Sr, and 6.3–120 ppm Zr. Those for garnets are: 71–180 ppm Sc, 140–6200 ppm Ti, 220–450 ppm V, 1.05–6.24% Cr, 1600–5220 ppm Mn, 33–92 ppm Co, and 66–250 ppm Zr.These data were used to assess a possible use of distribution of transition elements between clinopyroxene and garnet for geothermometry/geobarometry. The distribution coefficients of V and Mn show good correlations with (Ca/Ca+Mg+Fe)CPX, suggesting their potential usefulness.The abundances of these elements in minerals (and estimated whole-rocks) suggest that garnet lherzolite nodules in kimberlites can be classified into three groups. It is suggested that one of the groups (Group I) could be close to the pristine mantle on the basis of Ti and Zr abundances as well as REE systematics. Arguments on Ti/Zr ratios among different nodule types suggest that abundant granular garnet lherzolites could be cumulates crystallized from a residual liquid after ilmenite was extracted.IPG Contribution No. 281  相似文献   

19.
In parts of the deeply weathered and semi-arid environments of the Cobar area (NSW, Australia), detection of mineralisation using conventional soil sampling and total metal analysis is impeded. This is due to the intense leaching of trace elements within the weathered profile, discontinuous coverage of transported materials and the existence of diffuse regional geochemical anomalies of ill-defined source. Selective chemical extractions, applied to various regolith components, and biogeochemistry offer a means of isolating localised geochemical patterns related to recent dispersion of trace elements through the overburden. Lag geochemical patterns across the McKinnons deposit (Au) and Mrangelli prospect (Pb–Zn–As) reflect mechanical dispersion processes and minor hydromorphic effects. Concentrations of more mobile elements tend to be higher in the non-magnetic fraction, due to higher proportions of goethite and poorly crystalline hematite than in the magnetic fraction. The subdued soil geochemical responses for metals extractable by cold 40% hydrochloric acid (CHX) and for total element concentration reflect the leached nature of the residual profile, low grade of mineralisation, dilution by aeolian components and disequilibrium of fine fractions with coarser, relict Fe-oxides. The stronger contrast for CHX for most metals, compared with total extraction, indicates surface accumulation of trace elements derived from underlying mineralisation. Enzyme leach element anomalies are intense but generally located directly over bedrock sources or major structural breaks, irrespective of the nature of the overburden. Though mechanisms for the dispersion of trace elements extracted by enzyme leaching are not well established, the lack of lateral transport suggests vertical migration of volatile metal species (atmimorphic dispersion). The strong, multi-element response to mineralisation in cypress pine needles indicates significant metal recycling during the present erosional cycle. However, a comparison of the trace element concentrations in vegetation (cypress pine needles) and selective extractions of soils indicates that recycling by the plants is not the dominant mechanism for transportation of metals through the overburden. The vegetation may be responding to hydromorphic dispersion patterns at depth. The use of selective extractions may be useful in detecting mineralisation through deeply leached profiles, but offers even greater potential when integrated with biogeochemistry to detect targets buried by significant thickness of transported cover.  相似文献   

20.
A new method for the speciation of Fe and Mn at mineral surfaces is proposed using X-ray absorption fine structure in conversion electron yield mode (CEY-XAFS). This method generally reflects information on the species at the sub-μm scale from the particle surface due to the limited escape depth of the inelastic Auger electron. The surface sensitivity of this method was assessed by experiments on two samples of granite showing different degrees of weathering. The XANES spectra of the Fe-K and Mn-K edge clearly gave different information for CEY and fluorescence (FL) modes. These XANES spectra of Fe and Mn show a good fit upon application of least-squares fitting using ferrihydrite/MnO2 and biotite as the end members. The XANES spectra collected by CEY mode provided more selective information on the secondary phases which are probably present at the mineral surfaces. In particular, CEY-XANES spectra of Mn indicated the presence of Mn oxide in unweathered granite despite a very small contribution of Mn oxide being indicated by FL-XANES and selective chemical-extraction analyses. Manganese oxide could not be detected by micro-beam XANES (beam size: 5 × 5 μm2) in unweathered granite, suggesting that Mn oxide thinly and ubiquitously coats mineral surface at a sub-μm scale. This information is important, since Mn oxide can be the host for various trace elements. CEY-XAFS can prove to be a powerful tool as a highly sensitive surface speciation method. Combination of CEY and FL-XAFS will help identify minor phases that form at mineral surfaces, but identification of Fe and Mn oxides at mineral surfaces is critical to understand the migration of trace elements in water-rock interaction.  相似文献   

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