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1.
Manganese oxides are important geomaterials, widespread in terrestrial and Martian environments. Characterisation of the oxidation state of Mn is a central issue in science; this task has been addressed up to the present by X‐ray spectroscopy or diffraction techniques. The former, however, requires access to synchrotron facilities, while the latter does not provide crystal‐chemical information at the local scale. In this work, we compare a large set of Raman data from well‐characterised samples, already published by the same authors of this paper or as found in the literature. We show a clear correlation between the oxidation state of Mn and the wavenumber of peculiar bands; octahedrally co‐ordinated Mn2+ is recognised by a band around 530 cm?1, Mn3+ by a band around 580 cm?1 and Mn4+ by a band around 630 cm?1, while tetrahedrally co‐ordinated Mn2+ is recognisable by a band around 650 cm?1. Strongly distorted Mn3+ octahedra are indicated by the appearance of Jahn–Teller modes. Our method allows a reliable, easily accessible tool to characterise the oxidation states of Mn in oxides, also suitable for microscale mapping. It provides a robust analytical basis for the use of these minerals as redox indicators in geology/geochemistry, in exoplanetary research or for monitoring technological processes.  相似文献   

2.
Natural processes and anthropogenic activities may result in the formation and/or introduction of perchlorate (ClO4−) at elevated levels into the environment. Perchlorate in soil environments on Earth and potentially in Mars may modify the dynamics of metal release and their mobilization. Serpentine soils, known for their elevated metal concentrations, provide an opportunity to assess the extent that perchlorate may enhance metal release and availability in natural soil and regolith systems. Here, we assess the release rates and extractability of Ni, Mn, Co and Cr in processed Sri Lankan serpentine soils using a range of perchlorate concentrations (0.10–2.50 w/v ClO4−) via kinetic and incubation experiments. Kinetic experiments revealed an increase of Ni, Mn, Co and Cr dissolution rates (1.33 × 10−11, 2.74 × 10−11, 3.05 × 10−12 and 5.35 × 10−13 mol m−2 s−1, respectively) with increasing perchlorate concentrations. Similarly, sequential and single extractions demonstrated that Ni, Mn, Co and Cr increased with increasing perchlorate concentrations compared to the control soil (i.e., considering all extractions: 1.3–6.2 (Ni), 1.2–126 (Mn), 1.4–34.6 (Co) and 1.2–6.4 (Cr) times greater than the control in all soils). Despite the oxidizing capability of perchlorate and the accelerated release of Cr, the dominant oxidation state of Cr in solution was Cr(III), potentially due to low pH (<2) and Cr(VI) instability. This implies that environmental remediation of perchlorate enriched sites must not only treat the direct hazard of perchlorate, but also the potential indirect hazard of related metal contamination.  相似文献   

3.
Ten highly weathered soils in southeastern Nigeria were sampled from their typical A and B horizons for analyses. The objectives were to determine the different forms of Fe and Al oxides in the soils and relating their occurrence to phosphate availability and retention in the soils. The soils are deep and often physically degraded but are well drained and coarse in the particle size distribution. They are mostly dominated by kaolinite in their mineralogy with very high values of SiO2. The soils are acidic with low soil organic carbon (SOC) contents. The elements in the exchange complex are also low thus reflecting in the low CEC of the soil. Available phosphorus (P) in the soils are generally low while total P ranged from 157 to 982 mg kg−1 with an overall average of 422 mg kg−1. Total Fe in the soil is highest and their order represented as follows: Fet > Fed > Feox ≥ Fep. The pyrophosphate extractable Fe was always higher in the top soil than in the subsoil and was attributed to the fact that these forms of Fe are associated with organic matter which is more abundant in topsoil than in subsoil. Like in Fe forms, the order of Al occurrence could generally be presented as; Alt > Ald > Alox > Alp. More Fe and Al oxides in the soils are strongly crystalline while a small quantity is poorly crystalline Fe forms. The amorphous forms of both Fe and Al are very low in the soils when compared with the crystalline forms. The oxides that show very strong affinity to total P are Fed–Feox, Fed, Ald, Fet, Feox and Alox/Ald. To overcome this problem of P retention in the soil, we recommend constant liming of these soils to neutralize them, application of organic matter and of high dosage of phosphate fertilizer to the soils.  相似文献   

4.
A soil geochemical survey was conducted in a 27,000-km2 study area of northern California that includes the Sierra Nevada Mountains, the Sacramento Valley, and the northern Coast Range. The results show that soil geochemistry in the Sacramento Valley is controlled primarily by the transport and weathering of parent material from the Coast Range to the west and the Sierra Nevada to the east. Chemically and mineralogically distinctive ultramafic (UM) rocks (e.g. serpentinite) outcrop extensively in the Coast Range and Sierra Nevada. These rocks and the soils derived from them have elevated concentrations of Cr and Ni. Surface soil samples derived from UM rocks of the Sierra Nevada and Coast Range contain 1700–10,000 mg/kg Cr and 1300–3900 mg/kg Ni. Valley soils west of the Sacramento River contain 80–1420 mg/kg Cr and 65–224 mg/kg Ni, reflecting significant contributions from UM sources in the Coast Range. Valley soils on the east side contain 30–370 mg/kg Cr and 16–110 mg/kg Ni. Lower Cr and Ni concentrations on the east side of the valley are the result of greater dilution by granitic sources of the Sierra Nevada.Chromium occurs naturally in the Cr(III) and Cr(VI) oxidation states. Trivalent Cr is a non-toxic micronutrient, but Cr(VI) is a highly soluble toxin and carcinogen. X-ray diffraction and scanning electron microscopy of soils with an UM parent show Cr primarily occurs within chromite and other mixed-composition spinels (Al, Mg, Fe, Cr). Chromite contains Cr(III) and is highly refractory with respect to weathering. Comparison of a 4-acid digestion (HNO3, HCl, HF, HClO4), which only partially dissolves chromite, and total digestion by lithium metaborate (LiBO3) fusion, indicates a lower proportion of chromite-bound Cr in valley soils relative to UM source soils. Groundwater on the west side of the Sacramento Valley has particularly high concentrations of dissolved Cr ranging up to 50 μg L−1 and averaging 16.4 μg L−1. This suggests redistribution of Cr during weathering and oxidation of Cr(III)-bearing minerals. It is concluded that regional-scale transport and weathering of ultramafic-derived constituents have resulted in enrichment of Cr and Ni in the Sacramento Valley and a partial change in the residence of Cr.  相似文献   

5.
Partitioning of transition elements in Pacific pelagic sediments (35 samples) was performed by sequential chemical leaching with barium chloride/triethanolamine (easily extractable fraction), acidic cation exchange resin (carbonate phases), and hydroxylamine hydrochloride and dilute hydrochloric acid solutions (hydrous oxides). Residual metal percentages are highest in red-brown clays and siliceous ooze, intermediate in calcareous materials and low in micronodules (2 samples, > 125 μm): residual metal contents seem to be controlled predominantly by the rate of admixture of volcanoclastic materials. At higher bulk metal concentrations, the non-residual fractions of Mn, Cu, Ni and Zn generally increase both in red-brown pelagic clays and in siliceous ooze. Mn, Ni, and Co concentrations are mainly associated with the easily reducible fraction (0.1 M NH2OH·HCl), whereas Fe, Cu, and Zn exhibit higher percentages in the hydrochloric acid soluble fractions (0.3 M HCl); Zn and Cu are associated to some extent with the carbonate phase, copper with the easily extractable fraction.  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.
Organic material in metal contaminated soils around an abandoned magnetite mine–smelter complex in the critical Highlands watershed protects the groundwater and surface water from contamination. Metals in these waters were consistently below local and national water standards. Two groups of soil types cover the area: (1) Group A disturbed metal-rich soils, and (2) Group B undisturbed organic soils. Chromium and nickel were more elevated than other metals with Cr more widespread than Ni. In Group A, Cr correlated strongly with sesquioxides in the lower horizons (Fe2O3: r = 0.74, p < 0.025; Al2O3: r = 0.92, p < 0.005). In Group B, Cr correlated strongly (r = 0.96, p < 0.005) with soil organic matter (SOM) in the O-horizons. Ni–Cr (Group A: 52 and 70% in O- and lower horizons, respectively; Group B: ~100% in both horizons) and V–Cr correlations (78% only in Group A lower horizons) suggest similar retention mechanisms for these elements. Average soil \textpH\textCaCl2 {\text{pH}}_{{{\text{CaCl}}_{2} }} for both groups ranged between 3.65 and 5.91, suggesting that soil acidity is determined by organic acids and solubility of Al3+ releasing H+ ions. SOM and sesquioxides contribute significantly to creating naturally occurring filtration systems, removing metals, and protecting water quality. High Ca, Fe, and Ti in Group A soils suggest slag and ash were mixed into the soils. Some low-Cr sources include magnetite, slag, and ash (100, 100 and 200 mg/kg, respectively). Constant ZrO 2 :TiO 2 ratios in the lower soils indicate soil formation from breakdown of underlying tailing rocks, contributing Cr to these layers.  相似文献   

8.
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   

9.
Urban roadside soils are the “recipients” of large amounts of heavy metals from a variety of sources including vehicle emissions, coal burning waste and other activities. The behavior of heavy metals in urban roadside soils depends on the occurrence as well as the total amount. Accordingly, knowledge of the interactions between heavy metals and other constituents in the soil is required to judge their environmental impact. In this study, correlations of heavy metal concentrations (Pb, Zn, Cu, Ag, Se, Ni, Cr and Ba) to iron extracted using dithionite–citrate–bicarbonate (DCB) buffer (FeDCB), fulvic acids and particle size fractions were examined from the Xuzhou urban roadside soils. Heavy metals except for Cr and fulvic acids had a positive significant correlation with FeDCB, indicating these metals and fulvic acids are principally associated with the surfaces of iron oxides of the soils. Significant positive correlations were also found between the contents of fulvic acids and heavy metals, showing these heavy metals (especially for Cu, Ni and Cr) form stable complexes with fulvic acids. Such finding is of importance with regard to the increased mobilization of heavy metals, e.g., into freshwater ecosystems. Ag, Se and Cr are independent of particle size fractions because of their low concentrations of Ag and Se in the studied soils. Pb, Zn, Cu, Ba and Ag are mainly enriched in the finer soil particles (especially <16 μm).  相似文献   

10.
Analytical perspective on trace element species of interest in exploration   总被引：1，自引：0，他引：1  
Analysis of soil and sediment samples, using selective extraction methods to distinguish different phases, is of particular interest in exploration geochemistry to locate deeply buried mineral deposits. There are various mechanisms of binding labile elements in the secondary environment, including physical and chemical sorption, precipitation, chelation and complexation. Phases present in soils and sediments which are likely to scavenge ‘free' elements include amorphous Mn and Fe oxides, the humic and fulvic components of humus, and clays. This paper reviews these forms of trace elements and the methods in current use to quantify them. Examples of precision data, both for control and survey samples, are given with respect to trace elements dissolved from the ‘soluble organic' component of humus, Mn oxides and amorphous Fe oxides. The high sensitivity of inductively coupled plasma mass spectrometry (ICP–MS) is required to measure accurately and precisely a large suite of trace elements, especially where only small fractions of elements are dissolved by such leaches as the commercially available Enzyme and MMI (Mobile Metal Ion) extractions. The relative standard deviations (RSD) obtained for 33 elements (e.g. Ag, Cd, In, I) in the standard reference sample (SRM), TILL-2, are in the range 0.5–8% for the hydroxylamine hydrochloride (NH2OH·HCl) leach designed to extract hydrous Fe and Mn oxides. The corresponding RSDs for elements in the reactive Mn oxide phase extracted by the Enzyme leach are in the range 3–19% except for some trace elements at levels close to detection limit (e.g. Cd, Bi). The RSDs obtained for field duplicates are inferior to those for analytical replicates (i.e. sample splits), probably a reflection of different concentrations of the host phase. In one soil survey, the Fe extracted by a 0.25 M NH2OH·HCl leach ranged conservatively from 0.2 to 1.7% whereas the Mn extracted by the Enzyme leach varied extensively, from 0.3 to >999 ppm. In contrast, precision, at 1–7% RSD, for field duplicates was found to be comparable with that for both analytical duplicates and the SRM, LKSD-4, for elements associated with the humic and fulvic component of humus samples sieved to <177 μm.  相似文献   

11.
Sequestration of Ce3+ by biogenic manganese oxides (BMOs) formed by a Mn(II)-oxidizing fungus, Acremonium strictum strain KR21-2, was examined at pH 6.0. In anaerobic Ce3+ solution, newly formed BMOs exhibited stoichiometric Ce3+ oxidation, where the molar ratio of Ce3+ sequestered (Ceseq) relative to Mn2+ released (Mnrel) was maintained at approximately two throughout the reaction. A similar Ce3+ sequestration trend was observed in anaerobic treatment of BMOs in which the associated Mn(II) oxidase was completely inactivated by heating at 85 °C for 1 h or by adding 50 mM NaN3. Aerobic Ce3+ treatment of newly formed BMO (enzymatically active) resulted in excessive Ce3+ sequestration over Mn2+ release, yielding Ceseq/Mnrel > 200, whereas heated or poisoned BMOs released a significant amount of Mn2+ with lower Ce3+ sequestration efficiency. Consequently, self-regeneration by the Mn(II) oxidase in newly formed BMO effectively suppressed Mn2+ release and enhanced oxidative Ce3+ sequestration under aerobic conditions. Repeated treatments of heated or poisoned BMOs under aerobic conditions confirmed that oxidative Ce3+ sequestration continued even after most Mn oxide was released from the solid phase, indicating auto-catalytic Ce3+ oxidation at the solid phase produced through primary Ce3+ oxidation by BMO. From X-ray diffraction analysis, the resultant solid phases formed through Ce3+ oxidation by BMO under both aerobic and anaerobic conditions consisted of cerianite with crystal sizes of 5.00–7.23 Å. Such nano-sized CeO2 (CeO2,BMO) showed faster auto-catalytic Ce3+ oxidation than that on well-crystalized cerianite under aerobic conditions, where the normalized pseudo-first order rate constants for auto-catalytic Ce3+ oxidation on CeO2,BMO was two orders of magnitude higher. Consequently, we concluded that Ce3+ contact with BMOs sequesters Ce3+ through two oxidation paths: primary Ce3+ oxidation by BMOs produces nano-sized crystalline cerianite, and subsequent auto-catalytic Ce3+ oxidation efficiently occurs using dissolved oxygen as the oxidizing agent. Pretreatment of newly formed BMOs with La3+ solution resulted in decreased rate constants for primary Ce3+ oxidation by BMO due to site blocking by La3+ sorption. The results presented herein increase our understanding of the role of BMO in oxidative Ce3+ sequestration process(es) through enzymatic and abiotic paths in natural environments and provide supporting evidence for the potential application of BMOs towards the recovery of Ce3+ from contaminated waters.  相似文献   

12.
The redox processes regulating transport of Mn in the water column of a eutrophic, dimictic lake (Lake Norrviken, Sweden) are interpreted based on a one-dimensional diffusion-reaction model for Mn(II). It is found that rates and rate constants for oxidation and reduction vary greatly with depth and also with time during the season of stratification. Calculated rates show that Mn(II) oxidation and reduction generally occur in narrow depth intervals (25–50 cm). This is in good agreement with measured profiles of particulate Mn (MnO x ). Maximum oxidation rate constants (assuming first order kinetics) at each date are in the first half of the season <1 d–1, but then increases to a rather constant value of about 25 d–1. These high rate constants are indicative of microbiological involvement in the Mn(II) oxidation. This is further evidenced by SEM-EDS analysis showing Mn enriched particles morphologically similar toMetallogenium. Reductive dissolution of Mn oxides occurs mainly in the zone just below the zone of maximum oxidation rate. The release of Mn(II) is accompanied by production of alkalinity and CO2. The relation between production rates of Mn(II) and alkalinity indicates that Mn oxides act as terminal electron acceptors in the bacterially mediated oxidation of organic matter. However, the Mn2+/CO2 ratio is significantly lower than what is expected from this process. It is suggested that the Mn reduction is coupled to fermentation. Close coexistence of Mn reduction and oxidation at high rates, such as found in the water column of this lake, facilitates rapid and continuous regeneration of reducible Mn oxides. This gives rise to a quantitatively important mechanism of organic matter oxidation in the water column.  相似文献   

13.
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14.
Chromium (Cr) is a heavy metal that exists in soils in two stable oxidation states, +III and +VI. The trivalent species is an essential nutrient, whereas the hexavalent species is highly toxic. This study investigated the environmental impact of CrIII potentially released into soil from wastes and various materials by determining the risk of oxidation of initially soluble inorganic CrIII into hazardous CrVI. The principal aim was to describe the pH-dependent mechanisms that regulate 1) the formation of CrVI from the easily soluble CrIII and 2) the potential bioavailability of CrIII and that of CrVI species produced in the oxidation of CrIII in agricultural soil (fine sand, organic carbon 3.2%). The amount of CrVI formed in oxic soil conditions was regulated by two counteracting reactions: 1) oxidation of CrIII into CrVI by manganese oxide (MnIVO2) and 2) the subsequent reduction of CrVI by organic matter back to CrIII. The effect of pH on this net-oxidation of CrIII and on the chemical availability of both CrIII and CrVI species was investigated in soil samples incubated with or without excessive amounts of synthetic MnO2, over the chemically adjusted pH range of 3.9–6.3 (+22 °C, 47 d). In soil subsamples without added MnO2, the net-oxidation of CrIII into CrVI (1 mM CrCl3 in soil suspensions, 1:10 w/V) was negligible. As for the MnO2-treated soils, at maximum only 4.7% of added CrIII was oxidized – regardless of the high oxidation potential of these subsamples. The lowest production of CrVI was observed under acidic soil conditions at pH ∼4. At low pH, the net-oxidation diminished as result of enhanced reduction of CrVI back to CrIII. At higher pHs, the oxidation was limited by enhanced precipitation (or adsorption) of CrIII, which lowered the overall amount of CrIII susceptible for oxidation. Moreover, the oxidation reactions by MnO2 were inhibited by formation of Cr(OH)3 coverage on its surface. The pH-dependent chemical bioavailability of added CrIII differed from that of the CrVI formed. At elevated pHs the chemical availability of CrIII decreased, whereas that of CrVI produced increased. However, the risk of CrVI formation through oxidation of the easily soluble inorganic CrIII was considered to be low in agricultural soils high in organic matter and low in innate MnO2.  相似文献   

15.
Citrate released by plants, bacteria, and fungi into soils is subject to abiotic oxidation by MnO2(birnessite), yielding 3-ketoglutarate, acetoacetate, and MnII. Citrate loss and generation of products as a function of time all yield S-shaped curves, indicating autocatalysis. Increasing the citrate concentration decreases the induction period. The maximum rate (rmax) along the reaction coordinate follows a Langmuir-Hinshelwood dependence on citrate concentration. Increases in pH decrease rmax and increase the induction time. Adding MnII, ZnII, orthophosphate, or pyrophosphate at the onset of reaction decreases rmax. MnII addition eliminates the induction period, while orthophosphate and pyrophosphate addition increase the induction period. These findings indicate that two parallel processes are responsible. The first, relatively slow process involves the oxidation of free citrate by surface-bound MnIII,IV, yielding MnII and citrate oxidation products. The second process, which is subject to strong positive feedback, involves electron transfer from MnII-citrate complexes to surface-bound MnIII,IV, generating MnIII-citrate and MnII. Subsequent intramolecular electron transfer converts MnIII-citrate into MnII and citrate oxidation products.  相似文献   

16.
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   

17.
The Field Research Center (FRC) including five contaminated sites and a clean background area was established in Oak Ridge, Tennessee, as a part of the U.S. Department of Energy’s Natural and Accelerated Bioremediation Research (NABIR) program. This study investigates the mineralogy and mineralogical pathways of saprolite at the FRC background site to provide a fundamental basis for the remediation strategy for contaminated sites. The background site is underlain interbedded shales, siltstones, and limestones with nearly identical characteristics to the contaminated sites. Bulk samples of saprolite were collected by hand picking approximately at 1 m depth (C horizon) from the soil surface. The soil pH of 4.3 and cation exchange capacity (CEC) of 10.5 cmol/kg measured are in the range of the typical shallow depth saprolite layer in this area. Total Fe by citrate-bicarbonate-dithionate (CBD) and ammonium oxalate extractable (amorphous) were 17.6 and 0.61 g/kg, respectively. Total Mn extracted by NH2OH·HCl was 0.17 g/kg. X-ray diffraction (XRD) and scanning electron microscopy (SEM) analyses indicate that quartz, illite, and microcline (K-feldspar) are the dominant minerals, occupying 95% of mineral composition. The saprolite samples analyzed have shown characteristics of oxic conditions overall, and the degrees of weathering for three sampling locations were various, most for S1 and least for S3, likely influenced either by the flow channels developed through saprolite or by seasonal fluctuation of the groundwater table. The source of the manganese oxide that observed from the site is likely to be Mn-rich muscovite in the shale or Mn-rich biotite in the blackish band in the limestone. The results such as abundant Mn and Fe contents identified encouraging prospects for conducting remediation projects in FRC sites.  相似文献   

18.
Effect of chemical fertilizers (urea, NH4Cl, Ca(NO3)2, KCl and KH2PO4) on the fractionation of Cu, Cr and Ni was studied by a 4-month incubation experiment. Using sequential extraction procedure, it was found that the application of fertilizers could change the distribution of Cu, Cr and Ni in the fractions of soil. Applying urea (CO(NH2)2) significantly decreased the concentrations of Cu, Cr and Ni in water soluble plus exchangeable (WE) fraction, but increased those in Fe–Mn oxides bound (FM) fraction (p < 0.01). However, application of NH4Cl caused an increase in the WE fraction by 27.7% for Cu, 111.5% for Cr and 20.4% for Ni. The CO(NH2)2 raised the soil pH from 4.51 to 4.96, whereas NH4Cl lowered the pH of soil by 0.44 units. The WE fraction of the three heavy metals was significantly increased, while the FM fraction was significantly decreased by adding KCl (p < 0.01). Moreover, the supply of KH2PO4 reduced the WE and carbonate bound (CB) fractions of Cu, Cr and Ni in the soil, however, it raised Cu and Ni in the residual (RS) fraction and Cr in the FM fraction. In addition, the mobility index indicated that KCl and NH4Cl increased the mobility of Cu, Cr and Ni in the soil, whereas urea and KH2PO4 decreased the mobility of the three metals in the soil. These results suggest that applying chemical fertilizers does not only provide plant nutrients, but may also change the speciation and mobility of heavy metals in the soil.  相似文献   

19.
Heavy metals are governed by parent material of soils and influenced by the soil physicochemical properties and soil and crop management practices. This paper evaluates total heavy metal concentrations in rainfed soils under diverse management practices of tropical India. Vertisols (clayey soils with high shrink/swell capacity) had the highest concentrations of heavy metals. However, chromium (Cr) content was above the threshold value in Aridisol [calcium carbonate (CaCO3)]-containing soils of the arid environments with subsurface horizon development. Concentration increased at lower depths (>30 cm). Basaltic soils showed higher concentrations of nickel (Ni), copper (Cu) and manganese (Mn). Cadmium (Cd), cobalt (Co), Cu and Mn concentrations were higher in soils cultivated to cotton, whereas Cr concentration was above the threshold level of 110 mg kg?1 in food crop cultivated soils. As the specific soil surface is closely related to clay content and clay type, soil’s ability to retain heavy metals is more closely tied to the specific surface than to the soil cation exchange capacity. Higher positive correlations were found between heavy metal concentrations and clay content [Cd(r = 0.85; p ≤ 0.01); Co (r = 0.88; p ≤ 0.05); Ni (r = 0.87; p ≤ 0.01); Co (r = 0.81; p ≤ 0.05); Zn (r = 0.49; p ≤ 0.01); Cr (r = 0.80; p ≤ 0.05); Mn (r = 0.79; p ≤ 0.01)]. The amounts of nitrogen–phosphorus–potassium applied showed a positive correlation with Co and Ni (r = 0.62; p ≤ 0.05). As several soils used for growing food crops are high in Ni, Cr and Mn, the flow of these metals in soil–plant–livestock/human chain needs further attention.  相似文献   

20.
To examine the pathways that form Mn(III) and Mn(IV) in the Mn(II)-oxidizing bacterial strains Pseudomonas putida GB-1 and MnB1, and to test whether the siderophore pyoverdine (PVD) inhibits Mn(IV)O2 formation, cultures were subjected to various protocols at known concentrations of iron and PVD. Depending on growth conditions, P. putida produced one of two oxidized Mn species - either soluble PVD-Mn(III) complex or insoluble Mn(IV)O2 minerals - but not both simultaneously. PVD-Mn(III) was present, and MnO2 precipitation was inhibited, both in iron-limited cultures that had synthesized 26-50 μM PVD and in iron-replete (non-PVD-producing) cultures that were supplemented with 10-550 μM purified PVD. PVD-Mn(III) arose by predominantly ligand-mediated air oxidation of Mn(II) in the presence of PVD, based on the following evidence: (a) yields and rates of this reaction were similar in sterile media and in cultures, and (b) GB-1 mutants deficient in enzymatic Mn oxidation produced PVD-Mn(III) as efficiently as wild type. Only wild type, however, could degrade PVD-Mn(III), a process linked to the production of both MnO2 and an altered PVD with absorbance and fluorescence spectra markedly different from those of either PVD or PVD-Mn(III). Two conditions, the presence of bioavailable iron and the absence of PVD at concentrations exceeding those of Mn, both had to be satisfied for MnO2 to appear. These results suggest that P. putida cultures produce soluble Mn(III) or MnO2 by different and mutually inhibitory pathways: enzymatic catalysis yielding MnO2 under iron sufficiency or PVD-promoted oxidation yielding PVD-Mn(III) under iron limitation. Since PVD-producing Pseudomonas species are environmentally prevalent Mn oxidizers, these data predict influences of iron (via PVD-Mn(III) versus MnO2) on the global oxidation/reduction cycling of various pollutants, recalcitrant organic matter, and elements such as C, S, N, Cr, U, and Mn.  相似文献   

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