Cobalt,copper, and manganese adsorption by aluminium and iron oxides and humic acid

Abstract

Adsorption of cobalt (Co), copper (Cu), and manganese (Mn) by synthetic aluminium oxide, ferrihydrite, goethite, extracted humic acid, and a sandy soil sample were determined as a function of metals concentration (0–1.2 mM) and pH (3.8–8.2). For each pH and adsorbent, the Langmuir adsorption maximum (adsorption capacity) was calculated. The position of the adsorption curves for Co, Cu, and Mn as a function of pH has been shown to be related to the first hydrolysis constant of the cations in solution (pK₁). The sequence of preference of the three metals to the studied adsorbents decreased in order Cu >> Co > Mn. The results obtained from this study showed that the Co, Cu, and Mn adsorption characteristics of soils are probably controlled to large extent by their organic matter and oxides contents.     

The sorption of some heavy metals by the lower oxides of manganese

The manganese mineral partridgeite (α-Mn₂O₃) sorbs cobalt in marked preference to copper, nickel or zinc, but this preference is not shown by the mineral manganite (γ-MnOOH). In hausmannite (Mn₃O₄), the slow sorption of cobalt and nickel exceeds that of zinc. Similar tests on manganosite (MnO) were inconclusive, due to the instability of this oxide).     

Molybdate sorption by oxides of aluminium and iron

The sorption of molybdate by goethite, hematite, bayerite and α-Al₂O₃ was studied as a function of molybdate concentration and pH. The sorption isotherms exhibited double sorption plateaus in which the amount of Mo sorbed in the second plateau was double that in the first. This was attributed to the polymerization of molybdates as the concentration increases. Furthermore Mo sorption was found to be associated with a cosorption of Na cations, probably present to maintain electroneutrality in the surface zone. The sorption showed high sensitivity towards the pH, attaining a maximum at pH 4. For the iron oxides the decrease in sorption was much less pronounced on the acid side of the pH maximum and occured at lower pH values than that of the Al oxides. Molybdate sorption is explained in terms of a ligand exchange reaction between molybdate and surface hydroxyls.     

The influence of iron oxides on phosphate adsorption by soil

Soils from Denmark and Tanzania were extracted with ammonium acetate (controls), EDTA to dissolve amorphous iron oxides, and dithionite-EDTA (DE) to dissolve crystalline iron oxides. The phosphate adsorption capacities of the extracted soils were taken as the maximum quantity of phosphate adsorbed computed from the Langmuir equation. The decreases in the phosphate adsorption capacity following EDTA extraction and DE extraction were attributed to the removal of iron oxides. Close correlations (P<0.001) were found (i) between EDTA-extractable iron (amorphous iron oxides) and the decrease in phosphate adsorption capacity following EDTA extraction, and (ii) between the difference between DE-extractable iron and EDTA-extractable iron (crystalline iron oxides) and the further decrease in phosphate adsorption capacity following DE extraction. The phosphate adsorption capacity, estimated to be approximately 2.5 μmol P m^?2, was in good agreement with the capacity of various synthetic iron oxides. The calculated phosphate adsorption capacity of soil iron oxides, obtained from the contents and specific surfaces of amorphous and crystalline iron oxides together with the phosphate adsorption capacity per m² for synthetic iron oxides, compared favourably with the measured phosphate adsorption capacity.     

Oxidation and sorption of arsenite by manganese dioxide as influenced by surface coatings of iron and aluminum oxides and calcium carbonate

Manganese dioxide (birnessite) was coated with two levels of Fe and Al oxides and CaCO₃, and the influence of these coatings on the surface features and the reactivity of MnO₂ with respect to the oxidation and sorption of As(III) (arsenite) was examined. For all untreated and coated MnO₂ samples, the depletion (oxidation plus sorption) of As(III) by the samples follows first-order kinetics. The rate constants are smaller for the samples with the high levels of coating of Fe and Al oxides and CaCO₃ on MnO₂ than they are for the untreated MnO₂ and the MnO₂ with the low levels of coating. The extent of masking of the electron-accepting sites on the MnO₂ for converting the toxic As(III) to the less toxic As(V) significantly varies with the kinds and levels of coatings. Coatings of Fe and A1 oxides and CaCO₃, on MnO₂ distinctively affect the sorption of As. Manganese oxide evidently catalyzes the sorption of As by Al oxide through oxidation of As(III) to As(V). The relative affinities of the oxides of Mn, Fe, and Al and CaCO₃, toward As(III) and As(V) account for the coating effects.     

Comparative physiological study of iron,manganese and copper absorption by plants

In the previous reports, influence of metabolic inhibitors, such as NaCN, 2,4-dinitrophenol and EDTA, on the absorption of ⁵⁹Fe, ⁵⁴Mn and ⁶⁴Cu(1) and the distribution of these elements in root cell were studied using the separation technique by centrifugal forces (2). These experiments revealed that rice and barley plants behave differently in their mode of absorption and distribution of these elements.     

Characterization of iron,manganese, and copper synthetic hydroxyapatites by electron paramagnetic resonance spectroscopy

The incorporation of micronutrients (e.g., Fe, Mn, Cu) into synthetic hydroxyapatite (SHA) is proposed for slow release of these nutrients to crops in NASA's Advanced Life Support (ALS) program for long-duration space missions. Separate Fe3+ (Fe-SHA), Mn2+ (Mn-SHA), and Cu2+ (Cu-SHA) containing SHA materials were synthesized by a precipitation method. Electron paramagnetic resonance (EPR) spectroscopy was used to determine the location of Fe3+, Mn2+, and Cu2+ ions in the SHA structure and to identify other Fe(3+)-, Mn(2+)-, and Cu(2+)-containing phases that formed during precipitation. The EPR parameters for Fe3+ (g=4.20 and 8.93) and for Mn2+ (g=2.01, A=9.4 mT, D=39.0 mT and E=10.5 mT) indicated that Fe3+ and Mn2+ possessed rhombic ion crystal fields within the SHA structure. The Cu2+ EPR parameters (g(z)=2.488, A(z)=5.2 mT) indicated that Cu2+ was coordinated to more than six oxygens. The rhombic environments of Fe3+ and Mn2+ along with the unique Cu2+ environment suggested that these metals substituted for the 7 or 9 coordinate Ca2+ in SHA. The EPR analyses also detected poorly crystalline metal oxyhydroxides or metal-phosphates associated with SHA. The Fe-, Mn-, and Cu-SHA materials are potential slow release sources of Fe, Mn, and Cu for ALS and terrestrial cropping systems.     

Influence of iron oxides on the non-specific anion (chloride) adsorption by soil

Soils from Denmark and Tanzania were extracted with ammonium acetate (controls), EDTA to dissolve amorphous iron oxides, and dithionite-EDTA (DE) to dissolve crystalline iron oxides. The amounts of chloride adsorbed by the extracted soils from 1 m NaCl at pH 5 and pH 7 were determined. The differences (ΔCl) between chloride adsorption at pH 5 and pH 7, attributed to variably charged groups, decreased when iron oxides were removed by EDTA and DE extraction. Close correlations (P>0.001), with negligible intercepts, were found (i)between EDTA-extractable iron (amorphous iron oxides) and the decrease in ΔCl following EDTA extraction, and (ii) between the difference between DE-extracted iron and EDTA-extractable iron (crystalline iron oxides) and the further decrease in ΔCL following DE extraction. The difference between ΔCl for acetate-extracted and DE-extracted samples was calculated from the contents and specific surfaces of amorphous and crystalline iron oxides, together with ΔCl per m² for synthetic iron oxides. Calculated and measured values were in very good agreement, indicating that soil iron oxides, in relation to chloride adsorption, may be treated as if they consist of only two fractions.     

The relative efficiency of ionic iron(III) and iron(II) utilization by the rice plant

Uptake of iron by rice plants was equally rapid when supplied as ionic iron(II) or iron(III) at pH 3 and 4. Iron(III) uptake was reduced at pH 5 and uptake of iron when supplied as FeEDTA was relatively low at all three pH levels.

At pH 4 in the presence of plant roots, reduction of iron(III) to iron(II) occurred as indicated by Fe²⁺ BPDS formation. BPDS in a 3:1 ratio to iron(III) suppressed iron uptake by about 70%. The reduction was observed to be located in the endodermis of young roots and exodermis of older roots.

A capacity to oxidize iron(II) at the root surface was also observed under local anaerobic and relatively high pH conditions.

The significance of these two counteracting processes in affecting the oxidation state of iron at the root surface is discussed.     

Retention of cobalt by an oxisol in relation to the content of iron and manganese oxides

Abstract

The study aims at determining the cobalt retention properties of various soil components. Therefore, cobalt (Co) sorptions and extractions were carried out using an Oxisol sample before (untreated) and after successive removal of organic matter and active manganese (Mn) oxides (H₂O₂‐treated) and iron (Fe) oxides (H₂O₂+CBD‐treated). A synthetic goethite was included for comparison. Sorption of the four sorbents was determined over a range of Co concentrations (initially 10^‐8 M to 10^‐4 M), pH values (3 to 8) and reaction times (2 hours to 504 hours). The Co species sorbed was Co(ll), since oxygen exclusion during sorption had no effect on the amount sorbed. The pH‐dependent sorption curve (sorption edge) was shifted to lower pH at decreasing initial Co concentration and increasing reaction time. The displacements, in particular of the sorption edges corresponding to the lowest initial Co concentrations, to successively higher pH following removal of Mn oxides, organic matter and Fe oxides could be attributed to sorption onto sites of decreasing Co affinity [Mn oxides (and organic matter) > Fe oxides > kaolinite]. Extractions of sorbed Co at pH 5.5–7.5 with 2 M HCI showed that the extractability decreased with increasing sorption time and decreasing initial Co concentration. The untreated and H₂O₂‐treated soil samples retained sorbed Co at least as firmly as the synthetic goethite, whereas the H₂O₂+CBD‐treated sample (kaolinite) was clearly less effective. The results emphasized the importance of the soil Mn and Fe oxides for Co retention in soils but also the necessity of taken interior sorption sites into consideration.     

Copper retention by Danish Spodosols in relation to contents of organic matter and aluminum,iron, and manganese oxides

Abstract

The importance of various soil components on copper (Cu) retention by Spodosois was investigated. Copper sorption and extraction were conducted on samples from the B horizon from six Danish Spodosois. The investigation was conducted on untreated samples, on hydrogen peroxide‐treated samples (to remove organic matter), on oxalate‐treated samples [to remove amorphous to poorly crystalline aluminum (Al) and iron (Fe) oxides], on hydroxylamine‐treated samples [to remove manganese (Mn) oxides]. Subfractions treated with hydrogen peroxide (H₂O₂) were further treated with oxalate and citrate‐bicarbonate‐dithionite (CBD). Sorption of Cu from an initial 10^‐6 M solution after 48 hours was determined in the pH range 3 to 7 using 0.1M sodium nitrate (NaNO₃) as the background electrolyte. The pH‐dependent sorption curve (sorption edge) was shifted to a higher pH with decreasing Al oxide content in the soils, and for the treated sample after removal of organic matter and Al and Fe oxides. A negligible effect was seen after removal of the Mn oxides because of their low abundance. Extraction of sorbed Cu at pH 4 to 6 with 0.1M nitric acid (HNO₃) for 24 hours confirmed the sorption results, in inasmuch as removal of the Al (and Fe) oxides increased Cu extractability. Therefore, it was concluded that in the soils investigated, Cu retention is mainly determined by the oxalate‐extractable Al fraction with a minor contribution due to crystalline Fe oxides.     

Effect of litters on the mobility of zinc, copper, manganese, and iron in the upper horizons of podzolic soils

The concentrations of water-soluble Cu, Zn, Mn, and Fe in the litters of the peaty-podzolic-gleyic and pale-podzolic soils of the Central Forest State Biosphere Reserve are inversely proportional to the pH and directly proportional to the total titratable acidity of the extracts and the content of the water-soluble organic matter (WSOM). During the interaction of the litter solutions with the mineral soil horizons, the content of metals in the solutions can vary depending on the pH, the WSOM concentration in the input solutions, the WSOM amphiphility, and the nature of the metal. The amount of water-soluble Mn, Cu, and Zn in the Eih horizon of peaty-podzolic-gleyic soils is directly proportional to the content of WSOM and inversely proportional to the pH of the litter solutions; the Fe concentration increases parallel to both parameters.     

Genotypic differences in concentrations of iron,manganese, copper,and zinc in polished rice grains

Identification of genotypic differences in micronutrient concentrations of staple food crops is essential if plant breeding strategies are to improve human mineral nutrition. The concentrations of zinc (Zn), iron (Fe), copper (Cu), and manganese (Mn) in polished grains of 285 rice (Oryza sativa L.) genotypes and the relationship between concentrations of the four micronutrient elements and concentrations of protein and lysine were examined. Significant differences (P<.01) were found in the concentrations of Zn, Fe, Cu, and Mn in polished rice with a fairly normal distribution among rice genotypes. On average, Cu and Zn concentrations of Indica rice were about 2‐fold higher than Japonica rice, while Fe concentrations of Japonica rice were slightly higher than Indica rice. Among Indica rice genotypes, red rice contained higher Zn than white rice. Protein and lysine concentrations differed considerably among the genotypes, but no close relationship between the micronutrients and protein or lysine concentrations was observed among genotypes. Sixteen genotypes with significantly higher grain Zn, Fe, Cu, and Mn concentrations were identified.     

Competitive sorption of copper,nickel, and zinc by an Oxisol

Abstract

The competitive sorption of copper (Cu), nickel (Ni), and zinc (Zn) in an Oxisol suspension was investigated using the Sheindrof‐Rebhun‐Sheituch (SRS) equation. Experimental data were obtained for a system containing these cations as single components, binary, and ternary mixtures. The associated competitive coefficients a_ij can be viewed as a way to quantify competitive interaction. The competition coefficients obtained for the cations indicated that the sorption of Ni and Zn by the soil was significantly inhibited by the presence of Cu, while the inhibition exerted in the reverse situation was milder. After a _ij ‐values were substituted in the SRS equation, the sorption values predicated by this equation for the ternary solute mixture Cu‐Ni‐Zn, were compared to values determined experimentally. The SRS equation modeled sorption successfully for the range of solute concentrations used.     

Effects of sulfur,zinc, iron,copper, manganese,and boron applications on sunflower yield and plant nutrient concentration

Abstract

Sulfur, zinc, iron, copper, manganese, and boron application did not affect the seed yield or oil percentage of sunflower (Hilianthus annuus L.) on both dryland and irrigated soils in North Dakota in 1981. Field averages indicated significant Zn, Mn, and B uptake by sunflower at the 12‐leaf stage as a result of fertilization with these elements. Increased Zn uptake was also observed in the uppermost mature leaf at anthesis from zinc fertilization.

Although sunflower yield from boron fertilization was not significantly different from the check, a trend was observed in which boron fertilization seemed to decrease sunflower yield. Sunflower yields from the boron treatment were the lowest out of seven treatments in three out of four fields. Also, sunflower yield from the boron treatment was significantly lower than both iron and sulfur treatments when all fields were combined.     

Effects of moist storage and different drying temperatures on the extractability of iron,copper, manganese,and zinc in soil samples

Abstract

The objective of this study was to investigate the effect of different pretreatments on the extraction of cationic micronutrients [iron (Fe), copper (Cu), manganese (Mn), and zinc (Zn)] from four different soils. Samples were either stored in the field‐moist state for seven days before drying or dried immediately. Three drying treatments were used: air‐dried (72 hours), oven‐dried at 40°C (48 hours), or oven‐dried at 105°C (24 hours). Micronutrients were then extracted with 0.1N HC1 or diethenetriamine‐pentacetic acid (DTPA). Storage, drying temperature, extractant, and soil type all influenced micronutrient extractability. In general, a higher temperature increased the level of micronutrient extracted. However, the reverse effect was also observed. The effect of storage was variable and probably depended on the sample moisture content. We conclude that the results from routine analysis and experimentally determined indices can only be compared if soil samples are subjected to the same pretreatments. Hence, rigorous standardization of the sample preparations is imperative for accurate determination of plant‐available micronutrients.     

Adsorption of Cr(VI) ion on synthetic hydrated oxides of iron

Abstract

The adsorption of Cr(VI) ion on synthetic hydrated oxides of iron (goethite (α-FeOOH) and lepidocrocite (γ-FeOOH)) with different crystallinities was studied in order to remove the Cr(VI) ion from polluted water. At pH 4.5, the amounts of the adsorbed Cr(V1) ion on goethite and lepidocrocite were 51.9 and 62.2 mmol g^?, respectively. Probably, this is due to the fact that the structure of lepidocrocite is more open than that of goethite. Lepidocrocite, therefore, is more effective for the removal of Cr( V1) ion from Cr(Vl)-contaminated and acidic groundwater and sewage.     

Comparison of different models for phosphate sorption as a function of the iron and aluminium oxides of soils

Phosphate sorption on topsoil and subsoil samples from different soils located in the eastern part of Germany was studied. Two models were fitted to sorption data obtained after 4 and 40 d of gentle shaking. The models differ with respect to the fractions of iron and aluminium (hydr)oxides that are considered and whether the phosphate initially sorbed in the soil is taken into zccount. Oxalate-extractable P, (P_ox), appears to be a major part of the total soil P. The total P sorption measured, F, was predominantly related to the amounts of amorphous iron (Fe_ox) and aluminium (Al_ox). A significant relation between crystalline iron (Fe_d– Fe_ox) and total P sorption was not found. Reversibly adsorbed phosphate (P_i), measured after 40 d reaction time, was a function of clay content and content of amorphous iron and aluminium (hydr)oxides.     

Significance of hydrous iron oxides in enhancing P sorption of soils with the addition of sodium hydrosulfite (Na2S2O4)

Phosphorus sorption (P_sor) of soils is affected by redox conditions. It has been shown that P_sor of lowland soils at a pH value of about 4.3 increases when a small amount of sodium hydrosulfite (Na₂S₂O₄) is added and decreases when an excess amount of (Na₂S₂O₄) is added to the mixture of a soil and P solution. Hydrous Fe-Al oxides, manganese dioxide (MnO₂) exchangeable Ca, models of reactive components with P in soils, were examined to identify the factors responsible for the increase of P_sor in lowland soils when a small amount of Na₂S₂O₄ was added. For clarifying the contribution of the hydrous Fe-Al oxides, goethite and 7 hydrous Fe-Al oxides (Fe/Al atomic ratio: 1/0, 5/1, 2/1, 1/1, 1/2, 1/5, and 0/1) were used. The P_sor of all these materials increased when they were treated with a small amount of Na₂S₂O₄ although the increase was the smallest for the hydrous Al oxide among the 7 oxides. Thus, the hydrous Fe oxides, and Al oxide to a smaller extent, play an important role in the increase in P_sor of the lowland soils treated with a small amount of Na₂S₂O₄ The P_sor of the hydrous Fe oxides was not appreciably affected by the addition of MnO₂. The increase in P_sor of the Ca-saturated Hachirogata soil was almost the same as that of the Nasaturated Hachirogata soil, indicating that exchangeable Ca did not affect appreciably the increase of P_sor in reduced soils at a pH value of about 4.3.     

Effect of the main soil components on the sorption of copper,zinc, and lead by urban soils

The sorption of copper, zinc, and lead by two urban soils with different levels of contamination was studied. Changes in the sorption capacity and fixation strength of the metals were revealed after the destruction of the main components playing the important role in the fixation of metals by the soil.