Mobilization of iron by phytosiderophores as affected by other micronutrients

It has been shown previously (Treeby et al., 1989) that phytosiderophores, released by roots of iron deficient grasses (Gramineae), mobilize from calcareous soils not only iron (Fe) but also zinc (Zn), manganese (Mn) and copper (Cu). Mobilization of Fe may therefore be impaired by other micronutrient cations. This has been studied in both, model experiments with Fe hydroxide and with a calcareous soil (15% CaCO₃, pH 8.6) amended with micronutrients as sulfate salts.Mobilization of Fe from Fe hydroxide by phytosiderophores (epi-3-hydroxymugineic acid) was not affected by the addition of CaCl₂, MgSO₄ and MnSO₄, slightly inhibited by ZnSO₄ and strongly inhibited by CuSO₄. In a calcareous soil amended with increasing levels of ZnSO₄, MnSO₄ and CuSO₄, mobilization of Fe by phytosiderophores remained uneffected by Zn and Mn amendments but was progressively impaired by increasing levels of Cu amendment, correlated with corresponding enhancement of Cu mobilization.High concentrations of ZnSO₄ and MnSO₄ and relatively high concentrations of CuSO₄ were required for inhibition of Fe mobilization by phytosiderophores. It is therefore concluded that in most calcareous soils phytosiderophores efficiently mobilize Fe, and that phytosiderophores play an important role in Fe acquisition by grasses grown on calcareous soils.     

Distribution of selected elements within flax plants as affected by FeEDDHA

Summary Flax growing on a calcareous soil in the greenhouse developed Mn toxicity symptoms. The toxicity was eliminated by application of 2 ppm FeEDDHA-Fe. FeEDDHA had major effects on distribution of Mn, Zn, Fe and P among selected plant parts. Application of the chelate reduced Mn concentration in older leaves, the tissue most susceptible to Mn toxicity, associated stem tissue, plant tops, and roots from 2295 to 133 ppm, 62 to 7 ppm, 550 to 34 ppm, and 42 to 34 ppm, respectively. Analysis of older leaves is recommended for diagnosing Mn toxicity in flax.FeEDDHA reduced Zn concentration in plant tops and this was chiefly reflected in greatly reduced leaf concentrations, especially in older leaves. FeEDDHA increased plant Fe concentration and the effect was greatest in root and older leaf tissues. The overall effect of FeEDDHA on P concentration was small but large increases occurred in younger leaf tissue due to application of the chelate. Relative distributions of K, Na, Ca, and Mg among plant parts were only slightly affected by FeEDDHA.     

The effects of nutrient supply,predominantly addition of iron,and rhizobial inoculation on the tolerance of Lupinus pilosus genotypes to a calcareous soil

Two glasshouse experiments were conducted to examine the effects of nutrient supply and rhizobial inoculation on the performance of Lupinus pilosus genotypes differing in tolerance to calcareous soils. In experiment 1, plants were grown for 84 days in a calcareous soil (50% CaCO₃; soil water content 90% of field capacity) at four nutrient treatments (no-added nutrients, added nutrients without Fe, added nutrients with soil applied FeEDDHA, added nutrients with foliar applied FeSO₄). In experiment 2, plants were grown for 28 days with supply of NH₄NO₃ without inoculation or inoculated with Bradyrhizobium sp. (Lupinus). Chlorosis in the youngest leaves was a good indicator of the relative tolerance of the genotypes to the calcareous soil in both experiments, except the treatment with FeEDDHA at 5 mg kg^–1 soil which was toxic to all genotypes. Chlorosis scores correlated with chlorophyll meter readings and chlorophyll concentrations. The foliar application of FeSO₄ did not fully alleviate chlorotic symptoms despite concentrations of active or total Fe in the youngest leaves being increased. Adding nutrients and chemical nitrogen did not change the severity of chlorosis or improve the growth of the plant. The nutrient supply did not alter the ranking of tolerance of genotypes to the calcareous soil. The results suggest that nutrient deficiency or poor nodulation was not a major cause of poor plant growth on calcareous soils and that bicarbonate may exert a direct effect on chlorophyll synthesis. The mechanism for tolerance is likely to be related to an ability to exclude bicarbonate or prevent its transport to the leaves.     

Geochemistry of recent marine sediments in the Bardawil lagoon,northern Sinai,Egypt

The concentrations of major (Al, Fe, Mg, Ti, K and Na) and minor (Ba, Sr, V, Cu, Mn, Cr, Ni, Zn, Pb and Mo) elements as well as carbonate, organic carbon and total nitrogen have been determined in surface sediments collected at 12 stations from the Bardawil lagoon. The aim of the study was to characterize the geochemistry of the sediments in three different environments, the lagoon, the salt pans and the inlet between the lagoon and the Mediterranean Sea. Higher CaCO₃ percentage (53.5–70.5%) were found in the salt pans where biogenic calcareous components and carbonate rock fragments were found in sufficient quantities in the sediment fractions. Based on high C/N ratios, the organic carbon fraction of the Bardawil lagoon surface sediments is clearly dominated by terrigenous material. The distribution of Al, Fe, Mg and Ti are essentially controlled by the mineralogy of the sediments. The ratios of Ba, Sr, Cu, Mn, Pb and Mo to Al are all high in the salt pans and reflect changes in mineralogy and sediment texture.     

Heavy Metals and Trace Element Concentrations in Intertidal Soils of Four Estuaries of SW Iberian Peninsula

Soils from four estuaries of SW Iberian Peninsula, affected by anthropogenic influence (urban, industrial and agricultural activities), were analyzed for the occurrence of a variety of metals and trace elements including Al, As, B, Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, P, Pb, S and Zn. The soils presented very high levels of salinity (high concentrations of Na, K and Mg), organic matter and, consequently, of C and N concentrations. In contrast, very low values of CaCO₃, Ca and P were found. In addition, it should be highlighted that in certain localities (Piedras 1 and 2 and Guadiana in Huelva, Spain, and Ria Formosa, Faro, Portugal) the concentrations of Pb, S and Zn were extremely high, reaching levels of pollution.     

Considerations on the shuttle mechanism of FeEDDHA chelates at the soil-root interface in case of Fe deficiency

Aim

A mechanism of action for the performance of Fe chelates as soil-applied fertilizer has been hypothesized by Lindsay and Schwab (J Plant Nutr 5:821–840, 1982), in which the ligand participates in a cyclic process of delivering Fe at the root surface and mobilizing Fe from the soil. This “shuttle mechanism” seems appealing in view of fertilizer efficiency, but little is known about its performance. The chelate FeEDDHA is a commonly used Fe fertilizer on calcareous soils.

Methods

In this study, the performance of the shuttle mechanism has been examined for FeEDDHA chelates in soil interaction and pot trial experiments.

Results

The specificity of EDDHA ligands for chelating Fe from soils of low Fe availability is limited. Experimental support for a shuttle mechanism in soil-plant systems with FeEDDHA was found: specific metal mobilization only occurred upon FeEDDHA-facilitated Fe uptake. The mobilized metals originated at least in part from the root surface instead of the soil.

Conclusion

The results from this study support the existence of a shuttle mechanism with FeEDDHA in soil application. If the efficiency of the shuttle mechanism is however largely controlled by metal availability in the bulk soil, it is heavily compromised by complexation of competing cations: Al, Mn and particularly Cu.     

Effects of phosphorus and iron fertilizers on the growth of two soybean varieties at two soil temperatures

The influence of FeEDDHA (0, 0.2 and 2 μg Fe g⁻¹ soil) and NaH₂PO₄·H₂O (0 and 120 μg Pg⁻¹ soil) on the growth of two Fe-ineffective soybean (Glycine max L. Merr.) varieties (anoka and T203) on a calcareous soil at two soil temperatures (16 and 24°C) was compared under greenhouse conditions. The two soybean varieties differed in the following respects: (a) T203 accumulated smaller concentrations of Fe in washed tops than Anoka under comparable conditions; (b) T203 was more susceptible to Fe deficiency and its accentuation by high levels of fertilizer P than Anoka; (c) T203 accumulated lower quantities of Mn in tops than Anoka under comparable conditions; (d) T203, but not Anoka, developed Mn deficiency symptoms when treated with P and 2 μg Fe g⁻¹ at 16°C. Fe deficiency was more severe in both varieties at the higher soil temperature due apparently to: (a) greater plant concentration of P in tops at 24°C; and/or (b) an increased rate of plant growth and greater dilution of Fe in young tissue at 24°C. Foliar P concentration was increased much more than foliar Fe concentration by an increase in soil temperature. Severely Fe deficient T203 plants grown without FeEDDHA at 24°C accumulated less foliar Mn than their FeEDDHA counterparts. Comparisons of Fe effectiveness of various soybean cultivars based on relative responses to FeEDDHA can be influenced by differential effects on Mn nutrition.     

Mobilisation of iron and manganese by plant-borne and synthetic metal chelators

Phytosiderophores released by roots of iron-deficient grasses mobilise Fe, Zn, Mn and Cu in calcareous soils. Mobilisation of Fe, Zn and Cu can be explained as the chelation of these metal cations by phytosiderophores. Mobilisation of Mn could not be so explained because phytosiderophores have a much smaller affinity for Mn than for Fe, Cu and Zn. Model experiments have been made with freshly precipitated Fe(OH)₃ and different soils to study the mobilisation of iron and manganese by plant-borne chelating phytosiderophores, the synthetic metal chelators DTPA and the microbial metal chelator sulphonated ferrioxamine B (FOB). Compared with the synthetic chelator DTPA, the plant-borne chelating phytosiderophores mobilised Fe very efficiently, but no change was observed in the Mn mobilisation by phytosiderophores.Different phytosiderophores, as well as the microbial metal chelator FOB, were used to compare the mobilisation of iron and manganese in a calcareous soil.     

Accumulation of cadmium and selected elements in flax seed grown on a calcareous soil

Seed of flax (Linum usitatissimum L.) grown on calcareous and neutral soils sometimes accumulates relatively high concentrations of Cd. The influence of a post-flowering application of NH₄NO₃ (115 mg N kg^-1), CdSO₄ (1 mg Cd kg^-1), FeEDDHA (2 mg Fe kg^-1), NaH₂PO₄ (120 mg P kg^-1) and ZnSO₄ (8 mg Zn kg^-1) on seed accumulation of Cd, Fe, N, Mn, P and Zn by flax grown on a Calciaquoll was studied in two experiments under greenhouse conditions. Seed yields were increased by the N and Zn treatments, and the N×Zn interaction was positive. Zinc deficiency delayed flowering and boll formation by up to 20 days and reduced seed size. In the absence of added Cd, seed accumulated up to 0.33 mg Cd kg^-1. This Cd accumulation was reduced by approximately 50 and 17% by added Zn and Fe, respectively, but was little affected by P fertilizer and post-flowering N stress. In the presence of added Cd, seed Cd exceeded 3.3 mg Cd kg^-1, and the antagonistic effects of Fe and Zn on seed Cd were absent. Seed N, P, Fe and Zn concentrations were increased on average by 10, 45, 31 and 97% by the N, P, Fe and Zn fertilizer treatments, respectively. FeEDDHA reduced seed Mn concentration by approximately 58%. However, seed Mn concentration was much less than that found in vegetative tissue at flowering. Soil-applied Zn may reduce seed Cd concentration in flax under field conditions, and may increase marketability of flax for food use.     

Accumulation of Minerals by Leccinum scabrum from Two Large Forested Areas in Central Europe: Notecka Wilderness and Tuchola Forest (Pinewoods)

Leccinum scabrum sporocarps and associated topsoils from two areas in Poland have been characterized for contents and bioconcentration potential of Ag, Al, Ba, Ca, Cd, Co, Cu, Fe, Hg, K, Mg, Mn, Na, Ni, P, Pb, Rb, Sr and Zn. Topsoil and fruitbody element composition varied between the two study sites, most likely as a result of local soil geochemistry. Element content of the labile fraction in topsoil from both sites followed the ‘pseudo‐total’ fraction and median values (mg kg^?1 dry matter) were: K 380 and 340, Mg 760 and 840, P 1100 and 920, Al 3800 and 8100, Ag 0.31 and 0.28, Ba 28 and 37, Ca 920 and 790, Cd 0.23 and 0.23, Co 2.0 and 1.7, Cu 3.2 and 3.6, Fe 2800 and 6300, Mn 280 and 180, Na 99 and 110, Ni 7.8 and 8.8, Pb 12 and 18, Rb 1.3 and 2.1, Sr 4.8 and 4.0 and Zn 22 and 19, respectively. Only for some elements such as K, Mg, Al, Ag, Ca, Co, Mn, Na, Ni, Sr and Zn we found concentration differences between the two study sites for the caps of sporocarps. With the exception of Al, Mn, Na and Pb, stipes showed a similar tendency. Caps had a higher concentration of K, Rb, P, Mg, Al, Ag, Cu, Fe, Zn, Cd, Pb and Ni compared to stipes, while Na, Ba and Sr contents were higher in stipes. The comparison of soil and fruitbody concentrations indicates that L. scabrum bioconcentrate some elements while others are bioexcluded.     

Influence of washing on elemental analysis of leaves of fieldgrown crop plants

Summary Information is limited on soil contamination of leaves from field-grown row crops, especially with respect to aluminum (Al) analyses. The objective of this study was to determine the influence of washing leaf samples with either deionized water or detergent solution on elemental analyses for several agronomic crop plants. The crop plants sampled were corn (Zea mays L.), soybean (Glycine max L. Merr.), grain sorghum (Sorghum bicolor L. Moench), and wheat (Triticum aestivum L.). The crops were grown on a range of soil types, soil pH values, and tillage practices. Samples of upper leaves and lower leaves were collected separately. The samples were either not washed, washed with deionized water, or washed with detergent solution. After drying, grinding, and digesting, the samples were analyzed for Al, nitrogen (N), phosphorus (P), potassium (K), calcium (Ca), magnesium (Mg), iron (Fe), manganese (Mn), zinc (Zn), and copper (Cu). For all crop plants and conditions studied, there was no effect on measured N, P, K, Ca, Mg, Mn, Zn, or Cu concentrations, but measured Al and Fe concentrations were influenced by washing. In general, washing had a greater effect on Al analyses than on Fe analyses. Soybean samples were most affected by washing, while wheat samples seemed to be least affected. The results reflected greater contamination of lower leaves than upper leaves. Decontamination procedures appear necessary prior to Al and Fe analyses of field-grown crop plants.     

Accumulation of electropositive and amphoteric elements in leaves in relation to genetic-fixed ability for biosynthesis of anthocyanins

Summary By means of semi-quantitative spectral analysis in UV-region (carbon electrodes) have been found: 1) in young leaves ofPersica vulgaris Miller formaatropurpurea Schneid. more Na, K, Cu, Mg, Ba, B, Al, Si, P, Cr, Mn, Fe, Ni than in the older leaves 2) in leaves of bud-mutation characterized by increased ability for biosynthesis of anthocyanins more K, Mg, Ca, Sr, Al, Si, P, Cr, Mn, Fe, Ni and less Ag, Zn than in normal leaves ofEuonymus fortunei (Turcz.) Hand.-Mazz. var.argentei-marginata Rehd. characterised at source plant by high accumulation-coefficient of Ag (=500). Influence of ions on anthocyanins formation has been discussed.     

Metals in some dominant vascular plants, mosses, lichens, algae, and the biological soil crust in various types of terrestrial tundra, SW Spitsbergen, Norway

Arctic environments are commonly considered to be relatively pristine because of minimal local human activity. However, these areas receive air pollution from lower latitude regions. Our goal was to determine concentrations of metals (Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, and Zn) in dominant species of vascular plants, mosses, lichens, algae, and in the biological soil crust (BSC), and topsoil (0–3 cm) from various types of tundra in the southwestern part of Spitsbergen, Norway. Results indicate that mosses are more efficient bioaccumulators of Cd, Co, Cr, Cu, Fe, Mn, and Zn than lichens. The highest levels of Co, Cr, Cu, Fe, Hg, Mn, Ni, and Pb were found in the BSC, and the moss species Racomitrium lanuginosum, Sanionia uncinata, and Straminergon stramineum from the polygonal tundra, initial cyanobacteria-moss wet tundra, snow bed cyanobacteria-moss tundra, and flow water moss tundra alimented by melting ice or snow. The observed higher concentrations of Cu and lower concentrations of Hg in mosses, lichens, and vascular plants compared with values observed 20 years earlier were apparently associated with changes in the atmospheric deposition of contaminants over Spitsbergen due to changes in the long-distance transport of anthropogenic emissions from industrialized areas. Prasiola crispa and Salix polaris may be useful bioindicators of Cd and Zn, and the BSC, R. lanuginosum, S. uncinata, and S. stramineum as bioindicators of Co, Cr, Cu, Fe, Hg, Mn, Ni, and Pb. These results may be extrapolated across other areas of Spitsbergen with similar climates.     

Toxicity and accumulation of copper and nickel in maize plants cropped on calcareous and acidic field soils

Field experiments in calcareous and acidic field soils were conducted to study the effects of copper (Cu) and nickel (Ni) added to soils on maize growth and metal accumulation in maize plants. The results revealed that the critical concentrations of Cu added to soils that decreased maize grain yield by 10% (EC₁₀) were 711 mg kg^?1 for calcareous soil with a pH of 8.9, and 23 mg kg^?1 for acidic soil with a pH of 5.3. The toxicity thresholds of EC₁₀ did not differ significantly for Cu and Ni. A different pattern of Cu and Ni accumulation in maize plants was also found. The accumulation of Cu in above-ground parts of the plants increased initially as the concentrations of Cu added to soils increased, after which they decreased to a constant level. As the concentrations of Ni added to soils increased, the accumulation of Ni in stems and leaves increased linearly, but the accumulation of Ni in the grains was nonlinear. Additionally, the results revealed that Ni was transported to grains more easily than Cu. The results also showed that the concentrations of Cu and Ni in soil solutions as toxicity predictors and the critical concentrations of Cu and Ni in maize were all soil-dependent.     

Usage of sewage effluent in irrigation of some woody tree seedlings. Part 3: Swietenia mahagoni (L.) Jacq.

A pot experiment was investigated to study the effect of sewage irrigation treatments (primary and secondary effluents) compared with tap water on the growth and chemical constituents of mahogany seedlings (Swietenia mahagoni (L.) Jacq.) as well as soil chemical properties. The experiment was conducted at a greenhouse in the nursery of Timber Trees Research Department of Sabahia, Horticultural Research Station in Alexandria, Egypt, from June 2003 to December 2004 for three irrigation periods (6, 12 and 18 months). The sewage effluent waters were taken from oxidation ponds located in New Borg EL-Arab city and used directly for irrigation.The primary effluent treatment was superior than other treatments in improving the growth parameters (plant height, stem diameter, leaf area, leaves number, fresh and dry weights of leaves, shoots and roots and shoot/root ratio) and showed the highest concentration and total uptake of N, P, K, Cd, Ni, Pb and Fe in plant parts, followed by secondary effluent then tap water. The data revealed that soil salinity in terms of electrical conductivity of saturated paste (EC), CaCO₃%, organic matter% and soluble anions and cations were influenced significantly by primary or secondary effluent treatment. The data also showed that the use of sewage effluent for irrigation increased N, P, K and DTPA-extractable-heavy metals (Cd, Cu, Ni, Pb, Fe, Mn and Zn). The effects of sewage effluent on growth parameters and elements content in plant parts and treated soil were more pronounced as water treatments were used for long period.The results suggested that the use of sewage effluent in irrigating mahogany trees grown on calcareous sandy loam soil was an important agriculture practice for improving soil properties, increasing fuel and timber production, and is an economic and safe way to dispose wastewaters.     

Forest leaf litter decomposition in the vicinity of a zinc smelter

Summary Concentrations of about 26,000 ppm Zn, 10,000 ppm Fe, 2,300 ppm Pb, 900 ppm Cd, 340 ppm Cu, and 0.40% S were measured in the O₂ litter horizon about 1 km from a zinc smelter at Palmerton, Pennsylvania. Samples taken about 6 km east of the smelter had concentrations of about 15,000 ppm Zn, 6,500 ppm Fe, 970 ppm Pb, 250 ppm Cd, 170 ppm Cu, and 0.26% S. Samples from a control area about 40 km east of the smelter had concentrations of 2,800 ppm Fe, 650 ppm Zn, 260 ppm Pb, 50 ppm Cu, 9 ppm Cd, and 0.13% S.Litter bags were used to estimate first-year weight loss in sassafras leaves and a mixture of chestnut oak/red oak leaves in the three sites. At the end of one year, average weight loss for sassafras was 39.3% in the control site, 21.8% at 6 km, and 17.5% at the 1 km site. For the chestnut oak/red oak mixture, average weight loss was 36.8% (40 km), 25.7% (6 km), and 19.1% (1 km). Numbers and diversity of soil microarthropods inhabiting the litter bags showed a corresponding decline at sites near the smelter. Concentrations of Ca, Cd, Cr, Cu, Fe, Mg, Mn, N, Na, Ni, P, Pb, S and Zn in the decomposing litter were also measured.The average amount of organic matter on the forest floor was estimated to be 3.8 kg/m² in the control site, about 3.8 kg/m² at 6 km, and about 8.1 kg/m² 1 km from the smelter. Average thickness of the litter horizons in these three sites was 6.0 cm (40 km), 7.0 cm (6 km), and 12.4 cm (1 km), suggesting a long-term depression of decomposition and mineral cycling near the smelter.     

Effects of soil acidification on the chemical extractability of Fe,Mn, Zn and Cu and the growth and micronutrient uptake of highbush blueberry plants

Summary The effects of soil acidification and micronutrient addition on levels of extractable Fe, Mn, Zn and Cu in a soil, and on the growth and micronutrient uptake of young highbush blueberry plants (Vaccinium corymbosum L. cv. Blueray) was investigated in a greenhouse study.Levels of 0.05M CaCl₂-extractable Fe, Mn, Zn and Cu increased as the pH was lowered from 7.0 to 3.8. However, the solubility (CaCl₂-extractability) of Fe and Cu was considerably less pH-dependent than that of Mn and Zn. With the exception of HCl-and DTPA-extractable Mn, micronutrients extractable with 0.1M HCl, 0.005M DTPA and 0.04M EDTA were unaffected or raised only slightly as the pH was lowered from 6.0 to 3.8. Quantities of Mn and Zn extractable with CaCl₂ were similar in magnitude to those extractable with HCl, DTPA and EDTA whilst, in contrast, the latter reagents extracted considerably more Cu and Fe than did CaCl₂. A fractionation of soil Zn and Cu revealed that soil acidification resulted in an increase in the CaCl₂- and pyrophosphate-extractable fractions and a smaller decrease in the oxalate-extractable fraction.Plant dry matter production increased consistently when the soil pH was lowered from 7.0 to 4.6 but there was a slight decline in dry matter as the pH was lowered to 3.8. Micronutrient additions had no influence on plant biomass although plant uptake was increased. As the pH was lowered, concentrations of plant Fe first decreased and then increased whilst those of Mn, and to a lesser extent Zn and Cu, increased markedly.     

Iron-chelates evaluation in a calcareous soil

A greenhouse pot experiment withLolium multiflorum, cv. Tetila, grown in a calcareous soil was carried out to determine the efficiency of iron-chelate (Fe-EDTA,-DTPA,-EDDHA and Rexene) as soil amendments. In the soil solution Fe was displaced more readily from EDTA chelate and less so from EDDHA chelate. A significant increase of Mn, Cu and Zn in the soil solution was observed, with Fe-DTPA; Cu and Zn with Fe-EDTA; Cu with Rexene and, with Fe-EDDHA after 14 days. Plant took up more Fe from Rexene treatment than from the other treatments, Fe-EDDHA was the least efficient. In general, Mn, Cu and Zn concentrations in the leaf diminish in all the treatments compared with the control.     

The effects of acidification on metal budgets of lakes and catchments

Metal (Cu, Ni, Zn, Fe, Mn and Al) budgets were measured for 5 lakes and their catchments near Sudbury, Ontario, an area severely affected by the emission and deposition of strong acids (H₂SO₄/SO₂) and metals. Three of the lakes were circum-neutral (pH 6.3–7.1) during the study period, while one lake had a pH of 4.8 and a fifth had very low pH ( 4.4).The lakes' catchments were all sources of Al, Mn and Ni, but were sinks for Cu and Zn. The Fe results were inconsistent; two lakes' catchments were sources while three were sinks.The acidic lakes were conservative (i.e. net retention of zero) with respect to Cu and Ni, while the circum-neutral lakes were effective sinks for these 2 metals. All of the lakes were sinks for Zn and Al, but the acidic lakes were less effective. All lakes were also Fe sinks. While there was no pattern relative to the lakes' pH's, there was a trend towards increasing Fe retention with increasing water replenishment time. The most acidic lake was actually a source of Mn, while the others were sinks.     

Systematic characterization on electronic structures and spectra for a series of complexes, M(IDB)Cl2 (M = Mn, Fe, Co, Ni, Cu and Zn): a theoretical study

Theoretical studies on the coordination stabilities, spectra and DNA-binding trend for the series of metal-varied complexes, M(IDB)Cl₂ (M = Mn, Fe, Co, Ni, Cu and Zn; IDB = N, N -bis(2-benzimidazolylmethyl) amine), have been carried out by using the DFT/B3LYP method and PCM model. The calculated coordination stabilities (S) for these complexes present a trend of S(Ni) > S(Co) > S(Fe) > S(Cu) > S(Zn) > S(Mn). It has been estimated from the molecular orbital energies of the complexes that the DNA-binding affinities (A) of the complexes are in the order of A(Zn) < A(Mn) < A(Fe) ≈ A(Co) < A(Ni) < A(Cu). The studied results indicate that the Cu, Ni and Co complexes with large coordination stabilities present the low virtual orbitals, consequently yielding to the favorable DNA-binding affinities. The spectral properties of excitation energies and oscillator strengths for M(IDB)Cl₂ in the ultraviolet region were calculated by TD-DFT/B3LYP method.