Characterization of the Fe(III)—fulvic acid reaction by Mössbauer spectroscopy

Fulvic acids have been isolated from a sandy loam (Countesswells series) and a clay soil (Tipperty series) and the products of their reaction with different amounts of iron over a range of pH from 0.5 to 11 analyzed by Mössbauer spectroscopy. Three distinct types of spectral component were detected at 77 K, a sextet from magnetically dilute Fe(III) and doublets from Fe(II) and Fe(III), the last arising from both organic complexes and poorly crystalline oxide species. In iron-fulvic acid mixtures the proportion of iron as Fe(II) increased as the pH was lowered from 5 to 1 by the addition of hydrochloric or nitric acid at all Fe to fulvic acid ratios (1:5 to 1:500). When the pH was lowered below 1 the amounts of Fe(II) decreased with the lower Fe to fulvic acid ratios, but increased with the higher ratios. The amounts of the Fe(III) component contributing to a doublet signal decreased with decreasing Fe:fulvic acid ratios. At low iron concentrations the iron appears to be strongly bound to the fulvic acid, but when the iron content is of the order of 1–2% uncomplexed Fe(III) species can be present. At pH > 2 these are hydrolysed ions which form poorly-crystalline oxides at higher pH. This was confirmed by analysis of spectra at 4.2 K. At pH < 2 free ions are present in solution. In solutions with high fulvic acid contents (greater than 100-fold excess) the reactions with iron are completely reversible, but in solutions with a lower proportion of fulvic acid to iron, where free ions are present, there is a lack of reversibility.     

EPR spectra of humic acids and their metal complexes

On the basis of ESR spectra, humic substances are believed to be hydroquinone type polymer radicals with considerable cation exchange and redox capacity. All 3d-transition metal humates appear to be ionic high spin complexes. Manganese (II) ions doped in raw peats and peat humic acids are coordinated octahedrally with six oxygen-containing functional groups, e.g., carboxylate, phenolic, hydroxyl, carbonyl ligands, whereas copper (II) ions are in square planar arrangement with two carboxylate and two aliphatic nitrogen ligands. Doping with vanadyl(II) ions results in a square pyramidal arrangement with four oxygen-containing ligands. Diamagnetic manganese(VII), chromium(VI), molybdenum (VI) and vanadium(V) oxoanions in acidic solution are reduced by humic acids into paramagnetic manganese(II), chromium(III), molybdenum(V) and vanadium(IV) ions. Diamagnetic copper(I) ions, on the other hand, are oxidized by humic acids into paramagnetic copper(II) ions.In contrast to polyronic acid gels with outer-sphere structure, 3d-transition metal ions are generally bound to humic acids as inner-sphere chelate complexes.     

Soil–Plant Nutrient Status and their Relations in Maize-Growing Fields of Wolaita Zone,Southern Ethiopia

This study investigates the soil–plant nutrient status and relationship in Wolaita, Southern Ethiopia. Maize leaves, soil samples and field history were collected. The result indicated that continuous cultivation without fallowing, complete crop residue removal and inadequate fertilization were common practices. The soil was low in organic carbon, total nitrogen, available phosphorus, potassium, sulfur, boron and copper. Tissue analysis indicated 100, 84, 54 and 28% deficiency of nitrogen, phosphorus, potassium and copper, respectively. Significant and positive correlations (r = 0.70, 0.40 and 0.50) of soil phosphorus, calcium and copper with tissue content were observed. Soil pH was correlated with tissue phosphorus (r = 0.4), iron (r =—0.3) and manganese (r = ?0.7). Overall, the levels of calcium, magnesium, iron, manganese and zinc were adequate for maize. Therefore, fertilizer application addressing nitrogen, phosphorus, potassium and copper deficiencies is recommended for the study area.     

复合氨基酸微量元素螯合肥制备工艺研究

以废弃鸡毛水解液为复合氨基酸来源,研究其与微量元素铁、锌、锰、铜螯合的最佳工艺条件,并利用有机溶剂沉淀分离法制备固体复合氨基酸亚铁、锌、锰、铜螯合物,以螯合率为指标考察影响制备工艺的主要因素。结果表明,最佳工艺参数为:复合氨基酸与亚铁、锌、锰和铜螯合反应的最佳配位体摩尔比均为2∶1;最佳pH值范围分别为5.0、8.0、4.0～5.0和6.0～7.0;反应温度为室温(222～6℃);反应时间为30.min。在上述条件下,复合氨基酸与各微量元素的螯合率均超过95%;所得复合氨基酸螯合物可与0.2.mol/L磷酸二氢钾复配,克服了传统微肥完全不能与磷酸盐复配的缺陷。     

中国稻田土壤有效态中量和微量元素含量分布特征

基于全国282个水稻土监测点,分析土壤有效态中、微量元素含量及区域特征(东北、长三角、长江中游、西南、华南),结合丰缺标准,揭示中、微量元素丰缺程度。结果表明:东北水稻土交换性镁和有效硼含量高于其他地区,有效锌含量最低;长三角有效锰含量最高、有效硫含量最低;长江中游有效铜含量最高,有效态铁、锰和钼含量最低;西南交换性钙含量高于其他地区,有效铜含量则低于其他地区;华南有效态铁、钼含量均高于其他地区,而交换性钙、镁含量低于其他地区。中国水稻土交换性钙、镁及有效铁、锰、铜含量整体丰富;长三角和华南缺硫水稻土比例分别为42.2%和41.8%;东北、长三角、长江中游、西南和华南缺锌水稻土比例分别为75.0%、52.3%、31.9%、53.2%和10.4%,缺硼分别为38.5%、65.2%、92.2%、88.6%和78.3%,缺钼28.6%、60.4%、82.6%、42.0%和33.4%。可见,东北和长三角水稻土以缺锌为主;长江中游以缺硼、钼为主;西南以缺硼为主;华南以缺硼为主。研究可为全国和区域尺度水稻土中微量元素的管理和合理施用提供依据。     

Nifedipine influence on mineral nutrient uptake by sorghum primary root tips

Seedling sorghum [Sorghum bicolor (L.) Moench. cv GP‐10, SC283, SC574, and Funk G522DR] primary root tips (1‐cm) content of calcium (Ca), phosphorus (P), zinc (Zn), boron (B), manganese (Mn), iron (Fe), magnesium (Mg), and copper (Cu) in response to a Ca²⁺‐channel blocker (nifedipine 0, 0.01, 0.1, or 1 μM) was measured after a 1‐hr exposure to Hoagland and Arnon complete mineral nutrient solution. Content of ions was significantly different among the cultivars. Responses to nifedipine were element‐cultivar‐blocker concentration dependent.     

Evidence for aliphatic mixed mode coordination in copper(II)–fulvic acid complexes

A comparative approach based on ion–selective electrode measurements is presented for studying Cu(II) complexing by fulvic acids. Metal binding curves (% free metal vs pH) and complexation capacity curves (% free metal vs total metal at fixed pH) for copper(II) fulvic acid systems are compared with those for appropriate model ligands.
It is inferred that citrate, malonate and amino acid moieties could dominate complexing to Cu(II) at pH 3 to 7. The involvement of amino acid moieties is supported by fluorescence quenching and by anodic stripping voltammetry (ASV) studies. The proportion of ASV–non labile complexes is reported for Cu(II) and Pb(II) fulvic acid systems at pH 4.8.
A mixed mode of coordination is proposed, with the dominant binding sites varying with pH and metal:ligand ratio.     

Effect of arsenic on concentrations and translocations of mineral elements in the xylem of rice

By using Particle-Induced X-ray Emission (PIXE) technique, the effect of arsenic (As) on the mineral contents and translocation in the xylem of rice (Oryza sativa L. cv. ‘Akihikari’) was studied. The results suggest that exogenous As increased the concentrations of phosphorus (P), calcium (Ca) magnesium (Mg), sulfur (S), and manganese (Mn) in xylem, while the concentrations of potassium (K) remained unchanged. The highest concentration of As to the rice roots did not have any clear effect on the translocation of P, Ca, S, and chlorine (Cl) in the xylem, indicating that the increasing concentrations of the minerals may be due to a condensation effect, resulting from the repression of water movement in xylem by As-toxicity. Among the metal micronutrients, As decreased the concentrations and translocations of iron (Fe), zinc (Zn), and copper (Cu).     

Spontaneous formation of thiuram disulfides in solutions of iron(III) dithiocarbamates

Dithiocarbamates are used as pesticides and rubber additives. Dithiocarbamates are the reduced forms of thiuram disulfides and both of these groups of substances induce allergic contact dermatitis. The allergic cross-reactivity pattern between dithiocarbamates and thiurams is unclear. The aim of this study was to investigate why these cross-reactions occur sometimes but not always. HPLC-analysis of buffer solutions of iron(III) dithiocarbamates demonstrated that thiuram disulfides were formed spontaneously and rapidly in high yield. No such oxidation was observed in solutions of copper(II), zinc(II), or sodium dithiocarbamates. However, sodium diethyldithiocarbamate and zinc diethyldithiocarbamate were oxidized in buffer solution when ferric salt was added. The influence of different metal ions on the oxidation reaction is probably an explanation for the cross-reactivity patterns seen between dithiocarbamates and thiurams. These findings also show that careful handling is necessary in analytical and biological studies with solutions of iron(III) dithiocarbamates. Oxidation of dithiocarbamates in aqueous buffer at physiological pH has not been shown before.     

Plant mineral contents of root tips from four sorghum cultivars after exposure to the anion channel blocker,sits

SITS (0, 0.01, 0.1, or 1.0 mM) influence on the absorption (1 hr) by 1‐cm root tips of Sorghum bicolor (L.) Moench cv GP‐10, SC 283, SC 574, or Funk G522DR seedlings of calcium (Ca), boron (B), phosphorus (P), zinc (Zn), manganese (Mn), iron (Fe), magnesium (Mg), and copper (Cu) from an Hoagland and Arnon complete mineral nutrient solution was evaluated by inductively coupled plasma emission spectrophotometry (ICP). Cultivar variation in response to SITS within each element was found. Multiple mechanisms of control for the absorption of each element among cultivars were evident.     

Evaluation of dry ashing in conjunction with ion chromatographic determination of transition metal ions in pig feed samples

The contents of transition metal ions iron, copper, zinc, and manganese were simultaneously determined in pig feed using an ion chromatographic technique (IC) preceded by dry ashing. Employing ion exchange, the ions were separated on an IonPac CS5A column used in combination with a pyridine-2,6-dicarboxylic acid based eluent. The separation was followed by spectrophotometric detection after postcolumn reaction with 4-(2-pyridylazo)resorcinol. Dry ashing parameters were varied to assess their role in potential analyte loss. Quantitative recoveries (>95%) were obtained for all analytes with a dry ashing method that included a moderate temperature-time regime and ash leaching support in the form of sonication and heat treatment. The use of HCl as leaching acid and the presence of alkaline earths in the matrix solution did not interfere with the chromatographic separation.     

Mineral concentrations in leaves and stems of various forages of the Colombian paramo

Abstract

A study was conducted to determine the elemental composition of two plant fractions (leaves and stems) of several forage species in three sheep farms of the paramo in Colombia. The elemental composition of the forage species, and the relationship between soil chemistry and the elemental composition of the forages were also determined. Sampling periods corresponded to the end of the rainy season (May‐June 1987), and the middle end of the dry season (February 1988). Leaves were higher (P<0.05) than stems in the following: calcium, phosphorus, magnesium, potassium, iron, molybdenum, crude protein, and IVOMD. Overall percentage of deficiencies were related to the requirements for sheep as follows: calcium (88%, 13%), phosphorus (50%, 27%), magnesium (85%, 41%), potassium (13%,3%), sodium (94%, 96%), iron (10%, 4%), copper (82%, 65%), manganese (7%, 0%), zinc (46%, 42%), cobalt (92%, 85%), selenium (77%, 65%), crude protein (45%, 8%) for stems and leaves, respectively.

Based on analyses, elemental, crude protein and IVOMD concentrations of forage species, tended to differ. Soil‐forage correlation coefficients of the same mineral for the rainy season were calcium (r = 0.81), magnesium (r = 0.89), potassium (r = 0.71), zinc (r = 0. 69). For the dry season, correlations were calcium (r = 0.61) and magnesium ( r = 0.58). Results indicated low correlation coefficients between most soil and forage elements, and that they are not of great value in assessing the elemental status of grazing sheep in the paramo.     

云南省主要地质背景区铜、锰、锌、镁、钾在岩石-土壤-饲料系统的分布与迁移规律研究

对云南省6个主要地质背景区的土壤、岩石和饲料样品的铜、锰、锌、镁和钾元素进行测定分析。结果表明:玄武岩和碳酸盐岩红壤区土壤和饲料钾、镁、锌、锰和铜元素含量较丰富;碳酸盐岩、碎屑岩和玄武岩混合型黄红壤区居中;而由碎屑岩和变质岩发育的土壤区土壤和饲料钾、镁、锌、锰和铜元素最低。饲料中钾、镁、锌、锰和铜的含量受地质背景值,特别是土壤中元素的丰度的影响不大。     

Unique patterns of dietary adequacy in three cultures of Canadian Arctic indigenous peoples

BACKGROUND: Information is needed on dietary adequacy of Arctic indigenous populations in Canada. Extensive work has been completed on composition of Arctic food and food use, and dietary reference intakes are available. OBJECTIVE: To complete the first comprehensive dietary adequacy assessment of three populations of adult Arctic indigenous people. SETTING AND SUBJECTS: Dietary assessment interviews were conducted with randomly selected indigenous adults during two seasons in 44 representative communities of Yukon First Nations (n = 797), Dene/Métis, (n = 1007) and Inuit (n = 1525). METHODS: Twenty-four-hour recalls were used to derive adjusted distributions of usual nutrient intakes in four age/gender groups for assessment of dietary adequacy for carbohydrate, dietary fibre, protein, n-3 fatty acids, n-6 fatty acids, calcium, copper, iron, magnesium, manganese, phosphorus, selenium, zinc, vitamin A, riboflavin, folate, vitamin B6, vitamin C, vitamin D and vitamin E. RESULTS: Nutrients with high prevalence of adequacy for most age/gender groups in all three cultures were protein, carbohydrate, n-3 fatty acids, iron, copper, zinc, manganese, selenium, riboflavin and vitamin B6; some individuals exceeded the upper intake level for iron, zinc, selenium, vitamin A and vitamin D. Estimated average requirement nutrients of concern for adequacy were magnesium, folate, vitamin A, vitamin C and vitamin E; however, a few age/gender groups were exceptions. Prevalence of inadequacy for AI nutrients which may be undesirably high were fibre, n-6 fatty acids and calcium. Vitamin D was more adequate in Inuit women and men than for Yukon First Nations or Dene/Métis. CONCLUSIONS: Unique patterns of dietary adequacy exist among Arctic indigenous peoples. Local wildlife food sources and market food sources should be maximised for their nutrient contributions to Arctic diets.     

Efficiency of remediation of technogenic barrens around the Pechenganikel works in the Kola Subarctic

Remediation of the technogenic barrens around the Pechenganikel works on the Kola Peninsula resulted in the improvement of the soil properties, namely, in a decrease in acidity and enrichment with nutrients, which continued for several years. However, the reaction of most of the treated soils remained strongly acid, and the concentrations of available calcium, magnesium, potassium, and phosphorus were much lower than their background levels and the demands of the plants for nutrients (especially, for magnesium and potassium). The soils were depleted in available manganese and zinc. Most of the treated soils contained the same (or higher) amounts of available nickel and copper compounds in comparison with their untreated analogues. The willow plantations on the remediated plots were in a satisfactory state, but they experienced a deficit of magnesium, manganese, and zinc; they consumed elevated amounts of nickel and copper. Recommendations on the nutrient regime of the soils aimed at decreasing the mobility and biological availability of heavy metals were made.     

A convenient wet digestion procedure for multielement analysis of plant materials

Abstract

For the determination of total element contents in plant material by atomic spectrometry after wet digestion, both dissolution and oxidation of the matrix are necessary. This was achieved by a sequential digestion procedure using first hydrogen fluoride (HF) for dissolution of silicate, followed by oxidation with nitric acid (HNO₃) and hydrogen peroxide (H₂O₂). The final solution is 0.2M HNO₃, and contains only traces of HF. Application of the method for the determination of aluminium (Al), boron (B), calcium (Ca), cadmium (Cd), copper (Cu), iron (Fe), potassium (K), magnesium (Mg), manganese (Mn), sodium (Na), phosphorus (P), lead (Pb), sulfur (S), and zinc (Zn) in various materials showed good agreement with certified reference materials.     

Effect of aluminum on growth and chemical composition of marigolds

Marigold (Tagetes erecta L. cv. ‘Discovery Yellow’, “Perfection Yellow’, ‘Inca Yellow’, and ‘Merrymum Yellow') were grown in aluminum (Al) solution culture concentrations of 0, 1, or 4 mg/L. Aluminum increased root length and weight, but had no effect on stem and leaf weight. Uptake and stem and leaf tissue nutrient concentration of phosphorus (P), calcium (Ca), and magnesium (Mg) were reduced by the Al treatments. The Al treatments increased stem and leaf concentrations of potassium (K) and decreased the concentrations of manganese (Mn), iron (Fe), copper (Cu), and zinc (Zn). No typical Al‐toxicity symptoms were observed in the roots. Root stunting caused by Fe toxicity was alleviated by the Al treatments.     

Nutrient content of Kenaf (Hibiscus cannabinus) at five growth stages

Abstract

Kenaf (Hibiscus cannabinus) grown during the wet season in the Ord Irrigation Area of Western Australia was sampled at five growth stages. The samples were separated into bark, wood, tops plus foliage and, where applicable, seed. Each fraction was analysed for zinc, manganese, iron, copper, sodium, potassium, calcium and magnesium by atomic absorption spectroscopy, and for nitrogen and phosphorus by colorimetry. Concentrations of these elements in each plant fraction are presented. Calculation of total above‐ground nutrient content of the crop indicated a high content of potassium throughout the growth cycle (up to .280 kg/ha), an initially high content of nitrogen (150 kg/ha) stabilising at a lower level (about 75 kg/ha) up to maturity, and an increasing content of zinc (150 g/ha to 350 g/ha) and calcium (65 kg/ha to 105 kg/ha) with age. A higher content of iron at maturity was also apparent (up to 1400 g/ha). A comparison with other reported data is made.     

Concentrations of nutrient elements in parts of siratro as affected by phosphorus supply and plant age

Abstract

The distribution of some nutrient elements in various parts of Siratro plants of different age and phosphorus status was examined in order to assess which plant parts were best to sample for chemical analysis of nutrient status and to estimate the relative mobility of these elements within the shoot.

With increasing physiological age of leaves, concentrations of nitrogen, phosphorus, sulphur and potassium decreased, concentrations of calcium, aluminium, manganese and boron increased and concentrations of magnesium, iron, zinc and copper were little affected. Concentrations of nitrogen, phosphorus, sulphur, calcium, aluminium, boron, zinc and copper in plant parts between the tip and the third youngest, expanded leaf changed little with plant age, suggesting that analysis of this portion of the shoot would be a suitable guide to the sufficiency, or otherwise, of these elements in Siratro plants. By contrast, potassium concentration in all plant parts was markedly depressed by increasing plant age, suggesting that a standardized sampling time would be necessary for interpretation of plant potassium status. Concentrations of magnesium, iron and manganese in all plant parts also decreased with plant age, but to a lesser extent than potassium.

Concentrations of all elements, except nitrogen and phosphorus, decreased slightly with increasing phosphorus supply. This decrease could best be attributed to a dilution of these elements with increased plant growth, induced by phosphorus.

The present results suggested that potassium, and possibly iron and magnesium, were redistributed in Siratro shoots with time whereas other elements were relatively immobile.     

施镁对缺镁葡萄叶片和果实矿质元素含量的影响

在大田条件下,对缺镁的葡萄园进行了土施和叶面喷施硫酸镁肥的试验,探讨缺镁条件下,施镁对葡萄叶片和果实矿质营养吸收的影响,为葡萄施肥提供理论依据。采用裂区试验,主区设4个土施硫酸镁梯度,分别为0、112.5、150、187.5 kg/hm2,副区设3个叶面喷施硫酸镁浓度,分别是0%、0.2%、0.4%。结果表明:土施和叶面喷施硫酸镁在增加缺镁葡萄镁含量的同时,促进了钾、钙和锰的吸收,但降低了叶片和果实中锌含量,对铁和铜的影响不显著。土施镁肥极显著增加了叶片和果实中镁含量,叶面喷施极显著增加了叶片镁含量,但对果实镁含量影响不显著;土施150 kg/hm2同时叶面喷施0.4%硫酸镁肥,可提高叶片和果实中镁及其它矿质元素的含量。