Nature-inspired soluble iron-rich humic compounds: new look at the structure and properties

Purpose

Humic substances (HS) being natural polyelectrolyte macromolecules with complex and disordered molecular structures are a key component of the terrestrial ecosystem. They have remarkable influence on environmental behavior of iron, the essential nutrient for plants. They might be considered as environmental friendly iron deficiency correctors free of synthetic iron (III) chelates disadvantages. The main goal of this study was to obtain water-soluble iron-rich humic compounds (IRHCs) and to evaluate their efficiency as chlorosis correctors.

Materials and methods

A facile preparation technique of IRHCs based on low-cost and available parent material was developed. The iron-containing precursor (ferrous sulfate) was added dropwisely into alkaline potassium humate solution under vigorous stirring and pH-control. A detailed characterization both of organic and inorganic parts of the compounds was provided, the iron species identification was carried out jointly by EXAFS and Mössbauer spectroscopy. Bioassay experiments were performed using cucumber Cucumis sativus L. as target plants. Plants were grown in modified Hoagland nutrient solution, prepared on deionized water and containing iron in the form of IRHCs. Total iron content in dry plants measured by spectrophotometry after oxidative digestion and the chlorophyll a content determined after acetone extraction from fresh plant were used as parameters illustrating plants functional status under iron deficiency condition.

Results and discussion

The high solubility (up to130 g/l) and iron content (about 11 wt%) of the IRHCs obtained allow considering them to be perspective for practical applications. A set of analytical methods has shown that the main iron species in IRHCs are finely dispersed iron (III) oxide and hydroxide nanoparticles. An application of the precursor solution acidification allows to obtain compounds containing a significant part of total iron (up to 30 %) in the form of partly disordered iron (II–III) hydroxysulphate green rust GR(SO₄ ^2?). Bioavailability of iron from IRHCs was demonstrated using bioassay in cucumber plants grown up on hydroponics under iron deficiency conditions.

Conclusions

The application of iron oxides chemistry for humic substance containing solution was proved to be an effective approach to synthesis of IRHCs. Using bioassay on cucumber plants C. sativus L. under iron deficiency conditions, the efficiency of compounds obtained as chlorosis correctors was demonstrated. Application of water-soluble IRHCs led to significant increase of chlorophyll a content (up to 415 % of the blank) and iron content in plants (up to 364 % of the blank) grown up on hydroponics.     

Nutrient Loading by Precipitation in the Maracaibo Lake Basin, Venezuela

Nutrient content and pH of rain samples collected at nine sites during 1988-1996 were studied to determine the amounts of N, P and S added by precipitation over Maracaibo Lake basin. The basin is a wide depression occupied by Lake Maracaibo and extensive alluvial plains and delimited by a mountainous zone of variable physiolgraphic characteristics with different cattle ranching and industrial activities. Rain pHs averaged ≈ 4 to 6, individual samples occasionally reached as low as pH 3 in the south basin. NH₄ ⁺ levels were significantly higher (up to 2.6 mg/l NH₄-N) than NO₃ ^? plus NO₂ ^?. Phosphorus levels were low, ranging from undetectable to 1.5 mg/l. The amounts of inorganic N/ha/yr added ranged from ≈ 5.4 Kg in the north to ≈ 8 Kg in the south basin; around the lakeshore, it was estimated that ≈ 9.8–16.8 Kg TN/ha (≈ 55 % as organic-N) are annually deposited. The annual amounts of SO₄-S/ha added range from ≈ 10 to 13 Kg. The contribution of precipitation to P in the ecosystem is very small; ≈ 0.02 – 0.8 Kg of PO₄-P/ha/yr was added in basin. The results of this study show that precipitation represents a significant factor for the total nitrogen and sulfur loading to Maracaibo Lake Basin.     

Effects of type of added salt and ionic strength on physicochemical and functional properties of casein isolates produced by electroacidification

A procedure developed for soybean protein precipitation which was based on electrodialysis was tested for the production of acid casein from reconstituted skim milk. In a previous paper, the performance of bipolar membrane electroacidification (BMEA) was evaluated under different conditions of ionic strength (micro(added) = 0, 0.25, 0.5, or 1.0 M) and added salt (CaCl(2), NaCl, or KCl) (1). The aim of this study, which is the complement of the work on evaluation of BMEA performance, was to evaluate the functionality of the protein isolates produced by BMEA and to compare the BMEA isolates to commercial isolates and an isolate produced by chemical acidification. It was not possible to show differences between the functional properties of isolates produced by BMEA, except at 1 M CaCl(2) micro(added), due to the variability of the isolates. However, the results showed that it is possible to obtain isolates similar to commercial isolates and that the addition of salt during the process does not induce variations in functional properties. From results on mineral concentrations, it appeared that the addition of monovalent cations did not influence the retention of monovalent or divalent cations in the BMEA isolates, while addition of divalent cations (CaCl(2)) influenced the retention of magnesium. According to previous results on evaluation of BMEA performances under different conditions of ionic strength and added salt, the difference observed for the BMEA isolate produced at 1.0 M CaCl(2) was confirmed.     

Geographical distribution of Alzheimer's disease cases at birth and the geochemical profile of Saguenay-Lac-Saint-Jean/Québec,Canada (image project)

Accepting as founded the hypothesis of a multifactorial origin for the Alzheimer's disease (AD), we explore the possible links between the geographical distribution of AD cases according to their birth place and the geochemical profile of the Saguenay-Lac-Saint-Jean (SLSJ) territory in the province of Québec. The method used for factor analysis of correspondances (FAC) and another one based on the differences between the residential and municipal geochemical concentrations (DRMC) have been used for this purpose. The geochemical matrix of SLSJ relates the highest concentrations of nickel, copper and zinc to the sector surrounding the Jonquière municipality. Moreover, high concentrations of iron, lead and manganese were found in the northern sector of the Lac Saint-Jean. The DRMC method corroborates this strong correlation between iron, lead and manganese. Furthermore, these concentrations do not differ from the north-american geochemical standards. No single geochemical element seems to be associate with the spatial distribution of cases. It is, however, still possible that a certain synergistic effect between two or several elements could be implied in the development of the disease. According to the results of the soil analysis, there does not seem to be any association between the spatial distribution of cases and the concentration of aluminum, a chemical element that has been thought to be implied in the etiology of AD. These results are compared with those obtained by other workers in the micronesian islands, where abnormally high frequencies of amyotrophic lateral sclerosis and parkinsonism dementia have already been observed.     

Effects of Alum-treated Waste Water Sludge on Barley Growth

Alum sludge derived from a municipal wastewater plant was used as a soil amendment in a greenhouse study with barley (Hordeum vulgare) as the test crop. Treatment variables included the soil pH (4.5, 5.1 and 6.5), the amount of Al in the sludge (control = 30 mg Al_T/g; alum sludges = 38 and 52 mg Al_T/g), and the sludge application rate (100 and 270 kg N_T/ha). Soil amendment with the two alum sludges reduced soil pH, increased Al³⁺ activity in the soil solution, and reduced barley growth over the 6-week experiment. Barley growth decreased as the Al³⁺ activity in the sludged soil solution increased, but for a given Al³⁺ the phytotoxicity of Al was markedly pH dependent. For example, at a pH of 5.0 ± 0.1 an Al³⁺ activity of 0.5 μM was sufficient to inhibit plant growth by about 50% this IC₅₀ value increased five-fold to about 2.5 μM when the soil pH was 4.5 ± 0.1. This decrease in the toxicity of Al50 with acidification was explained in terms of a competitive interaction between the H⁺-ion and Al³⁺ at the root surface. Stepwise multiple regression allowed the prediction of aerial leaf biomass from soil pH and sludge application rate.     

Origin of French virgin olive oil registered designation of origins predicted by chemometric analysis of synchronous excitation-emission fluorescence spectra

The authentication of virgin olive oil samples requires usually the use of sophisticated and very expensive analytical techniques, so there is a need for fast and inexpensive analytical techniques for use in a quality control methodology. Virgin olive oils present an intense fluorescence spectra. Synchronous excitation-emission fluorescence spectroscopy (SEEFS) was assessed for origin determination of virgin olive oil samples from five French registered designation of origins (RDOs) (Nyons, Vallée des Baux, Aix-en-Provence, Haute-Provence, and Nice). The spectra present bands between 600 and 700 nm in emission due to chlorophylls a and b and pheophytins a and b. The bands between 275 and 400 nm in emission were attributed to alpha-, beta-, and gamma-tocopherols and to phenolic compounds, which characterize the virgin olive oils compared to other edible oils. The chemometric treatment (PLS1) of synchronous excitation-emission fluorescence spectra allows one to determine the origin of the oils from five French RDOs (Baux, Aix, Haute-Provence, Nice, and Nyons). Results were quite satisfactory, despite the similarity between two denominations of origin (Baux and Aix) that are composed by some common cultivars (Aglandau and Salonenque). The interpretation of the regression coefficients shows that RDOs are correlated to chlorophylls, pheophytins, tocopherols, and phenols compounds, which are different for each origin. SEEFS is part of a global analytic methodology that associates spectroscopic and chromatographic techniques. This approach can be used for traceability and vindicates the RDOs.     

Metabolism of the lignan macromolecule into enterolignans in the gastrointestinal lumen as determined in the simulator of the human intestinal microbial ecosystem

Estrogenic plant compounds from the human diet such as the lignan secoisolariciresinol diglucoside (SDG, 1) can exert biological activity in the human body upon ingestion and bioactivation to enterodiol (END, 5) and enterolactone (ENL, 6). Bioavailability of lignans is influenced by the food matrix and gut microbial action, of which the latter is subject to a large interindividual variation. In this study, the fate of the lignan precursor SDG, present in the lignan macromolecule of flax seed ( Linum usitatissimum), was determined during an artificial stomach and small intestinal digestion and during metabolism by two different enterolignan phenotypes in a TWINSHIME environment (TWIN Simulator of the Human Intestinal Microbial Ecosystem). The lignan macromolecule acted as a delivery system of SDG in the large intestine. SDG was only hydrolyzed into secoisolariciresinol (SECO, 2) through microbial action in the ascending colon, after which it was bioactivated into enterolignans from the transverse colon onward. Single demethylation was a first step in the bioactivation, followed by dehydroxylation. Enterolignan phenotypes remained stable throughout the experimental period. The establishment of END and ENL production equilibria reflected the subdominance of ENL-producing bacteria in the gastrointestinal tract.