Iodine toxicity in a plant-solution system with and without humic acid

Aqueous iodine (I_2(aq)) is a potent disinfectant that is being evaluated as a soil sanitizer for agricultural fields and a water purification treatment for the International Space Station. Rice (Oryza sativa L.) plants were grown in solution culture containing different I compounds at approximately 0, 18, or 30 μM total I [I_2(aq) + iodide (I⁻)] consisting of 0, 6, and 20 μM I as I_2(aq), respectively. In addition, humic acid (HA) was added to half the treatments. Most I_2(aq) was electrochemically reduced to the endpoint metabolite I⁻ within 24 h with HA promoting the response. Plants receiving the highest dose of I_2(aq), particularly those in treatments without HA, had the least growth and the greatest biomass I concentrations. Roots from both I_2(aq) treatments without HA were periodically sampled for bacteria. Viable and direct caints of bacterial cell density declined with increasing I_2(aq) concentrations within the first hour after treatment application. However, cell densities recovered within 96 hours and eventually surpassed the control treatment cell density. Additionally, the resulting high viable: direct count density ratio suggests that opportunistic species likely dominated the post I_2(aq) environment.     

添加生化抑制剂和腐植酸的稳定性增效尿素在黄土中的施用效果

采用田间盆栽试验,研究生化抑制剂与生物刺激素腐植酸结合制成的高效稳定性增效尿素肥料在黄土中的氮素转化特征、增产效果和氮素肥料表观利用率,以探明其施用效果,为开发适宜黄土施用的新型增效尿素肥料提供理论依据。本研究以不施氮肥(CK)和施尿素氮肥(N)为对照,在尿素中分别添加腐植酸(F)、N-丁基硫代磷酰三胺(NBPT)、3,4-二甲基吡唑磷酸盐(DMPP)和2-氯-6-三甲基吡啶(CP),以及腐植酸与3种生化抑制剂分别组合(NBPT+F、DMPP+F、CP+F)。结果表明: 与N处理相比,F、NBPT+F、DMPP+F和CP+F处理均能显著提高玉米的产量、叶片叶绿素含量、叶面积指数和植株吸氮量,对土壤铵态氮和硝态氮含量也有显著影响。与单独施用生化抑制剂相比,添加腐植酸可提高玉米叶片叶绿素含量。与CP相比,CP+F玉米的植株吸氮量、叶绿素含量、氮肥吸收利用率均显著提高;与NBPT相比,NBPT+F硝化抑制率提高10.7%,但玉米产量、叶面积指数、植株吸氮量和氮肥利用率等均有所降低;与DMPP相比,DMPP+F显著降低了玉米产量、叶面积指数、植株吸氮量、氮肥利用率和硝化抑制率等。综合玉米产量、植株吸氮量、氮肥吸收利用率以及土壤铵态氮、硝态氮含量等指标,在黄土地区施用尿素肥料时,建议添加腐植酸和CP以提升尿素性能,从而提高产量和肥料利用率。     

The lability of copper ions sorbed on humic acid

Abstract

Interaction between copper (II) ions and humic acids can yield at least three different types of complex. The soluble forms promote migration of the metal ion in environmental systems and the labile content can be more ‘biologically active’. In our study, the distribution of copper between ‘fixed’, ‘non-labile’ and ‘labile’ complex forms at different pH values has been evaluated by equilibrating Cu-loaded humic acid with ion exchange resins of different types (and counter ion forms). Metal loadings of 35 to 225 μmol g^?1 were obtained by equilibrating 10 or 50 mg of purified acid with Cu (II) solutions (10^?4 M, pH 2 to 4.5). After removal of the aqueous phase, the Cu-loaded particles were re-suspended in water and a porous cage containing excess resin exchanger was added to each sample vial. After overnight mixing, the cage was retrieved and phases separated. Analysis of the aqueous phase determined the non-labile soluble copper released at the equilibrium pH; the ‘labile’ fraction value was found by back-extracting the washed resins into 0.05 M EDTA (pH 7). At pH <6, about one fifth of the sorbed Cu was labile and about 5% was released as a soluble non-labile complex. The majority of the Cu remained firmly fixed to the solid phase. Above pH 6, the substrate dissolved and the percentage present as a non-labile species increased from 5 to 75% as the pH changed from 5 to 8.5. Around pH 7, the labile content peaked at around 40%, but this fraction value dropped to ?10% at pH 8.5 (due in part to metal hydroxide formation). The type of synthetic exchanger used controlled the system pH, and the associated functional groups (sulfonate, carboxylate or chelating) had some influence on the distribution patterns observed. The distribution was also influenced by the amount of Cu (II) sorbed on the substrate.     

The complexation of aqueous metal ions relevant to biological applications. 1. Poorly soluble zinc salts and enhanced solubility with added amino acid

Abstract

The effect of added amino acid (glycine, alanine and serine) on the solubility of zinc citrate, zinc succinate and zinc oxalate was investigated. Equilibrated solutions were prepared and titrated to endpoint at pH 5.5 with Na₂EDTA using Xylenol Orange indicator. In every case, a significant enhancement in solubility was seen as the amino acid increased from 1 to 50 molar excess. The increase was non-linear, and, with zinc succinate, showed saturation effects. In these cases, solution composition may be more complicated than initially thought, including mixed-ligand complexes and increasing percent free metal ion as the proportion of amino acid increases.     

The toxicity of cadmium to barley plants as affected by complex formation with humic acid

An ‘alternating solution’ culture method was used to study the effects of chloride ions and humic acid (HA) on the uptake of cadmium by barley plants. The plants were transferred periodically between a nutrient solution and a test solution containing one of four levels of HA (0, 190, 569 or 1710 μg cm⁻³) and one of five levels of Cd (0, 0.5, 1.0, 2.5 or 5.0 μg cm⁻³) in either a 0.006M NaNO₃ or 0.006M NaCl medium. Harvest and analysis of shoots and roots was after nineteen days. The distribution of Cd in the test solutions between Cd²⁺, CdCl⁺ and HA-Cd was determined in a separate experiment by dialysis equilibrium. In the nitrate test solutions Cd uptake was clearly controlled by Cd²⁺ concentration and was therefore reduced by HA complex formation. In the absence of HA, chloride suppressed Cd uptake indicating that Cd²⁺ was the preferred species. However complex formation with Cl⁻ enhanced uptake when HA was present because of an increase in the concentration of inorganic Cd species relative to the nitrate system. The ratio root-Cd/shoot-Cd remained at about 10 across a wide range of shoot-Cd concentrations, from about 3 μg g⁻¹ (sub-toxic) up to 85 μg g⁻¹ (80% yield reduction). The ability of the barley plants to accumulate ‘non-toxic’ Cd in their roots was thus very limited. Humic acid also had no effect on Cd translocation within the plant and the root/shoot weight ratio did not vary with any treatment. At shoot-Cd concentrations in excess of 50 μg g⁻¹, K, Ca, Cu and Zn uptake was reduced, probably the result of root damage rather than a specific ion antagonism. The highest concentration of HA also lowered Fe and Zn uptake and there was a toxic effect with increasing HA concentration at Cd=0. However the lowest HA level, comparable with concentrations found in mineral soil solutions, only reduced yield (in the absence of Cd) by <5% while lowering Cd uptake across the range of Cd concentrations by 66%–25%.     

Edaphic mobility of complete humic acid and fractions of high and medium molecular weight

Soil mobility of a complete humic acid and high and medium molecular weight fractions was determined by a soil TLC method. High and medium molecular weight fractions were obtained by ultrafiltration and then labeled with radioiodine. Infrared, visible- and UV spectra, as well as isotachophoretic studies, showed marked differences among the three humic fractions. The results obtained made evident the presence of soil mobile humic fractions of medium molecular weight. Alkalinization increased the soil mobility of humic acid.     

Separation of low molecular weight humic acids with Sephadex G25

Summary A method is pressented using Sephadex G25 to separate the smallest molecules from a humic acid sample. This procedure can also be used to select a certain molecular range.     

Modeling of inorganic contaminant transport in dense bentonite

To assess the safety of the waste disposal site, a knowledge of the molecular diffusion coefficient through the bentonite‐clay barrier is required. The methods commonly used to determine molecular diffusion coefficient in clay are very time consuming. Because of the large number of species involved in the radioactive waste disposal site, a model that allows diffusion coefficient to be predicted for use is desirable. Models based on free water have been proposed but are found to be inadequate for compacted bentonitic clays. A model that incorporates clay‐species‐water interaction is presented for dense bentonite. The modeling results show that the diffusion coefficient depends on the charge nature and size of the diffusing species, water chemistry, temperature, and soil structure. The predicted diffusion coefficients for some species are shown to be in excellent agreement with those measured in dense bentonite.     

Quenching of fluorescence of phenolic compounds and modified humic acids by cadmium ions

The interaction of a number of phenolic compounds, being ‘model fragments’ of humic acids, with cadmium ions was investigated. The fluorescence quenching method was used to determine the complexation constants of these compounds with cadmium ions. It was established that bonding of phenolic compounds by cadmium ions at рН 7 is weak and reaches a maximum value of 15% for interaction with resorcinol. It was demonstrated that modification of humic acids by the mechanoactivation method increases by three times bonding of cadmium ions, which is caused by strengthening the acid properties of carboxyl and hydroxyl groups at the aromatic ring. Copyright © 2016 John Wiley & Sons, Ltd.     

The complexation of aqueous metal ions relevant to biological applications. 2. Reactions of copper(II) citrate and copper(II) succinate with selected amino acids

Abstract

Addition of amino acids, glycine, alanine, and serine, to poorly soluble copper(II) salts [copper(II) citrate and copper(II) succinate] all increase solubility of the copper(II) salts. Relative increases in solubility follow the polarity trend in the selected amino acids, with serine creating the greatest increase in solubility. Simultaneous equilibria calculations indicate the formation of mixed-ligand complexes in the copper(II) succinate–amino acid systems, the first time such mixed-ligand complexes have been observed. In contrast, mixed-ligand complexes are not predicted in the copper(II) citrate–amino acid systems. Potential bioavailability of copper(II) appears to be increased by the inclusion of amino acids in solution, roughly in parallel with the increase in solubility of the copper(II) salt. Therefore, measurement of the change in solubility caused by addition of amino acids to aqueous solution gives qualitative insight to the potential increase in bioavailability of the metal ion.     

Diffusion of lactose in kappa-carrageenan/locust bean gum gel beads with or without entrapped growing lactic acid bacteria

Effective diffusion coefficients (De) of lactose in kappa-carrageenan (2.75% wt/wt)/locust bean gum (0.25% wt/wt) (LBG) gel beads (1.5-2.0-mm diameter)with or without entrapped lactic acid bacteria (LAB) were determined at 40 degrees C. The effects of lactose concentration, bacteria strain (Streptococcus salivarius subsp. thermophilus and Lactobacillus casei subsp. casei) and cell content at various steps of the fermentation process (after immobilization, pre-incubation of the beads and successive fermentations) were measured on De as a first step for process modelling. Results were obtained from transiend concentration changes n well-stirred lactose solutions in which the beads were suspended. A mathematical model of unsteady-state diffusion in a sphere was used, and De was obtained from the best fit of the experimental data. Diffusivity of lactose in cell-tree beads was significantly lower than in pure water mainly because of the obstruction effect of the polymer chains and the hydration region. Furthermore, effective diffusivity and equilibrium partition factor were independent of lactose concentration in the range from 12.5 to 50 g/L. No significant difference was found for De (effective diffusivity) and Kp (partition) coefficients between beads entrapping S. thermophilus (approximately 5 x 10(9) CFU/mL) and cell-free beads. On the other hand higher cell counts obtained with L. casei (close to 1.8 x 10(11) CFU/mL) increased mass transfer resistance resulting in lower effective diffusivities and Kp. Finally, the effects of the type of bacteria and their distribution in the beads on the diffusivity were also discussed.     

Encapsulation of plant growth-promoting bacteria in alginate beads enriched with humic acid

The key to achieving successful, reproducible results following the introduction of beneficial microbes into soil relies on the survival rate of the inoculated bacteria in a heterogeneous soil environment and hence an improved encapsulation method was developed. Owing to the constraints associated with the inoculum formulation, in this study, encapsulation of a plant growth promoting bacteria (PGPB) isolate Bacillus subtilis CC-pg104 was attempted with alginate by enriching the bead microenvironment with humic acid. High viability of the encapsulated bacteria was observed with minimum cell loss upon storage for 5 months. Steady and constant cell release from the bead was observed for 1 week at different pH. Encapsulated cells remained active as evidenced by their ability to solubilize calcium phosphate in vitro. Successful plant growth promotion of lettuce by the encapsulated bacteria under gnotobiotic and sterile environment was also achieved. Feasibility of this improved encapsulation technique is mainly due to the dual benefits of humic acid to microbe and plant and its chemical properties allowing an easy mixing with alginate without interfering in the formation of the alginate gel beads by cross-linking with Ca2+ ions. Thus, the encapsulation method described in this study can be effectively used to protect the PGPB inoculum from adverse conditions of the soil for their successful establishment in the rhizosphere.     

Composition and metal ion complexation behavour of humic fractions derived from corn tissue

Decomposition of fresh plant residues produces humic fractions with different molecular size and composition. It was hypothesized that the functional group-type and content of humic fractions depended on molecular size, which was expected to influence heavy-metal complexation behavior. In this study, corn (Zea maysL.) stalks and leaves were collected from the field and decomposed for an 8-month period to produce humic substances which were separated into three water soluble fractions, HF1, HF2 and HF3, from highest to lowest relative molecular size. Functional group determination showed that total, carboxylic and phenolic OH acidity increased as relative molecular size of humic fractions decreased. Furthermore, C/O ratios decreased, whereas N/C and H/C ratios remained relatively unaffected as relative molecular size of humic fractions decreased. Formation of Ca²⁺, Cd²⁺ and Cu²⁺ -humic fraction complexes and how these complexes were affected by pH and relative (humic fraction) molecular size were studied using potentiometric titration. Metal-humic complexes exhibited at least two types of sites with respect to Ca²⁺, Cd²⁺ and Cu²⁺ complexation. Relative molecular size had a large significant influence on total metal-ion complexation, but it had a relatively small influence on complex stability at low levels of metal-ion complexation. Strength of metal-ion humic complexes followed the order Cu²⁺ > Cd²⁺ > Ca²⁺ and was affected by pH, especially for low affinity sites. Carboxylic and phenolic OH groups were most likely involved in complex formation. Magnitude of the metal-humic formation constants at the lowest equilibrium metal-ion concentration, under the various pH values tested, varied from 5.39 to 5.90 for Ca²⁺, from 5.36 to 6.01 for Cd²⁺ and from 6.93 to 7.71 for Cu²⁺. Furthermore, the formation constants appeared to be positively influenced by decreasing molecular size of water-soluble humic fraction, and increasing pH. These results inferred that soil management practices causing build-up of humic substances would affect mobility and bioavailability of metal-ions.     

Phosphorus fertilizer recovery from calcareous soils amended with humic and fulvic acids

Precipitation of Ca phosphates negatively affects recovery by plants of P fertilizer applied to calcareous soils, but organic matter slows the precipitation of poorly soluble Ca phosphates. To study the effect of high molecular weight organic compounds on the recovery of applied P, a mixture of humic and fulvic acids was applied to calcareous soils with different levels of salinity and Na saturation which were fertilized with 200 and 2000 mg P kg^–1 as NH₄H₂PO₄. Recovery was measured as the ratio of increment in Olsen P-to-applied P after 30, 60 and 150 days, and associated P forms were studied using sequential chemical fractionation and ³¹P NMR spectroscopy. Application of the humic-fulvic acid mixture (HFA) increased the amount of applied P recovered as Olsen P in all the soils except in one soil with the highest Na saturation. In soils with high Ca saturation and high Olsen P, recovery increased from < 15% in the absence of amendment to > 40% at a 5 g HFA kg^–1 amendment rate (30 days incubation and 200 mg P kg^–1 fertilizer rate). This is ascribed to inhibition of the precipitation of poorly soluble Ca phosphates, consistent with the sequential chemical extraction (reduction of the HCl extractable P) and P concentration in 0.01 M CaCl₂ (1:10 soil:solution ratio) extracts. ³¹P NMR spectra revealed that in non-amended samples, most spectral shifts were due to poorly soluble P compounds (carbonate apatite); on the other hand, at the 5 g HFA kg^–1 rate, significant amounts of amorphous Ca phosphate and dicalcium phosphate dihydrate (DCDP) were identified. The increase in the recovery of applied P due to HFA reveals a positive effect of the application of organic matter as soil amendments on the efficiency of P fertilizers and also explains that manures and other organic sources of P were more efficient increasing available P than inorganic P fertilizers in calcareous soils.     

Ageing and endurance training effects on quantity and quality of pulmonary vascular bed in healthy men

It has recently been demonstrated that in healthy individuals, peak oxygen consumption is associated with a greater pulmonary capillary blood volume and a more distensible pulmonary circulation. Our cross-sectional study suggests that, in healthy men aged 20 to 60 years (n = 63), endurance sport practice (vigorous-intensity domain of the International Physical Activity Questionnaire) is associated with better quantity (pulmonary capillary blood volume) and quality (slope of increase in lung diffusion for carbon monoxide on exercise) of the pulmonary vascular bed, partly counterbalancing the deleterious effects of ageing, which remains to be demonstrated in a prospective longitudinal design.     

The enzyme-bound copper of dopamine beta-monooxygenase. Reaction with copper chelators, preparation of the apoprotein, and kinetics of the reconstitution by added copper.

The enzyme-bound copper of dopamine beta-monooxygenase reacted rapidly with the chelator bathocuproine disulfonate; the reaction in the presence of ascorbate was completed in 2 min at 25 degrees C with 1mM chelator. This reaction and also the reaction with EDTA could be used to prepare the apoenzyme, which in both cases was completely reactivated in less than 10 s. The reactivation data gave apparent Michaelis constants for copper 0.03 -- 0.2 micron. Trace amounts of copper in buffers and assay mixtures gave significant reactivation without added copper, unless they had been treated with a chelating resin. Titrations using the different chelation rates of free and enzyme-bound copper indicated that four copper atoms are bound per enzyme molecule of four subunits. The native enzyme was more stable against thermal inactivation than the apoenzyme, but this stability was only partially restored by addition of copper to the apoenzyme.