Time and substrate dependent exudation of carboxylates by Lupinus albus L. and Brassica napus L.

Root exudates influence significantly physical, chemical and biological characteristics of rhizosphere soil. Their qualitative and quantitative composition is affected by environmental factors such as pH, soil type, oxygen status, light intensity, soil temperature, plant growth, nutrient availability and microorganisms. The aim of the present study was to assess the influence of growth substrate and plant age on the release of carboxylates from Lupinus albus L. and Brassica napus L. Both plant species were studied in continuously percolated microcosms filled with either sand, soil or sand + soil (1:1) mixture. Soil solution was collected every week at 7, 14, 21, 28 and 35 days after planting (DAP). Carboxylate concentrations were determined by reversed-phase liquid chromatography - electrospray ionization - time of flight mass spectrometry (LC-ESI-TOFMS). Oxalate, citrate, succinate, malate and maleate were detected in soil solutions of both plant species. Their concentrations were correlated with the physiological status of the plant and the growth substrate. Oxalate was the predominant carboxylate detected within the soil solution of B. napus plants while oxalate and citrate were the predominant ones found in the soil solutions of L. albus plants. The sampling determination of carboxylates released by plant roots with continuous percolation systems seems to be promising as it is a non-destructive method and allows sampling and determination of soluble low molecular weight organic compounds derived from root exudation as well as the concentration of soluble nutrients, which both might reflect the nutritional status of plants.

Removal of sulfonamide antibiotics from water: Evidence of adsorption into an organophilic zeolite Y by its structural modifications.

Sulfonamide antibiotics are persistent pollutants of aquatic bodies, known to induce high levels of bacterial resistance. We investigated the adsorption of sulfadiazine, sulfamethazine, and sulfachloropyridazine sulfonamides into a highly dealuminated faujasite zeolite (Y) with cage window sizes comparable to sulfonamide dimensions. At maximal solubility the antibiotics were almost completely (>90%) and quickly (t<1min) removed from the water by zeolite. The maximal amount of sulfonamides adsorbed was 18-26% DW of dry zeolite weight, as evidenced by thermogravimetric analyses and accounted for about one antibiotic molecule per zeolitic cage. The presence of this organic inside the cage was revealed by unit cell parameter variations and structural deformations obtained by X-ray structure analyses carried out using the Rietveld method on exhausted zeolite. The most evident deformation effects were the lowering of the Fd-3m real symmetry in the parent zeolite to Fd-3 and the remarkable deformations which occurred in the 12-membered ring cage window after sulfadiazine or sulfachloropyridazine adsorption. After sulfamethazine adsorption, zeolite deformation caused a lowering in symmetry up to the monoclinic P2/m space group. The effective and irreversible adsorption of sulfonamides into organophylic Y zeolite makes this cheap and environmentally friendly material a suitable candidate for removing sulfonamides from water.

Sulfonamide antibiotics embedded in high silica zeolite Y: a combined experimental and theoretical study of host-guest and guest-guest interactions.

A combined experimental and computational study of the interactions of three sulfonamides--sulfadiazine, sulfamethazine, and sulfachloropyridazine--embedded into the cages of high silica zeolite Y is here proposed. For all host-guest systems, the close vicinity of aromatic rings with zeolite framework was evidenced by multidimensional and multinuclear ((1)H, (13)C, (29)Si) SS-NMR measurements. Host-guest and guest-guest interactions were also elucidated by in situ FTIR spectroscopy and confirmed by ab initio computational modeling. Single molecules of sulfamethazine and sulfachloropyridazine were stabilized inside the zeolite cage by the vicinity of methyl and amino groups, respectively. Sulfadiazine is present in both monomeric and dimeric forms. Multiple weak H-bonds and van der Waals type interactions between organic molecules and zeolite are responsible for the irreversible extraction from water of all the examined sulfa drugs.

The influence of aluminium availability on phosphate uptake in Phaseolus vulgaris L. and Phaseolus lunatus L.

Aluminium toxicity is one of the major limiting factors of crop productivity on acid soils. High levels of available aluminium in soil may induce phosphorus deficiency in plants. This study investigates the influence of Aluminium (Al) on the phosphate (P(i)) uptake of two Phaseolus species, Phaseolus vulgaris L. var. Red Kidney and Phaseolus lunatus L. The two bean species were treated first with solutions of Al at different concentrations (0, 25, 50 and 100microM, pH 4.50) and second with solutions of P(i) (150microM) at pH 4.50. The higher the Al concentration the higher the Al concentration sorbed but P. vulgaris L var. Red Kidney adsorbed significantly more Al than P. lunatus L. Both species released organic acids: P. vulgaris L var. Red Kidney released fumaric acid and P. lunatus L. fumaric and oxalic acids which could have hindered further Al uptake. The two bean species showed a sigmoid P(i) uptake trend but with two different mechanisms. P. vulgaris L var. Red Kidney showed a starting point of 3h whereas P. lunatus L. adsorbed P(i) immediately within the first minutes. In addition, P. vulgaris L var. Red Kidney presented significantly higher P(i) uptake (higher uptake rate 'k' and higher maximum adsorption 'a' of the kinetic uptake model). The Al treatments did not significantly influence P(i) uptake. Results suggest that P. lunatus L. might adopt an external Al detoxification mechanism by the release of oxalic acid. P. vulgaris L var. Red Kidney on the other hand seemed to adopt an internal detoxification mechanism even if the Al sorbed is poorly translocated into the shoots. More detailed studies will be necessary to better define Al tolerance and/or resistance of Phaseolus spp.

Hydrolysis and adsorption of cyhalofop-butyl and cyhalofop-acid on soil colloids.

A study was undertaken to investigate the stability of cyhalofop-butyl (2 R)-2-[4-(4-cyano-2-fluorophenoxy)phenoxy]butylpropanoate (CyB), an aryloxyphenoxy-propionic herbicide, at different pH values. The hydrolysis of CyB was faster in nonsterile than in sterile water. In sterile medium, CyB degraded only to (2 R)-2-[4-(4-cyano-2-fluorophenoxy)phenoxy]propanoic acid (CyA), whereas in nonsterile water, also the metabolites (2 R)-2-[4-(4-carbamoyl-2-fluorophenoxy)phenoxy]propanoic acid (CyAA) and (2 R)-2-[4-(4-carboxyl-2-fluorophenoxy)phenoxy]propanoic acid (CyD) were detected. The adsorption of CyB onto clays, iron oxide, and dissolved organic matter (DOM), using a batch equilibrium method, was also studied. A lipophilic bond is responsible for CyB adsorption on DOM. CyB was adsorbed on Fe(III)- and Ca-clays through hydrogen bonding between the carbonyl oxygen and water surrounding the exchangeable cations. In the interlayer of K-clay, CyB was hydrolyzed to CyA, which remained adsorbed therein as a monomer. The acid CyA was adsorbed only by the Fe-oxide through complexation. The CyA-Fe-oxide complex was stable and did not undergo degradation.

Effect of undesalted dissolved organic matter from composts on persistence, adsorption, and mobility of cyhalofop herbicide in soils.

The effect of undesalted dissolved organic matter (DOM) extracted from composts on the degradation, adsorption, and mobility of cyhalofop herbicide in soils was studied. A paddy-field sediment poor in organic matter (OM), an OM-rich forest soil, and DOM from agroindustrial or municipal waste compost were used. DOM increased the cyhalofop-acid but not the cyhalofop-butyl solubility in water. The degradation of cyhalofop-butyl in the sediment was slow, giving cyhalofop-acid as the only metabolite, whereas in forest soil, the process was faster, and three byproducts were detected. Soil pretreatment with DOM did not modify the degradation pattern but only reduced the adsorption of cyhalofop-butyl by soil, whereas it increased the adsorption of cyhalofop-acid. Among the cationic components of DOM solutions, the potassium ion seems to be related to the increased adsorption of the cyhalofop-acid in both OM-poor and OM-rich soils, yielding reversible complexes with the former and favoring hydrophobic interactions with the latter.

Structural elucidation of phototransformation products of azimsulfuron in water.

The photodegradation of the sulfonylurea herbicide azimsulfuron, N-[[(4,6-dimethoxypyrimidin-2-yl)amino]carbonyl]-1-methyl-4-(2-methyl-2H-tetrazole-5-yl)-1H-pyrazole-5-sulfonamide (AZS), was studied in water at different wavelengths and in the presence of photocatalysts. AZS was rapidly degraded by UV light, affording three photoproducts. The main product, accounting for about 70% of photodegraded herbicide, was identified as 6-amino-5-[(4,6-dimethoxypyrimidin-2-yl)methylamino]-1,5,6,8-tetrahydro-7-oxa-8lambda(6)-tia-1,2,5,6-tetraza-azulen-4-one (ADTA) by single-crystal X-ray diffraction. With simulated sunlight irradiation, the reaction was slower and 2-amino-4,6-dimethoxypyrimidine (DPA) and 1-methyl-4-(2-methyl-2H-tetrazole-5-yl)-1H-pyrazole-5-sulfonamide (MPS), arising from a photohydrolytic cleavage of the sulfonylurea bridge, were the only byproducts observed. The reactions followed first-order kinetics. The addition of dissolved organic matter (DOM) did not modify significantly the AZS photodegradation rate. The presence of Fe2O3 accelerated more than twice the reaction rate affording two major products, DPA and MPS, together with minor amounts of N-[[(5-hydroxy-4,6-dimethoxypyrimidin-2-yl)amino]carbonyl]-1-methyl-4-(2-methyl-2H-tetrazole-5-yl)-1H-pyrazole-5-sulfonamide (AZS-OH). The greatest degradation rate was detected in the presence of TiO2. Only the photohydroxylation product AZS-OH was observed, which was transformed rapidly into oxalic acid.

Characterisation of Ca- and Al-pectate gels by thermal analysis and FT-IR spectroscopy.

Thermal analysis (TG-DTA) and FT-IR spectroscopy have been performed on calcium-pectate membranes to investigate their structure and the consequent variation caused by aluminium sorption. Calcium-polygalacturonate (Ca-PG) membranes, model systems of the soil-root interface, were exposed to aluminium solutions at different concentrations (25-800 microM). Three different pHs (3.50, 4.00 and 4.50) were chosen to study the influence of different aluminium species, such as [Al(H2O)6]3+, [Al(OH)(H2O)5]2+ and [Al(OH)2(H2O)(4)]+, on the structure of the Ca-PG membrane. The DTA profiles and FT-IR spectra showed how aluminium sorption induces structural modifications leading to a reorganisation of the chain aggregates and a weakening of the structure. Higher pH, that is, 4.00 and 4.50, and thus hydrolytic aluminium species and related higher calcium content maintain a more regular structure than at pH 3.50. At pH 3.50, both the effect of [Al(H2O)6]3+ and a major calcium release had a greater impact and thus induced a greater weakening of the structure.

Sorption and degradation of azimsulfuron on iron(III)-rich soil colloids.

The sorption of N-[[(4,6-dimethoxypyrimidin-2-yl)amino]carbonyl]-1-methyl-4-(2-methyl-2H-tetrazole-5-yl)1H-pyrazole-5-sulfonamide (AZS) on an iron oxide, iron(III)-humate, and an Fe3+-saturated clay was studied using a batch equilibrium method. Generally, 20 mg of each colloid was equilibrated with 20 mL of AZS solution (1.5-12.7 microM). The sorption on iron-montmorillonite and iron oxide was rapid, and the equilibrium was attained within 1.5 and 5 h, respectively. In the case of Fe-saturated humic acid the equilibrium time was 20 h. After equilibration, the phases were centrifuged (19000g, 15 min) and the supernatant was sampled and analyzed by HPLC. The values of Freundlich constants indicate that iron oxide (Kads = 199.5) shows the highest sorptive capacity toward AZS, followed by iron(III)-clay (Kads = 146.6) and iron(III)-humate (Kads = 108.2). With elapsing time, AZS degradation was observed in all colloidal suspensions. Iron-humate (t(1/2) = 136 h) is most effective in promoting AZS degradation, followed by iron oxide (t(1/2) = 204 h) and iron-clay (t(1/2) = 385 h). The metabolites 2-amino-4,6-dimethoxypyrimidine and 1-methyl-4-(2-methyl-2H-tetrazole-5-yl)-1H-pyrazole-5-sulfonamide, arising from a hydrolytic cleavage of the sulfonylurea bridge, were the only byproducts observed. A Fourier transform infrared study suggests that the sorption of AZS on iron-clay involves the protonation of one of the two basic pyrimidine nitrogens induced by the acidic water surrounding the saturating Fe3+ ions. Instead, the formation of a six-membered chelated complex favors the sorption of AZS on iron oxide.

Azimsulfuron sorption--desorption on soil.

The sorption and desorption of the herbicide azimsulfuron, N-[[(4-dimethoxypyrimidin-2-yl)amino]carbonyl]1-methyl-4-(2-methyl-2H-tetrazole-5-yl)1H-pyrazole-5-sulfonamide, were studied using five soils. Sorption isotherms conformed to the Freundlich equation. It was found that pH is the main factor influencing the sorption and that the sorption on soils was negatively correlated with pH. The highest level of sorption was measured on soils with low pH and high organic carbon content. Moreover, inorganic soil colloids, for example, smectite clay minerals and iron oxides, contributed to the sorption of azimsulfuron. Desorption was hysteretic on soils with high organic and inorganic colloid contents.

Evolution of organic matter from sewage sludge and garden trimming during composting.

To use compost appropriately in agriculture it is extremely important to estimate the stabilization level of the organic matter. In this work, two different piles of compost were studied by means of (i) humification parameters (degree of humification--DH, humification rate--HR, humification index--HI) prior to and after enzymatic hydrolysis of the extracted organic carbon, (ii) water-soluble organic carbon (WSOC) and (iii) water-soluble nitrogen. A significant relationship between composting time, WSOC and humification parameters after enzymatic hydrolysis (DHenz; HRenz; HIenz) was found.

Adsorption and desorption of triasulfuron by soil.

The adsorption and desorption of the herbicide triasulfuron [2-(2-chloroethoxy)-N-[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl]benzenesulfonamide] by three soils, soil organic matter (H(+) and Ca(2+)-saturated), and an amorphous iron oxide were studied. Adsorption isotherms conformed to the Freundlich equation. It was found that pH is the main factor influencing the adsorption in all of the systems. Indeed, the adsorption on soils was negatively correlated with pH. The highest level of adsorption was measured on soils with low pH and high organic carbon content. Moreover, it was found that humic acid is more effective in the adsorption compared with calcium humate (the pH values of the suspensions being 3.5 and 6, respectively). Experiments on amorphous iron oxide confirmed the pH dependence. Desorption was hysteretic on soils having high organic carbon content.

Determination of free L- and D-alanine in hydrolysed protein fertilisers by capillary electrophoresis.

of racemisation of hydrolysed protein fertilisers (HPFs) using an The objective of this study was to determine the degree inexpensive and easy to handle analytical method for qualitative control of the products. Using a polyacrylamide coated capillary and a run buffer containing 0.1 M Tris-borate+2.5 mM EDTA-Na2+0.1% sodium dodecylsulfate+10 mM beta-cyclodextrin a quantitative separation of D- and L-alanine (Ala) was made from an not treated HPF sample derivatised with dansyl chlorine by capillary electrophoresis. The D-Ala:[D-Ala+L-Ala] ratio, called degree of racemisation (RD), was calculated. The analysis of ten commercial HPFs has shown that more than 60% of HPFs have an RD > or = 40%. while only one product has shown an RD <5%. These results showed that most of the HPFs on the market are obtained with strong hydrolytic processes and high contents of D-amino acids are probably less effective as plant nutrients or even potentially dangerous to plants.