Chlorpyrifos-methyl solubilisation by humic acids used as bio-surfactants extracted from lignocelluloses and kitchen wastes.

Chlorpyrifos-methyl (CLP-m) is a widely used organophosphate insecticide that can accumulate in soil and become toxic to humans. CLP-m can be removed from soil by its solubilisation using synthetic surfactants. However, synthetic surfactants can accumulate in soil causing contamination phenomena themselves. Bio-surfactants can be used as an alternative to synthetic ones, reducing costs and environmental issues. In this work, humic acid (HA) extracted from raw biomasses, i.e. lignocelluloses (HAL) and lignocelluloses plus kitchen food waste (HALF), corresponding composts (C) (HALC and HALFC) and leonardite (HAc), were tested in comparison with commercial surfactants, i.e. SDS, Tween 20 and DHAB, to solubilize CLP-m. Results obtained indicated that only biomass-derived HA, composted biomass-derived HA, and SDS solubilized CLP-m: SDS = 0.006; HAL = 0.007; HALC = 0.009 g; HALF = 0.025; HALFC = 0.024) (g CLP-m g(-1) surfactant). Lignocelluloses HAs (HAL, HALF) solubilized CLP-m just as well as SDS while lignocellulosic plus kitchen food waste HA (HALF, HALFC) showed a three times higher CLP-m solubilisation capability. This difference was attributed to the higher concentration of alkyl-Carbon that creates strong links with CLP-m in the hydrophobic micelle-core of the surfactants.

Cultivating Chlorella vulgaris and Scenedesmus quadricauda microalgae to degrade inorganic compounds and pesticides in water.

This work evaluates the possibility of cultivating Scenedesmus quadricauda and Chlorella vulgaris microalgae in wastewater from the hydroponic cultivation of tomatoes with the aim of purifying the water. S. quadricauda and C. vulgaris were also used in purification tests carried out on water contaminated by the following active ingredients: metalaxyl, pyrimethanil, fenhexamid, iprodione, and triclopyr. Fifty-six days after the inoculum was placed, a reduction was found in the concentration of nitric nitrogen, ammonia nitrogen, and soluble and total phosphorus. The decrease was 99, 83, 94, and 94 %, respectively, for C. vulgaris and 99, 5, 88, and 89 %, respectively, for S. quadricauda. When the microalgae were present, all the agrochemicals tested were removed more quickly from the water than from the sterile control (BG11). The increase in the rate of degradation was in the order metalaxyl > fenhexamid > iprodione > triclopyr > pyrimethanil. It was demonstrated that there was a real degradation of fenhexamid, metalaxyl, triclopyr, and iprodione, while in the case of pyrimethanil, the active ingredient removed from the substrate was absorbed onto the cells of the microalgae. It was also found that the agrochemicals used in the tests had no significant effect on the growth of the two microalgae. The experiment highlighted the possibility of using cultivations of C. vulgaris and S. quadricauda as purification systems for agricultural wastewater which contains eutrophic inorganic compounds such as nitrates and phosphates and also different types of pesticides.

Metabolic and molecular methods to evaluate the organoclay effects on a bacterial community.

The aim of this work was to evaluate the influence exerted by two different commercial organoclays (DELLITE 43B and DELLITE 67G) on a model microbial consortium using microbial metabolic characterization with BIOLOG system and denaturing gradient gel electrophoresis (DGGE) molecular approach. The information obtained from the molecular analyses, in their complex, account for the differences in species composition induced on the reference consortium by the contact with the organoclays under study. DELLITE 43B resulted to produce a marked selective effect, stimulating the quantitative increase especially of Pseudomonas pseudoalcaligenes. A weaker effect was found for DELLITE 67G. On the other hand, Biolog analyses indicated a depressing action exerted by DELLITE 43B on the metabolic activity of the model microbial consortium as a whole. The presence of P. pseudoalcaligenes and B. borstelensis in the bacterial community after the treatments confirmed that a positive change in the microbial structure consortium occurred.

Organically modified clays as binders of fumonisins in feedstocks.

This study reports an investigation on the ability of organically modified clays to bind mycotoxins, fumonisins B1 (FB1) and B2 (FB2). Organically modified clays are commercia materials prepared from natural clays, generally montmorillonite, by exchanging the inorganic cation with an ammonium organic cation. A screening experiment conducted on 13 organically modified clays and 3 nonmodified clays, used as controls, has confirmed that the presence of an organic cation in the clay interlayer promoted the adsorption of both fumonisins. On the basis of the results of the screening test, four modified clays and a Na-montmorillonite were selected for the determination of the adsorption kinetics and isotherms. On all the tested materials adsorption took place within one hour of contact with fumonisins solutions. Adsorption isotherms have pointed out that the modified clays exhibited a higher adsorptive capacity than the unmodified clay. It was also demonstrated that, notwithstanding the reduced structural difference between FB1 and FB2, they were differently adsorbed on the modified clays. Addition of 2% modified clays to contaminated maize allowed a reduction of more than 70% and 60% of the amount of FB1and FB2 released in solution. Although in vivo experiments are required to confirm the effectiveness of the organically modified clays, these preliminary results suggest that these materials are promising as fumonisins binders.

Organo-clays and nanosponges for acquifer bioremediation: adsorption and degradation of triclopyr.

To avoid the problem of groundwater contamination, mitigation techniques have been proposed that consist of creating barriers made of suitable materials that can facilitate the adsorption and degradation of the pollutants. This study aims at evaluating the capacity of two organo-clays (Dellite 67 G and Dellite 43 B) and one nanosponge to adsorb the herbicide, triclopyr. Triclopyr was chosen because it is a good example of a moderately mobile, leacheable molecule. The rate of degradation of the molecule in the soil, both with and without the presence of the materials under examination, was also determined. Both the organo-clays adsorbed more than 90% of the herbicide. The nanosponge and the soil adsorbed less than 10% triclopyr. When the soil was added with the two organoclays, adsorption increased to 92%. When added to the soil, the materials accelerated the degradation of triclopyr. The half-life in soil was 30 days, whereas in soil with Dellite 67 G and Dellite 43 B it was 10 and 6 days respectively. The addition of the nanosponge to the soil decreased the half life by 50%. These results lead us to suggest that they be used in creating reactive barriers for the remediation of soils and aquifers.

The adsorption and degradation of chlorpyriphos-methyl, pendimethalin and metalaxyl in solid urban waste compost.

To evaluate the feasibility of using compost to prepare substrates for the disposal of pesticide residues, adsorption and degradation studies were carried out on three widely used agricultural pesticides: chlorpyriphos-methyl, pendimethalin and metalaxyl. Obtained from solid urban waste, this compost has been shown to be able to adsorb high levels of chlorpyriphos-methyl and pendimethalin (85%, 100%) whereas metalaxyl was only adsorbed at a level of 37%. However, adding smectite to the compost increased the adsorption of metalaxyl by 117%. Chlorpyriphos-methyl and pendimethalin degraded quickly with half-lives of 1.7 and 14.5 days, respectively, whereas metalaxyl proved more persistent (a half-life of 84 days). Adding ammonium nitrate to the compost accelerated metalaxyl degradation to a half-life of 15 days.

Degradation of poly (lactic acid) and nanocomposites by Bacillus licheniformis.

BACKGROUND, AIM, AND SCOPE: The disposal problem due to non-degradable petroleum-based plastics has raised the demand for biodegradable polymers. The degradation of poly (lactic acid) (PLA) has been studied for several years, but the understanding of involved mechanisms is still incomplete. Based on our previous studies, and it is hypothesized an enzymatic involvement, the aim of this study was to continue investigations on the degradation of PLA and its nanocomposites by Bacillus licheniformis. MATERIALS AND METHODS: Biodegradation of PLA and its nanocomposites (CLOISITE 30B and SOMASIF MEE) was performed on compression-molded, 25 × 25 × 0.6-mm films. Firstly, two plastic films were dipped into sterile nutrient broth inoculated with B. licheniformis and incubated at 32°C. Then, to verify if biodegradation was due to extracellular esterase, the culture broth was filtered to remove B. licheniformis cells, and the plastic materials were put into this broth. RESULTS AND DISCUSSION: PLA degradation by B. licheniformis was accelerated by the presence of organoclays. After 5 months in liquid culture, nanocomposites showed only the 10% of residual mass, compared with the 60% of pure PLA. Extracellular esterase activity was detected in the filtered culture broth confirming that PLA biodegradation was probably due to this enzyme action.

Effects of organoclays on soil eubacterial community assessed by molecular approaches.

The aim of this study was to evaluate the effects of the commercial organoclays, CLOISITE 30B, NANOFIL 804 and DELLITE 26C on soil eubacterial community. An enrichment test was carried out on Nutrient Broth containing the organoclay and the microorganisms previously isolated from soil. Four transfers were made, each after 7 days incubation. The molecular analyses on the eubacterial community were performed before treatment and 7 days after each transfer. DNA was extracted, amplified with eubacterial primers, finally analysed by amplified ribosomal DNA restriction analysis (ARDRA) and denaturing gradient gel electrophoresis (DGGE). The profiles of the samples treated with each organoclay showed the absence, the appearance and an increase in the intensity of some bands. These bands were excised from the gels, and the related microorganisms were identified by DNA sequencing, as Pseudomonas putida, Alcaligenes xylosoxidans, Pseudomonas monteilii and Pseudomonas aeruginosa. NAN804 treatment did not have any influence on soil eubacterial community, CLO30B had a slight toxic effect only on P. putida, instead the DEL26C treatment had a stronger toxic effect on P. putida and a slight toxic effect on P. monteilii. Finally, all the tested organoclays stimulated the growth of both A. xylosoxidans and P. aeruginosa.

Removal of fenhexamid and pyrimethanil from aqueous solutions by clays and organoclays.

The ability of a sodium montmorillonite (CLONa) and two commercial available organoclays having interlayer organic cations possessing different functional groups (CLO20A and CLO30B) was investigated for adsorbing two pesticides namely fenexamid (FEX) and pyrimethanyl (PMT). The two organoclays displayed a higher affinity with the pesticides than the unmodified clay, but the improvement in adsorption capacity varied according to the characteristics of the pesticide and the interlayer organic cation. FEX was adsorbed to a greater extent than PMT by both organoclays, which may be due to the higher hydrophobicity of FEX thereby indicating considerable hydrophobic interaction between the adsorbent/adsorbate systems. Our findings may find application in the removal of water-soluble pesticides from aquifers.

Solubility and adsorption behaviors of chlorpyriphos-methyl in the presence of surfactants.

In the present work changes in the adsorption of the pesticide chlorpyrifos-methyl (CLP-m) on soil colloids induced by application of surfactants were determined using a batch equilibrium method. The surfactants used were sodium dodecyl sulphate (SDS), Tween 20, and dihexadecyldimethylammonium bromide (DHAB). The adsorption isotherms of CLP-m in aqueous medium and in surfactant solutions at concentration equal to the critical micelle concentration (CMC) fitted the Freunlich adsorption equation generally with R(2) values greater than 0.96. While the addition of SDS and DHAB decreased the pesticide adsorption, the addition of Tween 20 increased the pesticide adsorption. The increases or decreases in the adsorption in the experiment revealed that the behavior of CLP-m in soil water-systems mainly depends on the type of surfactant. Moreover water solubility of CLP-m changes by the three surfactants below and above their CMC were studied. While the solubility of CLP-m was enhanced by SDS both below and above the CMC, the solubility of the pesticide was enhanced by DHAB only above the CMC. Tween 20 did not influence the solubility of CLP-m.

Fate and degradation of triasulfuron in soil and water under laboratory conditions.

The behavior and fate of triasulfuron (TRS) in water and soil systems were examined in laboratory studies. The degradation of TRS in both buffer solution and soil was highly pH-sensitive. The rate of degradation could be described with a pseudo first-order kinetic and was much faster at pH 4 than at pH 7 and 9. Aqueous hydrolysis occurred by cleavage of the sulfonylurea bridge to form 2-(2-chloroethoxy) benzenesulfonamide (CBSA) and [(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino] (AMMT). AMMT was unstable in aqueous solutions in any pH condition but it degraded more quickly at pH 4 and 9. CBSA did not degrade in aqueous solutions or in enriched cultures but it underwent a quick degradation in the soil. The rates of TRS degradation in sterile and non-sterile soils were similar, suggesting that microorganisms played a minimal role in the breakdown process. This hypothesis is supported by the results of studies on the degradation of TRS by enriched cultures during which the molecule underwent a prevalently chemical degradation.

Use of model soil colloids to evaluate adsorption of phenanthrene and its mobilization by different solutions.

Inorganic (a montmorillonite; a complex of montmorillonite and aluminium hydroxide) and organo-mineral model soil colloids (a complex of montmorillonite, aluminium hydroxide and humic acid) were tested for their capacity to adsorb and desorb phenanthrene. The adsorption-desorption isotherms demonstrated that the inorganic surfaces were able to bind the pollutant, although to a lesser extent than the organo-mineral complex. The capacity of different aqueous solutions to desorb phenanthrene after 1, 7, and 30 days' contact with the model colloids was tested in order to assess their efficacy with respect to the aging effect. The solutions used were 0.01 N CaCl(2), dissolved soil organic matter (DOM), a model root exudates solution (aqueous solution of saccharose, fructose, glucose, fumaric acid, ferrulic acid, and leucine), and three commercial surfactants (sodium dodecyl sulfate, Tween 20, and didecyldimethylammonium bromide). The desorptive capacity of these solutions were compared with that of organic solutions (water-ethanol and n-hexane-ethanol). More than 85% phenanthrene was desorbed after 30 days aging by organic solutions. Among the aqueous solutions, the best results were obtained with dissolved soil organic matter solution and the model root exudates solution which were able to desorb up to 50% phenanthrene after 30 days aging. Such naturally occurring aqueous solutions should be preferred to synthetic compounds to mobilize phenanthrene in contaminated sites without further contaminating the environment.

Behavior of fenhexamid in soil and water.

A study was conducted to investigate fenhexamid (FEX) behavior in soil and in water. FEX proved to be rather stable at acid pH but showed slight degradation at neutral and alkaline pH. After 101 days of FEX spiking of a soil sample, 94% at pH 4, 12% at pH 7 and 23% at pH 9 of the active ingredient was still present. In natural water the rate of FEX disappearance appeared to be slow which may be due to abiotic rather than biotic processes. The soil degradation tests showed low persistence of the active ingredient if a good microflora activity is guaranteed (DT(50) about 1 day). Moreover, in absence of microorganisms, FEX proved to be stable. Humidities of 25 and 50% of Water Holding Capacity (WHC) influenced in equal measure the rate of degradation. From the same soil, a bacterium was isolated and identified as Bacillus megaterium, which was able to metabolize FEX with the hydroxylation of the cyclohexane ring. Moreover, FEX showed an elevated affinity for humic acid (73%), smectite (31%), and ferrihydrite(20%) and low affinity for vermiculite (11%) and kaolinite (7%).

Evaluation of the bioavailability of the herbicide prosulfocarb through adsorption on soils and model soil colloids, and through a simple bioassay.

Adsorption isotherms of prosulfocarb were determined on soils with different physicochemical properties. The extent of adsorption increased with the organic carbon content, but the results also suggested the involvement of some inorganic soil surfaces. In order better to understand the role of each soil surface, adsorption-desorption isotherms were determined on model soil colloids consisting of a soil humic acid, a montmorillonite, a synthetic aluminium hydroxide and their associations. The highest adsorption was observed on the humic acid, but it was also confirmed that the montmorillonite interacted with prosulfocarb. In contrast, the aluminium hydroxide was not active and its association with montmorillonite provoked a decrease in adsorption compared with montmorillonite alone. Except for humic acid, the highest adsorption took place on the ternary association montmorillonite-aluminium hydroxide-humic acid. On each surface tested, the adsorption was largely reversible and decreased at increasing pH. The herbicidal activity of prosulfocarb was tested by the determination of the germination and growth of a typical weed, Lolium multiflorum Lam, in contact with prosulfocarb solutions at different concentrations. The herbicide did not prevent the germination of the seeds but inhibited the growth of the roots and leaves. The same test was performed in the presence of the ternary system to evaluate the influence of adsorption on the plant bioavailability. It was concluded that the presence of an adsorptive surface reduced the herbicidal activity and that the simple bioassay proposed could be useful in predicting the extent of adsorption in a given soil.

Cinosulfuron: chemical and biological degradability, adsorption and dissipation in flooded paddy field sediment.

Cinosulfuron is a sulfonylurea herbicide largely used in the extensive cultures of flooded rice in North Italy. The degradation of cinosulfuron has been investigated in sterile aqueous solutions at 30 degrees C at different pH values. It was rapidly degraded at acidic pH (half-lives 3, 9 and 43 days at pH 4, 5 and 6, respectively) while the half-life was > 1 year at pH 7 and 9. Two degradation products formed by cleavage of the sulfonylurea bridge were identified by LC-MS. Degradation by selected mixed microbial cultures tested in aerobic and anaerobic conditions was very slow and attributable to chemical hydrolysis due to the acidic pH of the cultural broths. Degradation took place in freshly collected rice field water treated for two years with cinosulfuron but, in this case also, chemical hydrolysis prevailed over microbial degradation. In contrast, in flooded sediment simulating the paddy field environment, the dissipation rate of cinosulfuron was higher than expected from chemical hydrolysis according to the pH of the system, indicating the involvement of soil microflora. Although the herbicide exhibited a reduced affinity for the sediment surfaces demonstrated by the low value of the K(f) Freundlich coefficient (0.87 on a micromolar basis), the rapid dissipation observed in the simulated paddy field should prevent its leaching to ground water.

Behavior of Chlorpyrifos-methyl in soil and sediment.

This research was carried out with the aim of obtaining information regarding the possible environmental impact of Chlorpyrifos-methyl, an organophosphoric insecticide used in agriculture for its phytoiatric action against Hemiptera, Lepidoptera, Coleoptera, and Diptera. Studies relating to the degradation kinetics of the insecticide in two soils and one sediment have shown a rapid degradation process in all three. The prevalent form of degradation would appear to be the chemical type, because the degradation kinetics in a sterile soil have not demonstrated that micro-organisms play a significant part. The adsorption isotherms showed that the insecticide has a greater affinity for the sediment (Kf=143) as opposed to the soils (Kf=65) and that the adsorption process is practically irreversible. Moreover, hydrolysis tests in buffered solutions at pH 4, 7, and 9 revealed that the molecule is particularly unstable with a basic pH.

Simulating pesticide leaching and runoff in rice paddies with the RICEWQ-VADOFT model.

There is a current need to simulate leaching and runoff of pesticide from rice (Oryza sativa L.) paddies for assessing environmental impacts on a valuable agricultural system. The objective of this study was to develop a model for determining predicted environmental concentration (PEC) in soil, runoff, and ground water through the linkage of two models, rice water quality model (RICEWQ) and vadose zone transport model (VADOFT), to simulate pesticide fate and transport within a rice paddy and underlying soil profile. Model performance was evaluated with a field data set obtained from a 2-yr field experiment in 1997 and 1998 in northern Italy. The predictions of amount of pesticide running off from the paddy field and accumulating in the paddy sediment were in agreement with measured values. Leaching into the vadose zone accounted for approximately 19% of the applied dose, but only a small amount of chemical (<0.1%) was predicted to reach ground water at a 5-m depth due to sorption and transformation in the soil. The permeability of the soil and the water management practices in the paddy field were shown to have a strong influence on pesticide fate. These factors need to be well characterized in the field if model predictions are to be successful. The combined model developed in this work is an effective tool for exposure assessments for soil, surface water, and ground water, in the particular conditions of rice cultivation.

Bioavailability and biodegradation of prosulfocarb in soil.

Active microbial degraders of the herbicide prosulfocarb (PSC) were isolated to evaluate their performance in soil with a view to their use for bioremediation. The isolated cultures (a microbial consortium and a Pseudomonas sp. strain) were active when tested in mineral medium with PSC as the only carbon source, but had an adverse effect on the soil indigenous microflora. Biodegradation in the inoculated soils was thus lower than in the uninoculated soil when only the indigenous microflora was present. Further tests showed that the strong affinity of PSC for soil organic matter affected its bioavailability and hence its biodegradation by the inocula. Bioremediation of PSC contaminated soils could thus be undertaken by biostimulation of indigenous microflora.