Ibuprofen-enhanced biodegradation in solution and sewage sludge by a mineralizing microbial consortium. Shift in associated bacterial communities.

Ibuprofen (IBP) is a widely used drug of environmental concern as emerging contaminant due to its low elimination rates by wastewater treatment plants (WWTPs), leading to the contamination of the environment, where IBP is introduced mainly from wastewater discharge and sewage sludge used as fertilizer. This study describes the application of a consortium from sewage sludge and acclimated with ibuprofen (consortium C7) to accelerate its biodegradation both in solution and sewage sludge. 500 mg L-1 IBP was degraded in solution in 28 h, and 66% mineralized in 3 days. IBP adsorbed in sewage sludge (10 mg kg-1) was removed after bioaugmentation with C7 up to 90% in 16 days, with a 5-fold increase in degradation rate. This is the first time that bioaugmentation with bacterial consortia or isolated bacterial strains have been used for IBP degradation in sewage sludge. The bacterial community of consortium C7 was significantly enriched in Sphingomonas wittichii, Bordetella petrii, Pseudomonas stutzeri and Bosea genosp. after IBP degradation, with a special increase in abundance of S. wittichii, probably the main potential bacterial specie responsible for IBP mineralization. Thirteen bacterial strains were isolated from C7 consortium. All of them degraded IBP in presence of glucose, especially Labrys neptuniae. Eight of these bacterial strains (B. tritici, L. neptuniae, S. zoogloeoides, B. petrii, A. denitrificans, S. acidaminiphila, P. nitroreducens, C. flaccumfaciens) had not been previously described as IBP-degraders. The bacterial community that makes up the indigenous consortium C7 appears to have a highly efficient biotic degradation potential to facilitate bioremediation of ibuprofen in contaminated effluents as well as in sewage sludge generated in WWTPs.

Genome analysis for the identification of genes involved in phenanthrene biodegradation pathway in Stenotrophomonas indicatrix CPHE1. Phenanthrene mineralization in soils assisted by integrated approaches.

Phenanthrene (PHE) is a highly toxic compound, widely present in soils. For this reason, it is essential to remove PHE from the environment. Stenotrophomonas indicatrix CPHE1 was isolated from an industrial soil contaminated by polycyclic aromatic hydrocarbons (PAHs) and was sequenced to identify the PHE degrading genes. Dioxygenase, monooxygenase, and dehydrogenase gene products annotated in S. indicatrix CPHE1 genome were clustered into different trees with reference proteins. Moreover, S. indicatrix CPHE1 whole-genome sequences were compared to genes of PAHs-degrading bacteria retrieved from databases and literature. On these basis, reverse transcriptase-polymerase chain reaction (RT-PCR) analysis pointed out that cysteine dioxygenase (cysDO), biphenyl-2,3-diol 1,2-dioxygenase (bphC), and aldolase hydratase (phdG) were expressed only in the presence of PHE. Therefore, different techniques have been designed to improve the PHE mineralization process in five PHE artificially contaminated soils (50 mg kg-1), including biostimulation, adding a nutrient solution (NS), bioaugmentation, inoculating S. indicatrix CPHE1 which was selected for its PHE-degrading genes, and the use of 2-hydroxypropyl-ß-cyclodextrin (HPBCD) as a bioavailability enhancer. High percentages of PHE mineralization were achieved for the studied soils. Depending on the soil, different treatments resulted to be successful; in the case of a clay loam soil, the best strategy was the inoculation of S. indicatrix CPHE1 and NS (59.9% mineralized after 120 days). In sandy soils (CR and R soils) the highest percentage of mineralization was achieved in presence of HPBCD and NS (87.3% and 61.3%, respectively). However, the combination of CPHE1 strain, HPBCD, and NS showed to be the most efficient strategy for sandy and sandy loam soils (LL and ALC soils showed 35% and 74.6%, respectively). The results indicated a high degree of correlation between gene expression and the rates of mineralization.

Genome sequence of Stenotrophomonas indicatrix CPHE1, a powerful phenanthrene-degrading bacterium.

Environmental pollution caused by polycyclic aromatic hydrocarbons (PAHs) involves a high-risk and have received considerable attention due to their carcinogenic, teratogenic, and mutagenic properties. Phenanthrene (PHE) is a low molecular weight PAH, which has three benzene rings. It is one of the most common PAH found in contaminated environments mainly due to its low volatilization ability and hydrophobic character. A PHE degrading bacterium was isolated from an industrial contaminated soil using enrichment culture techniques. Based on macroscopic, microscopic examination and phylogenetic analysis, this bacterium was classified as Stenotrophomonas indicatrix and named strain CPHE1. Several authors have reported about bacteria stains, which can degrade PHE, but this is the first time where the ability of S. indicatrix to biodegrade and mineralize PHE has been demonstrated.

Isolation of Novel Bacterial Strains Pseudomonas extremaustralis CSW01 and Stutzerimonas stutzeri CSW02 from Sewage Sludge for Paracetamol Biodegradation.

Paracetamol is one of the most used pharmaceuticals worldwide, but due to its widespread use it is detected in various environmental matrices, such as surface and ground waters, sediments, soils or even plants, where it is introduced mainly from the discharge of wastewater and the use of sewage sludge as fertilizer in agriculture. Its accumulation in certain organisms can induce reproductive, neurotoxic or endocrine disorders, being therefore considered an emerging pollutant. This study reports on the isolation, from sewage sludge produced in wastewater treatment plants (WWTPs), of bacterial strains capable of degrading paracetamol. Up to 17 bacterial strains were isolated, but only two of them, identified as Pseudomonas stutzeri CSW02 and Pseudomonas extremaustralis CSW01, were able to degrade very high concentrations of paracetamol in solution as a sole carbon and energy source, and none of them had been previously described as paracetamol degraders. These bacteria showed the ability to degrade up to 500 mg L-1 of paracetamol in only 6 and 4 h, respectively, much quicker than any other paracetamol-degrader strain described in the literature. The two main paracetamol metabolites, 4-aminophenol and hydroquinone, which present high toxicity, were detected during the degradation process, although they disappeared very quickly for paracetamol concentrations up to 500 mg L-1. The IC50 of paracetamol for the growth of these two isolates was also calculated, indicating that P. extremaustralis CSW01 was more tolerant than S. stutzeri CSW02 to high concentrations of paracetamol and/or its metabolites in solution, and this is the reason for the much lower paracetamol degradation by S. stutzeri CSW02 at 2000-3000 mg L-1. These findings indicate that both bacteria are very promising candidates for their use in paracetamol bioremediation in water and sewage sludge.

A comprehensive feasibility study of effectiveness and environmental impact of PAH bioremediation using an indigenous microbial degrader consortium and a novel strain Stenotrophomonas maltophilia CPHE1 isolated from an industrial polluted soil.

Polycyclic Aromatic Hydrocarbons (PAHs) are major toxic and recalcitrant pollutants in the environment. This study assessed the capacity of an isolated soil microbial consortium (OMC) to biodegrade PAHs. OMC was able to reach 100% biodegradation of naphthalene, acenaphthylene, acenaphthene, fluorene and phenanthrene in solution, and up to 76% and 50% of anthracene and fluoranthene, respectively, from a mix of 16 PAHs. To measure phenanthrene (PHE) mineralization, OMC and eight strains isolated from OMC were used and identified by PCR amplification of the gene 16S ribosomal RNA. A novel Stenotrophomonas maltophilia CPHE1, not previously described as a PAH degrader, was able to mineralize almost 40% PHE and biodegrade 90.5% in solution, in comparison to OMC that reached 100% PHE degradation, but only 18.8% mineralization. Based on metabolites identified during PHE degradation and on the detection of two genes (PAH RHDα and nahAc) in OMC consortium, two possible via were described for its degradation, through salicylic and phthalic acid. PAH RHDα, which codified the first step on PHE biodegradation pathway, was also found in the DNA of S. maltophilia CPHE1. An ecotoxicology study showed that PHE bioremediation after inoculating S. maltophilia CPHE1 for 30 days decreased by half the solution toxicity.

Bioaugmentation of PAH-Contaminated Soils With Novel Specific Degrader Strains Isolated From a Contaminated Industrial Site. Effect of Hydroxypropyl-ß-Cyclodextrin as PAH Bioavailability Enhancer.

A PAHs-contaminated industrial soil was analyzed using PCR amplification of the gene 16S ribosomal RNA for the detection and identification of different isolated bacterial strains potentially capable of degrading PAHs. Novel degrader strains were isolated and identified as Achromobacter xylosoxidans 2BC8 and Stenotrophomonas maltophilia JR62, which were able to degrade PYR in solution, achieving a mineralization rate of about 1% day-1. A. xylosoxidans was also able to mineralize PYR in slurry systems using three selected soils, and the total extent of mineralization (once a plateau was reached) increased 4.5, 21, and 57.5% for soils LT, TM and CR, respectively, regarding the mineralization observed in the absence of the bacterial degrader. Soil TM contaminated with PYR was aged for 80 days and total extent of mineralization was reduced (from 46 to 35% after 180 days), and the acclimation period increased (from 49 to 79 days). Hydroxypropyl-ß-cyclodextrin (HPBCD) was used as a bioavailability enhancer of PYR in this aged soil, provoking a significant decrease in the acclimation period (from 79 to 54 days) due to an increase in PYR bioavailable fraction just from the beginning of the assay. However, a similar global extension of mineralization was obtained. A. xylosoxidans was then added together with HPBCD to this aged TM soil contaminated with PYR, and the total extent of mineralization decreased to 25% after 180 days, possibly due to the competitive effect of endogenous microbiota and the higher concentration of PYR in the soil solution provoked by the addition of HPBCD, which could have a toxic effect on the A. xylosoxidans strain.

Extraction of PAHS from an aged creosote-polluted soil by cyclodextrins and rhamnolipids. Side effects on removal and availability of potentially toxic elements.

This study evaluated the effect of several cyclodextrins (CDs) and a rhamnolipid (RL) on the removal of polycyclic aromatic hydrocarbons (PAHs) from a co-contaminated soil which had received historically creosote and inorganic wood preservatives for almost 100 years, and the effect of such extractions on the potentially toxic elements (PTEs). The influence on such processes of an electrolyte (0.01 M Ca(NO3)2) was also studied. Up to 15.4% of the ∑16 PAHs were extracted using RL in the absence of the electrolyte as washing solution, but decreases until reaching 0.60% in the presence of Ca2+ due to RL precipitation and partial inactivation. Only up to 2% of the ∑16 PAHs was extracted with CDs (4-ring PAHs in higher concentrations), but the electrolyte had no effect on extraction. In relation to PTEs, CDs proved to be inefficient for their extraction, and even RL in the presence of the background electrolyte. But in the absence of electrolyte PTEs extraction by RL increased. Apart from that, the availability of Ni, Cr, and As, those more associated to Fe and Al soil surfaces, increased after extraction with RLs in the presence of Ca2+ (about 100% for Cr and Ni and 200% for As). Under these conditions Fe and Al availability increased two- and ten-fold, respectively, indicating that Fe-Al soil surfaces were altered. Therefore, the ionic strength and the cations present in the soil solution of soils have to be considered when RLs are used as extractants for remediation purposes.

Technological applications of organo-montmorillonites in the removal of pyrimethanil from water: adsorption/desorption and flocculation studies.

Pyrimethanil (2-aniline-4, 6-dimethylpyrimidine, PRM) is used in fruit packing plants to control fungal infections and diseases. The effluents greatly polluted with this fungicide, as a point source contamination, need to be technologically treated for their regeneration before they reach water bodies. This work evaluates the use of organo-montmorillonites, synthetized in our laboratory, for their application in adsorption and coagulation/flocculation processes for the removal of PRM from water. The adsorption-desorption performance of PRM in a raw montmorillonite (Mt) and several organo-montmorillonites (organo-Mt) obtained by different amounts and types of exchanged surfactants (octadecyltrimethylammonium (ODTMA) and didodecyldimethylammonium (DDAB) bromides and benzyltrimethylammonium chloride (BTMA)) was studied. The PRM adsorption on raw Mt was assigned mainly to an interlayer occupancy, while hydrophobic interactions between PRM and the surfactants in the exchanged samples increased PRM adsorption, which was correlated with the surfactant loading. PRM desorption showed irreversible behavior in raw Mt, which changed to reversible for organo-Mt samples, and was also correlated with the increase of surfactant loading.Two of the organo-Mt with high surfactant loading (twice the CEC) were assayed for the removal of commercial PRM in coagulation/flocculation tests, and their performance was compared to that of the native clay (Mt). The use of the organo-Mt produced flocculation at a very low ratio (0.5 g L-1), whereas no flocculation was observed with Mt. These results proved the feasibility of the use of organo-Mt for the treatment of wastewater contaminated with PRM using a low organo-Mt/liquid ratio.

Effect of controlled release formulations of diuron and alachlor herbicides on the biochemical activity of agricultural soils.

The use of pesticides in agriculture is essential because it reduces the economic losses caused by pests, improving crop yields. In spite of the growing number of studies concerning the development and application of controlled release formulations (CRFs) of pesticides in agricultural soils, there are no studies about the effects of such formulations on the biochemical properties. In this paper the dissipation of diuron and alachlor in three agricultural soils for 127days, applied either as commercial or CRFs, was determined as well as their concomitant effects on soil biochemical properties. Dehydrogenase, urease, ß-glucosidase and phosphatase activities were measured thought the experimental period. The application of alachlor as CRF increases its half-life time in soils, whereas no differences were noticed between diuron formulations due to its slower degradation, which takes longer than its release from the CRF. At the end of the incubation period, the enzymatic activities were the same after the use of diuron either as commercial or CRF, recovering the soil previous status. For alachlor formulations, no differences in enzymatic activities were again observed between both formulations, but their levels in soils were enhanced. Therefore, the use of these CRFs does not adversely affect the soil biochemical properties.

Assisted attenuation of a soil contaminated by diuron using hydroxypropyl-ß-cyclodextrin and organic amendments.

Diuron desorption and mineralisation were studied on an amended and artificially contaminated soil. The amendments used comprised two different composted organic residues i.e., sewage sludge (SS) mixed with pruning wastes, and urban solid residues (USR), and two different solutions (with inorganic salts as the micronutrients and hydroxypropyl-ß-cyclodextrin (HPBCD)). After applying micronutrients to activate the soil flora, 15.5% mineralisation could be reached after 150 days, indicating that the soil has a potential capacity to mineralise the herbicide through biostimulation-assisted attenuation. Diuron mineralisation was also improved when HPBCD solutions were applied. Indeed, the extent of herbicide mineralisation reached 29.7% with this application. Moreover, both the lag phase and the half-life time (DT50) were reduced to 33 and 1,778 days, respectively, relative to the application of just micronutrients (i.e., 39 and 6297 days, respectively). Organic amendments were also applied (i.e., USR and SS) on the contaminated soil: it was found that the diuron mineralisation rate was improved as the amendment concentration increased. The joint application of all treatments investigated at the best conditions tested was conducted to obtain the best diuron mineralisation results. The micronutrient amendment plus 4% USR or SS amendment plus HPBCD solution (10-fold diuron initially spiked) caused an extent of diuron mineralisation 33.2 or 46.5%, respectively.

Removal of waterborne microorganisms by filtration using clay-polymer complexes.

Clay-polymer composites were designed for use in filtration processes for disinfection during the course of water purification. The composites were formed by sorption of polymers based on starch modified with quaternary ammonium ethers onto the negatively charged clay mineral bentonite. The performance of the clay-polymer complexes in removal of bacteria was strongly dependent on the conformation adopted by the polycation on the clay surface, the charge density of the polycation itself and the ratio between the concentrations of clay and polymer used during the sorption process. The antimicrobial effect exerted by the clay-polymer system was due to the cationic monomers adsorbed on the clay surface, which resulted in a positive surface potential of the complexes and charge reversal. Clay-polymer complexes were more toxic to bacteria than the polymers alone. Filtration employing our optimal clay-polymer composite yielded 100% removal of bacteria after the passage of 3L, whereas an equivalent filter with granular activated carbon (GAC) hardly yielded removal of bacteria after 0.5L. Regeneration of clay-polymer complexes saturated with bacteria was demonstrated. Modeling of the filtration processes permitted to optimize the design of filters and estimation of experimental conditions for purifying large water volumes in short periods.

Decontamination of polycyclic aromatic hydrocarbons and nonylphenol from sewage sludge using hydroxypropyl-ß-cyclodextrin and evaluation of the toxicity of leachates.

A decontamination technique based in cyclodextrin extraction has been developed to eliminate nonylphenol (NP) and 16 polycyclic aromatic hydrocarbons (PAHs; the US Environmental Protection Agency priority pollutants list) from sewage sludge. In a first step, PAHs and NP were characterised in six sludges to determine contamination levels according to limit values proposed by the European Union Sludge Directive draft. There were few variations in the total PAHs content with levels of 1.88 to 3.05 mg kg(-1). Three-ring PAHs predominated, but fluoranthene and pyrene were also present. None of the sludge exceeded the PAHs limit proposed by the European Union's draft Directive. On the contrary, NP content in four of the six sludges was over the recommended limits of 50 mg kg(-1) for NP ethoxylates. With the aim of obtaining NP values below the concentration limits proposed to use the sewage sludge as agricultural amendments, a preliminary study using hydroxypropyl-ß-cyclodextrin (HPBCD) extractions as a decontamination technique was carried out. About 90% of NP content was removed with only one extraction with HPBCD, whereas after three sequential extractions using an aqueous solution without HPBCD, the NP extraction percentage was less than 1%. Simultaneously, PAHs extraction percentages obtained with HPBCD were also much higher than when aqueous solution was used, especially in the case of two- and three-ring PAHs. Finally, the potential environmental hazard of HPBCD leachates to aquatic organisms (Daphnia magna) was tested. These results indicate that the treatment of sewage sludge with cyclodextrin could allow their safe use as fertiliser in agriculture.

Factors affecting the design of slow release formulations of herbicides based on clay-surfactant systems. A methodological approach.

A search for clay-surfactant based formulations with high percentage of the active ingredient, which can yield slow release of active molecules is described. The active ingredients were the herbicides metribuzin (MZ), mesotrione (MS) and flurtamone (FL), whose solubilities were examined in the presence of four commercial surfactants; (i) neutral: two berols (B048, B266) and an alkylpolyglucoside (AG6202); (ii) cationic: an ethoxylated amine (ET/15). Significant percent of active ingredient (a.i.) in the clay/surfactant/herbicide formulations could be achieved only when most of the surfactant was added as micelles. MZ and FL were well solubilized by berols, whereas MS by ET/15. Sorption of surfactants on the clay mineral sepiolite occurred mostly by sorption of micelles, and the loadings exceeded the CEC. Higher loadings were determined for B266 and ET/15. The sorption of surfactants was modeled by using the Langmuir-Scatchard equation which permitted the determination of binding coefficients that could be used for further predictions of the sorbed amounts of surfactants under a wide range of clay/surfactant ratios. A possibility was tested of designing clay-surfactant based formulations of certain herbicides by assuming the same ratio between herbicides and surfactants in the formulations as for herbicides incorporated in micelles in solution. Calculations indicated that satisfactory FL formulations could not be synthesized. The experimental fractions of herbicides in the formulations were in agreement with the predicted ones for MS and MZ. The validity of this approach was confirmed in in vitro release tests that showed a slowing down of the release of a.i. from the designed formulations relative to the technical products. Soil dissipation studies with MS formulations also showed improved bioactivity of the clay-surfactant formulation relative to the commercial one. This methodological approach can be extended to other clay-surfactant systems for encapsulation and slow release of target molecules of interest.

Enhanced solubilisation of six PAHs by three synthetic cyclodextrins for remediation applications: molecular modelling of the inclusion complexes.

Solubilisation of six polycyclic aromatic hydrocarbons (PAHs) (acenaphthene, anthracene, fluoranthene, fluorene, phenanthrene and pyrene) by three synthetic cyclodextrins (CDs) (2-hydroxypropyl-ß-CD, hydroxypropyl-γ-CD and randomly methylated-ß-CD) was investigated in order to select the CD which presents the greatest increase in solubility and better complexation parameters for its use in contaminated scenarios. The presence of the three cyclodextrins greatly enhanced the apparent water solubility of all the PAHs through the formation of inclusion complexes of 1:1 stoichiometry. Anthracene, fluoranthene, fluorene and phenanthrene clearly presented a higher solubility when ß-CD derivatives were used, and especially the complexes with the randomly methylated-ß-CD were favoured. On the contrary, pyrene presented its best solubility results when using 2-hydroxypropyl-γ-CD, but for acenaphthene the use of any of the three CDs gave the same results. Complementary to experimental phase-solubility studies, a more in-depth estimation of the inclusion process for the different complexes was carried out using molecular modelling in order to find a correlation between the degree of solubilisation and the fit of PAH molecules within the cavity of the different CDs and to know the predominant driving forces of the complexation.

Cyclodextrin inclusion complex to improve physicochemical properties of herbicide bentazon: exploring better formulations.

The knowledge of the host-guest complexes using cyclodextrins (CDs) has prompted an increase in the development of new formulations. The capacity of these organic host structures of including guest within their hydrophobic cavities, improves physicochemical properties of the guest. In the case of pesticides, several inclusion complexes with cyclodextrins have been reported. However, in order to explore rationally new pesticide formulations, it is essential to know the effect of cyclodextrins on the properties of guest molecules. In this study, the inclusion complexes of bentazon (Btz) with native ßCD and two derivatives, 2-hydroxypropyl-ß-cyclodextrin (HPCD) and sulfobutylether-ß-cyclodextrin (SBECD), were prepared by two methods: kneading and freeze-drying, and their characterization was investigated with different analytical techniques including Fourier transform infrared spectroscopy (FT-IR), differential thermal analysis (DTA), X-ray diffractometry (XRD) and differential pulse voltammetry (DPV). All these approaches indicate that Btz forms inclusion complexes with CDs in solution and in solid state, with a stoichiometry of 1:1, although some of them are obtained in mixtures with free Btz. The calculated association constant of the Btz/HPCD complex by DPV was 244±19 M(-1) being an intermediate value compared with those obtained with ßCD and SBECD. The use of CDs significantly increases Btz photostability, and depending on the CDs, decreases the surface tension. The results indicated that bentazon forms inclusion complexes with CDs showing improved physicochemical properties compared to free bentazon indicating that CDs may serve as excipient in herbicide formulations.

Enhanced mineralization of diuron using a cyclodextrin-based bioremediation technology.

The phenylurea herbicide diuron [N-(3,4-dichlorophenyl)-N,N-dimethylurea] is widely used in a broad range of herbicide formulations and, consequently, it is frequently detected as a major soil and water contaminant in areas where there is extensive use. Diuron has the unfortunate combination of being strongly adsorbed by soil organic matter particles and, hence, slowly degraded in the environment due to its reduced bioavailability. N-Phenylurea herbicides seem to be biodegraded in soil, but it must be kept in mind that this biotic or abiotic degradation could lead to accumulation of very toxic derived compounds, such as 3,4-dichloroaniline. Research was conducted to find procedures that might result in an increase in the bioavailability of diuron in contaminated soils, through solubility enhancement. For this purpose a double system composed of hydroxypropyl-ß-cyclodextrin (HPBCD), which is capable of forming inclusion complexes in solution, and a two-member bacterial consortium formed by the diuron-degrading Arthrobacter sulfonivorans (Arthrobacter sp. N2) and the linuron-degrading Variovorax soli (Variovorax sp. SRS16) was used. This consortium can achieve a complete biodegradation of diuron to CO2 with regard to that observed in the absence of the CD solution, where only a 45% biodegradation was observed. The cyclodextrin-based bioremediation technology here described shows for the first time an almost complete mineralization of diuron in a soil system, in contrast to previous incomplete mineralization based on single or consortium bacterial degradation.

Photostabilization of the herbicide norflurazon microencapsulated with ethylcellulose in the soil-water system.

Ethylcellulose-microencapsulated formulations (ECFs) of norflurazon have been shown to reduce leaching, maintaining a threshold concentration in the topsoil than the commercial formulation (CF). Since photodegradation contributes to field dissipation of norflurazon, the objective of the present work was to study if such formulations can also protect from its photodescomposition. For this purpose, aqueous solutions of CF and ECFs, containing the most important soil components (goethite, humic and fulvic acids and montmorillonite) were tested. To get a more realistic approach, studies in soil were also performed. The results were well explained by a simple first order model. DT(50) value was 3h for CF under irradiation, which was considerably lower than those corresponding to the systems where ECF was used (35 h for ECF; 260 h for ECF-goethite; 53 h for ECF-humic acids; 33 h for ECF-montmorillonite; and 28 h for ECF-fulvic acids). ECF protected against photodegradation in both aqueous solution and soil due to the gradual release of the herbicide, which reduced the herbicide available to be photodegraded. These lab-scale findings proved that ECF could reduce the herbicide dosage, minimizing its photolysis, which would be especially advantageous during the first hours after foliar and soil application.

Reduced metribuzin pollution with phosphatidylcholine-clay formulations.

BACKGROUND: Metribuzin is a widely used herbicide that has been identified as a groundwater contaminant. In this study, slow-release formulations of metribuzin were designed by encapsulating the active ingredient in phosphatidylcholine (PC) vesicles and adsorbing the vesicles onto montmorillonite. RESULTS: The maximum active ingredient content in the slow-release formulations was 246 g kg(-1) . Infrared spectroscopy results revealed that the hydrophobic interactions between metribuzin and the alkyl chains on PC were necessary for encapsulation. In addition, water bridges connecting the herbicide and the PC headgroup enhanced the solubility of metribuzin in PC. Adsorption experiments in soils were performed to evaluate the relationship between sorption and leaching. Funnel experiments in a sandy soil revealed that the herbicide was not irreversibly retained in the formulation matrix. In soil column experiments, PC-clay formulations enhanced herbicide accumulation and biological activity in the top soil layer relative to a commercial formulation. PC-clay formulations also reduced the dissipation of metribuzin by a factor of 1.6-2.5. CONCLUSIONS: A reduction in the recommended dose of metribuzin can be achieved by employing PC-clay formulations, which reduces the environmental risk associated with herbicide applications. Moreover, PC and montmorillonite are non-toxic and do not negatively affect the environment.

Effects of soil characteristics on metribuzin dissipation using clay-gel-based formulations.

Metribuzin (MTB) is a herbicide widely used for weed control in growing soybeans and other crops and has been identified in many parts of the world as a groundwater contaminant. To prepare controlled-release formulations (CRFs) of MTB, it was entrapped within a sepiolite-gel-based matrix with one of two proportions of clay/herbicide and used as either a gel or powder after freeze-drying. To determine how its persistence in soil is affected by formulation and soil type, MTB was applied as a CRF or commercial formulation (CM) to soils with different properties. MTB dissipation in all soils investigated was reduced when the herbicide was applied as CRFs, especially in the case of sandy soil and the freeze-dried formulations, with DT(50) values of 57.5 and 104.1 days, respectively, versus 24.8 days for CM. A positive relationship between degradation rates, bioactivity, and soil pH was found. MTB adsorption-desorption studies on these soils were also performed, and no relationship between adsorption-desorption and the degradation rate of MTB was found, possibly because of the low adsorption capacity of the studied soils. MTB when applied as a CRF remains active longer than CM, avoiding the need to use more frequently herbicide applications.

Formulation affecting alachlor efficacy and persistence in sandy soils.

BACKGROUND: The development of controlled-release formulations of alachlor to extend the period of weed control was studied. This extended duration reduces the need for high herbicide application rates that could lead to environmental contamination. For this purpose, the influence of formulation, as well as the influence of soil characteristics, on alachlor efficacy and persistence in soil of a commercial formulation (CF) and different ethylcellulose microencapsulated formulations (MEFs) was evaluated. RESULTS: Higher alachlor rates yielded an enhanced initial herbicidal activity. The prolonged release of alachlor provided by the MEFs resulted in a higher herbicidal efficacy and a longer period of weed control compared with the effects of CF in the two soils tested (at 40 days after treatment, oat growth inhibition for CF and MEFs was 1.96% and 93.5% respectively). Soil characteristics strongly influenced alachlor efficacy and weed control by MEFs. The highest alachlor efficacy and persistence were observed in the soil with lowest microbial activity and clay and organic matter content. CONCLUSIONS: The use of MEFs can be advantageous because they permit the maintenance of the desired concentration of the herbicide in the soil for longer periods of weed control.