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.

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.

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.

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.

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.

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.

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.

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.

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.

Novel system for reducing leaching of the herbicide metribuzin using clay-gel-based formulations.

Metribuzin is an herbicide widely used for weed control that has been identified as a groundwater pollutant. It contaminates the environment even when it is used according to the manufacturer's instructions. To reduce herbicide leaching and increase weed control, new controlled release formulations were developed by entrapping metribuzin within a sepiolite-gel-based matrix using two clay/herbicide proportions (0.5/0.2 and 1/0.2) (loaded at 28.6 and 16.7% a.i.) as a gel (G28, G16) or as a powder after freeze-drying (LF28, LF16). The release of metribuzin from the control released formulations into water was retarded, when compared with commercial formulation (CF) except in the case of G28. The mobility of metribuzin from control released formulations into soil columns of sandy soil was greatly diminished in comparison with CF. Most of the metribuzin applied as control released formulations (G16, LF28 and LF16) was found at a depth of 0-8 cm depth. In contrast, residues from CF and G28 along the column were almost negligible. Bioassays from these control released formulations showed high efficacy at 0-12 cm depth. The use of these novel formulations could minimize the risk of groundwater contamination while maintaining weed control for a longer period.

Environmentally friendly formulations of alachlor and atrazine: preparation, characterization, and reduced leaching.

Atrazine and alachlor formulations were designed by encapsulating the herbicide molecules into phosphatidylcholine (PC) vesicles, which subsequently were adsorbed on montmorillonite. PC and montmorillonite are classified as substances of minimal toxicological risk by the U.S. EPA. PC enhanced alachlor and atrazine solubilities by 15- and 18-fold, respectively. A 6 mM PC:5 g/L clay ratio was found as optimal for PC adsorption on the clay. Active ingredient contents of the PC-clay formulations ranged up to 8.6% for atrazine and 39.5% for alachlor. Infrared spectroscopy showed hydrophobic interactions of herbicide molecules with the alkyl chains of PC, in addition to hydrophilic interactions with the PC headgroup. Release experiments in a sandy soil showed a slower rate from the PC-clay formulations than the commercial ones. Soil column experiments under moderate irrigation and bioactivity experiments indicate that a reduction in the recommended dose of alachlor and atrazine can be accomplished by using PC-clay formulations.

Adsorption and degradation of four acidic herbicides in soils from southern Spain.

BACKGROUND: Pesticide degradation and adsorption in soils are key processes determining whether pesticide use will have any impact on environmental quality. Pesticide degradation in soil generally results in a reduction in toxicity, but some pesticides have breakdown products that are more toxic than the parent compound. Adsorption to soil particles ensures that herbicide is retained in the place where its biological activity is expressed and also determines potential for transportation away from the site of action. Degradation and adsorption are complex processes, and shortcomings in understanding them still restrict the ability to predict the fate and behaviour of ionisable pesticides. This paper reports the sorption and degradation behaviour of four acidic pesticides in five soils from southern Spain. Results are used to investigate the influence of soil and pesticide properties on adsorption and degradation as well as the potential link between the two processes. RESULTS: Adsorption and degradation of four acidic pesticides were measured in four soils from Spain characterised by small organic matter (OM) contents (0.3-1.0%) and varying clay contents (3-66%). In general, sorption increased in the order dicamba < metsulfuron-methyl < 2,4-D < flupyrsulfuron-methyl-sodium. Both OM and clay content were found to be important in determining adsorption, but relative differences in clay content between soils were much larger than those in OM content, and therefore clay content was the main property determining the extent of herbicide adsorption for these soils. pH was negatively correlated with adsorption for all compounds apart from metsulfuron-methyl. A clear positive correlation was observed for degradation rate with clay and OM content (P < 0.01), and a negative correlation was observed with pH (P < 0.01). The exception was metsulfuron-methyl, for which degradation was found to be significantly correlated only with soil bioactivity (P < 0.05). CONCLUSIONS: Both OM and clay content were found to be important in determining adsorption, but relative differences in clay content between soils were much larger than those in OM content, and therefore clay content was the main property determining the extent of herbicide adsorption for soils of this type. pH was negatively correlated with adsorption for all compounds apart from metsulfuron-methyl. The contrasting behaviour shown for these four acidic pesticides indicates that chemical degradation in soil is more difficult to predict than adsorption. Most of the variables measured were interrelated, and different behaviours were observed even for compounds from the same chemical class and with similar structures.

A clay-vesicle system for water purification from organic pollutants.

Vesicle-clay complexes in which positively charged vesicles composed of didodecyldimethylammonium bromide (DDAB) were adsorbed on montmorillonite removed efficiently anionic (sulfentrazone, imazaquin) and neutral (alachlor, atrazine) pollutants from water. These complexes (0.5% w:w) removed 92-100% of sulfentrazone, imazaquin and alachlor and 60% of atrazine from a solution containing 10mg/L of it. A synergistic effect on the adsorption of atrazine was observed when all pollutants were present simultaneously (30 mg/L each), its percentage of removal being 85.5. Column filters (18 cm) filled with a mixture of quartz sand and vesicle-clay (100:1, w:w) were tested. For the passage of 1L (25 pore volumes) of a solution including all the pollutants at 10mg/L each, removal was complete for sulfentrazone and imazaquin, 94% for alachlor and 53.1% for atrazine, whereas removal was significantly less efficient when using activated carbon. A similar advantage of the vesicle-clay filter was observed for the capacities of removal.

Priority pesticides and their degradation products in river sediments from Portugal.

A multiresidue gas chromatography-mass spectrometry method was developed to determine 28 priority pesticides of different chemical families (organochlorine, organophosphorus, triazines, anilides) together with some of their transformation products in river sediment. Ultrasonic, Soxhlet and pressurized liquid extraction (PLE) methods were compared in spiking experiments using acetone:hexane (1:1) followed by alumina solid phase extraction cartridges or in-cell alumina clean-up for PLE. All extraction techniques produced acceptable recoveries for the pesticides under study, although Soxhlet extraction produced the lowest recoveries for 2,4-DDE, trifluralin, lindane, and hexachlorobenzene (<50%) whereas ultrasonic extraction resulted in low recoveries for hexachlorobenzene and lindane (<50%). However, PLE using in-cell alumina clean-up produced an overestimation of more apolar compounds, given the amount of coextracted compounds. Limits of detection at the low microg L(-1)-ng L(-1) levels were obtained with Soxhlet and ultrasonic extraction, while PLE produced higher variability due to the lack of exhaustive clean-up. Given the simplicity of ultrasonic extraction, this method was further employed to determine target compounds in river sediments collected in Portugal. Lindane was detected in practically all samples, followed by trace levels of the pesticides simazine, diazinon, fenitrothion, and parathion-methyl.

Effect of various cyclodextrins on photodegradation of a hydrophobic herbicide in aqueous suspensions of different soil colloidal components.

This paper investigated the photochemical behaviour of the herbicide norflurazon (NFL) in the presence of different soil colloidal components and several cyclodextrins (CDs). The interaction of NFL with CDs yielded the formation of inclusion complexes at 1:1 stoichiometric ratio in solution, with an increase of the herbicide solubility. The irradiation of NFL aqueous solutions in the presence of CDs showed that the higher the formation constant of NFL-CD complexes (Kc) and their solubility, the higher their photocatalytic effects, following the CDs in the order: RAMEB>HPBCD>beta-CD>alpha-CD>gamma-CD. The presence of the different soil colloidal components in aqueous suspension provoked the reduction of the NFL photodegradation rate, due to a screening effect, especially when goethite and humic acids were present. No disappearance of NFL was detected in parallel studies carried out in the dark, except in the case of humic acids, where a 5% adsorption of the initial amount of NFL was adsorbed in the dark control. The presence of the different CDs in such systems showed an inductive photodegradation effect on the herbicide. This could be largely explained by the inclusion effects of CDs in catalyzing interactions between NFL and certain reactive radicals generated by the different colloidal components. Although this work was carried out at laboratory scale and therefore, has limited applications, it reveals that cyclodextrins increase solubilization of hydrophobic herbicides and could lead to their increased photodegradation. This could be a promising method for pesticide-contaminated water remediation. However, it is important to consider the effect of the soil colloidal components in the different aquatic systems and their concentrations, since they can alter the photodegradative effects of the cyclodextrins.

Time-dependent sorption of norflurazon in four different soils: use of beta-cyclodextrin solutions for remediation of pesticide-contaminated soils.

High pesticide concentrations in soil from spills or discharges can result in point-source contamination of ground and surface waters. Cost-effective technologies are needed for on-site treatment that meet clean-up goals and restore soil function. Remediation is particularly challenging when a mixture of pesticides is present. beta-Cyclodextrins (BCD) solutions are employed to enhance the aqueous solubility of a hydrophobic organic compound. The interaction of norflurazon (NFL) with BCD yielded the formation of inclusion complexes at a 1:1 stoichiometric ratio in solution. The change of the sorption parameter K(d) as affected by the time, and desorption studies of NFL previously adsorbed on four different soils with different characteristics have been performed in the presence of 0.01 M BCD or 0.01 M Ca(NO(3))(2) acting as extractant solutions. NFL sorption increased with the residence time in soil, making it more resistant to be desorbed. Likewise, leaching experiments were performed in packed soil columns eluting initially with distilled water, with the aim to simulate the herbicide drainflow losses because of rainfall, approaching to a more realistic environment, and later with 0.01 M BCD solutions to extract the residual NFL bound. The results showed that removal efficiencies of the different flushing systems were significantly influenced by their affinity and selectivity for the contaminants in the soil matrix as well as BCD adsorption on soils, since this could act like a bridge between pesticide molecule and soil particles increasing the stay of NFL in soil. These results are further information to be in condition to predict the potential effect of the BCD solutions on soil chemical decontamination in the field situation assessing the likelihood for bioremediation of a pesticide contaminated-soil, since the increasing in hydrosolubility of the contaminants means the first step before microorganism uptaken.