Enantioselective biodegradation of mecoprop in aerobic and anaerobic microcosms

Natural attenuation of mecoprop has been studied by determining changes in enantiomeric fraction in different redox environments down gradient from a landfill in the Lincolnshire limestone. Such changes could be due to differential metabolism of the enantiomers, or enantiomeric inversion. In order to confirm the processes occurring in the field, microcosm experiments were undertaken using limestone acclimatised in different redox zones. No biodegradation was observed in the methanogenic, sulphate-reducing or iron-reducing microcosms. In the nitrate-reducing microcosm (S)-mecoprop did not degrade but (R)-mecoprop degraded with zero order kinetics at 0.65 mg l(-1)day(-1) to produce a stoichiometric equivalent amount of 4-chloro-2-methylphenol. This metabolite only degraded when the (R)-mecoprop disappeared. In aerobic conditions (S)- and (R)-mecoprop degraded with zero order kinetics at rates of 1.90 and 1.32 mg l(-1)day(-1) respectively. The addition of nitrate to dormant iron-reducing microcosms devoid of nitrate stimulated anaerobic degradation of (R)-mecoprop after a lag period of about 20 days and was associated with the production of 4-chloro-2-methylphenol. Nitrate addition to sulphate-reducing/methanogenic microcosms did not stimulate mecoprop degradation. However, the added nitrate was completely utilised in oxidising sulphide to sulphate. There was no evidence for enantiomeric inversion. The study reveals new evidence for fast enantioselective degradation of (R)-mecoprop under nitrate-reducing conditions.     

Microcosm studies of microbial degradation in a coal tar distillate plume

Investigation of a groundwater plume containing up to 24 g l(-1) phenolic compounds suggested that over a period of nearly 50 years, little degradation had occurred despite the presence of a microbial community and electron acceptors within the core of the plume. In order to study the effect of contaminant concentration on degradation behaviour, laboratory microcosm experiments were performed under aerobic and anaerobic conditions at four different concentrations obtained by diluting contaminated with uncontaminated groundwater. The microcosms contained groundwater with total phenols at ca. 200, 250, 660 and 5000 mg l(-1), and aquifer sediment that had been acclimatised within the plume for several months. The microcosms were operated for a period of 390-400 days along with sterile controls to ascertain whether degradation was microbially mediated or abiotic. Under aerobic conditions, degradation only occurred at concentrations up to 660 mg l(-1) total phenols. At phenol concentrations below 250 mg l(-1) a benzoquinone intermediate, thought to originate from the degradation of 2,5-dimethylphenol, was isolated and identified. This suggested an unusual degradative pathway for this compound; its aerobic degradation more commonly proceeding via catecholic intermediates. Under anaerobic conditions, degradation only occurred in the most dilute microcosm (total phenols 195 mg l(-1)) with a loss of p-cresol accompanied by a nonstoichiometric decrease in nitrate and sulphate. By inference, iron(III) from the sediment may also have been used as a terminal electron acceptor, in which case the amount of biologically available iron released was calculated as 1.07 mg Fe(III)/g of sediment. The study shows that natural attenuation is likely to be stimulated by dilution of the plume.     

Comparison of concentrations and stereoisomer ratios of mecoprop, dichlorprop and metolachlor in Ontario streams, 2006-2007 vs. 2003-2004

Mecoprop, dichlorprop and metolachlor concentrations and enantiomer signatures were determined in Ontario streams in 2006-2007 and compared to results from 2003 to 2004. Median concentrations of dichlorprop and metolachlor were not significantly different between the two campaigns, but mecoprop was higher in 2006-2007. Concentrations of mecoprop and dichlorprop in Lake Ontario surface water were 1-2 orders of magnitude lower than stream averages. Enantiomer fractions (EFs) > 0.5 of mecoprop in high-concentration stream water samples during 2006-2007 were related to replacement of racemic mecoprop by single (+) enantiomer mecoprop-P after 2004. EFs <0.5 in low-concentration samples suggested enantioselective degradation and/or interconversion. Metolachlor profiles were expressed as SF, the fraction of herbicidally active/(active + inactive) stereoisomers. Samples with higher concentrations of metolachlor had SFs similar to S-metolachlor which is enriched in the active stereoisomers. Low concentrations were associated with lower and more variable SFs, suggesting mixed input of racemic and S-metolachlor or stereoselective degradation.     

Degradation of herbicides in two sandy aquifers under different redox conditions.

We examined the potential for complete degradation (mineralisation) of the four [ring-U-14C]herbicides mecoprop, isoproturon, atrazine, and metsulphuron-methyl in two sandy aquifers representing aerobic, denitrifying, sulphate-reducing, and methanogenic conditions. Slurries with sediment and groundwater were set-up aerobically or anaerobically in the presence of the electron-acceptor prevailing at the sampling site, amended with 25 microg l(-1) herbicide, and incubated at 10 degrees C. Considerable mineralisation was only observed in sediment from the plough layer incubated aerobically. Here, 30% of 14C-mecoprop was recovered as 14CO2 after 15 days and 15% of isoproturon was recovered as 14CO2 after 267 days. Only 7% of mecoprop was recovered as 14CO2 after 313 days in sediment from the aquifer below sampled at 1.95-3.00 mbs (m below the surface). In denitrifying and methanogenic slurries, 3% of 14C added as mecoprop was recovered as 14CO2. Isoproturon was not mineralised except in the aerobic plough layer, and atrazine and metsulphuron-methyl were not mineralised under any of the conditions applied.     

Dissipation of racemic mecoprop and dichlorprop and their pure R-enantiomers in three calcareous soils with and without peat addition

Two racemic herbicides, mecoprop (R,S-MCPP) and dichlorprop (R,S-DCPP), as well as their enantiopure R-forms, were incubated in three calcareous soils at 15 degrees C and 80% of their field capacity to try to elucidate their behaviour in soil and compare the dissipation rates when racemic and enantiopure compounds are used. Quantitation of pesticides is made by HPLC and the R/S ratio by GC-MS. The inactive S-enantiomer from the racemic forms persists longer than the R-forms in silt and sandy loam soils, but for shorter time in the clay loam soil. The pure R-enantiomers, both for MCPP and DCPP, after incubation in soil, are partially converted into their S-forms. In all cases, the dissipation of racemic and pure enatiomeric forms is lower in the clay loam soil than in the silt and sandy loam soils. The R-forms' peristence, in the three soils, is approximately two times lower when they are incubated alone than when they are incubated as racemic compounds. When peat is added, the persistence of these herbicides in the silt and sandy loam soils increases, while in the clay loam soil it decreases. Besides, in the clay loam soil, the enantiomeric ratio (ER) changes from its S-preferential degradation to a preferential degradation of its R-form, so an increase in the persistence of the inactive S-form occurs.     

Speciation and persistence of doxycycline in the aquatic environment: Characterization in terms of steady state kinetics

The aim of the present work was to establish the kinetics for the degradation of doxycycline in the aquatic environment with a view to arriving at a kinetic model that can be used to predict the persistence of antibiotic with confidence. The degradation of doxycycline in both water and sediment phases of aquatic microcosm experiments, as well as in distilled water control experiments, was studied over a period of 90 days. An initial 21% loss due to adsorption by the sediment was observed in the microcosm experiment soon after charging. Biphasic zero-order linear rates of degradation, attributed to microbial degradation of the free and sediment or colloidal particle-adsorbed antibiotic, were observed for both water phase (2.3 × 10^?2 and 4.5 × 10^?3 μgg^?1 day^?1) and sediment phase (7.9 × 10^?3 and 1.5 × 10^?3 μgg^?1 day^?1) of the microcosm experiment. The covered distilled water control experiment exhibited a monophasic zero-order linear rate (1.9 × 10^?3 μgg^?1 day^?1) attributed to hydrolysis, while the distilled water experiment exposed to natural light exhibited biphasic liner rates attributed to a combination of hydrolysis and photolysis (2.9 × 10^?3 μgg^?1 day^?1) and to microbial degradation (9.8 × 10^?3 μgg^?1 day^?1). A kinetic model that takes into account hydrolysis, photolysis, microbial degradation as well as sorption/desorption by colloidal and sediment particles is presented to account for the observed zero-order kinetics. The implications of the observed kinetics on the persistence of doxycycline in the aquatic environment are discussed.     

Identification of a reactive degradation zone at a landfill leachate plume fringe using high resolution sampling and incubation techniques

Vertical small-scale variation in phenoxy acid herbicide degradation across a landfill leachate plume fringe was studied using laboratory degradation experiments. Sediment cores (subdivided into 5 cm segments) were collected in the aquifer and the sediment and porewater were used for microcosm experiments (50 experiments) and for determination of solid organic carbon, solid-water partitioning coefficients, specific phenoxy acid degraders and porewater chemistry. Results from a multi-level sampler installed next to the cores provided information on the plume position and oxygen concentration in the groundwater. Oxygen concentration was controlled individually in each microcosm to mimic the conditions at their corresponding depths. A highly increased degradation potential existed at the narrow plume fringe (37.7 to 38.6 masl), governed by the presence of phenoxy acids and oxygen. This resulted in the proliferation of a microbial population of specific phenoxy acid degraders, which further enhanced the degradation potential for phenoxy acids at the fringe. The results illustrate the importance of fringe degradation processes in contaminant plumes. Furthermore, they highlight the relevance of using high-resolution sampling techniques as well as controlled microcosm experiments in the assessment of the natural attenuation capacity of contaminant plumes in groundwater.     

Anaerobic degradation of five polycyclic aromatic hydrocarbons from river sediment in Taiwan

This study investigated the anaerobic degradation of five polycyclic aromatic hydrocarbons (PAHs) from Erren River sediment in southern Taiwan. The degradation rates of PAH were in the order: acenaphthene > fluorene > phenanthrene > anthracene > pyrene. The degradation rate was enhanced when the five compounds were present simultaneously in river sediment. Comparison of the PAH degradation rates under three reducing conditions showed the following order: sulfate-reducing conditions > methanogenic conditions > nitrate-reducing conditions. The addition of electron donors (acetate, lactate and pyruvate) enhanced PAH degradation under methanogenic and sulfate-reducing conditions. However, the addition of acetate, lactate or pyruvate inhibited PAH degradation under nitrate-reducing conditions. The addition of heavy metals, nonylphenol and phthalate esters (PAEs) inhibited PAH degradation. Our results show that sulfate-reducing bacteria, methanogen and eubacteria are involved in the degradation of PAH; sulfate-reducing bacteria constitute a major microbial component in PAH degradation. Of the microorganism strains isolated from the sediment samples, we found that strain ER9 expressed the greatest biodegrading ability.     

Mineralization of aged atrazine and mecoprop in soil and aquifer chalk.

The effect of ageing on the bioavailability and sorption of the herbicides atrazine and mecoprop was studied in soil and aquifer chalk sampled at an agricultural field near Aalborg, Denmark. The herbicides were incubated in sterile soil or chalk up to 3 months prior to inoculation with 5 x 10(7) cells g(-1) (dry weight) of a mecoprop degrading highly enriched culture (PM) or 1 x 10(9) cells g(-1) (dry weight) of the atrazine degrading Pseudomonas sp. strain ADP. As a measure of the bioavailable residues accumulated 14CO2 was measured for 2 months. In both soil and chalk ageing limited the rate of atrazine mineralization, and in chalk the extent of mineralization was reduced as well. The fraction of sorbed atrazine in the soil ranged between 50% and 62%, whereas a maximum of 12% was sorbed in chalk. No impact on the mineralization of aged mecoprop was seen as no sorption of this herbicide on either soil or chalk was measured.     

Anaerobic degradation of five polycyclic aromatic hydrocarbons from river sediment in Taiwan

This study investigated the anaerobic degradation of five polycyclic aromatic hydrocarbons (PAHs) from Erren River sediment in southern Taiwan. The degradation rates of PAH were in the order: acenaphthene > fluorene > phenanthrene > anthracene > pyrene. The degradation rate was enhanced when the five compounds were present simultaneously in river sediment. Comparison of the PAH degradation rates under three reducing conditions showed the following order: sulfate-reducing conditions > methanogenic conditions > nitrate-reducing conditions. The addition of electron donors (acetate, lactate and pyruvate) enhanced PAH degradation under methanogenic and sulfate-reducing conditions. However, the addition of acetate, lactate or pyruvate inhibited PAH degradation under nitrate-reducing conditions. The addition of heavy metals, nonylphenol and phthalate esters (PAEs) inhibited PAH degradation. Our results show that sulfate-reducing bacteria, methanogen and eubacteria are involved in the degradation of PAH; sulfate-reducing bacteria constitute a major microbial component in PAH degradation. Of the microorganism strains isolated from the sediment samples, we found that strain ER9 expressed the greatest biodegrading ability.     

Degradation of calcium lignosulfonate using gamma-ray irradiation

Gamma-ray irradiation was proven to be a promising means for the removal of calcium lignosulfonate (CaLS). At a dose rate of 55Gy min(-1), over 90% of CaLS was mineralized to CO(2), H(2)O and sulfates within 3-d irradiation. The degradation of CaLS with the initial CaLS concentrations ranging from 40 to 200mg l(-1) followed zero-order kinetics at the dose rates of 16-150Gy min(-1). The zero-order degradation rate constant was functionally related with irradiation dose rate. Experiments performed with or without addition of radical scavengers demonstrated that the role of *OH was predominant in CaLS degradation and the reductive species made minor contributions to CaLS degradation. Addition of appropriate amounts of H(2)O(2) significantly enhanced the mineralization of CaLS, e.g., addition of 10mM H(2)O(2) at a dose rate of 55Gy min(-1) elevated the mineralization rate constant by five times. The addition of Fenton's reagent to irradiated CaLS solutions facilitated the degradation of CaLS, but no obviously synergistic effect was observed.     

Using polymer mats to biodegrade atrazine in groundwater: laboratory column experiments

Large-scale column experiments were undertaken to evaluate the potential of in situ polymer mats to deliver oxygen into groundwater to induce biodegradation of the pesticides atrazine, terbutryn and fenamiphos contaminating groundwater in Perth, Western Australia. The polymer mats, composed of woven silicone (dimethylsiloxane) tubes and purged with air, were installed in 2-m-long flow-through soil columns. The polymer mats proved efficient in delivering dissolved oxygen to anaerobic groundwater. Dissolved oxygen concentrations increased from <0.2 mg l(-1) to approximately 4 mg l(-1). Degradation rates of atrazine in oxygenated groundwater were relatively high with a zero-order rate of 240-380 microg l(-1) or a first-order half-life of 0.35 days. Amendment with an additional carbon source showed no significant improvement in biodegradation rates, suggesting that organic carbon was not limiting biodegradation. Atrazine degradation rates estimated in the column experiments were similar to rates determined in laboratory culture experiments, using pure cultures of atrazine-mineralising bacteria. No significant degradation of terbutryn or fenamiphos was observed under the experimental conditions within the time frames of the study. Results from these experiments indicate that remediation of atrazine in a contaminated aquifer may be achievable by delivery of oxygen using an in situ polymer mat system.     

Characteristics of leachate from pyrolysis residue of sewage sludge

The pyrolysis residue (SP) of sewage sludge (SS) produced at 500 degrees C was subjected to batch and column leaching tests to investigate the release of its organic and inorganic constituents and metals. For comparison, incineration ash (SI) obtained from a SS incinerator was also tested. Pyrolysis and incineration reduced organic matter of SS from 0.78 kg kg(-1)-dry SS to 0.16 and 0.01 kg kg(-1)-dry SS, respectively. Heavy metals remained in SP without being volatilized, although Cd and Pb were transferred into the off-gas during incineration. In the batch leaching test with the leaching liquid-to-solid mass ratio (L/S)=10, the pH of the SS, SP, and SI filtrates was 6.3, 7.9, and 11.0, respectively. The total organic carbon concentrations were in the order SS (877 l mg l(-1))>SP (99 mg l(-1))>SI (26 mg l(-1)). The SP and SI filtrates met the landfill standard for the Cd and Pb concentrations (<0.3 mg l(-1)). In the column tests, although the SP contained more organic matter than that of SI, its carbon discharge into the leachate under aerobic conditions was similar to that of SI under anaerobic conditions. The leaching of heavy metals, such as Cd, Cr, Pb, and Zn, was also suppressed in SP during the active decomposition of organic matter. We demonstrated that pyrolysis reduces the potential release of pollutants from sewage sludge in landfill, making it a promising method of treating sewage sludge before landfilling.     

Bioaugmentation of polyethylene succinate-contaminated soil with Pseudomonas sp. AKS2 results in increased microbial activity and better polymer degradation

Pseudomonas sp. AKS2 isolated from soil degrades polyethylene succinate (PES) efficiently in the laboratory. However, this organism may not be able to degrade PES with similar efficiency in a natural habitat. Since in situ remediation is preferred for the effective removal of recalcitrant materials like plastic, in the current study, bioaugmentation potential of this organism was investigated. To investigate the potential of the AKS2 strain to bioaugment the PES-contaminated soil, a microcosm-based study was carried out wherein naturally attenuated, biostimulated, and AKS2-inoculated (bioaugmented) soil samples were examined for their ability to degrade PES. The results showed better degradation of PES by bioaugmented soil than other microcosms. Consistent with it, a higher number of PES-degrading organisms were found in the bioaugmented microcosm. The bioaugmented microcosm also exhibited a higher level of average well color development in BiOLOG ECO plate assay than the other two. The corresponding Shannon–Weaver index and Gini coefficient revealed a higher soil microbial diversity of bioaugmented microcosm than the others. This was further supported by community-level physiological profile of three different microcosms wherein we have observed better utilization of different carbon sources by bioaugmented microcosms. Collectively, these results demonstrate that bioaugmentation of PES-contaminated soil with AKS2 not only enhances polymer degradation but also increases microbial diversity. Bioaugmentation of soil with AKS2 enhances PES degradation without causing damage to soil ecology. Thus, Pseudomonas sp. AKS2 has the potential to be implemented as a useful tool for in situ bioremediation of PES.     

Degradation of nonylphenol by anaerobic microorganisms from river sediment

We investigated the degradation of nonylphenol monoethoxylate (NP1EO) and nonylphenol (NP) by anaerobic microbes in sediment samples collected at four sites along the Erren River in southern Taiwan. Anaerobic degradation rate constants (k1) and half-lives (t1/2) for NP (2 microg/g) ranged from 0.010 to 0.015 1/day and 46.2 to 69.3 days respectively. For NP1EO (2 microg/g), the ranges were 0.009-0.014 1/day and 49.5-77.0 days respectively. Degradation rates for NP and NP1EO were enhanced by increasing temperature and inhibited by the addition of acetate, pyruvate, lactate, manganese dioxide, ferric chloride, sodium chloride, heavy metals, and phthalic acid esters. Degradation was also measured under three anaerobic conditions. Results show the high-to-low order of degradation rates to be sulfate-reducing conditions > methanogenic conditions > nitrate-reducing conditions. The results show that sulfate-reducing bacteria, methanogen, and eubacteria are involved in the degradation of NP and NP1EO, with sulfate-reducing bacteria being a major component of the river sediment.     

Effect of mecoprop drift on some plant species of conservation interest when grown in standardized mixtures in microcosms

There has been an increasing awareness of potential impacts of herbicide drift on to vegetation in nature reserves and field margin habitats adjacent to treated areas. Previous work using single species bioassays has suggested that the effects of a single drift event are confined close to the sprayer (< 10 m). In the present study eight native dicotyledonous species, with and without a perennial grass (Lolium perenne), were grown in standardized microcosms in order to study (1) the effects of herbicide drift where plants were exposed to competition, and (2) the effects of a second spray application. The microcosms were arranged downwind (0-8 m) of a standard agricultural sprayer applying mecoprop at recommended rates. The effects of the herbicide drift on foliar symptoms of plant damage and end-of-season yield were assessed in each of two years. The main conclusions were that (1) growth of Stachys sylvatica and Lolium perenne (where sown) was enhanced near the sprayer and, (2) six other species (Digitalis purpurea, Galium mollugo, Hypericum hirsutum, Lychnis flos-cuculi, Primula veris and Ranunculus acris) showed some evidence of reduction in either performance (assessed non-destructively after a single exposure) or yield after two exposures. Three species (Lychnis flos-cuculi, Primula veris and Ranunculus acris) showed a reduction in flowering performance. Thus, mecoprop drift affected the aesthetic appearance, possibly the fecundity of some species and the balance between species in these microcosm experiments. The implications of these results for the persistence of attractive plant communities in sensitive areas are discussed.     

Remediation of an old landsfill site

The Baltic Sea Region has a large number of landfills that need remediation after care routines and control, in order to avoid future emissions to the environment and to fulfil the demands in the EU Waste Council Directive on the landfill of waste. Based on the Måsalycke test screening, an excavation of whole or of parts of the landfill can be seen as a potential measure for some of the old landfills. The material excavated in the test was screened into the fractions: < 18 mm, 182-50 mm and > 50 mm. The coarsest fraction (> 50 mm) contained 50% wood and paper. The medium-sized fraction (18–50 mm) contained stones and indefinable soil-like material, while the fine fraction contained peat-like material with some other small waste components. The spectral analysis of heavy metals indicated only high concentrations of zinc and there was no significant difference between the fine and the medium-sized fractions. The medium sized and the unsorted fraction was moisturized and refilled into the pit. The methane content in the landfill gas from the pit was 50–57% in the sorted material with a flow of 8–17 l/min and 38–57% in the unsorted fraction with a flow of 2–13 l/min during the first 1.5 year. The Måsalycke landfill is in the methanogenic phase and leachate concentrations are normal. Landfill mining can be used to prolong the landfill lifetime and/or used as a tool for remedial actions in contaminated sites.     

Anaerobic degradation of nonylphenol in soil

This study investigated the effects of various factors on the anaerobic degradation of nonylphenol (NP) in soil. The results show that the optimal pH for NP degradation was 7.0 and that the degradation rate was enhanced when the temperature was increased. The addition of compost enhanced NP degradation. The individual addition of the electron donors lactate, acetate, and pyruvate inhibited NP degradation. The high-to-low order of NP degradation rates under three anaerobic conditions was sulfate-reducing conditions > methanogenic conditions > nitrate-reducing conditions. The results show that sulfate-reducing bacteria, methanogen, and eubacteria are involved in the anaerobic degradation of NP, with sulfate-reducing bacteria being a major component of the soil. Of the anaerobic strains isolated from the soil samples, strain AT3 expressed the best ability to biodegrade NP.     

Electrochemical combustion of herbicide mecoprop in aqueous medium using a flow reactor with a boron-doped diamond anode

The anodic oxidation of 1.8l of solutions with mecoprop (2-(4-chloro-2-methylphenoxy)-propionic acid or MCPP) up to 0.64 g l(-1) in Na2SO4 as background electrolyte within the pH range 2.0-12.0 has been studied using a flow plant containing a one-compartment filter-press electrolytic reactor with a boron-doped diamond (BDD) anode and a stainless steel cathode, both of 20-cm2 area. Electrolyses carried out in batch under steady conditions and operating at constant current density between 50 and 150 mA cm(-2) always yield complete mineralization due to the great concentration of hydroxyl radical generated at the BDD anode. The degradation rate is practically independent of pH and Na2SO4 concentration, but it becomes faster with increasing MCPP concentration, current density, temperature and liquid flow rate. The effect of these parameters on current efficiency and energy cost has also been investigated. Generated weak oxidants such as H2O2 and peroxodisulfate ion have little influence on the mineralization process. The kinetics for the herbicide decay follows a pseudo first-order reaction with a higher rate constant when current density increases. Aromatic products such as 4-chloro-o-cresol, 2-methylhydroquinone and 2-methyl-p-benzoquinone, and generated carboxylic acids such as maleic, fumaric, lactic, pyruvic, tartronic, acetic and oxalic, have been identified as intermediates by chromatographic techniques. The initial chlorine is completely released in the form of chloride ion, which is slowly oxidized to Cl2 at the BDD anode. A reaction pathway for MCPP mineralization involving all products detected is proposed.     

Anaerobic degradation of nonylphenol in soil

This study investigated the effects of various factors on the anaerobic degradation of nonylphenol (NP) in soil. The results show that the optimal pH for NP degradation was 7.0 and that the degradation rate was enhanced when the temperature was increased. The addition of compost enhanced NP degradation. The individual addition of the electron donors lactate, acetate, and pyruvate inhibited NP degradation. The high-to-low order of NP degradation rates under three anaerobic conditions was sulfate-reducing conditions > methanogenic conditions > nitrate-reducing conditions. The results show that sulfate-reducing bacteria, methanogen, and eubacteria are involved in the anaerobic degradation of NP, with sulfate-reducing bacteria being a major component of the soil. Of the anaerobic strains isolated from the soil samples, strain AT3 expressed the best ability to biodegrade NP.