Microbial degradation op tripluralin by aspergillus carneus,fusarium oxysporum and trichoderma viride ∗

Abstract

³H‐Trifluralin was synthesized by condensation of ³H‐4‐chloro‐3,5‐dinitro‐α, α, α‐trifluorotoluene with di‐n‐propylamine.

After incubation of trifluralin with Aspergillus carneus, Fusarium oxysporum and Trichoderma viride for 10 days, a small percentage (less than 10%) of unchanged herbicide was recovered in the extractable fraction. This indicates a fairly rapid degradation of the herbicide by the fungal species. Other than trifluralin, the culture medium contained at least five labelled products: 2, 6‐dinitro‐N‐n‐propyl‐α, α, α‐tri‐fluoro‐p‐toluidine; 2, 6‐dinitro‐α, α, α‐trifluoro‐p‐toluidine; 2‐amino‐6‐nitro‐α, α,‐trifluoro‐p‐toluidine, 2, 6‐dinitro‐4‐trifluoromethyl phenol and a major polar product which constituted more than 50% of the total extractable transformation products. A pathway, which similates that of aerobic degradation of the herbicide in soil, is suggested for the microbiological degradation of trifluralin.     

Impact of redox conditions on metolachlor and metribuzin degradation in mississippi flood plain soils

Abstract

The effect of soil redox conditions on the degradation of metolachlor and metribuzin in two Mississippi soils (Forrestdale silty clay loam and Loring silt loam) were examined in the laboratory. Herbicides were added to soil in microcosms and incubated either under oxidized (aerobic) or reduced (anaerobic) conditions. Metolachlor and metribuzin degradation under aerobic condition in the Forrestdale soil proceeded at rates of 8.83 ngd^‐1 and 25 ngd^‐1, respectively. Anaerobic degradation rates for the two herbicides in the Forestdale soil were 8.44 ngd^‐1 and 32.5 ngd^‐1, respectively. Degradation rates for the Loring soil under aerobic condition were 24.8 ngd^‐1 and 12.0 ngd^‐1 for metolachlor and metribuzin, respectively. Metolachlor and metribuzin degradation rates under anaerobic conditions in the Loring soil were 20.9 ngd^‐1 and 5.35 ngd^‐1. Metribuzin degraded faster (12.0 ngd^‐1) in the Loring soil under aerobic conditions as compared to anaerobic conditions (5.35 ngd^‐1).     

Monitoring of pesticide residues in a cotton crop soil

Abstract

This paper reports on the residues of methyl parathion (O,O‐dimethyl O‐4‐nitrophenyl phosphorothioate), trifluralin (α, α, α‐trifluoro‐2, 6‐dinitro‐N, N‐dipropyl‐p‐toluidine), endosulfan [(1, 4, 5, 6, 7, 7‐hexachloro‐8, 9, 10‐trinorborn‐5‐en‐2, 3‐ylenebismethylene) sulfite] and dimethoate (O, O‐dimethyl S‐methylcarbamoylmethyl phosphorodithioate) in a cotton crop soil. Soil samples (0–15 cm) were collected at different periods from the cotton crop farm and subjected to Soxhlet extraction. The extracted material was analysed after clean‐up by a HP5890 II gas Chromatograph equipped with a ⁶³Ni electron‐capture detector (ECD‐⁶³Ni) and fitted with a 25m x 0,2mm i.d. fused silica capillary column [Ultra‐2 (5% phenylmethyl polysiloxane)]. The recoveries of the pesticide residues from the spiked control soil were determined after Soxhlet extraction and C₁₈ cartridges clean‐up by using radiotracer techniques with the corresponding ¹⁴C‐pesticides. The results show that in the cotton crop soil the pesticide residues under study were present in the range of 0.1 to 0.4 mg ? kg^‐1. Endosulfan was found to be rapidly degraded in the soil and formed a sulfate metabolite.     

Aerobic degradation of diuron by aquatic microorganisms

Abstract

Degradation of diuron [3‐(3,4‐dichlorophenyl)‐l,1‐dimethyl‐urea] by microorganisms obtained from pond water and sediment was determined under aerobic conditions. Enrichment procedures were used to isolate cultures capable of degrading the herbicide. Several mixed fungal/bacterial and mixed bacterial cultures were isolated that could degrade diuron. The mixed cultures degraded 67–99% of the added diuron forming from six to seven products which were separated via TLC. The major degradation product detected in most culture extracts was 3,4‐dichloroaniline. Other identified products formed were 3‐(3,4‐dichlorophenyl)‐1‐methylurea and 3‐(3,4‐dichlorophenyl)urea.     

Degradation of isoxaben in soils and an aqueous system.

The degradation of isoxaben [N-[3-(1-ethyl-1-methylpropyl)-5-isoxazolyl]-2,6-dimethoxybenzamide] was studied in soil and in an aqueous system. Soil studies were conducted in Erlenmeyer flasks (treated with 1 microg/g isoxaben) and mineralization studies in Biometer flasks (treated with 1 microg/g unlabeled and 14C-isoxaben) incubated at 23 C. Degradation in the aqueous system was performed in Erlenmeyer flasks under aerobic and anaerobic conditions incubated at 23 degrees C. Incubation mixtures were extracted at selected times and analyzed for isoxaben and degradation products by HPLC with product identification confirmed by GC-MS. After 8 weeks, 78% and 23% of the total isoxaben disappeared in nonsterile and sterile soils, respectively. After 12 weeks, approximately 1% of the labeled isoxaben was recovered as CO2 in the Biometer flask experiments; no volatile products were detected, and 5% and 33% of the total radioactivity was recovered from the nonsterile and sterile soils, respectively. In the aquatic system after 8 weeks, isoxaben had decreased from 1microg/g to 0.1 and 0.004 microg/g under aerobic and anaerobic conditions, respectively. Degradation products detected from the soil studies were 3-nitrophthalic acid and 4-methoxyphenol, and 3-nitrophthalic acid in the aqueous system studies. Microbial activity was considered to be a major factor in the degradation of isoxaben in this study.     

Biodegradation of Trifluralin in Harran Soil

Abstract

Degradation of trifluralin (α,α,α-trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine) was investigated in soils taken from three different locations at Harran region of Turkey under laboratory conditions. Surface (0–10 cm) soils, which were taken from a pesticide untreated field Gürgelen, Harran-1 and Ikizce regions in the Harran Plain, were incubated in biometer flasks for 350 days at 25°C. Ring-UL-¹⁴C-trifluralin was applied at the rate of 2 µg g^?1 with 78.7 kBq radioactivity per 100 g soil flask. Evolved ¹⁴CO₂ was monitored in KOH traps throughout the experiment. Periodically, soil sub-samples were removed and extracted by supercritical fluid extraction (SFE). Unextractable soil-bound ¹⁴C residues were determined by combustion. During the 350 days incubation period 6.6, 5.4, and 3.3% of the applied radiocarbon was evolved as ¹⁴CO₂ from the Harran-1, Gürgelen, and Ikizce soil, respectively. At the end of 350 days the SFE-extractable and bound ¹⁴C-trifluralin residues were 39.0 and 29.2% of the initially applied herbicide in Gürgelen soil. The corresponding values for Harran-1 and Ikizce soils were 36.2, 28.4% and 41.6, 18.5% respectively.     

Impact of redox conditions on metolachlor and metribuzin degradation in Mississippi flood plain soils

The effect of soil redox conditions on the degradation of metolachlor and metribuzin in two Mississippi soils (Forrestdale silty clay loam and Loring silt loam) were examined in the laboratory. Herbicides were added to soil in microcosms and incubated either under oxidized (aerobic) or reduced (anaerobic) conditions. Metolachlor and metribuzin degradation under aerobic condition in the Forrestdale soil proceeded at rates of 8.83 ngd(-1) and 25 ngd(-1), respectively. Anaerobic degradation rates for the two herbicides in the Forestdale soil were 8.44 ngd(-1) and 32.5 ngd(-1), respectively. Degradation rates for the Loring soil under aerobic condition were 24.8 ngd(-1) and 12.0 ngd(-1) for metolachlor and metribuzin, respectively. Metolachlor and metribuzin degradation rates under anaerobic conditions in the Loring soil were 20.9 ngd(-1) and 5.35 ngd(-1). Metribuzin degraded faster (12.0 ngd(-1)) in the Loring soil under aerobic conditions as compared to anaerobic conditions (5.35 ngd(-1)).     

Degradation of terbutryn in sediments and water under various redox conditions

Abstract

A laboratory study was conducted to examine the degradation of terbutryn [2‐(t‐butylamino)‐4‐(ethylamino)‐6‐(methylthio)‐s‐triazine] in sediment and water under different redox conditions. Terbutryn degraded slowly in static aerobic systems (loosely capped flask, 25°C) with half‐lives of 240 and 180 days in pond and river sediment, respectively. Degradation products, identified by co‐chromatography on TLC and HPLC systems, included hydroxy‐terbutryn, terbutryn‐sulfoxide and N‐deethyl terbutryn. Hydroxyterbutryn was the major degradation product in sediments and water representing 60–70% of the extractable radioactivity after 515 days incubation. Under nitrogen aeration in respirometer flasks (redox potential ‐46 to +210 mv) degradation of terbutryn was very slow with half lives greater than 650 days.     

The effect of oxygen on chemical dechlorination of dieldrin using iron sulphides

The degradation of dieldrin by ferric sulphide (FeS₂) in aqueous solution was investigated when shielded against sunlight. An oxidative dechlorination process was observed under aerobic and anaerobic conditions; oxygen volume changed the degradation rate of dieldrin and the generation rate of reaction products. The dechlorination rate under microaerophilic conditions was fastest among the anaerobic to air oxygen concentrations. For this experiment, over 99% of the dieldrin was degraded, and 90% of the released chloride was detected after 30 d under 10 μmol oxygen. The major reaction products were different depending on the dose of oxygen. In the case of aerobic conditions, low molecular weight organic acids, such as formic acid, lactic acid, and oxalic acid, were generated as major reaction products. However, under anaerobic conditions, C₁₆H₂₂O₄ (dibutyl phthalate) and C₆H₁₃ClO (3-chloro-4-methyl-2-pentanol) were detected as reaction intermediates, and small amounts of succinic acid, malonic acid, and formic acid were also generated. These reactions proceed by FeS₂ interface reactions with H₂O under anaerobic condition, or O₂ under aerobic condition.     

Dissipation of sulfamethoxazole and trimethoprim antibiotics from manure-amended soils

In this study, the dissipation of two antibiotics, sulfamethoxazole (SMX) and trimethoprim (TRM), in three soils under both aerobic and anaerobic conditions are evaluated. Under aerobic conditions, SMX dissipated rapidly through biodegradation but TRM was more persistent. Within the first 20 days in biologically active soils, >50% of the SMX was lost from the clay loam and loamy sand soils, and >80% loss was noted in the loam soil. Anaerobic dissipation of both compounds was more rapid than aerobic dissipation. The addition of manure to the soil only slightly increased the initial dissipation rate of the two compounds. Little effect was found on glucose mineralisation in soil following the addition of SMX and TRM, even as mixtures at high concentrations.     

Dissipation of sulfamethoxazole and trimethoprim antibiotics from manure-amended soils

In this study, the dissipation of two antibiotics, sulfamethoxazole (SMX) and trimethoprim (TRM), in three soils under both aerobic and anaerobic conditions are evaluated. Under aerobic conditions, SMX dissipated rapidly through biodegradation but TRM was more persistent. Within the first 20 days in biologically active soils, >50% of the SMX was lost from the clay loam and loamy sand soils, and >80% loss was noted in the loam soil. Anaerobic dissipation of both compounds was more rapid than aerobic dissipation. The addition of manure to the soil only slightly increased the initial dissipation rate of the two compounds. Little effect was found on glucose mineralisation in soil following the addition of SMX and TRM, even as mixtures at high concentrations.     

Biodegradation of lindane, methyl parathion and carbofuran by various enriched bacterial isolates

In the present study, lindane (1,2,3,4,5,6-hexachlorocyclohexane), methyl parathion (O-dimethylO-(4-nitro-phenyl) phosphorothioate) and carbofuran (2,3-dihydro-2,2-dimethyl-7-benzofuranyl methylcarbamate) degradation potential of different enriched bacterial cultures were evaluated under various environmental conditions. Enriched cultures behaved differently with different pesticides. Degradation was more in a facultative anaerobic condition as compared to that in aerobic condition. A specific pesticide enriched culture showed maximum degradation of that pesticide irrespective of pesticides and environmental conditions. Lindane and endosulfan enriched cultures behaved almost similarly. Degradation of lindane by lindane enriched cultures was 75 +/- 3% in aerobic co-metabolic process whereas 78 +/- 5% of lindane degradation occurred in anaerobic co-metabolic process. Degradation of methyl parathion by methyl parathion enriched culture was 87 +/- 1% in facultative anaerobic condition. In almost all the cases, many intermediate metabolites were observed. However, many of these metabolites disappeared after 4-6 weeks of incubation. Mixed pesticide-enriched culture degraded all the three pesticides more effectively as compared to specific pesticide- enriched cultures. It can be inferred from the results that a bacterial consortium enriched with a mixture of all the possible pesticides that are present in the site seems to be a better option for the effective bioremediation of multi-pesticide contaminated site.     

Biotic transformation of anticoccidials in soil using a lab-scale bio-reactor as a precursor-tool

Two anticoccidial agents, salinomycin and robenidine, heavily used in the worldwide veterinary meat production, were investigated for their potential biotic degradation by cultured soil bacteria. The degradation-study was performed in lab-scale bio-reactors under aerobic and anaerobic conditions incubated for 200 h with a mixed culture of soil bacteria. Samples were analyzed by LC-MS/MS and potential transformation products were tentatively identified. Salinomycin was degraded under aerobic conditions and traces could be found after 200 h, however, seems more persistent under anaerobic conditions. Four transformation products of salinomycin were discovered. Robenidine was degraded under aerobic and anaerobic conditions, however, traces of robenidine were observed after 200 h. Five biotic transformation products of robenidine were discovered.     

Anaerobic degradation of diethyl phthalate, di-n-butyl phthalate, and di-(2-ethylhexyl) phthalate from river sediment in Taiwan

We investigated anaerobic degradation rates for three phthalate esters (PAEs), diethyl phthalate (DEP), di-n-butyl phthalate (DBP), and di-(2-ethylhexyl) phthalate (DEHP), from river sediment in Taiwan. The respective anaerobic degradation rate constants for DEP, DBP, and DEHP were observed as 0.045, 0.074, and 0.027 1/day, with respective half-lives of 15.4, 9.4, and 25.7 days under optimal conditions of 30 °C and pH 7.0. Anaerobic degradation rates were enhanced by the addition of the surfactants brij 35 and triton N101 at a concentration of 1 critical micelle concentration (CMC), and by the addition of yeast extract. Degradation rates were inhibited by the addition of acetate, pyruvate, lactate, FeCl₃, MnO₂, NaCl, heavy metals, and nonylphenol. Our results indicate that methanogen, sulfate-reducing bacteria, and eubacteria are involved in the degradation of PAEs.     

Biotic and abiotic transformations of methyl tertiary butyl ether (MTBE)

Background Methyl tertiary butyl ether (MTBE) is a fuel additive which is used all over the world. In recent years it has often been found in groundwater, mainly in the USA, but also in Europe. Although MTBE seems to be a minor toxic, it affects the taste and odour of water at concentrations of < 30 μg/L. Although MTBE is often a recalcitrant compound, it is known that many ethers can be degraded by abiotic means. The aim of this study was to examine biotic and abiotic transformations of MTBE with respect to the particular conditions of a contaminated site (former refinery) in Leuna, Germany. Methods Groundwater samples from wells of a contaminated site were used for aerobic and anaerobic degradation experiments. The abiotic degradation experiment (hydrolysis) was conducted employing an ion-exchange resin and MTBE solutions in distilled water. MTBE, tertiary butyl formate (TBF) and tertiary butyl alcohol (TBA) were measured by a gas chromatograph with flame ionisation detector (FID). Aldehydes and organic acids were respectively analysed by a gas chromatograph with electron capture detector (ECD) and high-performance ion chromatography (HPIC). Results and Discussion Under aerobic conditions, MTBE was degraded in laboratory experiments. Only 4 of a total of 30 anaerobic experiments exhibited degradation, and the process was very slow. In no cases were metabolites detected, but a few degradation products (TBF, TBA and formic acid) were found on the site, possibly due to the lower temperatures in groundwater. The abiotic degradation of MTBE with an ion-exchange resin as a catalyst at pH 3.5 was much faster than hydrolysis in diluted hydrochloric acid (pH 1.0). Conclusion Although the aerobic degradation of MTBE in the environment seems to be possible, the specific conditions responsible are widely unknown. Successful aerobic degradation only seems to take place if there is a lack of other utilisable compounds. However, MTBE is often accompanied by other fuel compounds on contaminated sites and anaerobic conditions prevail. MTBE is often recalcitrant under anaerobic conditions, at least in the presence of other carbon sources. The abiotic hydrolysis of MTBE seems to be of secondary importance (on site), but it might be possible to enhance it with catalysts. Recommendation and Outlook MTBE only seems to be recalcitrant under particular conditions. In some cases, the degradation of MTBE on contaminated sites could be supported by oxygen. Enhanced hydrolysis could also be an alternative. - * The basis of this peer-reviewed paper is a presentation at the 9th FECS Conference on 'Chemistry and Environment', 29 August to 1 September 2004, Bordeaux, France.     

Degradation products of profenofos as identified by high-field FTICR mass spectrometry: Isotopic fine structure approach

This study was performed to identify the degradation products of profenofos “a phenyl organothiophosphate insecticide” in raw water (RW) collected from the entry point of Metropolitan Water Works Authority “Bangkaen, Thailand” and ultrapure water (UPW) with and without TiO₂ under simulated sunlight irradiation. Degradation of profenofos was followed with ultrahigh performance liquid chromatography (UHPLC) and follows pseudo first-order kinetic. Accordingly, high-field FTICR mass spectrometry coupled to an electrospray ionization source was used to reveal the degradation routes of profenofos and the isotopic fine structures (IFS) elucidations to approve the chemical structures of its degradation products. More degradation products were detected in UPW as compared to RW. Consequently, two main degradation pathways namely (i) interactive replacements of bromine and hydrogen by hydroxyl functional groups and (ii) rupture of PO, PS, CBr and CCl bonds were observed. None interactive replacement of chlorine by hydroxyl functional group was detected. Accordingly, mechanistical pathways of the main degradation products were established.     

Effect of some herbicides on activities of microorganisms and enzymes in soil

Abstract

Laboratory tests were conducted with eight herbicides, atrazine, butylate, ethalfluralin, imazethapyr, linuron, metolachlor, metribuzin and trifluralin, applied to a loamy sand at rate of 10 μg/g to determine if these materials caused any serious effects on microbial and enzymatic activities related to soil fertility. Some herbicides showed an effect on bacteria and fungi for the first week of incubation, but, subsequently, the populations returned to levels similar to those obtained in the controls. After several herbicide treatments there appeared to cause a slight depression of nitrification. Sulfur oxidation was better than that obtained with untreated soil in all treatments. Oxygen consumption was increased significantly after 96 hr incubation with atrazine. The soil dehydrogenase and amylase activities were inhibited by ethalfluralin treatment respectively for 1 wk and 1 day, and p‐nitrophenol liberation was inhibited for 2 hrs by all herbicide treatments. Results indicated that the herbicidal treatments at the level tested were not drastic enough to be considered deleterious to soil microbial and enzymatic activities which are important to soil fertility.     

Biodegradation of triclosan and formation of methyl-triclosan in activated sludge under aerobic conditions

Triclosan is an antimicrobial agent which is widely used in household and personal care products. Widespread use of this compound has led to the elevated concentrations of triclosan in wastewater, wastewater treatment plants (WWTPs) and receiving waters. Removal of triclosan and formation of triclosan-methyl was investigated in activated sludge from a standard activated sludge WWTP equipped with enhanced biological phosphorus removal. The removal was found to occur mainly under aerobic conditions while under anoxic (nitrate reducing) and anaerobic conditions rather low removal rates were determined. In a laboratory-scale activated sludge reactor 75% of the triclosan was removed under aerobic conditions within 150 h, while no removal was observed under anaerobic or anoxic conditions. One percent of the triclosan was converted to triclosan-methyl under aerobic conditions, less under anoxic (nitrate reducing) and none under anaerobic conditions.     

Field and laboratory studies of the fate and enantiomeric enrichment of venlafaxine and O-desmethylvenlafaxine under aerobic and anaerobic conditions

The stereoselectivity of R,S-venlafaxine and its metabolites R,S-O-desmethylvenlafaxine, N-desmethylvenlafaxine, O,N-didesmethylvenlafaxine, N,N-didesmethylvenlafaxine and tridesmethylvenlafaxine was studied in three processes: (i) anaerobic and aerobic laboratory scale tests; (ii) six wastewater treatment plants (WWTPs) operating under different conditions; and (iii) a variety of wastewater treatments including conventional activated sludge, natural attenuation along a receiving river stream and storage in operational and seasonal reservoirs. In the laboratory and field studies, the degradation of the venlafaxine yielded O-desmethylvenalfaxine as the dominant metabolite under aerobic and anaerobic conditions. Venlafaxine was almost exclusively converted to O-desmethylvenlafaxine under anaerobic conditions, but only a fraction of the drug was transformed to O-desmethylvenlafaxine under aerobic conditions. Degradation of venlafaxine involved only small stereoisomeric selectivity. In contrast, the degradation of O-desmethylvenlafaxine yielded remarkable S to R enrichment under aerobic conditions but none under anaerobic conditions. Determination of venlafaxine and its metabolites in the WWTPs agreed well with the stereoselectivity observed in the laboratory studies. Our results suggest that the levels of the drug and its metabolites and the stereoisomeric enrichment of the metabolite and its parent drug can be used for source tracking and for discrimination between domestic and nondomestic wastewater pollution. This was indeed demonstrated in the investigations carried out at the Jerusalem WWTP.     

同分异构体喹啉和异喹啉的缺氧降解性能比较

研究了同分异构体的含氮杂环化合物喹啉和异喹啉在缺氧条件下的降解情况,发现两者表现出不同的缺氧降解特性。喹啉可以在缺氧条件下得到有效降解,其缺氧降解的最佳碳氮比为8。在最佳碳氮比条件下,喹啉的缺氧降解过程符合一级动力学规律,在其降解过程中首先以硝酸盐为电子受体,当硝酸盐氮浓度为零时,亚硝酸盐氮浓度达到最高,此后喹啉的降解主要以亚硝酸盐为电子受体,并和亚硝酸盐氮同时达到最低浓度。异喹啉对硝酸盐的利用甚微,其降解主要表现为厌氧降解特征,降解过程符合零级动力学规律。