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1.
The fate of glyphosate and its degradation product aminomethylphosphonic acid (AMPA) was studied in soil. Labeled glyphosate was used to be able to distinguish the measured quantities of glyphosate and AMPA from the background values since the soil was sampled in a field where glyphosate had been used formerly. After addition of labeled glyphosate, the disappearance of glyphosate and the formation and disappearance of AMPA were monitored. The resulting curves were fitted according to a new EU guideline. The best fit of the glyphosate degradation data was obtained using a first-order multi compartment (FOMC) model. DT50 values of 9 days (glyphosate) and 32 days (AMPA) indicated relatively rapid degradation. After an aging period of 6 months, the leaching risk of each residue was determined by treating the soil with pure water or a phosphate solution (pH 6), to simulate rain over a non-fertilized or fertilized field, respectively. Significantly larger (p < 0.05) amounts of aged glyphosate and AMPA were extracted from the soil when phosphate solution was used as an extraction agent, compared with pure water. This indicates that the risk of leaching of aged glyphosate and AMPA residues from soil is greater in fertilized soil. The blank soil, to which 252 g glyphosate/ha was applied 21 months before this study, contained 0.81 ng glyphosate/g dry soil and 10.46 ng AMPA/g dry soil at the start of the study. Blank soil samples were used as controls without glyphosate addition. After incubation of the blank soil samples for 6 months, a significantly larger amount of AMPA was extracted from the soil treated with phosphate solution than from that treated with pure water. To determine the degree of uptake of aged glyphosate residues by crops growing in the soil, 14C-labeled glyphosate was applied to soil 6.5 months prior to sowing rape and barley seeds. After 41 days, 0.006 ± 0.002% and 0.005 ± 0.001% of the applied radioactivity was measured in rape and barley, respectively.  相似文献   

2.
The effect of six glyphosate concentrations on growth rate and aflatoxin B1 (AFB1) production by Aspergillus section Flavi strains under different water activity (aW) on maize-based medium was investigated. In general, the lag phase decreased as glyphosate concentration increased and all the strains showed the same behavior at the different conditions tested. The glyphosate increased significantly the growth of all Aspergillus section Flavi strains in different percentages with respect to control depending on pesticide concentration. At 5.0 and 10 mM this fact was more evident; however significant differences between both concentrations were not observed in most strains. Aflatoxin B1 production did not show noticeable differences among different pesticide concentrations assayed at all aW in both strains. This study has shown that these Aspergillus flavus and A. parasiticus strains are able to grow effectively and produce aflatoxins in high nutrient status media over a range of glyphosate concentrations under different water activity conditions.  相似文献   

3.
Abstract

A fluorometric method was developed to quantify glyphosate loss from glass surfaces after exposure to the natural forest environment. The method was based on the principle of converting glyphosate into glycine, followed by the fluorogenic labeling with o‐phthalaldehyde. A fluorometer (with λ Ex = 360 nm / λEm =430 nm) was used to quantify the derivatized fluorogenic compound. Response was linear over the concentration range of 143, 286, 572, 858 and 1144 μg of glyphosate (acid equivalent, AE) per mL of the diluted Vision® formulation. Three end‐use mixtures of Vision® were prepared, each at a concentration of 28.6 g AE/L, without and with two adjuvants, Ethomeen® T/25 at 4.5 mL/L and Silwet® L‐77 at 1.5 mL/L. Several dilutions of the end‐use mixtures were applied on glass slides without and with the coating of cuticular wax extracted from trembling aspen foliage. The slides were left for 5 days in a forest opening to determine rainfastness, volatilization and photostability of glyphosate. The residues were quantified using the method developed. Three calibration curves were required because Silwet decreased the fluorometric response of glyphosate, whereas Ethomeen increased it. The minimum detection limit was 143 μg of glyphosate/mL. Glyphosate was resistant to volatilization and sunlight‐mediated degradation, regardless of the presence of wax coating or the adjuvants. About 64% of the applied glyphosate was washed off after a 9.6 mm rainfall when no adjuvant was present. Both adjuvants provided some amount of rain‐protection to glyphosate, but Silwet reduced the washoff to a greater extent (46%) than Ethomeen (55%).  相似文献   

4.
In this study, the innocuousness of different biomixtures employed for glyphosate degradation was tested through Eisenia fetida earthworms. Eight biomixtures were prepared with local materials: alfalfa straw (AS), wheat stubble (WS), river waste (RW) and two different soils (A and B). Each biomixture was divided into two equal portions: one without glyphosate application (control substrate) and the other was sprayed with a commercial glyphosate formulation of 1,000 mg glyphosate a.i. kg?1 biomixture (applied substrate). The bioassay started when all sprayed biomixtures reached high percentages of glyphosate degradation (spent biomixtures). Three parameters were studied: survival, adults and juveniles biomass and reproduction. The results allowed the identification of three biomixtures (AWS, BWS and BWSRW) for good maintenance and development of E. fetida. In addition, at the end of the bioassay two of the viable biomixtures (AWS and BWS) showed the highest performance of juvenile earthworms compared to a reference soil. The Principal Component Analysis (PCA) indicated that the biomixtures containing high silt and clay percentages and minor density renders higher values of earthworm growth and reproduction. Therefore, these innocuous biomixtures can be used as organic amendments or recycled materials for new treatments on biobeds.  相似文献   

5.
An artificial neural network (ANN) model was developed to simulate the biodegradation of herbicide glyphosate [2-(Phosphonomethylamino) acetic acid] in a solution with varying parameters pH, inoculum size and initial glyphosate concentration. The predictive ability of ANN model was also compared with Monod model. The result showed that ANN model was able to accurately predict the experimental results. A low ratio of self-inhibition and half saturation constants of Haldane equations (< 8) exhibited the inhibitory effect of glyphosate on bacteria growth. The value of K(i)/K(s) increased when the mixed inoculum size was increased from 10(4) to 10(6) bacteria/mL. It was found that the percentage of glyphosate degradation reached a maximum value of 99% at an optimum pH 6-7 while for pH values higher than 9 or lower than 4, no degradation was observed.  相似文献   

6.
A dominant strain named Ochrobactrum sp. was isolated from soils contaminated with coal tar. The batch experiments were carried out to study the co-metabolic degradation of pyrene by Ochrobactrum MB-2 with naphthalene as the main substrate and the effects of several significant parameters such as naphthalene concentration, pH and temperature on removal efficiency were explored. The results showed that Ochrobactrum MB-2 effectively degraded naphthalene and that the addition of naphthalene favored the degradation of pyrene. The maximum elimination efficiency of naphthalene (10?mg?L?1) and pyrene (1?mg?L?1) was achieved at pH 7 and 25?°C, and the corresponding values were 99 and 41%, respectively. A competitive inhibition model based on the Michaelis–Menten equation was used to characterize the inhibitory effect of pyrene on naphthalene degradation. The values of the half-saturation coefficient for naphthalene (KS) and dissociation constant of enzyme-inhibitor complex (KC) were determined to be 4.93 and 1.38?mg?L?1, respectively.  相似文献   

7.

Persistence of triasulfuron [3-(6-methoxy-4methyl-1,3,5-triazin-2-yl)-1-{2-(2-chloroethoxy)-phenylsulfonyl}-urea] in soil was studied under wheat crop and laboratory conditions. Field experiment was conducted in the farms of Agronomy Division, Indian Agricultural Research Institute (IARI), New Delhi. Randomized block design (RBD) was followed with four replicates and two rates of treatments along with control and weedy check. Triasulfuron was applied as post-emergent application to wheat crop at two rates of application viz., 15 g and 20 g a.i. ha?1. Soil samples at 0 (3 h), 1, 3, 5, 7, 10, 15, 20, and 30-day intervals after application were drawn, extracted, cleaned up, and analyzed for herbicide residues by high performance liquid chromatography (HPLC) using C18 column and methanol: water (8:2) as mobile phase at 242 nm wave length. Effect of microbial activity and soil pH was studied under laboratory conditions. Dissipation of triasulfuron followed a first-order-rate kinetics. Residues dissipated from field soil with half-life of 5.8 and 5.9 days at two rates of application. The study indicated biphasic degradation with faster rate initially (t 1/2 = 3.7 days), followed by a slower dissipation rate at the end (t 1/2 = 9.4 days). Similar trend was observed with non-sterile soil in laboratory with a longer half-life. Acidic pH and microbial activity contributed toward the degradation of triasulfuron in soil.  相似文献   

8.
Thirty bacterial strains with various abilities to utilize glyphosate as the sole phosphorus source were isolated from farm soils using the glyphosate enrichment cultivation technique. Among them, a strain showing a remarkable glyphosate-degrading activity was identified by biochemical features and 16S rRNA sequence analysis as Ochrobactrum sp. (GDOS). Herbicide (3 mM) degradation was induced by phosphate starvation, and was completed within 60 h. Aminomethylphosphonic acid was detected in the exhausted medium, suggesting glyphosate oxidoreductase as the enzyme responsible for herbicide breakdown. As it grew even in the presence of glyphosate concentrations as high as 200 mM, Ochrobactrum sp. could be used for bioremediation purposes and treatment of heavily contaminated soils.  相似文献   

9.
This investigation was undertaken to determine the atrazine degradation by fungal enzyme extracts (FEEs) in a clay-loam soil microcosm contaminated at field application rate (5 μg g?1) and to study the influence of different soil microcosm conditions, including the effect of soil sterilization, water holding capacity, soil pH and type of FEEs used in atrazine degradation through a 24 factorial experimental design. The Trametes maximaPaecilomyces carneus co-culture extract contained more laccase activity and hydrogen peroxide (H2O2) content (laccase = 18956.0 U mg protein?1, H2O2 = 6.2 mg L?1) than the T. maxima monoculture extract (laccase = 12866.7 U mg protein?1, H2O2 = 4.0 mg L?1). Both extracts were able to degrade atrazine at 100%; however, the T. maxima monoculture extract (0.32 h) achieved a lower half-degradation time than its co-culture with P. carneus (1.2 h). The FEE type (p = 0.03) and soil pH (p = 0.01) significantly affected atrazine degradation. The best degradation rate was achieved by the T. maxima monoculture extract in an acid soil (pH = 4.86). This study demonstrated that both the monoculture extracts of the native strain T. maxima and its co-culture with P. carneus can efficiently and quickly degrade atrazine in clay-loam soils.  相似文献   

10.
The fate of glyphosate and its degradation product aminomethylphosphonic acid (AMPA) was studied in soil. Labeled glyphosate was used to be able to distinguish the measured quantities of glyphosate and AMPA from the background values since the soil was sampled in a field where glyphosate had been used formerly. After addition of labeled glyphosate, the disappearance of glyphosate and the formation and disappearance of AMPA were monitored. The resulting curves were fitted according to a new EU guideline. The best fit of the glyphosate degradation data was obtained using a first-order multi compartment (FOMC) model. DT(50) values of 9 days (glyphosate) and 32 days (AMPA) indicated relatively rapid degradation. After an aging period of 6 months, the leaching risk of each residue was determined by treating the soil with pure water or a phosphate solution (pH 6), to simulate rain over a non-fertilized or fertilized field, respectively. Significantly larger (p < 0.05) amounts of aged glyphosate and AMPA were extracted from the soil when phosphate solution was used as an extraction agent, compared with pure water. This indicates that the risk of leaching of aged glyphosate and AMPA residues from soil is greater in fertilized soil. The blank soil, to which 252 g glyphosate/ha was applied 21 months before this study, contained 0.81 ng glyphosate/g dry soil and 10.46 ng AMPA/g dry soil at the start of the study. Blank soil samples were used as controls without glyphosate addition. After incubation of the blank soil samples for 6 months, a significantly larger amount of AMPA was extracted from the soil treated with phosphate solution than from that treated with pure water. To determine the degree of uptake of aged glyphosate residues by crops growing in the soil, (14)C-labeled glyphosate was applied to soil 6.5 months prior to sowing rape and barley seeds. After 41 days, 0.006 +/- 0.002% and 0.005 +/- 0.001% of the applied radioactivity was measured in rape and barley, respectively.  相似文献   

11.
Abstract

A study was undertaken to determine the effect of Cu(II) in degradation of methylparathion (o,o-dimethyl o, 4-nitrophenyl phosphoriotioate) in acid medium. Initial electrochemical characterization of Cu(II) and methylparathion was done in an aqueous medium at a pH range of 2–7. Cu(II) was studied in the presence of different anions and it was observed that its electroactivity depends on pH and is independent of the anion used. Methylparathion had two reduction signals at pH ≤ 6 and only one at pH > 6. The pesticide's transformation kinetic was then studied in the presence of Cu(II) in acid buffered aqueous medium at pH values of 2, 4, and 7. Paranitrophenol appeared as the only electroactive product at all three pH values. The reaction was first order and had k values of 5.2 × 10?3 s?1 at pH 2, 5.5 × 10?3 s?1 at pH 4 and 9.0 × 10?3 s?1 at pH 7. It is concluded that the principal degradation pathway of methylparathion in acid medium is a Cu(II) catalyzed hydrolysis reaction.  相似文献   

12.
The purpose of this work was to demonstrate that a Fenton (H2O2/Fe) reaction was involved in DDT [1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane)] degradation in a culture of Penicillium sp. spiked with FeSO4. A commercial DDT mixture (10% DDE [1,1-dichloro-2,2-bis(p-chlorophenyl)ethylene], 30% o,p-DDT and 60% of p,p′ -DDT) of 10 mg L? 1 was used. Hydrogen peroxide (H2O2), tartaric acid and oxalic acid were identified at 18 h in culture media, with and without added DDT; this correlated positively with lowering of pH from 5.8 to 2.7. Lower concentrations of oxalic acid and H2O2 (7.9 and 52.6 mg L? 1, respectively) occurred in media with DDT at 30 h, in comparison to that one without DDT mixture (27.9 and 65.3 mg L? 1, respectively), at this time there was maximum degradation (87.7, 91.7 and 94.2%) for DDE, o,p-DDT and p,p′-DDT, respectively. We propose that the degradation of the DDT mixture by Penicillium sp. was through a Fenton reaction (H2O2/Fe) under acidic conditions produced in situ during the fungal culture amended with FeSO4.  相似文献   

13.
H. Kylin 《Chemosphere》2013,90(6):1821-1828
Environmental monitoring of pesticide residues in surface water is often done with time-integrated sampling where a specified volume is sampled each hour during, e.g., a week, thus avoiding at momentary high or low extreme concentrations. However, sampling over an extended period of time can result in losses of easily degradable analytes, why the stability of the target analytes over the timespan of the sampling must be checked. Glyphosate is one of the most widely used herbicides. Because of its chemical complexity, glyphosate binds differently to metals and colloids at different pH, and the degradation may also be affected. Recovery of glyphosate from spiked natural waters after 1 and 3 weeks of storage was higher when the samples were acidified to approximately pH 2 rather than at their natural pH. Keeping the samples refrigerated to 4 °C in darkness also enhanced recovery, while glyphosate losses were substantial from samples kept at their natural pH at 20 °C. Total loss of glyphosate was observed in some samples kept at natural pH, 20 °C, and daylight; a loss partly due to binding to metals or colloids that could only partially be reversed by acidification. For 1-week time-integrated sampling a small amount of hydrochloric acid in a piece of heat-sealed hydrophobic micro-porous tubing is added to the sampling bottles before deployment, a procedure that acidifies the samples during collection keeping them below pH 2 until analysis, thus minimising losses of glyphosate. The method also allows determination of the primary degradation product aminomethylphosphonic acid (AMPA).  相似文献   

14.

Bismuth molybdate (Bi2MoO6) nanostructures has attracted many researches as an advanced photocalysts for the organic contaminants. In this paper, bismuth molybdate Bi2MoO6 nanoparticles were synthesized using a simple hydrothermal method at varied pH (2, 4, 6, 8, and 10) for 15 h at 180 °C. The results reveal the variation pH precursor solutions have a significant impact on the morphology, phase formations, and photocatalytic activity of samples. The synthesized samples at low pH level were characterized by FESEM analysis revealing Bi2MoO6 nanoplates have formed while gradually convert to Bi2MoO6 spherical nanoparticle at high PH level as shown in energy dispersive X-ray spectroscopy (DES) peaks. The X-ray diffraction patterns reveal characteristic peaks corresponding to mixed phases of Bi2MoO6 and cubic Bi4MoO9 at high pH value. The optical absorption study exhibit Bi2MoO6 nanoplates absorbed visible light with blue shift when compared to the cubic Bi4MoO9 structures. Moreover, the photocatalytic activity results revealed that nanoplates in pH?=?4 sample has excellent photocatalytic activity for degradation of rhodamine (RhB), methylene orange (MO), and phenol under visible-light irradiation (λ?>?400 nm) as well as exhibit the photodegradation 90% of phenol within 300 min.

  相似文献   

15.
The H2O2/UVC process was applied to the photodegradation of a commercial formulation of glyphosate in water. Two organisms (Vibrio fischeri bacteria and Rhinella arenarum tadpoles) were used to investigate the toxicity of glyphosate in samples M1, M2, and M3 following different photodegradation reaction times (120, 240 and 360 min, respectively) that had differing amounts of residual H2O2. Subsamples of M1, M2, and M3 were then used to create samples M1,E, M2,E and M3,E in which the H2O2 had been removed. Acetylcholinesterase (AChE) and butyrylcholinesterase (BChE) activities were measured in tadpoles to determine possible sub-lethal effects. In V. fischeri, M1,E, which was collected early in the photodegradation process, caused 52% inhibition, while M3,E, which was collected at the end of the photodegradation process, caused only 17% inhibition. Survival of tadpoles was 100% in samples M2, M3, and in M1,E, M2,E and M3,E. The lowest percentages of enzymatic inhibition were observed in samples without removal of H2O2: 13.96% (AChE) and 16% (BChE) for M2, and 24.12% (AChE) and 13.83% (BChE) for M3. These results show the efficiency of the H2O2/UVC process in reducing the toxicity of water or wastewater polluted by commercial formulations of glyphosate. According to the ecotoxicity assays, the conditions corresponding to M2 (11 ± 1 mg a.e. L?1 glyphosate and 11 ± 1 mg L?1 H2O2) could be used as a final point for glyphosate treatment with the H2O2/UV process.  相似文献   

16.
A study was undertaken to determine the transformation kinetic of methylparathion (O, O, -dimethyl O-4 nitrophenylphosphorotioate) in the presence of Fe(III) between pH 2 and 7. The Fe(III) was not electroactive under the conditions used in this study, and polarographic signals were exhibited by methylparathion and main degradation product only. Data suggest that hydrolysis of methylparathion in an acid medium is catalyzed by Fe(III) and the pesticide did not degrade in this medium without this cation. Methylparathion degradation was observed at all the pHs studied and was independent of the predominant chemical form of Fe(III) in the aqueous medium. The reaction was first-order with pH-dependent rate constant (k) values ranging from 3.3 × 10? 3 h? 1 to 7.0 × 10? 3 h? 1. The k values increased as pH decreased, suggesting that Fe(III) acted as an electrophile in the reaction mechanism.  相似文献   

17.
Abstract

The hydrolysis of the insecticide tebufenozide was studied in the dark at 20 to 40°C in buffered (pH 4 to 10) distilled water, and at 20°C in unbuffered, sterilized and unsterilized stream water. Tebufenozide was very stable in acidic and neutral buffers at 20°C and the corresponding pseudo‐first‐order rate constants (kobsd) and half‐lives (T1/2) were 5.946 × 10‐4 and 13.10 × 10‐4 d‐1, and 1166 and 529 d, respectively. The hydrolytic degradation was dependent on pH and temperature. At pH 10 and at 20,30 and 40°C, the kobsd (10‐4 d‐1) and T1/2 (d) values were 34.22, 66.72 and 130.0; and 203, 104 and 53.3, respectively. The energy of activation (Ea) values for the hydrolysis of tebufenozide at pH 4, 7 and 10, calculated from the Arrhenius plots, were 83.50, 66.71 and 50.87 kJ/mol, respectively. Tebufenozide was stable in sterilized stream water in the dark (T1/2 = 734 d) but it degraded fairly rapidly in unsterilized stream water (T1/2 = 181 d). Sunlight photodegradation of the chemical was slower (T1/2 = 83.0 h) than the photolysis by ultraviolet radiations (T1/2 values at 254 and 365 nm were 9.92 and 27.6 h, respectively); nevertheless, it was still appreciable during the summer months at 46°31’ N latitude. The differences in degradation rates between the unsterilized and sterilized stream water and the degradation of the chemical in the sterile, distilled water in sunlight, suggests that microbial processes and photolysis are the two main degradative routes for tebufenozide in natural aquatic systems.  相似文献   

18.
A study was conducted to investigate fenhexamid (FEX) behavior in soil and in water. FEX proved to be rather stable at acid pH but showed slight degradation at neutral and alkaline pH. After 101 days of FEX spiking of a soil sample, 94% at pH 4, 12% at pH 7 and 23% at pH 9 of the active ingredient was still present. In natural water the rate of FEX disappearance appeared to be slow which may be due to abiotic rather than biotic processes. The soil degradation tests showed low persistence of the active ingredient if a good microflora activity is guaranteed (DT50 about 1 day). Moreover, in absence of microorganisms, FEX proved to be stable. Humidities of 25 and 50% of Water Holding Capacity (WHC) influenced in equal measure the rate of degradation. From the same soil, a bacterium was isolated and identified as Bacillus megaterium, which was able to metabolize FEX with the hydroxylation of the cyclohexane ring. Moreover, FEX showed an elevated affinity for humic acid (73%), smectite (31%), and ferrihydrite(20%) and low affinity for vermiculite (11%) and kaolinite (7%).  相似文献   

19.
Metabolism of [14C-u-phenyl]isoproturon [3-(4-isopropylphenyl)-1,1-dimethylurea] by two soil and freshwater microorganisms, green alga Chlorella kesslerei and cyanobacterium Anabaena inaequalis, was studied as a function of pH, pesticide concentration, and incubation time. Metabolized isoproturon, in the media, ranged from 0% (Chlorella at pH 5.5 after 1 d) to 22% (Anabaena at pH 5.5 after 10 d). Twenty-five percent faster degradation of isoproturon by Anabaena occurred at pH 5.5 versus pH 7.5, when measured over 10 d. Increased 14C incorporation into tissue, with time and at lower pH, was due mainly to bioaccumulation of [14C]isoproturon and/or its metabolites in the cells. Metabolic degradation resulted in four identifiable (by TLC) metabolites. Based on this, a degradation pathway is proposed, involving mono- and di-N-demethylation, hydroxylation of the isopropyl moiety, and hydrolysis to 4-isopropylaniline. Similarity in the metabolites produced suggests that the enzyme systems responsible for metabolizing isoproturon are almost identical in both photosynthetic micro-algae.  相似文献   

20.
The paper presents results of the studies photodegradation, photooxidation, and oxidation of phenylarsonic acid (PAA) in aquatic solution. The water solutions, which consist of 2.7 g dm?3 phenylarsonic acid, were subjected to advance oxidation process (AOP) in UV, UV/H2O2, UV/O3, H2O2, and O3 systems under two pH conditions. Kinetic rate constants and half-life of phenylarsonic acid decomposition reaction are presented. The results from the study indicate that at pH 2 and 7, PAA degradation processes takes place in accordance with the pseudo first order kinetic reaction. The highest rate constants (10.45?×?10?3 and 20.12?×?10?3) and degradation efficiencies at pH 2 and 7 were obtained at UV/O3 processes. In solution, after processes, benzene, phenol, acetophenone, o-hydroxybiphenyl, p-hydroxybiphenyl, benzoic acid, benzaldehyde, and biphenyl were identified.  相似文献   

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