The effect of soil:water ratios on the induction of isoproturon, cypermethrin and diazinon mineralisation

The rate of pesticide biodegradation does not remain constant with time, and is dependent on the physico-chemical properties of the soil and of the pesticide as well as on the biology of the soil. Prolonged or repeated contact between soil microbes and pesticides has been shown to result in an increase in the rate and extent of biodegradation. This work assessed the impact of the soil:water ratio on measurement of catabolic induction for ¹⁴C-isoproturon, ¹⁴C-diazinon and ¹⁴C-cypermethrin. Slurrying (1:1 and 1:3 soil:water) with agitation resulted in significantly higher rates and extents of mineralisation than the non-slurried system (P ? 0.05; 1:0 soil:water), except for the mineralisation of ¹⁴C-diazinon where the greatest extent of mineralisation occurred in non-slurried soil. Slurrying without agitation resulted in the significant lower mineralisation in all cases (P ? 0.05). There was a significant interaction between the soil:water ratio and length of contact (P ? 0.05). Whilst the use of slurried systems can enhance the extent and rate of mineralisation, there is no improvement in reproducibility, and so for the measurement of catabolic induction, the use of field conditions will lead to a more environmentally relevant measurement.     

Effects of temperature and water content on degradation of isoproturon in three soil profiles

The phenylurea herbicide isoproturon, 3-(4-isopropylphenyl)-1,1-dimethylurea (IPU), is widely used to control pre- and post-emergence of grass and broad-leaved weeds in cereal crops. Its degradation in soils is a key process for assessing its leaching risk to groundwater resources. The degradation properties of various samples from surface and subsurface soil (down to 1m depth) of a heterogeneous agricultural field were studied using (14)C-IPU. Laboratory incubations were carried out at 22 and 10 degrees C and at water contents 90% and 50% of the estimated water holding capacity (eWHC) corresponding to water potentials between -56 kPa and -660 MPa. Degradation was found to be more sensitive to water content variations than to temperature variations in the ranges that we used. For surface layers, at 10 and 22 degrees C, the degradation half-life increased by a factor 10 and 15, respectively, when water content decreased from 90% to 50% eWHC. Under optimal degradation conditions (i.e. 22 degrees C and 90% eWHC), 3-(4-isopropylphenyl)-1-methylurea (MDIPU) was the main metabolite in surface samples. At subsurface depths, IPU half-lives were larger than 100 d, IPU was the main compound after 92 d of incubation and the main metabolite was an unidentified polar metabolite. These results suggest a metabolic pathway involving hydroxylations for subsurface materials. IPU degradation was largely affected by water availability in both surface and subsurface horizons. Clay content seemed to play a major role in degradation processes in subsurface soil by determining through sorption IPU availability in soil solution and/or by limiting water availability for microorganisms.     

Evaluating equilibrium and non-equilibrium transport of bromide and isoproturon in disturbed and undisturbed soil columns

In this study, displacement experiments of isoproturon were conducted in disturbed and undisturbed columns of a silty clay loam soil under similar rainfall intensities. Solute transport occurred under saturated conditions in the undisturbed soil and under unsaturated conditions in the sieved soil because of a greater bulk density of the compacted undisturbed soil compared to the sieved soil. The objective of this work was to determine transport characteristics of isoproturon relative to bromide tracer. Triplicate column experiments were performed with sieved (structure partially destroyed to simulate conventional tillage) and undisturbed (structure preserved) soils. Bromide experimental breakthrough curves were analyzed using convective-dispersive and dual-permeability (DP) models (HYDRUS-1D). Isoproturon breakthrough curves (BTCs) were analyzed using the DP model that considered either chemical equilibrium or non-equilibrium transport. The DP model described the bromide elution curves of the sieved soil columns well, whereas it overestimated the tailing of the bromide BTCs of the undisturbed soil columns. A higher degree of physical non-equilibrium was found in the undisturbed soil, where 56% of total water was contained in the slow-flow matrix, compared to 26% in the sieved soil. Isoproturon BTCs were best described in both sieved and undisturbed soil columns using the DP model combined with the chemical non-equilibrium. Higher degradation rates were obtained in the transport experiments than in batch studies, for both soils. This was likely caused by hysteresis in sorption of isoproturon. However, it cannot be ruled out that higher degradation rates were due, at least in part, to the adopted first-order model. Results showed that for similar rainfall intensity, physical and chemical non-equilibrium were greater in the saturated undisturbed soil than in the unsaturated sieved soil. Results also suggested faster transport of isoproturon in the undisturbed soil due to higher preferential flow and lower fraction of equilibrium sorption sites.     

Spatial variability in the degradation rate of isoproturon in soil

Thirty samples of soil were taken at 50-m intersections on a grid pattern over an area of 250 x 200 m within a single field with nominally uniform soil characteristics. Incubations of isoproturon (3-(4-isopropylphenyl)-1,1-dimethylurea) under standard conditions (15 degrees C; -33 kPa soil water potential) indicated considerable variation in degradation rate of the herbicide, with the time to 50% loss (DT50) varying from 6.5 to 30 days. The kinetics of degradation also varied between the sub-samples of soil. In many of them, there was an exponential decline in isoproturon residues; in others, exponential loss was followed by more rapid rates of decline; in a few soil samples, rapid rates of loss began shortly after the start of the incubations. In more detailed studies with soils from a smaller number of sub-sites (20), measurements were again made of isoproturon degradation rate, and the soils were analysed for organic matter content, pH, and nutrient status (N, P, K). Measurements were also made of isoproturon adsorption by the soils and of soil microbial biomass. Patterns of microbial metabolism were assessed using 95 substrates in Biolog GN plates. Soils showing rapid biodegradation were generally of higher pH and contained more available potassium than those showing slower degradation rates. They also had a larger microbial biomass and greater microbial metabolic diversity as determined by substrate utilisation on Biolog GN plates. The implications of the results for the efficacy and environmental behaviour of isoproturon are discussed.     

Effect of sludge-amendment or nutrient addition on the biodegradation of the herbicide isoproturon in soil

Adding sludge to agricultural soil results in added organic matter, nutrients and metallic and/or organic pollutants. These components may modify the behaviour of pesticides in the soil. We monitored possible changes in the degradation of the herbicide isoproturon (production of CO2 and degradation products) in soil amended with sludge, heavy metals or nitrogen and phosphorus. The treated and control soils were incubated under controlled conditions for 60 days. The nitrogen and phosphorus had the greatest effect on isoproturon degradation, independent of the presence of pollutants. Mineralisation of the herbicide to CO2 was slow and seemed to be linked to a fast degradation and to the accumulation of a complex degradation product that was neither catabolized nor adsorbed, 4,4'-diisopropylazobenzene. This degradation pathway also produced smaller amounts of non-extractable residues. Sewage sludge had no significant effect on isoproturon degradation, despite a large increase of organic matter mineralisation (factor 2).     

Microbial aspects of the interaction between soil depth and biodegradation of the herbicide isoproturon

Factors controlling change in biodegradation rate of the pesticide isoproturon with soil depth were investigated in a field with sandy-loam soil. Soil was sampled at five depths between 0-10 and 70-80 cm. Degradation rate declined progressively down the soil profile, with degradation slower, and relative differences in degradation rate between soil depths greater, in intact cores relative to sieved soil. Neither the maximum rate of degradation, or sorption, changed with soil depth, indicating that there was no variation in bioavailability. Differences in degradation rate between soil depths were not associated with the starting population size of catabolic organisms or the number of catabolic organisms proliferating following 100% degradation. Decreasing degradation rates with soil depth were associated with an increase in the length of the lag phase prior to exponential degradation, suggesting the time required for adaptation within communities controlled degradation rates. 16S rRNA PCR denaturing gradient gel electrophoresis showed that degradation in sub-soil between 40-50 and 70-80 cm depths was associated with proliferation of the same strains of Sphingomonas spp.     

Assessing the chemical and biological accessibility of the herbicide isoproturon in soil amended with biochar

Decamethylcyclopentasiloxane (D5) is a cyclic volatile methyl siloxane (cVMS) commonly found in commercially available products. D5 is expected to enter the terrestrial environment through the deposit of biosolids from sewage treatment plants onto agricultural fields for nutrient enrichment. Little to no information currently exists as to the risks of D5 to the terrestrial environment. In order to evaluate the potential risk to terrestrial organisms, the toxicity of a D5 contaminated biosolid in an agricultural soil was assessed with a battery of standardized soil toxicity tests.D5 was spiked into a surrogate biosolid and then mixed with a sandy loam soil to create test concentrations ranging from 0 to 4074 mg kg⁻¹. Plant (Hordeum vulgare (barley) and Trifolium pratense (red clover)) and soil invertebrates (Eisenia andrei (earthworm) and Folsomia candida (springtail)) toxicity tests were completed to assess for lethal and sub-lethal effects. Plant testing evaluated the effects on seedling emergence, shoot and root length, and shoot and root dry mass. Invertebrate test endpoints included adult lethality, juvenile production, and individual juvenile dry mass (earthworms only). Soil samples were collected over time to confirm test concentrations and evaluate the loss of chemical over the duration of a test. The toxicity of the D5 was species and endpoint dependent, such that no significant adverse effects were observed for T. pratense or E. andrei test endpoints, however, toxicity was observed for H. vulgare plant growth and F. candida survival and reproduction. Chemical losses of up to 50% were observed throughout the tests, most significantly at high concentrations.     

Effect of different soil types on the enchytraeids Enchytraeus albidus and Enchytraeus luxuriosus using the herbicide Phenmedipham

Soil ecotoxicology studies are usually performed in standard soils, such as the OECD (Organization for Economic Cooperation and Development) artificial soil or the LUFA St. 2.2, a natural soil. When assessing the toxic effects in the environment, soil properties are often different from those in standard soils, which might lead to a different exposure situation for the test species and, therefore, to a different evaluation of the risk of the test substance. Selected to cover a broad range of properties and based on the Euro-Soils concept, 18 different soils were studied regarding their suitability to two test species: Enchytraeus albidus and Enchytraeus luxuriosus (Enchytraeidae). In reproduction tests, the test species reacted differently to the tested soils, but both enchytraeids did not survive in acid soils (i.e. pH相似文献   

Impact of varying soil structure on transport processes in different diagnostic horizons of three soil types

When soil structure varies in different soil types and the horizons of these soil types, it has a significant impact on water flow and contaminant transport in soils. This paper focuses on the effect of soil structure variations on the transport of pesticides in the soil above the water table. Transport of a pesticide (chlorotoluron) initially applied on soil columns taken from various horizons of three different soil types (Haplic Luvisol, Greyic Phaeozem and Haplic Cambisol) was studied using two scenarios of ponding infiltration. The highest infiltration rate and pesticide mobility were observed for the Bt₁ horizon of Haplic Luvisol that exhibited a well-developed prismatic structure. The lowest infiltration rate was measured for the Bw horizon of Haplic Cambisol, which had a poorly developed soil structure and a low fraction of large capillary pores and gravitational pores. Water infiltration rates were reduced during the experiments by a soil structure breakdown, swelling of clay and/or air entrapped in soil samples. The largest soil structure breakdown and infiltration decrease was observed for the Ap horizon of Haplic Luvisol due to the low aggregate stability of the initially well-aggregated soil. Single-porosity and dual-permeability (with matrix and macropore domains) flow models in HYDRUS-1D were used to estimate soil hydraulic parameters via numerical inversion using data from the first infiltration experiment. A fraction of the macropore domain in the dual-permeability model was estimated using the micro-morphological images. Final soil hydraulic parameters determined using the single-porosity and dual-permeability models were subsequently used to optimize solute transport parameters. To improve numerical inversion results, the two-site sorption model was also applied. Although structural changes observed during the experiment affected water flow and solute transport, the dual-permeability model together with the two-site sorption model proved to be able to approximate experimental data.     

Short term recovery of periphyton photosynthesis after pulse exposition to the photosystem II inhibitors atrazine and isoproturon

Aquatic organisms are exposed to fluctuating concentrations of herbicides which contaminate rivers following their use for agricultural or domestic purposes. The development of sensitive bioanalytical tests enabling us not only to detect the effects of those pollutants but to take into account this pattern of exposure should improve the ecological relevance of river toxicity assessment. In this respect, the use of chlorophyll fluorescence measurements is a convenient way to probe the effect of photosystem II (PSII) inhibitors on primary producers. This study was devoted to validate the combined use of two fluorescence parameters, the effective and the optimal quantum yields of PSII photochemistry (Φ_PSII and F_v/F_m), as reliable biomarkers of initial isoproturon (IPU) or atrazine (ATZ) toxicity to natural periphyton in a pulse exposition scenario. Φ_PSII and F_v/F_m were regularly estimated during a 7 h-exposure to each pollutant (0-100 μM) and also later after being transferred in herbicide-free water (up to 36 h). Our results showed that IPU was more toxic than ATZ, but with effects reversible within 12 h. Moreover, these two similarly acting herbicides (i.e. same target site) presented contrasted short term recovery patterns, regarding the previous exposure duration.     

染料厂污染土壤中六氯苯的水淹法厌氧降解

以乙酸为碳源,采用正交实验的方法,探讨了水淹法厌氧降解某染料厂污染土壤中六氯苯的效果,研究考察了初始pH、反应温度和固液比3个环境因素对六氯苯降解率的影响,确定了六氯苯最佳的厌氧降解条件。结果表明,初始pH对土壤中六氯苯的降解率影响最大。在初始pH为5,反应温度为45℃,固液比为1∶1的最佳反应条件下,六氯苯的降解率最高达到52.56%。     

Formation and release of residues of the 14C-labelled herbicide isoproturon and its metabolites bound in model polymers and in soil

The humic monomer catechol was reacted with (14)C-isoproturon and some of its metabolites, including (14)C-4-isopropylaniline, in aqueous solution under a stream of oxygen. Only in the case of (14)C-4-isopropylaniline, incorporation in oligomers, in fulvic acid-like polymers, and in humic acid-like polymers by covalent bonds was observed. The main oligomer was identified by mass spectrometry as a trimer, 4,5-bis-(4-isopropylphenylamino)-3,5-cyclohexadiene-1,2-dione. Biomineralization of (14)C-compounds to (14)CO(2) in a loamy soil and release of (14)C from soil columns into percolate water decreased in the order: free isoproturon >free 4-isopropylaniline>fulvic acid-like polymers>trimer>humic acid-like polymers. In soil columns, a small but measurable migration of (14)C from polymers from upper to deeper soil layers could be detected; most of this (14)C was bound again in a non-extractable form. It is concluded that aniline-derived pesticides bound in soil by covalent binding may not be fully undegradable, nor fully immobile.     

Effects of the phenylurea herbicide isoproturon on periphytic diatom communities in freshwater indoor microcosms

The toxic effects of the phenylurea herbicide Isoproturon -IPU: (3-(4-isopropylphenyl)-1, 1-dimethylurea)-were studied on the colonization of periphytic diatom communities, within indoor microcosms consisting of a mixed biotope (water column and natural sediment) and two biological species-rooted macrophyte cuttings (Elodea densa) and benthic bivalve molluscs (Corbicula fluminea). The periphyton, essentially composed of diatoms, was collected on artificial substrata (glass slides) in the upper layers of the water column, after two periods of exposure (34 and 71 days). IPU was initially added in the water or in the sediment compartment, at two nominal concentrations (L1 and L2 levels) for each contamination source-5 and 20 microg litre(-1) and 100 and 400 microg kg(-1) in sediment (w/w) respectively. The effects of IPU on the density and community structure of periphytic diatoms are described. A marked reduction in the diatom density was observed after 34 days exposure to the lower concentration of IPU in the water (5 microg litre(-1)). For the L2 levels, the very small number of live cells present did not permit quantification of the diatom density. After 71 days, recovery in community parameters occurred for the two contamination levels of the sediment and water column sources. Samples collected in the experimental units contaminated with the L2 levels were dominated by heterotrophic and smaller diatom species, such as Sellaphora seminulum. Data treatment based on factorial discriminant analysis enabled us to distinguish the different contamination conditions, with only 11 species from the 130 taxa identified.     

Influence of humic fractions on retention of isoproturon residues in two Moroccan soils

The influence of different fractions of soil organic matter on the retention of the herbicide isoproturon (IPU) has been evaluated. Water and methanol extractable residues of ¹⁴C labeled isoproturon have been determined in two Moroccan soils by β -counting–liquid chromatography. The quantification of bound residues in soil and in different fractions of soil humic substances has been performed using pyrolysis/scintillation-detected gas-chromatography. Microbial mineralization of the herbicide and soil organic matter has been also monitored. Retention of isoproturon residues after 30-days incubation ranged from 22% to 32% (non-extractable fraction). The radioactivity extracted in an aqueous environment was from 20% to 33% of the amount used for the treatment; meanwhile, methanol was able to extract another 48%. Both soils showed quantities of bound residues into the humin fraction higher than humic and fulvic acids. The total amount of residues retained into the organic matter of the soils was about 65 % of non-extractable fraction, and this percentage did not change with incubation time; on the contrary, the sorption rate of the retention reaction is mostly influenced by the clay fraction and organic content of the soil. Only a little part of the herbicide was mineralized during the experimental time.     

超临界水氧化法处理除草剂生产废水及热能的研究

利用 2 .2 L +1.7L超临界水氧化反应器对除草剂生产废水进行了处理实验。结果表明 :在温度 >60 0℃、压力 >3 2MPa,氧化反应时间为 180 s时 ,其 COD去除率达 98.1% ;氧化反应时间为 3 0 0 s时 ,其 COD去除率达 99.8%。处理后的排水达到国家规定的标准。同时利用氧弹法对该废水热值进行了测试 ,利用热平衡方程式对该试验装置的热效率进行了分析     

Sorption behaviour of acetochlor,atrazine, carbendazim,diazinon, imidacloprid and isoproturon on Hungarian agricultural soil

Laboratory studies were conducted to determine the sorption behaviour of six commonly used pesticides (acetochlor, atrazine, carbendazim, diazinon, imidacloprid and isoproturon) on Hungarian brown forest soil with clay alluviation (Luvisol) using the batch equilibrium technique. The sorption isotherms could be described by the Freundlich equation in non-linear form (n < 1) for all compounds, however in case of diazinon using the extended Freundlich equation proved to be a better approach. The adsorption constant related soil organic carbon content (Koc) calculated from Freundlich equation were 314 for acetochlor, 133 for atrazine, 2805 for carbendazim, 1589 for diazinon, 210 for imidacloprid and 174 for isoproturon. The octanol-water partition coefficients (Pow), which can be a useful parameter to predict of adsorption behaviour of a chemical on soil, and dissociation coefficients of these pesticides were calculated based on the chemical structure of them using a computerized expert system. The octanol-water partition coefficients were determined experimentally from high performance liquid chromatographic parameters as well. Good agreement was observed between experimental and the computer expert system estimated data. Computer estimated log Pow values ranged 0.5 and 3.86 for the examined pesticides, with imidacloprid and diazinon being the least and most hydrophobic respectively. Experimentally determined logPow ranged between 0.92 and 3.81 with the same tendency. It can be concluded that the Freundlich adsorption constants (Kf) are slightly related to the octanol-water partition coefficients of investigated chemicals, nevertheless no close correlation could be established because of the influence of further characteristics of solutes and soil.     

Sorption and degradation of imidacloprid in soil and water

Imidacloprid, the major component of many widely used insecticide formulations, is highly persistent in soils. In this study, the sorption of imidacloprid by six soils as well as its photodegradation and hydrolysis in water were studied. The soils differed significantly in organic matter content and other physical and chemical properties. Sorption increased with increasing soil organic matter content but was not significantly correlated with other soil properties. Removal of organic matter via H2O2 oxidation decreased the sorption. By normalizing the Freundlich coefficients (Kf) to organic matter contents, the variability in obtained sorption coefficient (Kom) was substantially reduced. These results indicate that soil organic matter was the primary sorptive medium for imidacloprid. The low heat of sorption calculated from Kom suggests that partition into soil organic matter was most likely the mechanism. The photodegradation and hydrolysis of imidacloprid in water followed pseudo-first-order kinetics; however, the latter process needed a six-time-higher activation energy. While both processes produced the same main intermediate, they occurred via different pathways. The hydrolysis of imidacloprid was not catalyzed by the high interlayer pH in the presence of metal-saturated clays, which appeared to result from the lack of the pesticide adsorption in the interlayers of clays.     

Microbial degradation pathways of the herbicide dichlobenil in soils with different history of dichlobenil-exposure

This is the first detailed study of metabolite production during degradation of the herbicide 2,6-dichlorobenzonitrile (dichlobenil). Degradation of dichlobenil and three potential metabolites: 2,6-dichlorobenzamide (BAM), 2,6-dichlorobenzoic acid (2,6-DCBA) and ortho-chlorobenzamide (OBAM) was studied in soils either previously exposed or not exposed to dichlobenil using a newly developed HPLC method. Dichlobenil was degraded in all four soils; BAM and 2,6-DCBA were only degraded in soils previously exposed to dichlobenil (100% within 35-56 days and 85-100% in 56 days, respectively), and OBAM in all four soils (25-33% removal in 48 days). BAM produced from dichlobenil was either hydrolyzed to 2,6-DCBA or dechlorinated to OBAM, which was further hydrolyzed to ortho-chlorobenzoic acid. BAM was rapidly mineralized in previously exposed soils only. All potential metabolites and the finding that BAM was a dead-end metabolite of dichlobenil in soils not previously exposed to dichlobenil needs to be included in risk assessments of the use of dichlobenil.     

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).     

Avoidance behaviour of Enchytraeus albidus: effects of benomyl, carbendazim, phenmedipham and different soil types

Enchytraeids are typical inhabitants of many soils, contributing to vital processes of this environmental compartment. Indirectly they are involved in regulating the degradation of organic matter, as well as improving the pore structure of the soil. Due to their behaviour, they are able to avoid unfavourable environmental conditions. Avoidance tests with enchytraeids, initially developed with earthworms by several authors, are quick and easy to perform. With these tests a first assessment of the toxicity of a (contaminated or spiked) soil is possible in just 48 h by using the reaction of the enchytraeids as measurement endpoint. In this period of time the organisms can choose between the control soil and the other soil (a contaminated or spiked or another soil with different physico-chemical properties). In the tests reported here, the enchytraeids were exposed to control soils spiked with the fungicides Benomyl and Carbendazim and the herbicide Phenmedipham. Several chemical concentrations were tested in order to evaluate the avoidance behaviour to toxic substances. In fact, often these short-term screening tests gave results showing avoidance at concentrations in a range similar to the acute test results but, higher than in chronic tests. Further tests are needed to decide whether the results gained in this study can be extrapolated to other chemicals. It is proposed to standardize the Enchytraeid Avoidance Test as it is currently done for the Earthworm Avoidance Test by the International Standard Organization (ISO).