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1.
In order to accurately predict the fate and behaviour of herbicides following application to hard surfaces, an understanding of the processes involved is required. Previous studies have demonstrated that herbicides with a low soil organic carbon partition coefficient (K(oc)) are preferentially removed from concrete and asphalt surfaces. It is possible, therefore, that sorption may play a role in retaining herbicides to hard surfaces. This study provides an indication of the extent to which herbicides may sorb to concrete and asphalt, and examines the results in the light of other research to identify the significance of sorption in describing herbicide losses after application. There was measurable sorption of herbicides to concrete and asphalt although this was limited compared with that to soils, especially for concrete. An exponential relationship between experimentally derived values of K(p) and literature values of K(oc) for asphalt was established (r(2) = 0.931); there was a weaker relationship for concrete (r(2) = 0.606). The experimentally derived K(p) values could be used to enhance the prediction of herbicide loss to receiving waters following application. It is probable that the fate of herbicides applied to concrete and asphalt surfaces depends more heavily on physical processes than is the case in soils.  相似文献   

2.
The kinetics of interaction with soil of three carbamate pesticides (I, II, III) used as nematicides and herbicides was studied at four different temperatures from solutions of six soil samples of Aligarh district. The values obtained for rate constants for adsorption and desorption were in good agreement with those obtained from the Lindstrom model, which proved useful in the simultaneous evaluation of adsorption (k1) and desorption (k2) rate constants. The rate constants for pesticides were in the order III > I > II on all the six soil samples. The data for rate constants, activation energies, heats of activation, entropy of activation and thermodynamic parameters indicated a partly physical and partly chemical adsorption of pesticide on the soil surfaces. Adsorption occurred via coordination and/or protonation of the exchangeable cations with the amidic carbonyl group, and hydrogen bonding and dipole association at the crystal edge and basal surfaces. The adsorptivity of the soils may be attributed to the organic matter content and percentage clay content.  相似文献   

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

4.
In vegetated filter strips (VFS) the presence of perennial vegetation, rhizodeposition of labile organic substrates and the accumulation of an organic residue thatch layer may enhance microbial numbers and activity, thereby increasing the potential for mineralisation of herbicides and herbicide metabolites retained during run-off events. The objective of this laboratory experiment was to compare the mineralisation of atrazine and metolachlor with that of their respective metabolites in VFS and cultivated soil. With the exception of total bacteria, propagule density of the microbial groups, endogenous soil enzymes and microbial diversity were higher in the VFS soil. This correlated with increased mineralisation of metolachlor and its metabolites in the VFS soil and indicates potential for VFS to curtail the subsequent transport of these compounds. In contrast, the mineralisation of atrazine and the majority of its metabolites was substantially reduced in VFS soil relative to cultivated soil. Consequently, the potential for subsequent transport of atrazine and many of its metabolites may be greater in VFS soil than in cultivated soil if reduced mineralisation is not offset by increased sorption in the VFS.  相似文献   

5.
Flumioxazin adsorption kinetics were described using a Greenville sandy clay loam soil. Adsorption kinetics experiments showed that 72% of total herbicide was absorbed after 1 h of continuous shaking and continued to increase to 78% after 72 h. Flumioxazin adsorption was then tested on seven agriculturally important soils throughout the southern USA. Adsorption isotherms for all soils had K(f) (Freundlich distribution coefficient) values that ranged from 8.8 to 0.4, with many near 1.5. Soil organic matter content was the parameter most highly correlated with flumioxazin adsorption (r(2) = 0.95, P < 0.001). Sorption to clay minerals had K(f) values ranging from 50 for bentonite to 4.7 for kaolinite. However, normalizing K(f) for sorbent surface area revealed that aluminum hydroxide (gibbsite) possessed the greatest flumioxazin sorption per unit area. Sorption to anionic exchange resin (K(f) 676) was greater than cationic exchange resin (K(f) 42). Molecular model calculations were performed to elucidate why sorption was greater to anionic exchangers. These calculations indicated that a region of dense electronegativity exists on the 3-dione moiety of the molecule. This would lead to greater flumioxazin sorption by positively charged surface sites. Desorption isotherms from soil exhibited no effect of hysteresis. Desorption from clay minerals was very rapid and flumioxazin in solution was undetectable after three desorption steps. From these data it was concluded that flumioxazin can become readily available in soil solution with increase in soil water content.  相似文献   

6.
Isoxaflutole, [4-(2-methanesulfonyl-4-trifluoromethylbenzoyl)-5-cyclopropyl isoxazole] is a relatively new pre-emergence herbicide which undergoes rapid conversion to a diketonitrile metabolite in soil. The half-life of isoxaflutole is very short but the half-life of diketonitrile is much longer and hence, diketonitrile remains for a extended period of time in soil. Sorption-desorption studies were conducted with five soils varying in physical and chemical properties. The batch equilibration technique was used for the sorption experiments, while completely mixed batch reactor systems with the decant and refill method was used for the desorption experiments. Four subsequent desorptions were examined after the sorption process in each soil with an equilibration period of seven days. An apparent sorption-desorption hysteresis was observed in all five soils. Organic matter content and the clay content of the soils were the two determining factors for hysteresis. In soils with high organic matter content, the sorption-desorption hysteresis was mainly governed by organic matter content, but in soils with low organic matter clay content played an important role. With the exception of the Chelsea soil, which had a very high organic matter content (57.4%), all other soils exhibited a high correlation between the clay content and hysteresis index (HI) values calculated at 0.75 ( r 2 = 0.960), 25 ( r 2 = 0.934) and 150 mg L−1 ( r 2 = 0.928). In conclusion, the potential for leaching through soil and crop injury due to isoxaflutole and its metabolite would decrease as soil organic matter and clay content increases.  相似文献   

7.
Pesticides in soil are subject to a number of processes that result in transformation and biodegradation, sorption to and desorption from soil components, and diffusion and leaching. Pesticides leaching through a soil profile will be exposed to changing environmental conditions as different horizons with distinct physical, chemical and biological properties are encountered. The many ways in which soil properties influence pesticide retention and degradation need to be addressed to allow accurate predictions of environmental fate and the potential for groundwater pollution. Degradation and sorption processes were investigated in a long-term (100 days) study of the chloroacetanilide herbicide, acetochlor. Soil cores were collected from a clay soil profile and samples taken from 0-30 cm (surface), 1.0-1.3 m (mid) and 2.7-3.0 m (deep) and treated with acetochlor (2.5, 1.25, 0.67 microg acetochlor g(-1) dry wt soil, respectively). In sterile and non-sterile conditions, acetochlor concentration in the aqueous phase declined rapidly from the surface and subsoil layers, predominantly through nonextractable residue (NER) formation on soil surfaces, but also through biodegradation and biotic transformation. Abiotic transformation was also evident in the sterile soils. Several metabolites were produced, including acetochlor-ethane sulphonic acid and acetochlor-oxanilic acid. Transformation was principally microbial in origin, as shown by the differences between non-sterile and sterile soils. NER formation increased rapidly over the first 21 days in all soils and was mainly associated with the macroaggregate (>2000 microm diameter) size fractions. It is likely that acetochlor is incorporated into the macroaggregates through oxidative coupling, as humification of particulate organic matter progresses. The dissipation (ie total loss of acetochlor) half-life values were 9.3 (surface), 12.3 (mid) and 12.6 days (deep) in the non-sterile soils, compared with 20.9 [surface], 23.5 [mid], and 24 days [deep] in the sterile soils, demonstrating the importance of microbially driven processes in the rapid dissipation of acetochlor in soil.  相似文献   

8.
The olive industry generates residues which can be applied as amendments to soils in their original form (olive cake) or after composting or vermicomposting processes. The addition, fresh or incubated, of these amendments to soil and of their different organic fractions was studied in relation to the sorption/desorption of three sulfonylurea herbicides, bensulfuron‐methyl, chlorsulfuron and prosulfuron. Herbicide sorption was low or very low, slightly promoted by the addition of the agricultural by‐products, especially olive cake, and mainly affected by pH of the soil solution, with the organic carbon content having no significant effect on herbicide retention. Desorption was only reduced when fresh olive cake was added. The incubation of soil and amendments for 3 months did not modify herbicide sorption, but made desorption reversible except for olive cake. The transformation of the organic matter of the amendments due to humification and maturity processes are likely to be responsible for this behaviour. Different organic fractions were removed to assess the influence of each fraction on sulfonylurea sorption. Only the removal of all studied organic fractions increased herbicide sorption, revealing the role of humin and mineral fractions in this process. Therefore, the use of organic amendments is not useful for reducing the risk of movement of ionisable molecules in soil.  相似文献   

9.
A model for the transport of pesticides in non-structured arable soil has been tested under field conditions. Three classes of sorption site are distinguished in the model. Sorption at class 1 sites is assumed to be at equilibrium whereas sorption at class 2 and class 3 sites is calculated using rate equations. Class 2 sites equilibrate on a time scale of days and class 3 sites equilibrate on a time scale of hundreds of days. In the model, the liquid phase is assumed to be homogeneous and completely mobile. The model was validated in two field experiments on a loamy sand soil using the herbicides cyanazine and metribuzin and using bromide ion as a tracer of liquid flow in soil. Ignoring sorption at class 3 sites resulted in large discrepancies between calculated and measured concentration profiles. Calculated concentration profiles were sensitive to the desorption rate constant for class 3 sites.  相似文献   

10.
It is shown that potentially persistent transformation products can be formed from the herbicides bromoxynil (3,5-dibromo-4-hydroxybenzonitrile) and ioxynil (3,5-diiodo-4-hydroxybenzonitrile), and possible leaching to groundwater is discussed. A similar process to the formation of BAM (2,6-dichlorobenzamide) from the herbicide dichlobenil (2,6-dichlorobenzonitrile) can be anticipated as bromoxynil and ioxynil are analogues of dichlobenil and they are degraded by the enzymes nitrilase, nitrile hydratase and amidase. A biodegradation study using cultured Variovorax sp. DSM 11402, a species commonly found in soil, demonstrated that ioxynil and bromoxynil were fully transformed into their corresponding amides in 2-5 days. These amides were not further degraded within 18 days, and formation of other degradation products was not observed. These results are in agreement with biodegradation experiments with dichlobenil. In soil, dichlobenil is transformed into its only observed degradation product BAM, which is persistent and mobile, and has been found in 19% of 5000 samples of Danish groundwater. Variovorax sp. is known to degrade the non-halogenated analogue benzamide, suggesting that degradation of the three amides may be hindered by the halogenated substituents (meta-Br; meta-I; ortho-Cl). This hypothesis is supported by QSAR modelling of fundamental properties. Using a new optimised liquid chromatography-tandem mass spectrometry (LC-MS/MS) method, the sorption and desorption properties of bromoxynil and ioxynil were characterised in sandy topsoil at four concentration levels. The estimated sorption coefficient K(d) was 1.4 L kg(-1) for bromoxynil and 5.4 L kg(-1) for ioxynil, indicating weak to moderate sorption to topsoil. Desorption of the herbicides showed that they were strongly and irreversible bound to the soil (K(des) > K(d)). The amount of herbicide desorbed depended on the initial concentration level. At low levels, K(des) values were higher, indicating stronger binding than at higher levels. The isocratic LC-MS/MS method developed for simultaneous detection of bromoxynil, ioxynil and their main degradation products is described. Using negative electrospray ionisation (ESI-), the detection limits were 0.4-1.0 microg L(-1), with relative standard deviations of 4-10% (n = 10) using direct injection without clean-up steps. The standard curves showed linearity in the range 5-100 microg L(-1) with r(2) > 0.992.  相似文献   

11.
12.
Herbicide movement in soils: principles, pathways and processes   总被引:3,自引:0,他引:3  
Carter 《Weed Research》2000,40(1):113-122
European legislation concerning ground- and surface-water quality and the protection of non-target organisms in surface-water from pesticide contamination has initiated more stringent data requirements from regulatory authorities concerning the movement of all pesticides in soils. Other interested parties, such as water companies, environment agencies and consumer-driven organizations, have sought to influence the use of herbicides and their impact on the environment. The resulting studies and associated research have led to a better understanding of the fate and behaviour of herbicides in the soil environment. The amount of herbicide that moves away from the area of application will depend on the physico-chemical properties of the chemical and the agroclimatic characteristics of the target site. Under average conditions, the amount of herbicide lost by movement from a soil profile is typically <0.1% to 1% of the applied mass but, under certain localized circumstances, can reach up to 5% or greater. Leaching, drain-flow and surface run-off are the main pathways responsible for herbicide movement within soils. The soil/herbicide processes determining the losses are also variable in both time and space. It is therefore necessary to understand the spatial characteristics of soils, their hydrology and the associated herbicide use patterns.  相似文献   

13.
The spatial variability in mineralization of atrazine, isoproturon and metamitron in soil and subsoil samples taken from a 135-ha catchment in north France was studied. Fifty-one samples from the top layer were taken to represent exhaustively the 31 agricultural fields and 21 soil types of the catchment. Sixteen additional samples were collected between depths of 0.7 and 10 m to represent the major geological materials encountered in the vadose zone of the catchment. All these samples were incubated with 14C-labelled atrazine under laboratory conditions at 28 degrees C. Fourteen selected surface samples which exhibited distinctly different behaviour for atrazine dissipation (including sorption and mineralization) were incubated with 14C-isoproturon and 14C-metamitron. Overall soil microbial activity and specific herbicide degradation activities were monitored during the incubations through measurements of total carbon dioxide and 14C-carbon dioxide respectively. At the end of the incubations, extractable and non-extractable (bound) residues remaining in soils were measured. Variability of herbicide dissipation half-life in soil surface samples was lower for atrazine and metamitron (CV < 12%) than for isoproturon (CV = 46%). The main contributor to the isoproturon dissipation variability was the variability of the extractable residues. For the other herbicides, spatial variability was mainly related to the variability of their mineralization. In all cases, herbicide mineralization half-lives showed higher variability than those of dissipation. Sorption or physicochemical soil properties could not explain atrazine and isoproturon degradation, whose main factors were probably directly related to the dynamics of the specific microbial degradation activity. In contrast, variability of metamitron degradation was significantly correlated to sorption coefficient (K(d)) through correlation with the sorptive soil components, organic matter and clay. Herbicide degradation decreased with depth as did the overall microbial activity. Atrazine mineralization activity was found down to a depth of 2.5 m; beyond that, it was negligible.  相似文献   

14.
The adsorption of diuron and isoproturon by a clay loam soil at 35% (3-16 kPa) and 62% (1 kPa) soil moisture content was studied by means of glass microfibre filters capable of sampling soil solution for herbicide analysis. Adsorption was rapid, with 40–80% of the final (24 h) sorption being achieved within 2 min. These equilibria were achieved more rapidly for diuron, which was also the more highly adsorbed. Adsorption of both herbicides was favoured by low soil moisture initially, but was enhanced by higher soil moistures at sorption times greater than 30 min. However, increasing the soil moisture from 31% (10 kPa) to 62% (1 kPa) had little effect on the final soil sorption capacity. Regarding the water status in the soil, it is thought that adsorption took place in small pores (<3 μm). Herbicides diffused rapidly into small pores and adsorption by wet soil was delayed for a short period of time (about 30 min).  相似文献   

15.
The Root Zone Water Quality Model (RZWQM) is a one-dimensional, numerical model for simulating water movement and chemical transport under a variety of management and weather scenarios at the field scale. The pesticide module of RZWQM includes detailed algorithms that describe the complex interactions between pesticides and the environment. We have simulated a range of situations with RZWQM, including foliar interception and washoff of a multiply applied insecticide (chlorpyrifos) to growing corn, and herbicides (alachlor, atrazine, flumetsulam) with pH-dependent soil sorption, to examine whether the model appears to generate reasonable results. The model was also tested using chlorpyrifos and flumetsulam for the sensitivity of its predictions of chemical fate and water and pesticide runoff to various input parameters. The model appears to generate reasonable representations of the fate and partitioning of surface- and foliar-applied chemicals, and the sorption of weakly acidic or basic pesticides, processes that are becoming increasingly important for describing adequately the environmental behavior of newer pesticides. However, the kinetic sorption algorithms for charged pesticides appear to be faulty. Of the 29 parameters and variables analyzed, chlorpyrifos half-life, the Freundlich adsorption exponent, the fraction of kinetic sorption sites, air temperature, soil bulk density, soil-water content at 33 kPa suction head and rainfall were most sensitive for predictions of chlorpyrifos residues in soil. The latter three inputs and the saturated hydraulic conductivity of the soil and surface crusts were most sensitive for predictions of surface water runoff and water-phase loss of chlorpyrifos. In addition, predictions of flumetsulam (a weak acid) runoff and dynamics in soil were sensitive to the Freundlich equilibrium adsorption constant, soil pH and its dissociation coefficient.  相似文献   

16.
BACKGROUND: Variations in soil properties with depth influence retention and degradation of pesticides. Understanding how soil properties within a profile affect pesticide retention and degradation will result in more accurate prediction by simulation models of pesticide fate and potential groundwater contamination. Metolachlor is more persistent than other acetanilide herbicides in the soil environment and has the potential to leach into groundwater. Reasonably, information is needed about the dissipation and eventual fate of metolachlor in subsoils. The objectives were to evaluate the adsorption and desorption characteristics and to determine the dissipation rates of metolachlor in both surface and subsurface soil samples. RESULTS: Adsorption of metolachlor was greater in the high‐organic‐matter surface soil than in subsoils. Lower adsorption distribution coefficient (Kads) values with increasing depth indicated less adsorption at lower depths and greater leaching potential of metolachlor after passage through the surface horizon. Desorption of metolachlor showed hysteresis, indicated by the higher adsorption slope (1/nads) compared with the desorption slope (1/ndes). Soils that adsorbed more metolachlor also desorbed less metolachlor. Metolachlor dissipation rates generally decreased with increasing soil depth. The first‐order dissipation rate was highest at the 0–50 cm depth (0.140 week?1) and lowest at the 350–425 cm depth (0.005 week?1). Degradation of the herbicide was significantly correlated with microbial activity in soils. CONCLUSION: Metolachlor that has escaped degradation or binding to organic matter at the soil surface might leach into the subsurface soil where it will dissipate slowly and be subject to transport to groundwater. Copyright © 2009 Society of Chemical Industry  相似文献   

17.
Two wild oat herbicides, benzoylprop-ethyl and flamprop-methyl were administered to lactating cows at low dose levels (0.3–3.0 mg/kg in total diet) and the excretion of total metabolites in milk, urine and faeces was measured. Total residues in tissues were also determined. Similarly a third and related herbicide flamprop-isopropyl was fed to cows, pigs and hens (at 0.5 mg/kg in total diet) and the residues were determined in excreta and tissues, including eggs. The amounts of the compounds fed were equivalent to approximately 10–300 times the total residue found in cereal treated in the field. Residues in milk in most cases were well below 0.001 mg/kg; in muscle samples <0.003 mg/kg; and in eggs, 0.0008 mg/kg, decreasing by 50% in approximately 3 days to 0.0001 mg/kg 4 days after the termination of treatment. Elimination of the herbicides from the animals was rapid in every case and this, together with the low residue levels, was attributed to very efficient metabolic de-esterification to the parent carboxylic acid metabolites (benzoylprop and flamprop). These metabolites possess physical properties ideally suited for excretion via the kidneys and bile into urine and faeces and, conversely, unsuited for transport into milk and eggs.  相似文献   

18.
The correct application of a new herbicide depends on knowledge concerning its behaviour within the cultivation system. The objective of this study was to evaluate the sorption–desorption process of aminocyclopyrachlor in soils with the addition of three aged organic materials from sugar cane and their transport via leaching. Sugar cane straw (12 t/ha), filter cake (90 t/ha) and vinasse (200 m3/ha) were added to a clayey soil 15, 30 and 60 days before herbicide application. Sorption and desorption were evaluated by the batch equilibrium method. For leaching assessments, the materials were applied to the soil surface. Sorption was relatively low in all treatments (Kd = 0.17–0.41 L/kg), although significantly higher in soil without organic material addition. A negative correlation between herbicide sorption and increased soil base saturation was observed, indicating competition for sorption sites. With the addition of vinasse, 71% of the herbicide reached the leachate, while <50% reached the leachate in the other treatments. Aminocyclopyrachlor availability was not reduced with organic material addition to the soil, which may be favourable for weed control. However, the presence of vinasse leads to the risk of leaching to deeper soil layers than the seed bank.  相似文献   

19.
BACKGROUND: Sorption‐desorption processes govern the movement of pesticides in soil. These processes determine the potential hazard of the pesticide in a given environment for groundwater contamination and need to be investigated. RESULTS: In the present study, sorption‐desorption processes of benfuracarb were investigated using a batch method in two mollisols. The kinetics of benfuracarb sorption in mollisols conformed to two‐compartment (1 + 1) first‐order kinetics. The fast sorption rate constant was about 3 times higher for silt loam than for loam soil. However, the slow sorption rate constants were statistically similar for both soils. The concentration‐dependent sorption‐desorption isotherms of benfuracarb could not closely conform to the Freundlich isotherm in mollisols of high organic C content. The computed values of both the sorption (log K) and desorption (log K′) capacities were higher for silt loam than for loam soil. The desorption index (n′/n) values in the range 30.0–41.3 indicated poor reversibility of sorbed benfuracarb in mollisols. CONCLUSION: In view of the strong sorption of benfuracarb in mollisols with only partial desorption, the possibility of the leaching of soil‐applied benfuracarb to contaminate groundwaters appears to be low. Copyright © 2010 Society of Chemical Industry  相似文献   

20.
手性除草剂研究进展   总被引:2,自引:0,他引:2  
以几大类已经商品化或具有较好市场前景的手性除草剂为对象,综述了各除草剂的除草活性、对非靶标生物的毒性及其在环境迁移中的对映异构体选择性现象及机理的研究成果。由于对映异构体间的生物学性质迥异,因此,手性除草剂对映异构体的活性、作用机理、代谢转化及其在生物体内的转移等都具有手性选择性差异。同时,手性除草剂对植物的选择性作用还会因作用对象及环境因素的改变而改变,其在环境中的选择性降解情况也十分复杂,不仅与该除草剂自身的理化性质有关,还与其所处的环境因素有关,诸如土壤类型、植物种类、微生物群落结构、温度、pH值等均会改变手性除草剂对映异构体的环境归趋。  相似文献   

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