Herbicide sorption to concrete and asphalt

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.     

Kinetics of interaction of three carbamate pesticides with Indian soils: Aligarh district

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.     

Adsorption and degradation of four acidic herbicides in soils from southern Spain

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.     

Mineralisation of atrazine, metolachlor and their respective metabolites in vegetated filter strip and cultivated soil

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.     

Sorption and desorption of flumioxazin to soil, clay minerals and ion-exchange resin

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.     

Effect of soil physical and chemical properties on the sorption-desorption hysteresis of the diketonitrile metabolite of isoxaflutole

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.     

Influence of Soil Moisture on Long-Term Sorption of Diuron and Isoproturon by Soil

Long-term sorption of diuron and isoproturon by a clay loam soil was investigated for nine weeks at two herbicide doses (0·6 or 3 mg kg⁻¹) and two soil moisture contents (35 or 62% w/w, i.e. 3·16 or 1 kPa) by measuring changes in herbicide concentrations in the soil solution sampled by means of glass microfibre filters in presence of sodium azide (200 mg litre⁻¹) which inhibited biodegradation for more than four weeks. After the first day equilibration period, where adsorption mainly occurred (>70% adsorbed), herbicide concentrations in the soil solution decreased (about 50% for diuron; up to 38% for isoproturon) for two weeks but equilibration required about one month. Small amounts of herbicides were sorbed during this process (<10% of the initial (24-h) adsorption). These were similar for both herbicides, although diuron was initially more adsorbed. Values of the partition coefficients of herbicides between soil and soil solution were increased (75–125% for diuron; 29–67% for isoproturon). High soil moisture enhanced sorption speed for both herbicides and increased final sorption only for diuron. Sodium azide inhibited long-term sorption of the more stable diuron and this effect was reversed by low temperature only at the low soil moisture. Sodium azide action might be complex (competition, effect on soil micro-organisms) and was not elucidated.     

Dissipation of acetochlor and its distribution in surface and sub-surface soil fractions during laboratory incubations

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.     

Sorption/desorption behaviour of sulfonylurea herbicides as affected by the addition of fresh and composted olive cake to soil

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.     

Field test of a mathematical model for non-equilibrium transport of pesticides in soil

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.     

Demonstrating formation of potentially persistent transformation products from the herbicides bromoxynil and ioxynil using liquid chromatography-tandem mass spectrometry (LC-MS/MS)

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.     

Herbicide movement in soils: principles, pathways and processes

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.     

Spatial variability in 14C-herbicide degradation in surface and subsurface soils

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.     

Desorption of diuron and isoproturon from undispersed clay loam soil

Studies were conducted to investigate the desorption of diuron and isoproturon adsorbed on undispersed clay loam soil, and the influence of residence time in soil on desorption. The soil was treated at 0·6 or 3 mg kg^-1, at 70% moisture content and in the presence of sodium azide to prevent degradation. Measurement of herbicide concentrations in soil solution sampled by means of glass microfibre filters showed that adsorption mainly occurred for one day but long-term sorption proceeded for >two weeks. After a one-day or three-week residence time, soil solution was partly replaced (28%). Measurement of concentrations in solution showed rapid desorption, with equilibria being achieved within 1 h (diuron) or a few hours (isoproturon). After 16 successive desorptions done at 30-min or 12-h intervals, equilibration times tended to be longer. For the short residence time, desorption and long-term sorption could occur simultaneously and equilibration might be faster. Residence time had no significant effect on desorption kinetics nor on the small hysteresis observed for diuron. The aging effect, involving long-term sorption only, decreased the proportion of diuron removed from the soil by successive desorptions but, for isoproturon, desorption frequency and desorption kinetics were more important. © 1997 SCI     

A Field Test of Root Zone Water Quality Model—Pesticide and Bromide Behavior

The Root Zone Water Quality Model (RZWQM) is a process-based model developed recently by USDA–ARS scientists. The model integrates physical, chemical and biological processes to simulate the fate and movement of water and agrochemicals over and through the root zone at a representative point in a field with various management practices. The model was evaluated using field data for the movement of water and bromide, and the transformation and transport of cyanazine and metribuzin in the soil profile. The model reasonably simulated soil water and bromide movement. Pesticide persistence was predicted reasonably well using a two-site sorption model that assumes a rate-limited (i.e. long-term) adsorption–desorption process with the additional assumption of negligible degradation of inter-aggregate adsorbed pesticides.     

Influence of soil moisture on short-term adsorption of diuron and isoproturon by soil

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).     

Mobility and persistence of four herbicides in soil of a South Australian vineyard

The use of persistent herbicides has increased the potential for contamination of soil, soil water and groundwater. The mobility, dissipation and fate of four herbicides, norflurazon, oxadiazon, oxyfluorfen and trifluralin, used in South Australian viticulture, have been studied in a typical sand‐over‐clay vineyard soil. Following herbicide application at field rates to plots up‐slope of miniature lysimeters, surface soil and soil water were sampled regularly over the period of annual rainfall. The concentration of each herbicide in the soil cores, surface soil and soil water was determined by GLC‐NPD following solid‐phase concentration procedures where necessary. Oxadiazon dissipated more quickly than the other three herbicides in the soil. Norflurazon was the most mobile of these herbicides in this soil. However all four herbicides were found in the soil water within the first year, though only norflurazon was found in the soil water in the subsequent year. Norflurazon moved laterally to a greater extent than the other herbicides. © 2000 Society of Chemical Industry     

The pesticide module of the Root Zone Water Quality Model (RZWQM): testing and sensitivity analysis of selected algorithms for pesticide fate and surface runoff

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.     

Excretion and residues of the herbicides benzoylprop-ethyl flamprop-isopropyl and flamprop-methyl in cows,pigs and hens

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.