Spatial variability in herbicide degradation in the subsurface environment of a groundwater protection zone

The aim of this study was to investigate the spatial variability in degradation and mineralization of atrazine and isoproturon in subsurface samples taken from sandy loam soils overlying gravel terraces which form part of a groundwater protection zone. Percussion drilling was used to obtain samples from 11 boreholes (maximum depth 3 m). Unlabelled atrazine or isoproturon, and ring-14C-labelled atrazine or isoproturon were added to samples, incubated at 25 degrees C for up to 16 weeks, and analyzed for the residual herbicide or [14C]carbon dioxide. All samples showed the potential to degrade these herbicides, although the percentage degradation decreased by a factor of 2-3 from the surface soil to a depth of 3 m. This was associated with a decrease in organic matter content, but there was no change in the potential to mineralize acetate, indicating that specific changes in the catabolic ability of the microbial population occurred with depth. The capacity of samples to mineralize atrazine and isoproturon to carbon dioxide decreased markedly with depth, with no mineralization potential observed at a depth of 80 cm.     

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.     

Degradation of atrazine and isoproturon in surface and sub-surface soil materials undergoing different moisture and aeration conditions

The influence of different moisture and aeration conditions on the degradation of atrazine and isoproturon was investigated in environmental samples aseptically collected from surface and sub-surface zones of agricultural land. The materials were maintained at two moisture contents corresponding to just above field capacity or 90% of field capacity. Another two groups of samples were adjusted with water to above field capacity, and, at zero time, exposed to drying-rewetting cycles. Atrazine was more persistent (t(1/2) = 22-35 days) than isoproturon (t(1/2) = 5-17 days) in samples maintained at constant moisture conditions. The rate of degradation for both herbicides was higher in samples maintained at a moisture content of 90% of field capacity than in samples with higher moisture contents. The reduction in moisture content in samples undergoing desiccation from above field capacity to much lower than field capacity enhanced the degradation of isoproturon (t(1/2) = 9-12 days) but reduced the rate of atrazine degradation (t(1/2) = 23-35 days). This demonstrates the variability between different micro-organisms in their susceptibility to desiccation. Under anaerobic conditions generated in anaerobic jars, atrazine degraded much more rapidly than isoproturon in materials taken from three soil profiles (0-250 cm depth). It is suggested that some specific micro-organisms are able to survive and degrade herbicide under severe conditions of desiccation.     

The ability of indigenous micro-organisms to degrade isoproturon, atrazine and mecoprop within aerobic UK aquifer systems

The potential for the herbicides isoproturon, atrazine and mecoprop to degrade in the major UK aquifers of chalk, sandstone and limestone was studied using laboratory microcosms spiked at 100 microg litre(-1). Significant mecoprop degradation was only observed in sandstone groundwater samples. Atrazine transformation, based on the formation of metabolites, did occur in most groundwater samples, but only at a rate of 1-3% per year. A potential to degrade isoproturon was observed in groundwater samples from each of the aquifer types, with the most rapid and consistent degradation occurring at the sandstone field site. Biodegradation was confirmed by the formation of monodesmethyl- and didesmethyl-isoproturon. Isoproturon degradation potential rates obtained from the groundwater microcosms could not be correlated with either dissolved organic carbon or numbers of bacteria in the groundwater. It was noted that the ability of the groundwater at a field site to degrade a pesticide was not related to performance of the soil above.     

Microbial aspects of atrazine biodegradation in relation to history of soil treatment

Among 15 soils with different cropping practices, seven which had an history of repeated atrazine applications showed accelerated degradation of this herbicide. By contrast, grassland or agricultural soils with no recorded atrazine application, at least for the last three years, had a low degradation potential. No direct relation was found between the rate of atrazine mineralisation and the size of the microbial biomass. In adapted soils, the amounts of extractable residues were lowered and the very high percentages of radioactivity from [ring-¹⁴C]atrazine recovered as [¹⁴C]carbon dioxide demonstrated that N-dealkylation and deamidation were the only processes for micro-organisms to derive carbon and energy for heterotrophic growth. Kinetics of microbial ¹⁴C accumulation revealed that atrazine ring carbon could be incorporated by direct oxidative condensation with structural components of the bacterial or fungal cell whereas side-chain carbon was preferentially used for biosynthesis of new protoplasmic cell material, as confirmed by the high turnover rate of radiolabelled microbial components. From the determination of the Michaelis–Menten parameters, V_m and K_m in the presence of different selective biocides, it was possible to conclude that fungi were probably less active in atrazine degradation than bacteria and that over years the microbial atrazine-degrading community showed an increased efficiency. © 1999 Society of Chemical Industry     

Variation of pesticide sorption isotherm in soil at the catchment scale

The variation of the sorption isotherm of pesticides has seldom been explored at the catchment scale. Such a study was conducted at the scale of a 187-ha agricultural catchment for three herbicides: atrazine, isoproturon and metamitron. Partition coefficient (Kd) values were measured in batch experiments on 51 topsoil samples, and showed moderate variability at the catchment scale (coefficient of variation CV approximately 30%). Values of Kd ranged from 0.47 to 1.70 litre kg(-1) for atrazine, 0.47 to 1.81 for isoproturon, and 0.55 to 2.21 for metamitron. A clustering method was used to reduce the number of samples on which to measure sorption isotherms to 14. Sorption isotherms agreed with the Freundlich rather than the linear model. Kf parameters had CV values similar to those for Kd, with values ranging from 0.78 to 2.13 mg(1 - Nf) litre(Nf) kg(-1) for atrazine, 0.61 to 1.82 for isoproturon, and 0.69 and 2.58 for metamitron. Nf exponents showed little variation (CV < 5%). Nf values were between 0.86 and 0.98 for atrazine, 0.85 and 0.90 for isoproturon, and 0.82 and 0.87 for metamitron. More than 97% of the Kf catchment-scale variations could be explained by the variations of the soil organic carbon content.     

Effect of recent cropping history and herbicide use on the degradation rates of isoproturon in soils

Five soil samples were taken from each of five fields with different crop management histories. Three of the fields were in an arable rotation, the fourth field was temporary grassland, and the final field was under permanent grass. Of the three arable fields, two had been cropped with winter wheat in three of the preceding 6 years, and the third had last been cropped with winter wheat once only, 6 years previously. With one exception, the winter wheat had been sprayed with the herbicide isoproturon. The rate of isoproturon degradation in laboratory incubations was strongly related to the previous management practices. In the five soils from the field that had been treated most regularly with isoproturon in recent years, <2.5% of the initial dose remained after 14 days, indicating considerable enhancement of degradation. In the soils from the field with two applications of the herbicide in the past 6 years, residues after 27 days varied from 5% to 37% of the amount applied. In soils from the other three sites, residue levels were less variable, and were inversely related to microbial biomass. In studies with selected soils from the field that had received three applications of isoproturon in the previous 6 years, kinetics of degradation were not first‐order but were indicative of microbial adaptation, and the average time to 50% loss of the herbicide (DT₅₀) was 7.5 days. In selected soils from the field that had received just one application of isoproturon, degradation followed first‐order kinetics, indicative of cometabolism. Pre‐incubation of isoproturon in soil from the five fields led to significant enhancement of degradation only in the samples from the two fields that had a recent history of isoproturon application.     

Adsorption and degradation of chlorsulfuron and metsulfuron-methyl in soils from different depths

Adsorption and degradation rates of chlorsulfuron and metsulfuron-methyl were measured in soil taken from depths of 0–20, 20–40 and 40–60 cm at eight sites. Adsorption of both herbicides was negatively correlated with soil pH, and positively correlated with soil organic matter content. When two soils with very high organic matter were excluded from the calculations, the correlations with organic matter content were no longer statistically significant but those with soil pH were affected only slightly. Degradation rates of both herbicides generally decreased with increasing depth in the soil and were positively correlated with microbial biomass and negatively correlated with soil pH. The possible significance of the results to persistence of the herbicides in the field is discussed.     

Rapid dissipation of atrazine in soils taken from various maize fields

A laboratory study was carried out in order to measure the degradation rate of atrazine in 36 different soils taken from maize ( Zea mays L.) fields in Belgium. These soils differed in their alrazme treatment histories. pH. organic matter content and type of organic and mineral fertili-zation, Half-lives of less than 10 days were found in more than 60% of the soils sampled. This rapid dissipation could be linked in a significant way to repeated pretreaiments with atrazine (intensive maize cropping) as well as to higher pH values (from neutral to alkaline), A low organic matter content might also be a factor explaining the rapid degradation of atrazine. but to a lesser extent than the first two factors. On the other hand mineral fertilization was shown to slow down atrazine dissipation. It is hypothesized that repeated treatments of atrazine cause a mi-crobial adaptation to atrazine degradation and that acidic soil conditions impede this adaptation. To date, this is the first time that evidence for widespread accelerated degradation of atrazine has been reported.     

Pesticide adsorption in the vadose zone: a case study on Eocene and Quaternary materials in Northern France

We present a set of adsorption coefficients measured on various Eocene and Quaternary materials sampled from the vadose zone of a catchment in Northern France for three herbicides, atrazine, isoproturon and metamitron. Some vadose zone materials were found to have higher adsorption coefficients than the topsoil. The adsorption coefficients were strongly dependent on the clay content of the material. From 83% to 97% of the variability in the adsorption coefficients could be explained by a linear relationship to the clay content. Adsorption coefficients normalized for clay content, Kclay, ranged between 1.6 and 17.6 litre kg(-1) for atrazine. Neglecting the adsorption properties of the vadose zone and relying exclusively on Koc values to predict mobility may bias regional or local risk assessment of groundwater contamination by pesticides. More information on the adsorption properties of geological materials should be collected to improve our ability to predict pesticide concentrations in groundwaters.     

Atrazine behaviour in the different pedological horizons of two Argentinean non-till soil profiles

Atrazine behaviour was investigated in the different pedological horizons from profiles of two non-tilled soils, a Typic Argiustoll and an Entic Haplustoll from the Argentinean pampas. As atrazine use in field conditions was associated with maize cropping, only one type of soil received atrazine every other year. Atrazine behaviour was characterized through the balance of ¹⁴C-U-ring atrazine radioactivity among the mineralized fraction, the extractable fraction and the non-extractable bound residues. The composition of the extractable fraction was characterized. Atrazine mineralization was the main dissipation mechanism in the superficial horizon of the Argiustoll because of microbial adaptation after repeated atrazine applications. In contrast, little atrazine mineralization was found in the Haplustoll profile, and it decreased with depth. The capacity of the soil organic matter to form bound residues was characterized using soil-size fractionation. Atrazine-bound residues depended on the soil organic matter content and the size of the fraction. Organic matter in the largest size fractions had a higher capacity to form atrazine-bound residues. In the Argiustoll profile, the atrazine degradation capacity decreased in the subsurface horizons (Bt₁ and Bt₂), where a large part of bound residues were formed. The deepest horizon (BC) of this profile had a high capacity to degrade atrazine reaching this horizon after a lag period. In the Haplustoll profile, atrazine mineralization and bound residue formation followed the organic carbon mineralization pattern.     

Enhanced degradation of some soil-applied herbicides

In a field experiment involving repeated herbicide application, persistence of simazine was not affected by up to three previous doses of the herbicide. With propyzamide, there was a trend to more rapid rates of degradation with increasing number of previous treatments. Persistence of linuron and alachlor was affected only slightly by prior applications. In a laboratory incubation with soil from the field that had received four doses of the appropriate herbicide over a 12–month period, there was again no effect from simazine pretreatments on rates of loss. However, propyzamide, linuron and alachlor all degraded more rapidly in the previously treated than in similar untreated soil samples. Propyzamide, linuron, alachlor and napropamide degradation rates were all enhanced by a single pretreatment of soil in laboratory incubations, whereas degradation rates of isoproturon, metazachlor, atrazine and simazine were the same in pretreated and control soil samples.     

The interaction between planting depth of four winter wheat cultivars, Alopecurus myosuroides Huds. and Bromus sterilis L. and their susceptibility to post-emergence applications of isoproturon and chlorotoluron

Seeds of four winter wheat cultivars, Slejpner, Galahad, Avalon and Penman, were sown at depths ranging from 6–75 mm in soil in pots, and isoproturon or chlorotoluron was then applied to the soil surface. For chlorotoluron-treated plants (both pre- and post-emergence) the dose required to produce a 50% effect (ED₅₀) was unaffected by depth of planting. In contrast, for isoproturon applied pre-emergence, the ED₅₀ for both Avalon and Slejpner was strongly affected by sowing depth. Although chlorotoluron was much more active in a second experiment when applied post-emergence to Slejpner wheat, the ED₅₀ for both herbicides increased with greater depth of sowing. Protection of wheat from isoproturon damage by deeper planting was enhanced if the adsorption capacity of the soil was raised from K_d 0.5 to 2.0 by incorporation of activated charcoal in the soil. Isoproturon entry into plants (as measured by the effect on rate of photosynthesis) was slower in those that had been sown deeper and were growing in more adsorptive soils, but there was no obvious relationship between these observations and isoproturon distribution in the soil profile. In nutrient culture the four wheat cultivars responded similarly to a range of doses of isoproturon. The chlorotoluron-sensitive cultivars, Slejpner and Galahad, were damaged by much lower doses of chlorotoluron than were Avalon and Penman. Bromus sterilis L. responded similarly to wheat with regard to its interaction with isoproturon and planting depth. Alopecurus myosuroides Huds., however, was less damaged by isoproturon when the zone above the seed was protected from the herbicide by growing the shoot through a plastic straw.     

Effect of cropping cycles and repeated herbicide applications on the degradation of diclofop-methyl, bentazone, diuron, isoproturon and pendimethalin in soil

A greenhouse study was conducted to investigate the ability of four crops (wheat, corn, oilseed rape and soybean) to influence the degradation of bentazone, diclofop-methyl, diuron, isoproturon and pendimethalin in soil. The present study showed that microbial biomass-carbon was significantly higher in planted soils than in bulk soil, especially with wheat and corn, after several cropping cycles. The biomass in corn and soybean planted soils was adversely affected by bentazone but recovered after three cropping cycles. In wheat-planted soils, diclofop-methyl application resulted in persistent increase of the amount of microbial biomass. Bentazone did not show accelerated degradation even after five successive treatments, differing from diclofop-methyl, for which two applications were sufficient to enhance significantly its rate of degradation. Enhanced degradation of diclofop-methyl was even more pronounced in wheat-planted soil. The rates of mineralisation of diuron, isoproturon and pendimethalin were not affected after the first cropping cycle, but were significantly increased in planted soils after five cropping cycles. The results confirm that plants may promote pesticide degradation in soil by stimulating biodegradation processes. In the case of diclofop-methyl, stimulation of accelerated degradation was observed.     

Accelerated Degradation and Mineralization of Atrazine in Surface and Subsurface Soil Materials

In surface soils, atrazine is considered to be a moderately persistent herbicide, with half-lives ranging generally from one to two months. In subsoils, however, its degradation is generally slower. This paper reports the degradation of atrazine in soil and subsoil samples taken from six Belgian maize fields. Rapid degradation can take place in some samples taken from surface and in some from subsurface soils. Subsoil samples were found to degrade atrazine either very strongly or not at all. Experiments with [ring-U-¹⁴C] atrazine showed that the micro-organisms responsible for the rapid degradation cleave the triazine ring and extensively mineralize the molecule. © 1997 SCI.     

Variation in soil organic matter accumulation and metabolic activity along an elevation gradient in the Santa Rosa Mountains of Southern California,USA

Variations in soil organic matter accumulation across an elevation can be used to explain the control of substrate supply and variability on soil metabolic activity. We investigated geographic changes in soil organic matter and metabolic rates along an elevation gradient(289–2,489 m) in the Santa Rosa Mountains, California, USA from subalpine and montane pine forests through chaparral to desert. From base(289 m) to summit(2,489 m), 24 sites were established for collecting soil samples under canopies and inter-canopy spaces, at 0–5 and 5–15 cm soil depths increments. Soil organic matter(SOM) content was determined using weight loss on ignition at 550°C and soil CO2 efflux(R) was measured at day 5(R5) and day 20(R20) of incubation. Changes in SOM content along the elevation gradient showed a significant relationship(P0.05) but R5 and R20 were not related to either elevation or SOM content. However, the ratio of R and SOM(R5/SOM) showed a strong relationship across the mountains at both soil depths. R5/SOM, as an indicator of carbon use efficiency, may be applicable to other semi-arid transects at larger scale modeling of soil metabolic processes.     

INTERACTION BETWEEN PARAQUAT AND MICROBES IN SOILS*

Summary. Laboratory experiments were conducted to determine if paraquat had any effect on soil micro-organisms and consequently on soil fertility. Numbers of bacteria and moulds tended to increase with incubation time as residual paraquat decreased. Lag periods of 1–5 days were observed in the development of soil microflora and concomitant degradation of paraquat. Under controlled culture conditions, Aerobacter aerogenes, Agrobacterium tumefaciens, Pseudomonas fluorescens and Bacillus cereus were able to utilize paraquat as sole carbon and nitrogen sources in synthetic media. Paraquat at 0–25, 0–5, 2–5 and 25 ppm cation was added to four different soils to study changes in microbial activities concomitant with decreases in herbicide concentration. Analytical recoveries were correlated inversely with clay mineral content, cation-exchange capacity and organic matter. Mineralization of peptone nitrogen by amnnonification and nitrification was stimulated by 0–25 ppm; higher rates up to 25 ppm had little influence. A bimodal effect or growth inversion was observed in several instances, with increased microbial development at intermediate concentrations. Paraquat at recommended field rates appeared to have no appreciable influence on general microbial activities of importance to soil fertility. Interaction entre U paraquat et les microbes dans les sols     

Capacity of model biobeds to retain and degrade mecoprop and isoproturon

Biobeds are used to increase the adsorption and degradation of pesticide spillage on sites used for mixing and loading and for cleaning of sprayers. The adsorption and the rate of degradation of 14C-labelled isoproturon and mecoprop (MCPP) at concentrations from 0.0005 to 25 000 mgkg(-1) were determined in biobed soil. Further leaching of the two herbicides was determined in a model biobed with a surface area of 2 m2. The biobed material showed enhanced ability to adsorb the two herbicides. Kd was 5.2 litre kg(-1) for isoproturon and 1.6 litre kg(-1) for MCPP in biobed material, which is higher than in natural soil. In different experiments with natural soil, Kd ranges from 0.07 to 0.6 litrekg(-1) for MCPP and from 1.5 to 4.6 litre kg(-1) for isoproturon in soils with varying organic carbon content. Degradation of MCPP was rapid at concentrations from 0.0005 to 500 mg kg(-1), delayed at 5000 mg kg(-1), and very slow at 25 000 mg kg(-1). For isoproturon, the relative degradation was most rapid at the lowest concentration and decreasing with increasing concentrations. After 120 days, between 55% and 8% 14C was evolved as 14CO2 at concentrations between 0.0005 and 25 000 mg kg(-1). The rate of evolution of 14CO2 indicated that degradation rates at low concentrations were of first-order and at higher concentrations of zero-order. Leaching of MCPP and isoproturon was determined in a newly established model biobed during a 2-year period. About 13% of applied MCPP and 1.4% of applied isoproturon leached out during the winter following the first autumn application (worst-case scenario). Leaching was completely prevented when the biobed had a well-developed grass cover and was covered during the winter.     

Adsorption,desorption and dissipation of metolachlor in surface and subsurface soils

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 (K_ads) 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/n_ads) compared with the desorption slope (1/n_des). 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