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.     

Diuron mineralisation in a Mediterranean vineyard soil: impact of moisture content and temperature

BACKGROUND: The diuron‐mineralising ability of the microbiota of a Mediterranean vineyard soil exposed each year to this herbicide was measured. The impact of soil moisture and temperature on this microbial activity was assessed. RESULTS: The soil microbiota was shown to mineralise diuron. This mineralising activity was positively correlated with soil moisture content, being negligible at 5% and more than 30% at 20% soil moisture content. According to a double Gaussian model applied to fit the dataset, the optimum temperature/soil moisture conditions were 27.9 °C/19.3% for maximum mineralisation rate and 21.9 °C/18.3% for maximum percentage mineralisation. The impact of temperature and soil moisture content variations on diuron mineralisation was estimated. A simulated drought period had a suppressive effect on subsequent diuron mineralisation. This drought effect was more marked when higher temperatures were used to dry (40 °C versus 28 °C) or incubate (28 °C versus 20 °C) the soil. The diuron kinetic parameters measured after drought conditions were no longer in accordance with those estimated by the Gaussian model. CONCLUSION: Although soil microbiota can adapt to diuron mineralisation, its activity is strongly dependent on climatic conditions. It suggests that diuron is not rapidly degraded under Mediterranean climate, and that arable Mediterranean soils are likely to accumulate diuron residues. Copyright © 2010 Society of Chemical Industry     

Study of diuron in soil solution by means of a novel simple technique using glass microfibre filters

Retention by a glass fibre filter of the liquid phase of a clay loam soil treated with ¹⁴C-diuron provides a novel method for analysis of the herbicide in soil solution. At 26.3% (w/w) soil moisture content, less than 10% of the applied diuron was found in solution, and this percentage decreased slightly with diuron dose. The herbicide was rapidly adsorbed on soil during the first day, but adsorption continued and the concentration of diuron in solution could be further reduced by 36–50% during the following 6 days. Drying the soil after treatment, with possible crystallization of herbicide applied at high doses, tended to fix the solution concentrations. Ethanol (3% v/v) in soil water favoured herbicide dissolution. Increasing soil moisture to 36.3% (w/w) slightly decreased the concentration of the herbicide in solution, but increased the percentage held in solution. Frost and a drying-rewetting cycle had little or no subsequent effect on diuron concentration in soil solution.     

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     

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).     

Untersuchungen zum Einfluss einer Pflanzenschutzmittelspritzfolge auf das Rückstandsverhalten von Terbutryn und die mikrobielle Aktivität im Boden. Teil II. Beeinflussung der mikrobiellen Aktivität

Studies on the effect of a pesticide spray sequence on the behaviour of terbutryn residues and on soil microbial activity. Part II. Influence on microbial activity In laboratory incubation experiments (at 10 and 20°C and 30 and 60% soil water-holding capacity) soil microbial activities (dehydrogenase, respiration after glucose amendment and nitrogen transformations) were scarcely affected by 20·9 and 28·0 mg kg^?1, respectively, of terbutryn in two soils of different sorption properties. In contrast, dinosebacetate, alone or mixed with terbulryn, triadimefon or parathion, inhibited dehydrogenase activity and respiration even at a low rate of application (2·87 mg kg^?1). Following application of a 10 times higher rate to a highly adsorbent soil there was an initial inhibition of nitrification followed by an enhanced rate of nitrogen mineralization. Triadimefon and parathion, alone and in combination with other pesticides, caused both stimulation and inhibition of microbial activity; the reason is not clear. The effects on dehydrogenase and respiration were confirmed in field experiments. Dehydrogenase activity was the most sensitive and so could be a useful test for the side-effects of pesticides on soil micro-organisms. Additional work on nitrogen transformations is needed to interpret the results.     

Residues of atrazine, simazine, linuron and diuron after repeated annual applications in a peach orchard

Annual applications of the herbicides atrazine, simazine, linuron and diuron at 45 kg/ha were made to the same plots for 9 consecutive years from 1963 to 1971 in a peach (Prunus persica (L.) Batsch.) orchard located on sandy loam soil near Harrow, Ontario. Soil samples from these plots were collected in late October for the last 3 years (1969–1971) and trees were cut down in December, 1969. Herbicide residues were determined by bioassays based on the fresh and dry weight of oats (Avena sativa L.) and in one year results were confirmed by chemical analysis. Significant accumulation of herbicides was not observed. The maximum residue levels measured in October over the 3 years of sampling were 7′3 kg/ha for diuron, 3–8 kg/ha for linuron, 1–6 kg/ha for simazine and 04 kg/ha for atrazine in the top 15 cm of the soil profile. Simazine and atrazine showed a rapid decrease in amount after treatment but diuron and linuron were degraded more slowly. Measurable residues of all herbicides were confined to the upper 15 cm of the soil profile and the majority of herbicide remained in the 0–5-cm soil layer. Oats were planted in the orchard plots from 1972 to 1974 to follow the disappearance of the herbicides. All herbicides caused highly significant yield decreases in 1972, atrazine causing the least (38%) and diuron the greatest (86%) reductions. Diuron reduced the yield of oats in 1973 and caused a highly significant decrease in the weight of young oat plants in 1974.     

Effects of glyphosate on soil microbial communities and its mineralization in a Mississippi soil

Transgenic glyphosate-resistant (GR) soybean [Glycine max (L.) Merr.] has enabled highly effective and economical weed control. The concomitant increased application of glyphosate could lead to shifts in the soil microbial community. The objective of these experiments was to evaluate the effects of glyphosate on soil microbial community structure, function and activity. Field assessments on soil microbial communities were conducted on a silt loam soil near Stoneville, MS, USA. Surface soil was collected at time of planting, before initial glyphosate application and 14 days after two post-emergence glyphosate applications. Microbial community fatty acid methyl esters (FAMEs) were analyzed from these soil samples and soybean rhizospheres. Principal component analysis of the total FAME profile revealed no differentiation between field treatments, although the relative abundance of several individual fatty acids differed significantly. There was no significant herbicide effect in bulk soil or rhizosphere soils. Collectively, these findings indicate that glyphosate caused no meaningful whole microbial community shifts in this time period, even when applied at greater than label rates. Laboratory experiments, including up to threefold label rates of glyphosate, resulted in up to a 19% reduction in soil hydrolytic activity and small, brief (<7 days) changes in the soil microbial community. After incubation for 42 days, 32-37% of the applied glyphosate was mineralized when applied at threefold field rates, with about 9% forming bound residues. These results indicate that glyphosate has only small and transient effects on the soil microbial community, even when applied at greater than field rates.     

异噁草酮对土壤微生物和土壤酶活性的影响

本试验检测了异噁草酮处理土壤后土壤中微生物群落数量和土壤酶活性变化,目的在于研究异噁草酮对土壤微生态产生的影响。结果表明:土壤中异噁草酮有效成分浓度为200、500μg/kg和700μg/kg时,促进土壤中细菌和真菌数量增长,该数量在处理7d之内就会明显变化,并且此影响随异噁草酮使用浓度的提高而增强,但异噁草酮对放线菌的数量无显著影响。施用异噁草酮后,土壤酶活性反应程度由高到低的顺序为:转化酶多酚氧化酶过氧化氢酶。本研究中异噁草酮施入土壤后,除对多酚氧化酶有明显抑制作用,且该抑制作用在短时间内可恢复外,对土壤微生物数量和土壤酶活性都有促进作用。     

Anaerobic microbial degradation of diuron by pond sediment

Anaerobic degradation of the herbicide diuron, 3-(3,4-dichlorophenyl-1,1)dimethylurea, was studied. Enrichment cultures were established with seven different media in the presence of diuron (40 mg/liter). Media included combinations of sediment extract, mineral salts, and various organic amendments. Cultures were inoculated with aliquots of sediment collected from a pond previously treated with diuron and were maintained under an atmosphere of 95% N₂ and 5% CO₂. All enrichment cultures completely degraded diuron in 17–25 days. In all cultures showing diuron degradation, the product identified as 3-(3-chlorophenyl)-1,1-dimethylurea appeared in approximately stoichiometric amounts. Reinjection of diuron into each culture after 26 days resulted in rapid degradation of the parent herbicide with the appearance of proportionately more 3-(3-chlorophenyl)-1,1-dimethylurea. No other product was detected after 80 days in culture and the metachloro derivative was not degraded further during this time.     

Detection of triazine and urea herbicide residues by various characteristics of oat seedlings in bioassays

Atrazine, simazine, diuron, and linuron applied to soil increased the percentage moisture of oat (Avena sativa L.) shoots in bioassays at the lowest dose tested of 0·25 ppm. Further increases occurred up to 2 ppm but at higher concentrations the percentage moisture decreased. At all doses of each herbicide, shoot dry weight was decreased. In oats grown on soil collected from a peach orchard which had received repeated annual applications of these herbicides, the percentage moisture of the oat shoots was higher than the control value whenever the oat dry weight was decreased and provided a method of residue detection as sensitive as dry weight measurements. Treatment of oats by soil application of the above herbicides in bioassays also caused increases in the electrical conductivity of an aqueous extract of the oat shoots per mg of dry weight and this characteristic was slightly more sensitive than dry weight in detecting herbicides in orchard soil. The conductivity of the extract per mg of water in the shoots, however, only increased as percentage moisture decreased. The weight of neutral water-soluble material in oat shoots decreased much more rapidly than dry weight in bioassays with standard herbicide concentrations. Determination of the weight of neutral water-soluble material in oat plants grown on orchard soil samples indicated the presence of herbicide residues in 50% of the cases in which residues were not detectable by dry weight. The weight of neutral material as a percentage of dry weight was almost as sensitive. Chemical analysis of soil in which oat plants had a decreased level of neutral water-soluble compounds indicated that this characteristic had a lower limit of detection for herbicide residues of approximately 0.10 ppm.     

Adsorption of isoproturon,diuron and metsulfuron-methyl in two soils at high soil:solution ratios

Rates of degradation of isoproturon, diuron and metsulfuron-methyl were measured in two soils incubated at two temperatures (5 and 25 °C) with soil moisture at a matric potential of ?5 kPa. Rates of change in soil solution concentration were also measured after extraction of water from the soil using a centrifugation technique. The data, in general, indicated a more rapid rate of decline in aqueous-phase concentrations of herbicide than in total soil concentrations, and hence a progressive increase in partition coefficient in favour of the adsorbed phase^. In all of the incubations, however, adsorption of the herbicide was initially less than that measured using standard equilibration techniques that involved shaking with large volumes of solution relative to weights of soil. This may be explained by the ready availability of more adsorption sites in the shaken systems. With isoproturon and diuron, the changes in adsorption with time were similar at the two incubation temperatures. This indicates that the apparent changes in adsorption with these two compounds were not caused by preferential degradation in the soil solution, but by a slow equilibration with adsorption sites. The results with the weakly adsorbed compound metsulfuron-methyl, however, suggested the possibility of preferential degradation in the solution phase because, when degradation was slow, the absolute amounts adsorbed remained constant or increased slightly, even although solution concentrations declined. Implications of the results for pesticide behaviour in soils in the field are discussed.     

ROOTING CHARACTERISTICS AND VARIETAL TOLERANCE OF SUGARCANE TO DIURON

Summary. The relative susceptibility of six commercial sugarcane varieties to diuron previously described was confirmed in a second similar experiment. A significant correlation was found between the susceptibility of these varieties to 10 kg/ha diuron and their rooting characteristics. The more susceptible varieties were found to produce larger sett-roots and smaller shoot-roots, both of which also tended to be more easily injured by diuron. The root injury appeared as'burnt'root tips resulting from contact with the layer of soil treated by the herbicide. The roots of tolerant varieties seemed to be immune to such injury and continued growing after penetrating the contaminated soil layers. Retarded plant growth appeared to result from the root injury.
Uptake of diuron through shoot-roots of the susceptible variety F 156 resulted in 68·5% growth retardation. This damage was reduced by 15·5% if the plants were allowed to develop sett-roots from two-bud cutting. Death of the plant resulted when both root systems received the same dose of herbicide.     

The fate of imazapyr in a Swedish railway embankment

The long-term fate of the herbicide imazapyr [2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)nicotinic acid] applied to a Swedish railway embankment was studied. Imazapyr was applied at 750 and 1500 g ha(-1) by a spraying train used for full-scale herbicide treatment operations. Soil and groundwater were sampled twice a year for 8 years after application of the herbicide, and the dissipation of imazapyr was studied by HPLC analysis of the residues in soil and groundwater. A clean-up procedure including solid-phase extraction was performed prior to detection by HPLC. Recoveries of imazapyr from soil and water samples were 76-98% and 61-90%, respectively, and detection levels were 0.003 mg kg(-1) and 0.05 microg litre(-1), respectively. Sorption, desorption and microbial amount and activity were also measured at the two locations. The organic matter content correlated positively and the pH negatively to the adsorption of imazapyr on soil, and increasing organic matter contents decreased desorption. Apart from the 0-10-cm top layers of both sites, the microbial amount and activity were small. The main proportion of imazapyr was found in the upper 30 cm of the soil, and degraded with a half-life in the range 67-144 days. Small amounts were transported to lower soil layers and to the groundwater in proportion to the amounts applied. Traces of imazapyr were detected in the groundwater even 8years after application. It was concluded that environmental risks from the use of herbicides on railway embankments could be reduced by including adsorption layers in the embankment during their construction and by reducing the dose of the herbicide used.     

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     

Effect of chloroxuron on some microbial activities in soil

The effect of chloroxuron on some soil microbial activities, i.e. carbon dioxide evolution, mineralisation of nitrogen, dehydrogenase activity and on microbial colony counts, was assessed by applying different concentrations of the herbicide to soils incubated under laboratory and glasshouse conditions. Experimental results showed no adverse effects on microbial activities in the soils studied when chloroxuron was applied in concentrations up to 100 ppm. Mineralisation of nitrogen and carbon dioxide production were slightly enhanced by the herbicide.     

添加有机物对莠去津污染土壤微生物生物量的动态影响

土壤微生物生物量C和N及其C/N比是反映土壤质量的重要生物学指标。研究了除草剂莠去津污染土壤(每kg土壤中含莠去津10 mg)中分别添加3种不同有机物料(腐熟猪粪、水稻秸秆和紫云英,用量均为每1 kg土壤中加入有机物料10 g)对上述生物学指标的动态影响。结果表明,莠去津污染土壤后,土壤微生物生物量C和N及其C/N比率均明显降低;加入有机物料后,土壤微生物生物量C和N及其C/N比率均显著增加,增加幅度与加入有机物料的组成和生物特性有关,依次为腐熟猪粪＞紫云英＞水稻秸秆。     

The effect of Diuron on the soluble nucleotide pool and growth of bean and corn seedlings

The effect of Diuron [3-(3,4-dichlorophenyl)-1,1-dimethylurea] on the acid-soluble nucleotides and growth of bean and corn seedlings was examined. Seeds were germinated in sterile vermiculite and the seedlings fed with different concentrations of diuron through the roots. In the control plants there was a predominance of adenine and uridine nucleotides over guanine and cytosine nucleotides with ATP and UDP-glucose (UDPG) being the most abundant. Seedlings fed with 50 μM diuron showed a significant increase in ATP level and then a subsequent decrease with increasing diuron concentrations. There was a considerable decrease in the total nucleotide content of both types of seedlings fed with 125 and 250 μM diuron, the effect being much more pronounced in the ones treated with 250 μM. The decrease in the total nucleotide content resulted in reduced metabolic activity of the seedlings as was shown by the decrease in chlorophyll and in reduced fresh and dry weights.     

Evidence for the Accelerated Degradation of Isoproturon in Soils

The herbicide isoproturon was degraded rapidly in a sandy loam soil under laboratory conditions (incubation temperature, 15°C; soil moisture potential, -33 kPa). Degradation was inhibited following treatment of the soil with the antibiotic chloramphenicol, but unaffected by treatment with cycloheximide, thus indicating an involvement of soil bacteria. Rapid degradation was not observed with other phenylurea herbicides, such as diuron, linuron, monuron or metoxuron incubated in the same soil under the same experimental conditions. Three successive applications of isoproturon to ten soils differing in their physicochemical properties and previous cropping history induced rapid degradation of the herbicide in most of them under laboratory conditions. There were, however, no apparent differences in ease of induction of rapid degradation between soils which had been treated with isoproturon for the last five years in the field and those with no pre-treatment history. A mixed bacterial culture able to degrade isoproturon in liquid culture was isolated from a soil in which the herbicide degraded rapidly.     

Untersuchungen zum Abbau des Herbizids Chlorphenpropmethyl im Boden und durch Mikroorganismen

Investigations on the breakdown of the herbicide chlorfenpropmethyl in the soil hy microorganisms The herbicide 2-chloro-3-(4-chlorophenyl)propionic acid methyl ester (chlorfenprop-methyl) was hydrolized within a few hours in sandy and loamy soils. The product of the hydrolysis, 2-chloro-3-(4-chlorophenyl)propionic acid (CPP), was metabolized in both soils with a half-life period of 4–8 days when the initial concentration was 22 ppm and of just one day when the initial concentration was 4.4 ppm. In soil 4-chloro-benzoic acid was identified as an intermediary product of the CPP breakdown, and, in mixed cultures of soil micro-organisms, 4-chloro-cinnamic acid as well, In autoclaved soil and soil sterilized with NaN₃ the breakdown of CPP did not take place. The enrichment and isolation of the micro-organisms responsible for the first step in the breakdown of CPP was not possible. Two strains of bacteria isolated from the experimental soils and tentatively attributed to the genera Flavobacterium and Brevibacterium respectively, broke the metabolite 4-chloro-cinnamic acid down to 4- chloro-benzoic acid; two strains of the genus Arthrobacter grew on the 4-chloro-benzoic acid as the only carbon source. The results on the whole support the view that chlorfenpropmethyl is first hydrolized to CPP which is then broken down via 4-chloro-cinnamic acid to 4-chloro-benzoic acid. Further breakdown of 4-chloro-benzoic acid follows by ring cleavage.