Kinetics of linuron and metribuzin degradation in soil

The disappearance of linuron and metribuzin was studied during laboratory incubation of soil samples which had been taken from several depths at three sites, and treated with the pesticides. Temperature and water content of the soils were varied. There was a tendency for the rate of loss to be slower in soil taken from deeper horizons than in surface soil but the differences were not large. In only ten out of forty experiments did the value 1 for the apparent order of reaction fall within 95% confidence limits. In the remaining experiments the apparent reaction order was greater than 1 with eight values higher than 4. For one soil, the reaction order for linuron was markedly lower for incubation at 22°C compared with incubations at 10°C. The results could be explained on the basis that the systems were complex, involving consecutive or competing reactions. An alternative possibility is that the apparent complexities were artifacts brought about by the inherent limitations of the laboratory incubation system.     

The effect of age on the availability of linuron and simazine residues in soil

Residues of linuron and simazine were measured by both bioassay and gas-chromatographic methods in soil from field plots that had been treated either 20 weeks (both compounds). 41/2 years (linuron) or 51/2 years (simazine) previously. There were no significant differences between the results obtained with the two methods; therefore the relationship between extractable herbicide and that available to plants was independent of the age of the residue. Hence‘bound’residues, if they existed in these plots, had no phytocidal significance.     

Microbial N-dealkylation of atrazine: Effect of exogeneous organic substrates and behaviour of the soil microflora

It has been demonstrated that atrazine side-chain mineralisation could be substantially stimulated by addition of carbon-containing substrates such as cellulose, green manure, straw or sawdust in the presence of NH₄⁺ nitrogen but poorly affected by amendments with glucose. Cellulose has the most beneficial effect. For that substrate it has been shown that (i) simultaneous application of the organic amendment and atrazine results in kinetics for side-chain dealkylation showing a lag phase which is reduced or even eliminated by preliminary incubation with the amendment, (ii) rate and extent of mineralisation of the ethylamino side chain are significantly accelerated by decreasing the C/N ratio of the amendment. By comparison, mineralisation of the isopropylamino side chain is not appreciably affected by a change in the value of the C/N ratio as far as atrazine is applied within a two- to three-week period following the organic treatment after which a small deficit in N supply has a definite beneficial effect on mineralisation. Cellulose and, to a lesser extent, straw induce a biphasic change in bacterial number with more numerous and/or active atrazine degraders being predominantly found in the later-developing bacterial community. The fungal microflora is relatively unaffected by all types of carbon substrates but glucose and, unexpectedly, by atrazine at high ratio of application. Activation of atrazine mineralisation seems to be a co-metabolic process which is kinetically controlled by the rate of release from polymerised C substrates of easily available and readily metabolisable low-molecular-weight co-substrates. Transient production of glucose as an end-product of cellulose depolymerisation might induce catabolic repression of dealkylation enzyme systems and be responsible for a lag in atrazine side-chain mineralisation. © 1998 Society of Chemical Industry     

Studies on a mixed bacterial culture from soil which degrades the herbicide linuron

A stable mixed bacterial culture which degrades the herbicide linuron was isolated from soil by enrichment with linuron in a liquid mineral medium. Radio-respirometry studies showed that the culture mineralised linuron completely. No intermediate degradation products were detected in the medium. The culture was able to utilise linuron as a source of both nitrogen and carbon and was also able to degrade the related herbicides monolinuron and chlorbromuron and the possible intermediate degradation products of linuron: 3,4-dichlorophenyl-l-methylurea, 3,4-dichlorophenylurea and 3,4-dichloroaniline. The culture was unable to degrade the 1,1-dimethyl substituted ureas monuron, diuron or metoxuron. The culture contained Gram-negative aerobic rods, and Gram-positive aerobic non-spore-forming rods and cocco-bacilli. Of 124 isolates from the mixed culture, none degraded linuron in pure culture, indicating that a consortium of organisms is involved. Further investigation suggested that Pseudomonas spp. were important components of the population responsible for degradation.     

Effect of pH on the degradation of atrazine,dichlorprop, linuron and propyzamide in soil

The rates of disappearance of atrazine, dichlorprop, linuron and propyzamide were measured in two soils incubated at 22°C and 80% water holding capacity. Observations were made at four pH levels in each soil. Atrazine degradation was relatively insensitive to pH; it increased slightly with increasing pH in one soil and decreased in the other. The other compounds all degraded more slowly at low pH in both soils although dichlorprop had essentially disappeared in 14 days under all conditions, so that the effect of pH is not unlikely to be of practical interest. The ratios of the degradation rates of atrazine, linuron, and propyzamide varied with the soil and the pH.     

Effect of concentration on the decomposition rates in soil of atrazine,linuron and picloram

The decomposition of atrazine, linuron and picloram when incubated with two soils at four levels of application was measured for periods of 3 or 4 months. The applicability of zero-order, half-order, first-order and Michaelis-Menten kinetics was considered. None of the equations described the breakdown rates adequately in spite of the apparent theoretical advantage for using an expression of the Michaelis-Menten type. In each case the rate of decomposition increased as the initial herbicide concentration decreased.     

The effect of nutrients on the decomposition of the herbicides atrazine and linuron incubated with soil

The rates of disappearance of atrazine and linuron when incubated at 22°C with soil or soil containing added nutrient materials were determined with 2 contrasting soils. Inorganic salts, straw or a combination of both increased atrazine degradation in both soils. None of the treatments influenced linuron breakdown greatly. It is concluded that in these soils the rate limiting step in atrazine degradation could be microbiological, not chemical.     

Influence of light on paraquat activity in the tropics

The effect of light on the herbicidal acitivity of paraquat on the tropical perennial weed paspalum conjugatum has been studied in rubber and oil-palm plantations in Malaya. Results showed that paraquat (at 0.5 ib/acre; gave a more rapid desiccation when applied in full sunlight but gave more persistent control when applied under the 70% shade of older trees or in the evening compared with other times of day. A simlar two-fold improvement in the duration of weed control was achieved by the addition of the photosynthetic inhibitor bromacil (at 0.25 ib/acre) to paraquat. The response to the mixture suggested a synergistic reaction between the two compounds.     

The effect of temperature and water content on the rate of decomposition of the herbicide linuron in soil

Rates of linuron breakdown were measured in soil held at the water-holding capacity (WHC), ½ WHC and WHC and at two temperatures, 4°C or 22°C. Breakdown rates were greater at the higher temperature and increased with water content. The energy of activation for the degradation was calculated. Comparison with published figures leads to the speculation that the initial step in degradation by microorganisms is different from that in chemical processes. Effet de la température et de la teneur en eau sur le taux de decomposition du linuron dans le sol Les taux de dégradation du linuron ont été mesurés dans un sol maintenu à sa capacité de rétention, à la moitié et au quart de cette capacité, ainsi quà deux températures 4°C ou 22°C. Les taux de dégradation furent plus grands à la tem-pérature la plus haute et augmentérent avec la teneur en eau. L'energie d'activation pour la dégradation a été calculée. La comparaison avec des chiffres publiés conduit à penser que la première étape de la dégradation par des microorganismes est differente de celle qui intervient dans le processus chimique. Abbau von Linuron im Boden in Abhangigkeit von Temperatur mid Wassergehalt Der Abbau von Linuron im Boden wurde bei 100%, 50% und 25% Wasserkapazitat und bei zwei Termperaturstufen (4°C und 22°C) untersucht. Die Abbauraten nahmen mit steigender Temperatur und steigendem Wassergehalt des Bodens zu. Die fur den Abbau erforderliche Aktivierungs-energie wurde errechnet. Ein Vergleich der Ergebnisse mit Literaturangaben fuhrt zu der Vermutung, daβ der erste durch Mikrooganismen verursachte Abbauschritt verschieden ist von dem bei rein chemischem Vorgang.     

The kinetics of linuron and metribuzin decomposition in soil using different laboratory systems

Rales of linuron and metrihuzin breakdown in soil were studied in four laboratory systems: fresh soil incubated in polyethylene bags; air-dry soil resetted and incubated in polyethylene bags; complete soil cores; a perfusion apparatus. The apparent order of reaction. estimated using a power rate equation, varied from 0.45 to 2.90 and was not consistent with respect either to the compounds or the incubation methods. It is possible that diffusion controlled processes may be involved in producing this variation. The results of six of the eight experiments could be fitted to the first order rate equation (P= 0.01). When the first order model was statistically valid, half-life times were within 50% of the time for 50% disappearance calculated wiih the power rate expression but there were differences up to five-fold in the times for 90% disappearance, calculated by the two methods. It is suggested that decomposition experiments giving orders of reaction greater than I require verification in more than one experimental system     

花棒根际土壤微生物研究

在花棒林内,对不同林龄(5a、10a、20a)、不同深度的根际与非根际微生物的种类、数量进行了研究,结果表明有明显差异:在数量方面细菌占绝对优势(52.92%),放线菌次之(33.33%),真菌最少(13.75%)。在种类方面根际微生物的种类大于非根际。不同深度的土壤微生物数量也存在一定差异;变化为:细菌为0～10cm>20～30cm>10～20cm>30～40cm;真菌为0～10cm>10～20cm>20～30cm>30～40cm;放线菌为0～10cm>30～40cm>10～20cm>20～30cm。随着林龄的增加细菌数量减少;真菌数量呈上升趋势;放线菌表现为5a和10a大致相当,20a最少。     

The microbial biodegradation of paraquat in soil

The microbial degradation of [¹⁴C]paraquat using cultures from two agricultural soils was investigated. The experiments were carried out in the absence of light, under aerobic conditions. Degradation was rapid, with 50% mineralisation to [¹⁴C]carbon dioxide occurring within three weeks. HPLC, capillary electrophoresis and mass spectroscopy confirmed that the majority (>85%) of the remaining radiochemical in solution was [¹⁴C]oxalic acid, and that no paraquat remained.     

The effect of seven substituted urea herbicides on the soil microflora

Chloroxuron, diuron, fluometuron, metobromuron and monuron added to soil at 500 parts/million a.i. on a dry weight basis caused an initial stimulation of CO₂ production, followed by indications of inhibition. Nitrification was clearly inhibited, particularly by monuron and metobromuron. Metoxuron at 5 and 50 parts/million a.i. had no effect on CO₂ output and nitrification, but at 500 parts/million a.i. both were greatly reduced. Numbers of fungal propagules were temporarily lower at 50 parts/million a.i., and severely curtailed at 500 parts/million a.i. but total counts of bacterial propagules were greatly increased. Linuron had an inhibitory effect on CO₂ evolution at 500 parts/million a.i. but this varied in extent and duration; some reduction was also found at 50 parts/ million a.i. At 500 parts/million a.i. there was no effect on mineralisation of N but in soil supplemented with ammonium sulphate nitrification was reduced. Changes in microbial equilibrium occurred, but were less marked than with metoxuron. Cellulose decomposition was also reduced. Small amounts of 3,4dichloroaniline were found in linuron-treated soils, but microbial activities were not affected when 5 parts/million 3,4-dichloroaniline was added to the soil. However, at 140 parts/million microbial activities were affected adversely, but in a different pattern to that for linuron; nitrification was severely reduced, but numbers of fungal propagules were hardly affected, suggesting that the effects observed in linuron-treated soil were not due to this metabolite.     

盐碱地不同施氮量对土壤微生物区系与食葵产量的影响

在内蒙古河套灌区盐碱食葵田进行大田试验,以不施氮肥为对照(CK),设置了75 kg·hm~(-2)(N1)、150kg·hm~(-2)(N2)、225 kg·hm~(-2)(N3)、300 kg·hm~(-2)(N4)、375 kg·hm~(-2)(N5)五个氮肥施用水平,研究了不同氮肥施用量对土壤微生物区系和食葵产量的影响。结果表明:(1)盐碱地施用氮肥可提高土壤微生物数量和细菌优势菌菌群多样性,各处理0~20 cm土层根区土壤微生物数量大小顺序为N4N3N5N2N1CK,各施肥处理较CK差异极显著(P0.01);(2)盐碱地施用氮肥可促进食葵生长发育,提高产量,随氮肥施用量由低到高,食葵长势和干物质积累呈逐渐增加趋势,产量与施氮量呈抛物线型关系,各处理产量分别较CK提高0.06%、36.27%、61.95%、105.36%和85.03%;(3)适量施氮可抑制土壤积盐,食葵收获后,各处理积盐量大小顺序为N2CKN5N3N1N4;(4)土壤微生物的数量和优势菌菌群数与氮肥施用量、食葵根干重呈正相关关系,与土壤含盐量和积盐量呈负相关关系。综合试验结果,内蒙古河套灌区中度盐碱地食葵生产中氮肥适宜施用量为300 kg·hm~(-2)。     

Fonofos residues in an organic soil and vegetable crops following treatment of the soil with the insecticide

Fonofos (O-ethyl S-phenyl ethylphosphonodithioate) was applied to an organic soil as band treatment at the rates of 1.12 and 2.24 kg/ha. The persistence of the insecticide and its translocation into onions and two rotation crops (lettuces and carrots) was studied under field conditions. Proportionally more residues persisted in the soil from the higher rate of application. In autumn, 4 months after soil treatment, about 40-48 % of the initially recovered levels of fonofos remained in soil. However, the amount of fonofos present at the harvest time, during the second growing season was only 16–26% of the insecticide concentration found in spring. Onions harvested 4 months after application of fonofos had no detectable residue (> 0.005 mg/kg) whereas lettuces and carrots grown in the following year contained fonofos in various amounts. At the lower rate of application the insecticide residues in lettuces and carrots were < 0.005 and 0.025 mg/kg, respectively, and those from the higher application rate were 0.012 and 0.036 mg/kg. About 72–80% of the residue could be removed by peeling the carrots. No residue of the oxygen analogue, O-ethyl S-phenyl ethylphos-phonothioate (I) was detected in any soil or crop samples.     

Simulation of the persistence of atrazine, linuron and metolachlor in soil at different sites in the USA

The effects of soil temperature and soil moisture content on the rates of degradation of atrazine, linuron and metolachlor were measured in the laboratory in soil from different sites in the USA. Persistence of the herbicides was measured in the same soils in the field during the summers of 1978 and 1979. Weather records from the different sites for the periods of the field experiments were used in conjunction with appropriate constants derived from the laboratory data in a computer program to simulate persistence in the field. There was a general tendency for the model to overestimate the observed soil residues. For example, with atrazine, 40 of the 48 measured residues were lower than those predicted by the model; seven were more than 30% below and two were more than 50% below. With metolachlor, 16 of the 48 measured residues were more than 30% below those predicted and six were more than 50% below; almost identical results were obtained with linuron. When the model overestimated late-season residues by a large amount, the discrepancies between predicted and observed data were usually apparent from early in the experiment. Possible reasons for the discrepancies are discussed.     

Simulation of herbicide persistence in soil .II. Simazine and linuron in long-term experiments

The rates of degradation of simazine and linuron were measured in soil from plots not treated previously with these herbicides. Degradation of both compounds followed first-order kinetics and soil temperature and soil moisture content had a marked effect on the rate of loss. With linuron, half-lives increased from 36 to 106 days with a reduction in temperature from 30° to 5°C at 4% soil moisture, and from 29 to 83 days at 12% soil moisture. Similar temperature changes increased the half-life of simazine from 29 to 209 days and from 16 to 125 days at soil moisture contents of 4 and 12% respectively. A computer program which has been developed for simulation of herbicide persistence was used in conjunction with the laboratory data and the relevant meteorological records for the years 1964 to 1968 in order to test the model against previously published field persistence data for the two herbicides. The results with simazine showed a close correspondence between observed and predicted residue levels but those for linuron, particularly in uncropped plots, were satisfactory for limited periods only.     

The selective effect of heat treatment on the microflora of a greenhouse soil

Detailed information about the heat tolerance of soil micro-organisms, both pathogens and their nonpathogenic antagonists, is needed for the practice of soil pasteurization.A device for testing the thermal death point of micro-organisms in soil is described.The selective effect of heat treatment on the total numbers of bacteria, actinomycetes and fungi of a greenhouse soil (loam) was estimated. Of these groups the fungi proved to be the most sensitive to heat treatment. The heat tolerance of the species of this group was examined in more detail. In comparing the thermal death points of fourteen pathogenic fungi with those of the saprophytic fungal flora many species of the latter proved to be more heat-tolerant.Samenvatting In verband met de toenemende belangstelling voor pasteurisatie van kasgrond is een grondige kennis omtrent de afstervingstemperaturen van de bodemorganismen-zowel pathogenen als hun niet-pathogene antagonisten-noodzakelijk. In een voor dit doel geconstrueerd apparaat werd vochtige lucht van verschillende temperaturen door kleine hoeveelheden kasgrond geblazen. Daarna werd de grond geanalyseerd op de overlevende microflora. De schimmels bleken als groep verhitting minder goed te kunnen doorstaan dan de bacteriën en de actinomyceten. Vooral de Oömyceten waren zeer gevoelig. Zeer tolerant waren enkele donkersporige Deuteromyceten en diePenicillium-enAspergillus-soorten, welke een perfecte vorm hebben. De als antagonisten van pathogenen beroemdeTrichoderma-soorten bleken weinig tolerant.De afstervingstemperaturen van veertien pathogene schimmels bleken lager te liggen dan die van veel saprofyten.     

The effect of soil heat treatment and microflora on the efficacy of glyphosate in seedlings

Seedlings of wheat (Triticum aestivum L.) and beans (Phaseolus vulgaris L.) were less sensitive to glyphosate when grown in heat-treated soil than in raw soil. Pythium spp. and Fusarium spp. were not detected in heat-treated loam or muck soils at the time of glyphosate treatment, although fungi of several other genera were present. The efficacy of glyphosate on wheat or beans grown in heat-treated loam soil was restored when untreated aqueous soil extracts were added to the heat-treated soil. Bean seedlings grown in five different soil types varied in their sensitivity to glyphosate. The variation in LD₅₀ among autoclaved soils was lower than that among raw soils. Between 13- to 47-fold more glyphosate was required to kill the bean seedlings in any of the autoclaved soils compared with their corresponding raw soils. This differential effect was not observed on bean seedlings sprayed with either 2, 4-D or paraquat. LD₅₀ values for glyphosate on apple (Malus domestica Borkh.) seedlings growing in previously sterilized loam soil were reduced by inoculation of the soil with a representative Fusarium sp. or Pythium sp. obtained earlier from apple seedlings treated with glyphosate, but not by a Cylindrocarpon sp. from apple or Pythium ultimum Trow from glyphosate-treated bean. The efficacy of glyphosate on bean, wheat or apple seedlings can be affected by changes in certain microbial components of the soil. Effet d'un traitement du sol a la chaleur et de la microflore sur l'efficacité du glyphosate sur plantules Des plantules de blé (Triticum aestivum L.) et de haricots (Phaseolus vulgaris L.) ont été moins sensibles au glyphosate quand elles sont cultivées dans des sols traités par la chaleur que dans des sols bruts. Pythium spp et Fusarium spp. n'ont pas été détectés dans la terre traitée à la chaleur ou dans des sols fumés au moment de l'application du glyphosate, bien que des champignons de quelques autres genres aient été présents. L'efficacité du glyphosate sur blé et haricots cultivés en sol traité par la chaleur a été récupérée quand des extraits aqueux de sols non traités ont été additionnés au sol traité. Les plantules de haricots cultivés dans 5 types de sols ont varié dans leur sensibilité au glyphosate. La variation des DL₅₀ pour les sols autoclavés était plus faible en comparaison de celle des sols bruts. Il a fallu de 13 à 47 fois plus de glyphosate pour détruire les plantules de haricot dans tous les sols autoclaves que dans les sols bruts correspondants. Cet effet différentiel n'a pas été observé chez les plantules de haricots traités avec du 2,4 D ou du paraquat. Les valeurs de DL₅₀ pour le glyphosate sur des plantules de pommiers (Malus domestica Borkh.) cultivées sur des sols avec de la terre précédemment stérilisée, ont été réduites par l'innoculation du sol avec un Fusarium sp. ou Pythium sp. obtenu plutôt à partir de plantules de pommier traitées au glyphosate, mais pas avec du Cylindrocarpon du pommier, ou un Pythium ultimum venant d'un haricot traité au glyphosate. L'efficacité du glyphosate sur plantules de haricot, blé ou pommier peut être affecté par des changements de la composition microbiologique du sol. Die Wirkung von Boden-Hitzesterilisation und Mikroflora auf die Wirksamkeit von Glyphosat auf Keimpflanzen Keimpflanzen von Weizen (Triticum aestivum L.) und Buschbohne (Phaseolus vulgaris L.) waren, in hitzebehandeltem Boden wachsend, gegenüber Glyphosat weniger empfindlich als in unbehandeltem Boden. Pythium spp. und Fusarium spp. wurden in hitzebehandeltem Lehm- oder stark organischem Boden zur Glyphosatbehandlung nicht gefunden, obwohl andere Pilzgattungen vorhanden waren. Die Wirksamkeit des Glyphosats auf in hitzebehandeltem Boden gezogenen Weizen- oder Bohnenpflanzen stellte sich wieder ein, wenn unbehandelte wäßrige Bodenextrakte dem hitzebehandeltem Boden zugefügt wurden. Bohnenkeimpflanzen zeigten in 5 verschiedenen Bodenarten eine unterschiedliche Empfindlichkeit gegenüber Glyphosat. Die LD₅₀ variierte in autoklavierten Böden weniger als in unbehandelten. Zur Abtötung der Bohnen-keimpflanzen waren in den autoklavierten Böden 13- bis 47mal größere Wirkstoffmengen erforderlich als in den entsprechenden unbehandelten Böden. Diese Wirkungsunterschiede wurden bei mit 2,4-D oder Paraquat behandelten Bohnenkeimpflanzen nicht beobachtet. Wurden Apfelsämlinge (Malus domestica Borkh.) in sterilisiertem Lehmboden angezogen, so sanken die LD₅₀-Werte für Glyphosat bei Inokulation des Bodens mit repräsentativen Fusarium- oder Pythium-Arten, die zuvor von Glyphosat-behandelten Apfelsämlingen gewonnen worden waren, jedoch nicht mit einer Cylindrosporium-Art von Äpfeln oder Pythium ultimum Trow von Glyphosat-gehandelteten Bohnen. Die Wirksamkeit von Glyphosat auf Keimpflanzen von Bohnen, Weizen oder Äpfeln kann durch Veränderungen bestimmter mikrobiologischer Bodenkomponenten beeinflußt werden.