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.     

Photochemistry of halogenated benzene derivatives. Part IX. environmental aquatic phototransformation of bromoxynil (3,5-dibromo-4-hydroxybenzonitrile)

Photochemistry of the herbicide 3,5-dibromo-4-hydroxybenzonitrile (bromoxynil) (I) was investigated by irradiating at approximately 313 nm. Aqueous phase photoreactions of 0.078–7.800 × 10^?5m solutions of I were carried out at different pH values. Quantum yields for the loss of I in buffered solutions were 0.008 (±0.0004), 0.048 (±0.0024), and 0.044 (±0.0022) at pH 2.6, 7.0, and 11.0, respectively. In neutral and basic conditions, I absorbed more strongly at wavelengths > 290 nm, an environmentally significant region. Phototransformation of I was monitored by HPLC and UV-VIS spectrometry. All photoreactions of I gave rise to the generation of two products, 3-bromo-4-hydroxybenzonitrile and 4-hydroxybenzonitrile. The former photoproduct was tentatively identified from its mass spectral data. The photoproducts can be accounted for with a proposed mechanism involving free radicals.     

Comparative effects of dichlobenil and its phenolic alteration products on photo- and oxidative phosphorylation

Effects of dichlobenil (2,6-dichlorobenzonitrile) and its phenolic degradation products (2,6-dichloro-3-hydroxybenzonitrile and 2,6-dichloro-4-hydroxybenzonitrile) were compared on electron transport and phosphorylation in isolated spinach (Spinacia oleracea L.) chloroplasts and mung bean (Phaseolus aureus Roxb.) mitochondria. In chloroplasts, the hydroxylated derivatives inhibited both photoreduction and coupled photophosphorylation with water as the electron donor and with ferricyanide as oxidant, and cyclic photophosphorylation with phenazine methosulfate as the electron mediator under an argon gas phase. In mitochondria, the phenolic derivatives acted as uncouplers of oxidative phosphorylation as evidenced by the stimulation of ADP-limited respiration, circumvention of oligomycin-inhibited non-ADP-limited respiration, and the induction of ATPase activity. Treatment of excised mung bean hypocotyls by the phenolic derivatives also resulted in a very rapid and drastic lowering of ATP levels. In all assays, only limited, if any, interference was expressed by dichlobenil even at relatively high molar concentrations.Inhibition of oxidative and photophosphorylation by the phenolic degradation products, but not by dichlobenil, suggests that if there is a delay between the formation of the hydroxylated compounds and their conjugation, photosynthesis and respiration will be inhibited. Because biochemical and physiological processes depend on oxidative and photophosphorylation for the energy (ATP) needed to drive the reactions, interference with ATP production could be one of the major mechanisms through which phytotoxicity is expressed by the phenolic degradation compounds of the herbicide, if they should accumulate in the free from. Species selectivity may be related to the rate of formation of the phenolic products in different plants and the rapidity of conjugate formation.     

ABSORPTION, TRANSLOCATION AND METABOLISM OF DICHLOBENIL IN BEAN SEEDLINGS

Summary. A quantitative study was carried out on the absorption, translocation and metabolism of 2,6–dichlorobenzonitriie-¹⁴G (dichlobenil) in seedlings of Phaseolus vulgaris L. From an aqueous solution dichlobenil is absorbed by the roots and accumulates about three-fold; metabolism in the roots is of minor importance. From the roots the herbicide is translocated throughout the plant. In the leaves two competitive processes take place: the main part (90%) of the dichlobenil evaporates and another part is metabolized. The principal metabolic pathway is hydroxylation, followed by conjugation, 3–hydroxy-2,6–clichlorobenzonitriIe and 4–hydroxy-2,6–dichlorobenzonitrile analogues being formed in a ratio of about 4:1. Hydrolysis of dichlobenil into 2.6–dichlorobenzamide and 2,6–dichlorobcnzoic acid is only a minor metabolic route.
From a saturated atmosphere dichlobenil is taken up rapidly through the leaves but little translocation occurs to the roots. Following foliage application more of the applied dichlobenil Is metabolized because evaporation of dichiobenil as a competitive process is virtually eliminated.
Absorption, migration ei métabolisme du dichlobenil dans les plantules de haricot     

Soil persistence studies with bromoxynil, propanil and [14C]dicamba in herbicidal mixtures

The persistence of bromoxynil (3,5-dibromo-4-hydroxybenzonitrile), [¹⁴C]dicamba (3,6-dichloro-2-methoxybenzoic-7-¹⁴C acid) and propanil [N-(3,4-dichlorophenyl)propionamide] at rates equivalent to 1 kg ha^?1, were studied under laboratory conditions in a clay loam, a heavy clay and a sandy loam at 85% of field capacity and at 20±1°C, both singly and in the presence of herbicides normally applied with these chemicals as tank-mix or split-mix components. The degradation of bromoxynil was rapid with over 90% breakdown occurring within a week in the heavy clay and sandy-loam soils, while in the clay-loam approximately 80% of the bromoxynil had broken down after 7 days. In all three soils degradation was unaffected by the presence of asulam, diclofop-methyl, flamprop-methyl, MCPA, metribuzin or propanil. Propanil underwent rapid degradation in all soil treatments, with over 95% of the applied propanil being dissipated within 7 days. There were no noticeable effects on propanil degradation resulting from applications of asulam, barban, bromoxynil, dicamba, MCPA, MCPB, metribuzin or 2,4-D. The breakdown of [¹⁴C]dicamba in a particular soil was unaffected by being applied alone or in the presence of diclofop-methyl, flampropmethyl, MCPA, metribuzin, propanil or 2,4-D. The times for 50% of the applied dicamba to be degraded were approximately 16 days in both the clay loam and sandy loam, and about 50 days in the heavy clay.     

Effects of certain herbicides on the oxidative decarboxylation of tryptophan by peroxidase

Non-enzymic and peroxidase-catalysed oxidative decarboxylations of tryptophan (TPP) were studied. The in-vitro rate of enzymic reaction was affected by various herbicides at low concentrations (10^?5?10^?4_M): dinoseb, 2,4-D, dichlobenil and benazolin acted as inhibitors; on the other hand, chlorpropham, bromacil, diphenamid and 4-ethylamino-6-isopropylamino-1,3,5-triazin-2-ol (hydroxyatrazine) were stimulatory. The results of in-vivo experiments showed that chlorpropham and 2,4-D changed the activity of peroxidase from Brassica germinated seeds in vivo, as they do in vttro. Determinations of consumed TPP were carried out either by spectro-photometry or by chromatography.     

Persistence of dichlobenil in a sandy soil and effects of residues on plant growth

The persistence of dichlobenil following the application of dichlobenil granules was studied in a replicated plot experiment including both surface and incorporated treatments of 8·3 and 16·6 kg/ha ai. Soil analyses showed an initial half-life of about 4 weeks but the persistence increased with time and a year after application the half-life was about 1 year. Incorporation of the granules into the soil markedly increased the persistence of dichlobenil and its metabolite dichlorobenzamide. The most sensitive crop was carrot which was damaged by residues of only 1–2% of the recommended dose. Residues phytotoxic to carrots persisted for 2 years from the 8·3 kg/ha surface application and 5 years from the 18·6 kg/ha incorporated application. Lettuce was also highly sensitive to residues.     

Biodegradation of the herbicide bromoxynil and its plant cell wall bound residues in an agricultural soil

The mineralization and formation of metabolites and nonextractable residues of the herbicide [¹⁴C]bromoxyniloctanoate ([¹⁴C]3,5-dibromo-4-octanoylbenzonitrile) and the corresponding agent substance [¹⁴C]bromoxynil ([¹⁴C]3,5-dibromo-4-hydroxybenzonitrile) was investigated in a soil from an agricultural site in a model experiment. The mineralization of maize cell wall bound bromoxynil residues was also investigated in the agricultural soil material. The mineralization of [¹⁴C]bromoxynil and [¹⁴C]bromoxyniloctanoate in soil within 60 days amounted up to 42 and 49%, respectively. After the experiments, 52% of the originally applied [¹⁴C]bromoxynil and 44% of the [¹⁴C]bromoxyniloctanoate formed nonextractable residues in soil. Plant cell wall bound [¹⁴C]bromoxynil residues were also mineralized to an extent of about 21% within 70 days; the main portion of 76% persisted as nonextractable residues in the soil. In bacterial enrichment cultures and in soil two polar metabolites were observed; one of it could be identified as 3,5-dibromo-4-hydroxybenzoate and the other could be described tentatively as 3,5-dibromo-4-hydroxybenzamide.     

TRANSPORT AND METABOLISM OF DICHLOBENIL IN WHEAT AND RICE SEEDLINGS

Summary. The absorption, translocation and metabolism of the herbicide dichlobenil (2,6-dichlorobenzonitrile) in seedlings of wheat (Triticum vulgare) and rice (Oryza sativa) was investigated using a ¹⁴C-labelled preparation. Both plants absorbed the herbicide from water solutions through the roots and translocated it to the shoots. Accumulation was greater in the roots of rice. In wheat, dichlobenil was hydroxylated to form both 3-hydroxy-2,6-dichlorobenzo-nitrile and in smaller quantities, the 4-hydroxy analogue. These conversion products were present mainly as soluble and insoluble conjugates. The insoluble fraction, which apparently consists of phenols conjugated with plant polymers, increased with time. Though the same metabolic processes occurred in rice, the conversion rate was considerably lower. Correspondingly, the dichlobenil concentration was greater in rice than in wheat. No evidence of hydrolysis of dichlobenil was obtained. Migration et métabolisme du dichlobénil dans les plantules de blé et de riz Résumé. L'absorption, la migration et le métabolisme de l'herbicide dichlobenil (2,6-dichlorobenzonitrile) a étéétudiée dans des plantules de blé (Triticum vulgare) et de riz (Oryza sativa) en utilisant une préparation marquée au ¹⁴C. Dans les deux espéces, l'herbicide absorbéà partir de solutions aqueuses par les racines fut transporté dans la partie aérienne. L'accumulation fut plus importante dans les racines du riz. Dans le blé, le dichlobenil fut hydroxylé pour donner à la fois du 3-hydroxy-2,6-dich-lorobenzonitrile, et, en plus faibles quantités, le composé analogue 4-hydroxy. Ces produits de conversion furent identifiés principalement sous forme de composés solubles et insolubles. La fraction insoluble, qui consiste apparemment en composés avec des polymeres de la plante, s'accrut avec le temps. Bien que le processus métabolique füt le même dans le riz, le taux de conversion fut considérablement plus faible. Corrélativement, la concentration du dichlobénil fut'plus grande dans le riz que dans le blé. II ne fut pas acquis de preuves de l'hydrolyse du dichlobénil. Transport und Abbau von Dichlobenil in Weizen- und Reiskeimpflanzen Zusammenfassung. Absorption, Translokation und Abbau von ¹⁴C-Dichlobenil (2,6-Dichlorbenzonitril) in Keimpflanzen von Weizen (Triticum vulgare) und Reis (Oryza sativa) wurden untersucht. Beide Pflanzen absorbierten das Herbizid aus einer wässrigen Lösung durch die Wurzeln und leiteten es in die Sprosse. Die Akkumulierung war in den Wurzeln von Reis grösser. In Weizen wurde Dichlobenil hydroxyliert, wobei 3-Hydroxy-2,6-dichlorbenzonitril und in geringerer Menge das 4-Hydroxy-Analog entstanden. Diese Konversionssubstanzen waren hauptsachlich als losliche und unlosliche Konjugationsprodukte anwesend. Die unlösliche Fraktion, die offensichtlich aus Konjugationsprodukten mit Pflanzenpolymeren bestand, nahm mit der Zeit zu. Obwohl derselbe Stoffwechselprozess auch im Reis ablief, war doch die Konversions-geschwindigkeit wesentlich geringer. Dementsprechend war die Dichlobenilkonzentration in Reis grösser als in Weizen. Für eine Hydrolyse von Dichlobenil ergaben sich keine Anhaltspunkte.     

Activité des peroxydase, catalase et glycolate oxydase après traitement avec divers herbicides

Activity of peroxidase, catalase and glycollate oxidase after treatment with various herbicides Various herbicides were applied to 17-day-old cucumber seedlings growing in nutrient solution. After 1, 2 and 3 days, peroxidase, catalase and glycollate oxidase activities were measured in the leaves of seedlings treated with lethal doses of atrazine, chlortoluron, MCPA, alachlor and dichlobenil. The same determinations were carried out after 5 h on seedlings previously sprayed with paraquat and DNOC. Atrazine and chlortoluron inhibited peroxidase activity and slightly stimulated catalase activity. MCPA, alachlor and dichlobenil stimulated both enzymes and after 3 days the peroxidase/catalase relations were respectively 0.7, 7 and 14. DNOC and paraquat inhibited catalase. Glycollate oxidase activity increased in seedlings treated with atrazine, chlortoluron, MCPA and DNOC and decreased in those treated with dichlobenil and paraquat.     

CHEMICAL FALLOW CONTROL OF NUTSEDGE

Summary. Field experiments were conducted to find a herbicide for complete control of nutsedge ( Cyperus rotundus L.). We applied seventeen herbicides and some of their combinations as chemical fallow. EPTC and CP-31675 (6- tert -butyl-2-chloro-o-acetotoluidide) gave good but only temporary control of nutsedge. Dichlobenil at 2·5 or 5 lb/ac gave fair control for 1 year. Rates of 10 or 20 lb/ac of dichlobenil controlled nutsedge completely for 1 year but severely reduced the yield of oats planted 5 months after application. The highest rate completely killed tubers and prevented reinfestation for 1 year. Analyses indicated no residue of dichlobenil or of its metabolite, 2,6-dichlorobenzoic acid, in vegetative parts and seeds of oats planted 5 months after application of 2.5, 5 or 10 lb/ac of dichlobenil. At equivalent rates the herbicide TH-073-H (N-hydroxymethyl-2,6-dichlorothiolbenzamide) gave control of nutsedge similar to that with dichlobenil. The combinations of 8 lb/ac amitrole-T and 10 lb/ac dichlobenil or TH-073-H were just as effective in controlling nutsedge shoots and tubers as dichlobenil or TH-073-H applied alone. The mixture of dichlobenil plus CP-31675, each at 5 lb/ac, gave excellent control of nutsedge and tubers for 1 year. The herbicides terbacil ( 3-ter -Nbutyl-5-chloro-6-methyluracil) or Du Pont 733 ( 3-tert -butyl-5-bromo-6-methyluracil) at 10 lb/ac provided almost complete control of nutsedge. Application of terbacil to plants aged 4–6 weeks gave better results than application to mature nutsedge in the fall.
La lutte chimique contre le cypirus     

THE INHIBITION OF GIBBERELLIC ACID INDUCTION OF α-AMYLASE ACTIVITY IN BARLEY ENDOSPERM BY CERTAIN HERBICIDES

Summary. The influence of the four herbicides 2,6-dichlorobenzonitrile (dichlobenil), isopropyl-N-(3-chlorophenyl)carbamate (chlorpropham), 2-chloro-N-isopropylacetani-lide (propachlor) and 2-chloro-2′,6′-diethyl-N-(methoxymethyl)acetanilide (alachlor) on GA induction of a-amylase in the barley endosperm test was studied. Amylase induction by GA was inhibited by all four herbicides, dichlobenil and chlorpropham being more active in this respect. In all cases, inhibition increased with the addition of increasing concentrations of herbicide. Addition of the herbicides to the reaction mixture showed that none of them directly affected the enzyme—starch reaction. Inhibition de V induction par l'acide gibbirellique de activité de α-amylase dans l’endosperne de I'orge, sous faction de certains herbicides Résumé. Les auteurs ont étudié l'influence de 4 herbicides, le 2,6-dichlorobenzonitrile (dichlobénil), le. N-(3-chlorophényle) carbamate d'isopropyle (chlorpropham), la 2-chloro-N-iso-propylacétanilide (propachlore) et la 2-chloro-2′,6′-diéthyl-N-(méthoxy-méthyle) acétanilide (alachlore), sur l'induction par l'acide gibbérellique de l'α-amylase dans l'endosperme de I'orge. L'induction de l'amylase par l'acide gibbérellique fut inhibée par les quatre herbicides, le dichlobénil et le chlorpropham se montrant les plus actifs à cet égard. Dans tous les cas, l'inhibition s'accrut avec I'addition de concentrations croissantes d'herbicide. L'addition des herbicides au mélange en réaction montra qu'aucun d'entre eux n'affectait directement la réaction enzymatique de l'amidon. Die Hemmung der gibberellininduzierten α-Amylaseaktimtdt in Gerstenendosperm durch gewisse Herbizide Zusammenfassung. Der Einfluss der vier Herbizide 2,6-Dichlorbenzonitril (Dichlobenil), Isopropyl-N-(3-chlorphenyl)-carbamat (Chlorpropham), 2-Chlor-N-isopropylace-tanilid (Propachlor) und2-Chlor-2′,6′-diäthyl-N-(methoxymethyl)-acetanilid (Alachlor) auf die gibberellininduzierte α-Amylasebildung in Gerstenendosperm wurde untersucht. Die Induktion von α-Amylase durch Gibberellinsäure wurde von alien vier Herbiziden ge-hemmt. Am wirksamsten waren hierbei Dichlobenil und Ghlorpropham. In alien Fällen wurde die Hemmwirkung durch ansteigende Herbizidkonzentrationen verstärkt. Die Zugabe der Herbizide zu dem Reaktionsgemisch zeigte, dass keines von ihnen die Reaktion zwischen Enzym und Stärke direkt beeinflusste.     

Studies on low-volume application of plant growth substances; Part 1: Ethylene production,induced by 1-naphthylacetic acid,as a means of evaluating spray parameters

The evolution of ethylene, induced by 1-naphthylacetic acid (NAA), was studied as a means of evaluating spray parameters using cowpea [Vigna sinensis (Torner) Savi] under defined conditions as a test system. The dose-response curve was linear over the range of 1.4-14 μg per leaf. The marked production of ethylene following treatment with an active auxin, 2,4-D (2,4-dichlorophenoxyacetic acid), and the absence of its production following treatment with an inactive analogue (3,5-dichlorophenoxyacetic acid), established that ethylene production was hormonally induced. The effect of application volumes of 10-100 μ1 and of droplet sizes of 1-10 μ1 were evaluated using a constant dose (5 μg NAA per leaf); NAA was more effective when delivered to the leaf in the larger volumes but in the smaller droplet sizes.     

The Effect of Numerous Herbicides on the Germination of Orobanche aegyptiaca and Striga hermontheca

Abstract

Two hundred and thirty seven chemicals were tested to determine their effect on the germination of Orobanche aegyptiaca and Striga hermontheca. From their activity in these tests and a knowledge of their general properties the following are regarded as being the most promising for the pre-em. control of (1) Orobanche — oryzalin, dichlobenil, chlorthiamid, nitralin and chloramben. (2) Striga — 2, 4-D, MCPA and a range of other phenoxy compounds, chlorfenac, with MON 097, prynachlor, PH 40–21, PRB-8, RU 12068 and U 27658 showing the most interesting activity among the newer compounds.     

Adsorption of transformation products of atrazine by soil

The adsorption of atrazine and its transformation products, desisopropylatrazine (2-chloro-4-ethylamino-6-amino-l,3,5-triazine), desethyl-atrazine (2-chloro-4-amino-6-isopropylamino-l,3,5-triazine) and hydroxyatrazine (2-hydroxy-4-ethylamino-6-isopropylamino-l,3,5-triazine) to four top-soils was measured. Adsorption coefficients decreased in the order hydroxy atrazine, atrazine, desisopropylatrazine, and desethyl-atrazine: the distribution coefficient between organic matter and water (K_OM) ranged from 40 to 100 dm³ kg^?1 for atrazine, from 30 to 60 dm³ kg^?1 for desisopropylatrazine, from 20 to 50 dm³ kg^?1 for desethylatrazine and from 100 to 590 dm³ kg^?1 for hydroxy atrazine. Data are discussed in the context of earlier literature.     

Effects of isoxaben on sensitive and tolerant plant cell cultures : II. Cellular alterations and inhibition of the synthesis of acid-insoluble cell wall material

The herbicide isoxaben is selectively phytotoxic to dicotyledonous plants, whereas most monocots are tolerant. We previously selected a soybean cell culture tolerant to isoxaben. Some effects of the herbicide on wild-type soybean cells, tolerant soybean cells, and wheat cells were compared. Cytological observations showed that isoxaben induced some disorganization of sensitive soybean cells, especially at the plasma membrane-cell wall interface. Tolerant soybean cells appeared normal in the presence of isoxaben. The growth of wild-type soybean cells was roughly equally sensitive to isoxaben as to dichlobenil, a cellulose synthesis inhibitor. By comparison, the selected soybean line and a wheat cell culture were less sensitive to isoxaben than to dichlobenil. Glucose incorporation into acid-insoluble cell wall material was more inhibited by isoxaben than by dichlobenil in the wild-type soybean cell culture. In the tolerant soybean cell culture, the incorporation was slightly inhibited by isoxaben, but remained sensitive to dichlobenil. In the wheat cell culture, dichlobenil was also more inhibitory but only at high concentrations. Other compounds, inhibitors of cellulose biosynthesis, of glycosylation of lipids or protein, or of cell division, either had no effect on the synthesis of acid-insoluble cell wall material or exerted apparently unspecific inhibitions. The results are consistent with isoxaben inhibiting the synthesis of a cell wall polysaccharide, which could be cellulose.     

Fungitoxicity of bromo- and iodo-3,5-dinitrobenzoates

Esters of 2-bromo-, 4-bromo-, 2-iodo- and 4-iodo- 3,5-dinitrobenzoic acids show considerable antifungal activity in spore germination tests against Alternaria brassicicola, Botrytis cinerea, Septoria nodorum and Uromyces fabae. They act as protectant fungicides against Erysiphe graminis, Puccinia recondita and Septoria nodorum on wheat and Botrytis fabae on broad bean. The most active compounds are methyl and ethyl 4-bromo-3,5-dinitrobenzoates which give better control of wheat rust than oxycarboxin and methyl 4-iodo-3,5-dinitrobenzoate which is at least as effective as captan against Septoria leaf spot on wheat. Several of the esters are superior to captan in controlling chocolate spot on broad bean.     

Photodegradation of atrazine,atraton and ametryne in aqueous solution with acetone as a photosensitiser

The use of acetone as a photosensitiser on the rate of photodegradation of atrazine, atraton and ametryne in diluted aqueous solutions increased degradation 3- to 11-fold. The mechanism of the sensitised photoreaction was studied. The photochemical stability increased in the order methylthio-<chloro-.<methoxy-l,3,5-triazines. Sensitised photolysis of atrazine, ametryne and atraton yielded the analogous two de-N-alkyl- and the de-NN′-dialkyl- products as well as the corresponding hydroxy-triazines; irradiation of ametryne also resulted in the formation of de(methylthio)-1,3,5-triazines. With the exception of de(methylthio)triazine formation, sensitised photodecomposition of these triazine herbicides yields no other breakdown products than those obtained by enzymatic and chemical reactions.     

INTERACTIONS BETWEEN RESIDUAL HERBICIDES AT LOW CONCENTRATIONS*

Summary. Immediate and residual phytotoxicity of binary combinations of several residual soil-applied herbicides at 0·1 and 0·5 ppm was compared to the expected response calculated by Colby's formula. In one experiment diuron was combined with diphenamid, fluometuron, noruron, prometryne or simazine, and in another experiment trifluralin was combined with diuron or dichlobenil. The observed phytotoxicity of most combinations was only slightly different from the expected response. One combination, diuron 0·5 ppm + fluometuron 0·5 ppm, affected mustard significantly more than expected and this synergistic interaction remained appreciable after incubation of 2 months. Interactions entre les herbicides persistants a faible concentration     

Effects of repeated applications at high rates of chlorthiamid and dichlobenil to blackcurrants

Chlorthiamid and dichlobenil were applied to blackcurrants each year for five years at doses up to 54 kg ha^?1. Growth and yield were not affected but leaf margin chlorosis was caused at the higher rates. No nitrile residues of dichlobenil or chlorthiamid were found in the fruit but 2,6-dichlorobenzamide (DCB) was present in most samples tested. There were no adverse effects of the treatments on the taste and flavour of the canned fruit. Nitrile residues in the soil were largely confined to the top 15 cm layer. Amounts detected one year after the previous application did not increase with repeated treatments and were always less than 10% of the annual doses. Nitrile residues were less from dichlobenil than chlorthiamid. The rate of disappearance of soil residues present at the end of the 5-year treatment period was much slower than that of the freshly applied herbicide. During the period of treatment there was generally less DCB than nitrile in the 0-15 cm layer but more was found in deeper layers and small amounts were detected at all depths sampled (up to 105 cm). These residues had largely disappeared 3.5 years after the final treatment. Test crops sown on the plots two years after the final treatment varied in susceptibility to the residues as follows; barley and cabbage (unaffected) <wheat<lettuce<carrot (most susceptible). In the following year only the treatments with chlorthiamid at 27 and 54 kg ha^?1 caused a decrease in the growth of carrots but all the treatments caused skin abnormality.