Persistence studies with [14C] 2,4-D in soils previously treated with herbicides and pesticides

The persistence of [¹⁴C] 2,4-D at a rate equivalent to 1 kg/ha was compared under laboratory conditions in samples of heavy clay, sandy loam, and clay loam at 85% of field capacity moisture and 20 ± 1°C which had either received no pre-treatment, or had been pre-treated for 7 days at the 2 μg/g level with the herbicides benzoylprop-ethyl, diclofop-methyl, dinitramine, flamprop-methyl, nitrofen, picloram, tri-allate, trifluralin, and a combination of tri-allate and trifluralin. The breakdown of [¹⁴C] 2,4-D was also studied in the same soils that had similarly received pre-treatments of 2 μg/g of the cereal seed dressing Vitaflo-DB, the insecticide, malathion, and a combination of Vitaflo-DB and malathion. In each soil type, the half-life of the 2,4-D was similar regardless of whether the soil had, or had not, received any pre-treatment, indicating that none of the chemicals investigated adversely affected the soil degradation of 2,4-D.     

Penetration of triolein and methyl oleate through isolated plant cuticles and their effect on penetration of [14C]quizalofop-ethyl and [14C]fenoxaprop-ethyl

The penetration of two model seed oil compounds, [¹⁴C]triolein (TRI) and [¹⁴C]methyl oleate (MEO) through plant cuticles and their effects on the penetration of [¹⁴C]quizalofop-ethyl and [¹⁴C]fenoxaprop-ethyl were investigated. Experiments were carried out using isolated cuticles from rubber plant (Ficus elastica Roxb.) leaves and from tomato (Lycopersicon esculentum Mill,) and pepper (Capsicum annuum L.) fruits. Chemicals were deposited in droplets on to cuticle discs maintained on agar blocks under controlled conditions. TRI and MEO were used at 1% (V/V). The transfer of radiolabel through cuticles was negligible for TRI and varied from 6 to 13% after 72 h, according to species, for MEO, The penetration results obtained for quizalofop-ethyl (0.084 mg mL^-1) and fenoxaprop-ethyl (0.189 mg mL^-1) were very similar and varied according to species. The greatest diffusion intoagar was observed for pepper (12.8% and 10.7% after 72 h, for quizalofop-ethyl and fenoxaprop-ethyl respectively), the lowest for rubber plant cuticles (1.4 and 1.3% respectively). Addition of MEO produced significant increases in the penetration of quizalofop-ethyl and fenoxaprop-ethyl through rubber plant and tomato cuticles. TRI had an enhancing effect on the two herbicides only with rubber plant cuticles. Results are discussed with particular consideration of the variations between plant species and the possible mode of action of seed oil adjuvants.     

Bound and extractable 14C residues in canola (Brassica napus) plants treated with radiolabelled atrazine

The nature and distribution of ¹⁴C atrazine (2- chloro- 4 -ethylamino- 6 -isopropylamino-s-tria- zine) residues in resistant and susceptible canola (Brassica napus L.) varieties were studied. Radiolabelled atrazine was applied to the plants just before the flowering stage and continued for 10 days. The plants were harvested 3, 10 and 25 days after the end of the treatment. The roots, shoots and pods of each plant were exhaustively extracted with methanol. The ¹⁴C distribution between the methanol extracts and the plant matrix fractions (bound residues) was similar for the two varieties. High-pressure liquid Chromatographie analysis of the methanol extracts showed that they contained two unknown metabolites (possibly conjugates) in addition to atrazine. The bound ¹⁴C residues were released by supercritical methanol extraction and analysed by thin-layer chromato- graphy, gas chromatography and high-pressure liquid chromatography. Several ¹⁴C components in the released material were detected. Bound atrazine and its two dealkylated metabolites represented only a very small portion (10–18%) of the total bound ¹⁴C residues in the plants. Résidus ¹⁴C extractibles et liés chez des plantes de canola (Brassica napus) traitées avec de l'atrazine radioactivement marquée La nature et la distribution de résidus d'atrazine ¹⁴C (2-chloro 4-ethylamino-6-isopropylamino-s-triazine) chez des variétés de canola résistantes et sensibles ont étéétudiés. De l'atrazine radiomarquée a été appliquée aux plantes juste avant la floraison et poursuivie pendant 10 jours. Les plantes ont été récoltées 3, 10 et 25 jours après la fin du traitement. Les racines, tiges et gousses de chaque plante ont été complètement extractées avec du methanol. La distribution du ¹⁴C entre les extraits méthanol et les fractions de plantes matricielles (liées) a été similaire pour les 2 variétés. Des analyses HPLC des extraits méthanol ont montré qu'ils contenaient deux metabolites inconnus (probablement combinés) en plus de l'atrazine. Les résidus ¹⁴C liés étaient libérés par une extraction au méthanol supercritique et analysé par Chromatographie en couche mince, Chromatographie gazeuze et HPLC. Plusieurs composés dans le matériel libéré ont été détectés. L'atrazine liée et ses deux metabolites dealklyés représentaient seulement une très petite part (10–18%) de la totalité des résidus ¹⁴C liés dans les plantes. Gebundene und extrahierbare ¹⁴C-Rückstände in mit radioaktiv markiertem Atrazin behandeltem Raps (Brassica napus) Die Art und die Verteilung von Rückständen von ¹⁴C-Atrazin (2-Chlor-4-ethylamin-6-iso- propylamin-s-triazin) wurden in resistenten und empfindlichen Varietäten von Raps (Brassica napus) untersucht. Das radioaktiv markierte Herbizid wurde kurz vor der Blüte und 10 Tage weiter auf die Pflanzen ausgebracht. Die Pflanzenproben wurden 3, 10 und 25 Tage nach dem Ende der Behandlung gezogen. Wurzeln, Sprosse und Schoten wurden erschöpfend mit Methanol extrahiert. Die ¹⁴C-Verteilung in den Methanolextrakten und im Pflanzenmaterial (gebundene Rückstände) war bei beiden Sorten ähnlich. Bei der HPLC-Analyse wurden in den Methanolextrakten neben Atrazin 2 unbekannte Metaboliten (vermutlich Konjugate) gefunden. Die gebundenen ¹⁴C-Rückstände wurden im Überkritischen Verfahren mit Methanol extrahiert und dünnschicht-, gas-und HPL-chromatographisch analysiert. Verschiedene ¹⁴C-Verbindungen wurden gefunden. Gebundenes Atrazin und seine beiden de-alkylierten Metaboliten machten nur eine kleinen Anteil (10 bis 18%) der gesamten gebundenen ¹⁴C-Rückstände aus.     

Soil persistence experiments with [14C]2,4-D in herbicidal mixtures, and field persistence studies with tri-allate and trifluralin both singly and combined

The persistence of [¹⁴C]2,4-D at a rate equivalent to 1 kg/ha was studied in the laboratory on a heavy clay and a sandy loam at 85%of field capacity and 20°C both alone and in the presence of 1 kg/ha dicamba, dichlorprop, difenzoquat, TCA, and 2,4,5-T. The persistence of 2,4,5-T was also monitored in both soils under the same conditions in the presence and absence of [¹⁴C]2,4-D. All soils were extracted at weekly intervals using aqueous acidic acetonitrile and analysed for [¹⁴C]2,4-D remainining radiochemical techniques. The extracts containing 2,4.5-T were additionally analysed gas chromatographically for that herbicide. In each soil type the half-life of the 2,4-D was similar regardless of whether applied singly or in combination with the five herbicides tested. Similarly, [¹⁴C]2,4-D did not affect the breakdown of 2,4,5-T in either soil type. The persistence of tri-allate (1·5 kg/ha) and trifluralin (0·75 kg/ha) both singly and in combination were compared using small field plots at two locations in Saskatchewan. Applications were made during May of 1977 and 1978 and the plots were sampled and analysed for herbicide(s) remaining after 10 and 20 weeks, respectively. The results indicate that within experimental error the loss of both tri-allate and trifluralin from the plots treated with the mixture was the same as from plots treated with the individual compounds.     

Soil persistence studies with [14C]MCPA in combination with other herbicides and pesticides

The persistence of [¹⁴C]MCPA at a rate equivalent to 1 kg ha^?1 was studied under laboratory conditions in a clay loam, heavy clay and sandy loam at 85% of field capacity moisture and 20±1°C both alone and in the presence of tri-allate, trifluralin, tri-allate and trifluralin, malathion, Vitaflow DB, malathion and Vitaflow DB, bromoxynil, bromoxynil and asulam, bromoxynil and difenzoquat, dicamba, dicamba and mecoprop, linuron, MCPB, metribuzin, propanil, TCA, benzoylprop-ethyl, diclofop-methyl, and flamprop-methyl. Except in the soils treated with asulam, the half-lives of [¹⁴C]MCPA in all three soil types were similar, being approximately 13±1 days, thus indicating that none of the other chemicals studied adversely affected the soil degradation of MCPA. In the asulam treated soils, the half-lives of the MCPA were about 3 days longer than in non-asulam treated soils; the effect was most marked in the clay loam.     

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.     

STUDIEN ZUR VERTEILUNG VON 14C-MARKIERTEM 2,4-D IN VERSCHIEDEN EMPFINDLICHEN UNKRÄUTERN

Studies of the absorption and translocation of ¹⁴C-2,4-D in Chenopodium album L., Galinsoga parviflora Cav., Datura stramonium L. and Galium aparine L. in relation to their susceptibility gave the following results: In G aparine (resistant) there was little transport of 2,4-D applied to the leaves, and a probable relationship between resistance and the immediate binding of the 2,4-D in the treated leaf. D. stramonium (relatively resistant) transported 2,4-D in considerable amounts alter uptake through the leaf, while C. album (very susceptible) and G. parviflora (susceptible) were intermediate in respect of 2,4-D translocation. No relationship between susceptibility of these four species and 2,4-D uptake and translocation from the leaves could be established. After application to the root systems of the four species, 2,4-D was taken up and translocated in the shoot to varying extents. In G. aparine much 2,4-D was taken up and translocated. In contrast to leaf application, the herbicide was not immediately converted into a strongly-held immobile form. In C. album, G. parviflora and D. stramonium, however, no 2,4-D was translocated in the shoot. There was thus no correlation between susceptibility and shoot transport of 2,4-D in the four species studied. Distribution du 2,4-D marqué au ¹⁴C dans des espèces de mauvaises herbes présentant des sensibilités diverses     

Absorption and translocation of 14C fosamine by three woody plant species

Absorption and translocation of ¹⁴C fosamine (ethyl hydrogen (aminocarbonyl) phosphonate) and/or fosamine metabolites were monitored in intermediately susceptible seedling black cherry (Prunus serotina Ehrh.) and resistant seedling rhododendron (Rhododendron sp.) and magnolia (Magnolia sp.). The mid two-thirds of the third leaf below the apical bud of each plant was treated with 0·5 μCi ¹⁴C fosamine (carbonyl carbon labelled). Plants were harvested 3, 7 and 14 days following treatment. In black cherry the majority of ¹⁴C absorption and translocation occurred during the second week following treatment, while magnolia and rhododendron translocated and absorbed most of the ¹⁴C within 3 days after treatment. Retention of ¹⁴C in the treated portion of the treated leaf did not differ between species. However, total translocated ¹⁴C was greatest in black cherry, less in magnolia, und minimal in rhododendron. Magnolia translocated ¹⁴C basipetally, while black cherry translocated acropetally, as well as basipetally. Absorpiion et migration de la fosamine ¹⁴C chez trois espèces de plantes ligneuses L'absorptlon et la migration de La ¹⁴C fosamine ((amino carbonyl) phosphonate d'éthyle hydrogène) et/ou de ses métabolites, ont étéétudiées chez des plantules moyennement sensibles de Prunus serotina (Ehrh.) et chez des plantules résistantes de rhododendron (Rhododendron sp.) et de magnolia (Magnolia sp). Les deux tiers moyens de la troisième feuille en-dessous du bourgeon apical de chaque plant ont été traités avec 0.5 Ci ¹⁴C de fosamine (marquée sur le carbone du carbonyl). Les plantes ont été récoltées 3, 7 et 14 jours après le traitement. Chez P. serotina, la plus grande partie de l'absorption et de la migration du ¹⁴C a eu lieu durant la deuxième semaine après le traitement, alors que chez le magnolia et le rhododendron, le maximum d'adsorption et de migration s'est situé dans les trois jours qui ont suivi le traitement. La rétention du ¹⁴C dans la partie traitée n'a pas variè d'une espèce à l'autre. Toutefois, la quantité totale de ¹⁴C qui a migré a été plus grande chez P. serotina, moindre chez le magnolia et minimaie chez le rhododendron. Chez le magnolia, la migration du ¹⁴C s'opere dans le sens basipète, alors que chez le P. serotina. elle s'effectue aussi bien dans le sens acropète que dans le sens basipète. Aufnahme- und Trunstokaiion von ¹⁴C-Fosaminc bei drei Gehölzpflanzen Es wurde die Aufnahme und die Translokation von ¹⁴C Fosamine (O-Äthyl-aminocarbonylphosphonsäure) und/oder seiner Abbauprodukte bei drei Gehölzarten beobachtet. Verwendet wurden Sämlinge der Traubenkirsche (Prunus serotina Ehrh.), die eine mittlere Empfindlichkeit zeigt und Sämlinge des resistenten Rhododendron (Rhododendron sp.) und der ebenfalls resistenten Magnolie (Magnolia sp.). Die mittleren zwei Drittel des dritten Blattes unterhalb der Endknospe wurden bei jeder Pflanze mit 0.5 μCi ¹⁴C-Fosamine (markiert am Carbonylkohlenstoff) behandelt. Die Pflanzen wurden nach 3, 7 und 14 Tagen nach der Behandlung geerntet. Bei der Traubenkirsche wurde während der zweiten Woche am meisten ¹⁴C aufgenommen und transloziert, während dies bei der Magnolie und dem Rhododendron bereits innerhalb der ersten drei Tage der Fall war. Bezüglich der Retention von ¹⁴C in der behandelten Blattfläche unterschieden sich die drei Arten nicht. In der Traubenkirsche wurde aber am meisten ¹⁴C transloziert, weniger in der Magnolie und am wenigsten im Rhododendron. Die Magnolie translozierte das ¹⁴C basipetal, während die Traubenkirsche akropetal wie basipetal translozierte.     

Effect of some ethoxylated alkylphenols and ethoxylated alcohols on the transfer of [14C] chlorotoluron across isolated plant cuticles

The effect of several ethoxylated octylphenols (OP), nonylphenols (NP) and alcohols (AA) on the penetration of [¹⁴C]chlorotoluron through isolated box-tree (Buxus sempervirens L.) leaf cuticles was investigated. The herbicide solution was deposited as droplets onto cuticle discs maintained on agar blocks acting as receivers. The effects on chlorotoluron transfer across the cuticles depended on the degree of ethoxylation of the surfactant. For each series, the chlorotoluron transfer was considerably increased by surfactants with low ethylene oxide (EO) content (3 to 6 EO). This effect appeared 24 h after droplet application, then increased with time. It decreased with further increase in the ethoxylation number, and surfactants with a long ethylene oxide chain (OP16, NP20, NP40 and AA20) had no effect. Surfactant concentration (OP5) had a large influence on chlorotoluron transfer; penetration increased sevenfold when OP5 concentration was raised from 0.01 to 10 g l^?1. Diffusion of the two tritiated octylphenols, [3H]OP5 and [3H]OP16, was measured simultaneously during chlorotoluron transfer. The diffusion rate of the two surfactants across the cuticles was similar, but a higher amount of OP5 was retained within the cuticle during transfer. Study of the effect of surfactants on the cuticular waxes using differential scanning calorimetry showed that wax begins to melt at a lower temperature in the presence of the nonylphenols NP9 and NP4. Fusion enthalpy was close to -30 J g^?1. Effet de quelques alkylphénols et alcools éthoxylés sur la pénétration du [¹⁴C]chlortoluron à travers des cuticules végétales isolées Nous avons testé l'effet de plusieurs octylphénols (OP), nonylphénols (NP) et alcools éthoxylés (AA) sur la pénétration du [¹⁴C]chlortoluron à travers des cuticules isolées de feuilles de buis. L'herbicide en solution était déposé sous forme de gouttelettes sur des disques de cuticules plaées sur agar. Les effets observés dépendaient du degré d'ethoxylation du surfactant. Pour chaque série, le transfert du chlortoluron à travers les cuticules était considérablement accru avec les surfactants faiblement éthoxylés (3 à 6 oxydes d'éthylène). Cet effet apparaissait 24 h après l'application des gouttelettes puis augmentait avec le temps. Il diminuait avec l'accroissement du nombre d'éthoxylation et aucun effet n'était observé avec les surfactants à longue chaine d'oxydes d'éthylène (OP16, NP20, NP40 et AA20). La concentration en surfactant (OP5) avait une grande influence sur le transfert du chlortoluron dans l'agar, il augmentait sept fois entre 0.01 et 10 g l^?1. La diffusion des deux octylphénols (³H-OP5 et ³H-OP16) a été mesurée simultanément durant le transfert du chlortoluron. La vitesse de diffusion des deux surfactants à travers les cuticules était comparable, mais une quantité plus élevée d'OP5 était retenue dans les cuticules durant le transfert. L'étude par analyse calorimètrique à balayage de l'effet des surfactants sur les cires cuticulaires a montré que la fusion des cires commence à plus faible température en présence des nonylphénols NP9 et NP4. L'enthalpie de fusion était en général voisine de -30 J g^?1. Wirkung einiger ethoxylierter Alkylphenole und Alkohole auf den Transfer von [¹⁴C]Chlortoluron durch die Pflanzen-Cuticula Die Wirkung verschiedener ethoxylierter Octylphenole (OP), Nonylphenole (NP) und Alkohole (AA) auf die Penetration von [¹⁴C]Chlortoluron durch die isolierte Blatt-Cuticula von Buxbaum (Buxus sempervirens L.) wurde untersucht. Die Herbizidlösung wurde als Tröpfchen auf Cuticula-Scheiben, die auf Agarblöcken als Empfänger ausgelegt worden waren, ausgebracht. Die Wirkung auf den Chlortoluron-Transfer durch die Cuticula hing von der Ethoxylierung des Zusatzstoffes ab. In allen Serien wurde der Transfer durch Zusatzstoffe mit niedrigem Gehalt an Ethyloxiden (EO) erheblich gesteigert (3 bis 6 EO). Diese Wirkung trat 24 h nach der Applikation der Tröpfchen ein und nahm dann mit der Zeit zu. Mit dem Anstieg der Ethoxylierungszahl nahm die Wirkung ab, und Zusatzstoffe mit einer langen Ethylenoxidkette (OP16, NP20, NP40 und AA20) waren wirkungslos. Die Konzentration des OP5-Zusatzstoffes hatte großen Einfluß auf den Chlortolurontransfer; die Penetration war versiebenfacht, wenn die OP5-Konzentration von 0,01 auf 10 g l^?1 angehoben wurde. Die Diffusion der Octylphenole [³H]OP5 und [³H]OP16 wurde während des Chlortolurontransfers gemessen; die Diffusionsrate war ähnlich, aber von OP5 wurde ein größerer Anteil in der Cuticula zuückgehalten. Die Wirkung der Zusatzstoffe auf das Cuticularwachs wurde calorimetrisch untersucht, und es zeigte sich, daß das Wachs in Gegenwart der Nonylphenole NP9 und NP4 bei niedriger Temperatur zu schmelzen beginnt. Die Fusionsenthalpie lag bei -30 J g^?1     

EFFECT OF 2,4-D AND PICLORAM ON TRANSLOCATION OF 14C-ASSIMILATES IN VITIS VINIEERA L.

Summary. High concentrations of 2,4-D and picloram interfered with the downward movement of ¹⁴c-assimilates infield-grown vines. The interference in translocation was appreciably greater with picloram than it was with 2,4-D, Although basipetal translocation was retarded, translocation within the treated shoots continued from the vegetative part to the clusters. Translocation of 2,4-D appeared to follow the same route as ¹⁴c-assimilatcs for the most part. Formative effects were absent on untreated grape shoots although the adjacent shoots treated with 2,4-D or picloram on the same cordons were killed; however, formative effects were evident on some of the stump sprouts which developed after the vines were harvested. The malformed leaves on the stump sprouts were twelve or more nodes from the base of the shoots, while ¹⁴c was in the more basal leaves.
Thompson Seedless (Sultanina) rootings treated with 20 000 ppm 2,4-D or picloram transported less ¹⁴C to the roots than did the controls. Treatment with either herbicide resulted in a marked increase in the labelling of the stems.
Effet du 2,4-D et du pichlorame sur la migration de métabolites marqués au ¹⁴C dans Vitis vinifera L.     

Uptake and translocation of [14C]asulam and [14C]bromacil by roots of maize and bean plants

The uptake and translocation of ¹⁴C-ring-labeled asulam (methylsulfanilcarbamate) and bromacil (5-bromo-3-sec-butyl-6-methyluracil), were compared after root application to maize (Zea mays L.) and bean (Phaseolus vulgaris L.). Autoradiographs showed the distribution of bromacil throughout these and other plant species, and the retention of asulam in the roots. The recovery of both compounds in quantitative radioassays was between 90 and 100%. The absorption of bromacil and asulam was rather similar. Absorption of bromacil increased up to 20% of the applied dose in bean plants after 2 days of exposure, and up to 11% in maize plants after 4 days. Absorption of asulam in bean plants was 22% of the applied dose after 2 days, and 8% in maize plants after 4 days. The pattern of distribution of bromacil and asulam was completely different. After 4 h of exposure of the roots about half of the absorbed bromacil had accumulated in the shoots, while two-thirds or more was translocated to the shoots after exposure periods of 1 to 4 days. Not more than one-eighth of the absorbed asulam was found in the shoots. In consequence, the bromacil content in the transpiration stream relative to that in the ambient solution was much higher than that of asulam. The leakage of asulam from bean and maize roots into herbicide-free nutrient solution was lower than that of bromacil. The reasons for these differences are not yet clear. There was only some metabolism of asulam in maize, but not in bean plants. No metabolites of bromacil were detected in the two plant species.     

Biotransformation of [ring-U-14C]atrazine to dealkylated and hydroxylated metabolites in cell-suspension cultures

The biconversion of [¹⁴C]atrazine to deaikyt-ated and hydroxylated products was studied in heteroirophic cell-suspension cultures of carrot ( Daucus caroia L.), Agrostemma githago L. (corn cockle). Digitalis purpurea L. (purple foxglove), soyabean ( Giycine max L. Merr; four different cultivars). Datura stramonium L. (thorn-apple) and wheat ( Tritician aestivum L.). During 48 h of incubation, the herbicide was biotransformed by all species; turnovers yields differed considerably and were between 10.1% and 88.0% of applied ¹⁴C. Differences were also observed among the soyabean cultivars (10.1-73.5%). Hydroxy-atrazine, de-ethyl-, deisopropyl- and de-ethyt-deisopropylatrazine formed in the cultures were identified by thin-layer chromatography (tlc) (co-chromatography with reference compounds); deaikyiated metabolites were also proved by gas chromatography–mass spectrometry (gc–ms). In addition, highly polar transformation products emerged that were not identified. Portions of non-extractable residues were below 5% (one soyabean cultivar: 8.9%). Atrazine was metabolized by the cells, mainly to its dealkylated derivatives and hydroxyatrazine (totals of 9.4-54, 5%), whereas portions of highly polar products were lower (0.1-26.1%). Exceptions were A. githago (26.0 and 33.6%, respectively) and D, purpurea (4.5 and 25.2% respectively). Thus, plants generally contribute to the environmental degradation of atrazine.     

Metabolism of [14C]vernolate in soybeans

Penetration and metabolism of [¹⁴C]vernolate in soybean [Glycine max (L.) Merr. var Ransom] pods and seeds were measured 0, 1, 4, 24, 48, or 72 hr after treatment which occurred at 40 days after flowering. Total ¹⁴C recovery decreased ca. 50% within 4 hr and the loss of ¹⁴C was considered to be a measure of volatility. Total nonpolar extractants decreased in a logarithmic pattern which approached 10% of total ¹⁴C recovered within 24–48 hr. Total polar extractants increased in a logarithmic pattern to a maximum of 90% of total ¹⁴C recovered within 24 hr. Seed nonpolar extractants never exceeded 2% of the total ¹⁴C recovered while pod nonpolar extractants consisted of vernolate plus an unidentified component that did not thin-layer chromatograph (TLC) as the sulfone or sulfoxide. Pod polar extractants increased with time to ca. 75% of the total ¹⁴C recovered (24–48 hr) and decreased to ca. 58% at 72 hr after treatment. Seed polar extractants averaged ca. 10% of total ¹⁴C recovered for the first 48 hr after treatment and then increased to 30% of total ¹⁴C recovered. Thus, [¹⁴C]vernolate per se concentration decreased to <1% of applied material within 72 hr through volatilization and degradation of nonpolar extractants to polar products. Polar metabolites showed two major patterns of vernolate detoxification. One detoxification system produced ¹⁴C-metabolites whose R_f's were equivalent to that reported in corn (Zea mays L.) [J. P. Hubbell and J. E. Casida, [J. Agric. Food Chem. 25, 404 (1977)] and accounted for <30% of the pod polar extractants. A second detoxification system was most prevalent in soybean pod and seed tissues and resulted in very rapid modification of vernolate with an unidentified product that was 85% of the extracted ¹⁴C within 4 hr after treatment and which decreased in concentration with time. Therefore, unexplained vernolate detoxification system(s) exist in soybean pod and seed.     

Metabolic and elimination products of [14C]photodieldrin from bluegill fish

Bluegill fish, following exposure to [¹⁴C]photodieldrin eliminated 50% of the absorbed radioactivity in 3 weeks. Analysis of the products revealed that about 27% of the eliminated radioactivity was due to the unaltered photodieldrin while the rest consisted of at least 11 metabolites in free and conjugated forms. Photodieldrin ketone was the major excretory product. Solvent extracts of the whole fish examined showed 4 metabolites in addition to about 90% of the unmetabolized photodieldrin. The ketone derivative was the most predominant of the metabolic products.     

Metabolism of [14C]dieldrin in bluegill fish

The exposure of bluegill fish to 50 parts per billion [¹⁴C]dieldrin in a static system resulted in the absorption of 73.00% of the radioactivity in 48 hr. Following transfer of the fish to clean water, only 16.20% of the absorbed radiolabel was eliminated in 23 days. Out of the 93.65% of the absorbed radioactivity recovered, 9 radioactive spots were isolated which included unchanged dieldrin (74.39%), pentachloroketone (8.17%), and aldrin-trans-diol (8.04%) as major metabolites.     

Metabolic fate of [14C]photodieldrin in goldfish

Goldfish (Carassius auratus) exposed to 20 parts per billion [¹⁴C]photodieldrin in a static system absorbed 80% of the radioactivity within 20 hr. The absorbed radioactivity was eliminated slowly with a half-life of 3 weeks. Photodieldrin and a ketone derivative were the major form of the radiocarbon eliminated in water, accounting for, respectively, 59 and 10.4% of the eliminated radioactivity. The ketone derivative was characterized by cochromatography (thin-layer and gas chromatography, gc) and gc-mass spectrometry. Approximately, 15 other polar and nonpolar metabolites were detected in the aqueous medium. The radioactivity in the fish consisted of 13 metabolites along with photodieldrin. Photodieldrin and the ketone derivative were the most abundant residues in the fish, accounting for 77 and 5.4% of the radioactivity, respectively.     

The application of picloram-14C to bracken

Experimental systems were produced from fragments of bracken rhizome and picloram-¹⁴C was applied to frond laminae, rhizome apices, frond buds and roots and translocation assessed 7 days after treatment. The isotope was readily taken up by all organs and freely translocated to associated fractions of the rhizome except in the case of laminae from which distribution was very poor. Accumulation of activity in the roots was considerable following treatment of the frond buds but was limited in the frond buds. Poor translocation of herbicide from treated frond laminae is considered a possible explanation of poor control in the field when bracken is sprayed in July. Lapplication du picioram e¹⁴C à la fougère Des systèmes expérimentaux ont étéétablis en utilisant des fragments de rhizome de fougére et du piciorame ¹⁴C a été appliqué sur les limbes des frondes, les apex des rhizomes, les bourgeons des frondes et les racines. La migration fut évaluée sept jours aprés le traitement. L'isotope a été facilement absorbé par tous les organes et librement transporté aux fractions correspondantes du rhizome, sauf dans le cas des limbes è partir desquels la distribution a été très faible. L'accumulation de ractivité dans les racines a été considérable è la suite du traitement des bourgeons de frondes mais a été Iimitée dans les bourgeons de frondes. Une faible migration de I'herbicide depuis les limbes des frondes est considérée comme une explication possible du désherbage mediocre auchamp, lorsque la fougère est traitée en juillet. Die Anwendung von PicIoram-¹⁴C zu Adlerfarn Aus Rhizomstücken von Adlerfarn wurden Versuchsp-flanzen gezogen und auf die Wedelspreiten, Rhizomapices, Wedelknospen und Wurzein- Picloram-¹⁴C appliziert. Die Transiokation des Herbizids wurde eine Woche nach der Behandlung gemessen. Das lsotop wurde von alien Pflan-zenorganen schnell aufgenommen und in die dem Rhizom benachbarten Pflanzenteile transloziert; bei Behandlung der Wedelspreiten war jedoch nur eine geringe Verteilung fest-zustellen. Nach Behandlung der Wedelknospen war in den Wurzein eine beträchtliche, aber in den Wedelknospen nur eine geringe Aktivitätsanreicherung feststellbar. Für den schwachen Bekämpfungserfolg des Adierfarns im Freiland bei Spritzungen im Juli, wird die geringe Transiokation des Herbizids aus den Wedelspreiten als mögliche Erklärung angesehen.     

Metabolic fate of [14C]endrin in bluegill fish

Bluegill absorbed 85% of 1 ppb of endrin from water within 48 hr under static exposure conditions. The absorbed radiocarbon was eliminated linearly with a half-life of about 4 weeks. Analyses of eliminated radioactivity revealed only conjugated metabolites. 12-anti-Hydroxyendrin and 12-syn-hydroxyendrin were tentatively identified by cochromatography using thin-layer chromatography/autoradiography and gas chromatography. These metabolites were also present as conjugates in the fish organs. Seventy-three percent of the absorbed radioactivity recovered from fish extracts was in the form of unchanged endrin.     

The uptake and translocation of 14C-SAN-6706 and 14C-SAN-9789 in Vaccinium macrocarpon cv. Early Black

The uptake and translocation of ¹⁴C-labelled 4-chloro-5-(dimethytamino)-2-(α,α,α,-trifluoro-m-lolyl)-3(2H)-pyridazinone (SAN-6706) and 4-chloro-5-(melhylamino)-2-(α,α,α,-trifluoro-m-tolyt)-3(2H)-pyridazinone (SAN-9789) were studied in cranberry plants (Vaccinium macrocarpon Ait. cv. EarlyBlack). The plants were treated in water solution and sampled at 1,3,8 and 15 days. Other plants were treated for these times, washed free from extraneous herbicide, grown for 3 weeks longer in nutrient with no herbicide and then sampled to determine the fate of the herbicide. Both compounds were readily translocated and the amount of label present in the shoot increased with time. In plants grown for 3 more weeks after treatment there was translocation of the label from the root to the shoot. No radioactive label was detected in the cranberry fruit. Absorption et migration du ¹⁴C-SAN-6706 et du ¹⁴C-SAN-9789 chezVaccinium macrocarpon cv. Early Black L'absorption et la migration de la 4-chloro-5-(dimeAthyiamino)-2-(α,α,α-trifluoro-m-tolyl)-3(2H)-pyridazinone (SAN-6706) et de la 4-chloro-5-(méthylamino)-2-(α,α,α-trifluoro-m-tolyl)-3(2H) pyridazinone (SAN 9789), marquées au ¹⁴C, ont été eAtudiées chez la canneberge (Vaccinium macrocarponAit, cv. Early Black). Les plantes ont été traitées en solution aqueuse et échantillonnfées aprés 1, 3, 8 et 15 jours. D'autres plantes ont éteA traitées pour ces mêmes durées, Iavées pour éliminer les traces externes d'herbicide, et cultivées pendant 3 semaines de plus en milieu nutritif sans herbicide, et enfin échantillonnées pour determiner le devenir de L'herbicide. Les deux composes migrerent rapldement et la quantité de produit marqué présente dans la partie adrienne augmenta avec le temps. Dans les plantes cultivées 3 semaines supplémentaires aprés le traitement, il y eut migration du produit marque des racines vers les tiges. Aucun élément radioactif n'a été décelé dans les fruits de canneberge. Die Aufnahme und Translokatlon von ¹⁴C-SAN-6706 und¹⁴CSAN-9789 bei Vaccinium macrocarpon Sorte Early Black Es wurde die Aufnahme und Translokation von ¹⁴C-markiertem 4-Chlor-5-(dlmcthylamino)-2-(α,α,α;-trifluor-m-tolyl)-3(2H)-pyridazinon (SAN-6706) und 4-Chlor-5-(methylamino)-2-(α,α,α-trifluor-m-tolyl)-3(2H)-pyridazinon (SAN-9789) bei Preiselbeerpflanzen (Vaccinium macrocarpon Ait. Sorte Early Black) untersucht. Die Pflanzen wurden in Wasserkultur behandelt und nach 1, 3, 8 und 15 Tagen Proben genommen. Bei anderen Pflanzen, die auch über diese Perioden behandelt worden waren, wurde anschliessend das äuβerlich anhaftende Herbizid abgewaschen, für 3 weitere Wochen in NaUhrlösung ohnc Herbizid gehalten und dann Proben gezogen, um die Verteilung des Herbizids zu bestimmen. Beide Verbindungen wurden rasch transloziert und der Gehait an markierter Substanz im Spross nahm mit der Zeit zu, in den Pflanzen die für 3 weitere Wochen nach der Behandlung gewachsen waren, wurde Translokation voti der Wurzel in den Spross festgestellt. In der Preiselbeerfrucht konnte keine Radioaktivität festgestellt werden.