Dissipation rates in soil of 1,2-dichloropropane and 1,3- and 2,3-dichloropropenes

The rates of dissipation in soil and chloride-ion release, of the main components of dichloropropane-dichloropropene mixtures used as nematicides, were studied in sealed glass containers at different temperatures and moisture conditions. Half-lives of (Z)- and (E)-1,3-dichloropropenes at 20°C in soils were found to vary from 3 to 25 days; those of 1,2-dichloropropane and 2,3-dichloropropene were about four times and twice as long, respectively. The dissipation rates changed by a factor of about 2 per 10°C change in temperature. Judging from the release rates of waterextractable inorganic chloride in the soil (0-4% per week), the total degradation of all components applied at normal field rates was extremely slow. This indicated the formation of residues containing covalently bound chlorine. Only in ‘enrichment cultures’ was complete degradation indicated.     

Effect of temperature,organic amendment rate and moisture content on the degradation of 1,3‐dichloropropene in soil

1,3‐Dichloropropene (1,3‐D), which consists of two isomers, (Z)‐ and (E)‐1,3‐D, is considered to be a viable alternative to methyl bromide, but atmospheric emission of 1,3‐D is often associated with deterioration of air quality. To minimize environmental impacts of 1,3‐D, emission control strategies are in need of investigation. One approach to reduce 1,3‐D emissions is to accelerate its degradation by incorporating organic amendments into the soil surface. In this study, we investigated the ability of four organic amendments to enhance the rate of degradation of (Z)‐ and (E)‐1,3‐D in a sandy loam soil. Degradation of (Z)‐ and (E)‐1,3‐D was well described by first‐order kinetics, and rates of degradation for the two isomers were similar. Composted steer manure (SM) was the most reactive of the organic amendments tested. The half‐life of both the (Z)‐ and (E)‐isomers in unamended soil at 20 °C was 6.3 days; those in 5% SM‐amended soil were 1.8 and 1.9 days, respectively. At 40 °C, the half‐life of both isomers in 5% SM‐amended soil was 0.5 day. Activation energy values for amended soil at 2, 5 and 10% SM were 56.5, 53.4 and 64.5 kJ mol^?1, respectively. At 20 °C, the contribution of degradation from biological mechanisms was largest in soil amended with SM, but chemical mechanisms still accounted for more than 58% of the (Z)‐ and (E)‐1,3‐D degradation. The effect of temperature and amendment rate upon degradation should be considered when describing the fate and transport of 1,3‐D isomers in soil. Use of organic soil amendments appears to be a promising method to enhance fumigant degradation and reduce volatile emissions. Published in 2001 for SCI by John Wiley & Sons, Ltd     

Characterization of residues in soybeans grown in soil treated with 1,3-dichloropropene soil fumigant

The metabolism of cis- and trans-1,3-dichloropropene (1,3-D) was studied in soybean plants grown in soil treated 24 days prior to planting with [U-¹⁴C]E- and Z-1,3-dichloropropene at 380 liters ha^?1. Isolation and identification of the ¹⁴C residue from soybean plants at 84 days (forage) and 176 days (mature) after application showed that no 1,3-dichloropropene or its putative metabolites, 3-chloroallyl alcohol and 3-chloroacrylic acid, could be detected in any of the tissues. The components of the ¹⁴C residue included major plant constituents (i.e. fatty acids, protein, pigments, organic acids, sucrose and other carbohydrates, and lignin).     

Base-catalysed hydrolysis of (E)- and (Z)-mevinphos

The rates at which (E)- and (Z)-mevinphos are hydrolysed in aqueous solutions in the pH range 8.7–11.5, and in the temperature range 30–50°C, have been measured. The overall activation parameters have been calculated, and equations to allow calculation of the rates in any basic conditions are given. The complicated routes by which (E)- and (Z)-mevinphos are hydrolysed to simple molecules have been deduced. The rates for the individual steps in each route have been either measured experimentally, or have been calculated through analogue simulation of all the reactions, by matching the calculated to the observed ultraviolet spectral changes during hydrolysis. It is proposed that (Z)-2-carboxyl-1-methylvinyl dimethyl phosphate is not observed as a hydrolysis product of (Z)-mevinphos because it decomposes by an extremely fast intramolecular reaction. The reasons for the greater lability of (E)-mevinphos are also discussed.     

铜绿丽金龟对寄主植物挥发物的触角电生理及行为反应

为深入了解铜绿丽金龟的取食行为,探索开发安全高效的植物源引诱剂,应用昆虫触角电位反应仪和Y型嗅觉仪测试其对不同寄主植物挥发物的趋向行为差异,并根据室内行为结果配制诱剂进行大田试验。结果表明:铜绿丽金龟雄虫对水杨酸甲酯和(1,1’-联环戊基)-2-酮的触角电位反应(electroantennography,EAG)值显著高于其它试剂;石竹烯和水杨酸甲酯能引起雌虫触角较强的电位反应;乙酸顺式-3-己烯酯和石竹烯分别对雄虫和雌虫有较高的嗅觉选择反应率,分别达0.95和0.94。综合EAG和嗅觉试验结果,选择对雌、雄虫均有较好引诱效果的反式-2-己烯醛、乙酸顺式-3-己烯酯、石竹烯、(1,1’-联环戊基)-2-酮和水杨酸甲酯进行田间试验,最终筛选到铜绿丽金龟雄虫的最适引诱剂为每诱芯360 mg乙酸顺式-3-己烯酯,雌虫的最适引诱剂为每诱芯360 mg石竹烯,日诱虫量分别可达33.00±1.53头和29.33±1.45头。     

Higher-tier assessment of the potential for groundwater issues due to the use of 1,3-D soil fumigant; evaluation of the active ingredient, metabolites and potentially related chlorinated compounds

BACKGROUND: 1,3‐Dichloropropene (1,3‐D, CAS No. 542‐75‐6) is a broad‐spectrum soil fumigant used to control numerous species of soilborne plant‐parasitic nematodes. 1,3‐D consists of two isomers, (Z)‐ and (E)‐1,3‐D. There are a number of low‐level chlorinated compounds that could potentially be produced as a part of the 1,3‐D manufacturing process. 1,3‐D and its metabolites, as well as potentially related chlorinated compounds, represent potential groundwater contaminants. RESULTS: This study has investigated the hydrolytic stability, under biotic and abiotic conditions in the laboratory, of an extensive representative list of 1,3‐D and potentially related chlorinated compounds in order to predict their environmental fate. All of these compounds showed intrinsic hydrolytic instability under both abiotic and biotic test conditions. Furthermore, a monitoring programme was carried out. Twenty‐five wells were monitored in five Italian regions characterised by historical and existing use of 1,3‐D. The parent compound, its two major metabolites and potentially related chlorinated compounds were not detected in the well water at > 0.1 µg L^?1 at any sampling location. CONCLUSION: The soil fumigant (E,Z)‐1,3‐D, its metabolites and potentially related chlorinated compounds constitute a low risk to groundwater. Copyright © 2011 Society of Chemical Industry     

Transformation rate of 1,3-dichloropropene and 3-chloroallyl alcohol in topsoil and subsoil material of flower-bulb fields

The extent of the risk of (Z)- and (E)-1,3-dichloropropene and their transformation products (Z)- and (E)-3-chloroallyl alcohol causing a hazard to the quality of groundwater pumped up for public water supply from below flower-bulb fields has been evaluated. The 1,3-dichloropropenes were incubated at 10°C in water-saturated subsoil material from three such fields. A first stage with gradual transformation was followed by a second stage with comparatively rapid transformation and after three months negligible amounts remained. The 3-chloroallyl alcohols were incubated at 15°C in soils from the root zone of the same fields. Complete transformation had occurred in about a week or even less. The 3-chloroallyl alcohols were also incubated in the water-saturated subsoil material at 10°C. Again, a first stage with gradual transformation was followed by a second stage with fast transformation. In most instances, the concentrations had fallen to a very low level within three months. It was concluded that it is unlikely that residues in the upper groundwater would permeate into the deeper groundwater pumped up for public water supply.     

The uptake of metabolites of permethrin by plants grown in soil treated with [14C]permethrin

Sugar beet, wheat, lettuce and cotton were grown in soil treated with [¹⁴C]permethrin, the crops being sown at intervals of 30, 60 and 120 days after treatment of the soil. The uptake of radioactive residues into these crops was measured. Low radioactive residues (up to 0.86 μg g^?1) were detected in the mature plants sown 30 days after soil treatment, and this uptake declined significantly as the interval between soil treatment and sowing increased. Metabolites derived from the acid moiety of the permethrin molecule were shown to constitute the greater part of the residue transferring from the soil to the crops. (1RS)-cis- and (1RS)-trans-3-(2,2-dichlorovinyl)- 2,2-dimethylcyclopropanecarboxylic acid and 3-(2,2-dichlorovinyl)-1-methylcyclopropane-1,2-dicarboxylic acid were identified as the major acidic metabolites. The latter compound is a metabolite of permethrin which has not previously been identified in soil or plants.     

Degradation of the herbicide flamprop-isopropyl in soil under laboratory conditions

The degradation of the wild-oat herbicide flamprop-isopropyl, [isopropyl (±)-N-benzoyl-N-(3-chloro-4-fluorophenyl)alaninate], in four soils has been examined under laboratory conditions with sampling times of up to 45 weeks after treatment. The major degradation product of [¹⁴C]flamprop-isopropyl in all soils at up to 10 weeks after treatment was the carboxylic acid (±)-N-benzoyl-N-(3-chloro-4-fluorophenyl)alanine. This compound in turn underwent degradation by loss of the benzoyl group and the propionic acid moiety, with evolution of [¹⁴C]carbon dioxide to form 3-chloro-4-fluoroaniline (CFA). The CFA was formed slowly in soil and occurred mainly as a bound form. There was evidence to show that the CFA was subsequently converted into other polar products. The time for depletion of 50% of the applied herbicide was approximately 10 weeks in sandy loam and medium loam soils, 11 weeks in a clay loam soil and 23 weeks in a peat soil.     

Dégradation de l'isoproturon et disponibilité de ses résidus dans le sol

Degradation if isoproturon and availability of residues in soil The availability and degradation of ¹⁴C-ring-labelled isoproturon in soil was investigated over 140 days under controlled laboratory conditions. Degradation of the active ingredient followed and 65 days later only a minor fraction (0.6%) of the parent molecule remained extractable. A demethylated-isoproturon metabolite was detectable in soil from day 15 (2.6%). The amount of ¹⁴CO₂ derived from the ¹⁴C benzene ring label and liberated over time indicated that a total of 13.6% isoproturon was mineralized during the incubation period. In parallel, the amount of ¹⁴C residue extracted from the soil by water followed by methanol or remaining within the soil—analysed by combustion—was also determined at intervals. After 140 days, 72% of the radiolabel added remained in the soil as non-extractable residue. The degradation half-life of extractable isoproturon was an estimated 14 days.     

1(R)-(2,6-cis-dimethylmorpholino)- 3(S)-(p-tert-butylphenyl)cyclopentane: A representative of a novel,potent class of bio-rationally designed fungicides

Inhibition of the Δ⁸-Δ⁷ sterol isomerase in the ergosterol biosynthesis pathway is known to lead to fungistatic or even fungicidal effects. Our approach to the rational design of new putative inhibitors of the enzyme was based on the assumed mechanism of the enzymic transformation and in particular on the structure of the unstable carbocationic intermediate, i.e. the ‘transition-state-analogue’ principle. The synthesis and the biological properties of 1(R)-(2,6-cis- dimethylmorpholino)-3(S)-(p-tert-butylphenyl)cyclopentane, a representative of a novel, potent class of rationally designed fungicides, as well as the synthesis and biological activities of several other related compounds are described and discussed.     

Distribution and breakdown of DDT in orchard soil

Amounts of DDT and its breakdown products were determined in soil in an apple orchard in Herefordshire. Samples were taken for a number of years (1972–79) after use of the insecticide in the orchard had ceased in 1969. The results were compared with those obtained in an investigation of the same orchard in 1968. From 1968 to 1979, soil residues of pp′-DDT, p′--DDT and pp′--TDE decreased gradually whereas those of pp′--DDE increased, and there were linear relationships between log (concentration) and time. The calculated time for 50% decrease in concentration (Dt₅₀) was 11.7 years for pp′--DDT, 3.3 years for pp′--TDE and 7.1 years for op′--DDT; the time for doubling the concentration for pp′--DDE was 9.1 years. Regression analysis on the two major components (pp′--DDT+pp′--DDE) indicated that the total amount (2.7 mg kg^?1) was not decreasing with time. It was concluded that during a post-spray era, the breakdown of pp′--DDT to pp′--DDE was a significant feature of the persistence of DDT, and that, in contrast to the findings of other workers who sampled when DDT was being used, there were no losses by volatilisation. There was an exponential decrease in the amount of DDT residues with increasing soil depth and approximately 90% was found in the top 10 cm of the undisturbed soil profile.     

The elimination of (N-[[(4-chlorophenyl)amino]carbonyl]-2,6-difluorobenzamide) by the boll weevil

Boll weevils, Anthonomus grandis Boheman, were either dipped in or injected with a solution of [¹⁴C]diflubenzuron (N-[[(4-chlorophenyl)amino]carbonyl]-2,6-difluorobenzamide) or fed on cotton squares that had been treated with the chemical to determine its turnover time and metabolic fate. No significant differences were observed between male and female weevils in their ability to eliminate [¹⁴C]diflubenzuron. Only minor differences were observed when immersion and injection treatments were compared. When weevils were treated with 66.3 ng of [¹⁴C]deflubenzuron per weevil by injection, the insects contained 13 to 15% of the radiolabel after 6 days and 4 to 6% after 13 days. The remainder of the radiolabel was in the frass. When weevils fed for 66 hr on cotton squares that had been treated with a wettable [¹⁴C]diflubenzuron preparation (Dimilin W-25), the insects averaged 120 ng of diflubenzuron per weevil. Forty-four hours after removing insects from the treated squares, 50% of the radiolabel had been excreted. In all cases, the radiolabel found in the frass or in the weevil was unchanged diflubenzuron. There were no data to indicate that the boll weevil could metabolize appreciable amounts of diflubenzuron.     

Aerobic soil metabolism of metsulfuron-methyl

A laboratory study was conducted to determine the degradation rates and identify major metabolites of the herbicide metsulfuron-methyl in sterile and non-sterile aerobic soils in the dark at 20°C. Both [phenyl-U-¹⁴C]- and [triazine-2-¹⁴C]metsulfuron-methyl were used. The soil was treated with [¹⁴C]metsulfuron-methyl (0.1 mg kg⁻¹) and incubated in flow-through systems for one year. The degradation rate constants, DT₅₀, and DT₉₀ were obtained based on the first-order and biphasic models. The DT₅₀ (time required for 50% of applied chemical to degrade) for metsulfuron-methyl, estimated using a biphasic model, was approximately 10 days (9–11 days, 95% confidence limits) in the non-sterile soil and 20 days (12–32 days, 95% confidence limits) in the sterile soil. One-year cumulative carbon dioxide accounted for approximately 48% and 23% of the applied radioactivity in the [phenyl-U-¹⁴C] and [triazine-2-¹⁴C]metsulfuron-methyl systems, respectively. Seven metabolites were identified by HPLC or LC/MS with synthetic standards. The degradation pathways included O-demethylation, cleavage of the sulfonylurea bridge, and triazine ring opening. The triazine ring-opened products were methyl 2-[[[[[[[(acetylamino)carbohyl]amino]carbonyl]amino] carbonyl]-amino]sulfonyl]benzoate in the sterile soil and methyl 2-[[[[[amino[(aminocarbonyl)imino]methyl] amino]carbonyl]amino]sulfonyl]benzoate in the non-sterile soil, indicating that different pathways were operable. © 1999 Society of Chemical Industry     

Photolysis of Diniconazole-M under Sunlight

The photodegradation of diniconazole-M [(E)-(R)-1-(2,4-dichlorophenyl)-4,4-dimethyl-2-(1,2,4-triazol-1-yl)-1-pentene-3-ol] was studied as thin film on glass surface under sunlight. Photoproducts were separated and identified by NMR, IR, UV and mass spectroscopy. They were characterised as the (Z)-isomer of diniconazole-M, a cyclic alcohol and its corresponding ketone and an isoquinoline derivative. © 1997 SCI.     

Metabolism of amitrole in apple: II. Bound residues from mature fruits

Significant radioactivity detected in mature fruits, harvested from apple trees (Malus domestica Borkh., cv. ‘Golden Delicious’ and ‘Gloster’) that were soiltreated with [3,5-¹⁴C]amitrole, remained in the insoluble plant material after exhaustive extraction. These bound residues were solubilized with a mixture of pectinases and cellulases. Thus, separation and characterization of carbohydrates and xenobiotic moieties released during this procedure became possible. A part of the radiolabel was incorporated into natural products, indicating degradation of the applied amitrole and reassimilation of [¹⁴C] carbon dioxide.     

Sex attractant for the banana moth,Opogona sacchari Bojer (Lepidoptera: Tineidae): provisional identification and field evaluation

BACKGROUND: The banana moth, Opogona sacchari Bojer, is a polyphagous agricultural pest in many tropical areas of the world. The identification of an attractant for male O. sacchari could offer new methods for detection, study and control. RESULTS: A compound extracted from female O. sacchari elicited responses from antennae of male moths. This compound was identified as a 2/3,(Z)13‐octadecadienal by gas chromatography‐mass spectrometry. An analog, 2/3,(Z)13‐octadecadienol, was also detected in some extracts at roughly a 1:20 ratio (alcohol:aldehyde) but did not elicit responses from antennae of male moths. Electroantennograms of synthetic candidate dienals found the strongest responses from (Z, Z)‐2,13‐octadecadienal and (E, Z)‐2,13‐octadecadienal. In field trials, (E, Z)‐2,13‐octadecadienal attracted more male O. sacchari than (Z, Z)‐2,13‐octadecadienal. Attraction was not improved for either of these compounds when the corresponding stereoisomeric alcohol was added at ratios of 1:1, 1:10 or 1:100 (alcohol:aldehyde). Jackson sticky traps containing 250 µg lures of (E, Z)‐2,13‐octadecadienal caught as many males as did traps holding virgin females. CONCLUSION: (E, Z)‐2,13‐octadecadienal has been identified as an attractant for O. sacchari males and can be used as a monitoring lure of populations of this moth. Copyright © 2010 Society of Chemical Industry     

Volatile organic compounds (VOCs) from cereal plants infested with crown rot: their identity and their capacity for inducing production of VOCs in uninfested plants

When infested with Fusarium sp., the cereals Triticum aestivum L. emend. Fiori et Paol. cv. ‘Bombona’, Avena sativa L. cv. ‘Deresz’, and Hordeum vulgare L. cv. ‘Rastik’ can emit volatile organic compounds (VOCs). The VOCs differ both qualitatively and quantitatively from those emitted by non-infested wheat, oat, and barley plants. We detected increased amounts of VOCs released by green leaves (green leaf volatiles – GLVs): (Z)-3-hexenal, (E)-2-hexenal, (Z)-3-hexen-1-ol, (E)-2-hexen-1-ol, (Z)-3-hexen-1-yl acetate, 1-hexyl acetate as well as the other VOCs like (Z)-ocimen, linalol, linaloloxide, benzyl acetate, indole, and β-caryophyllene. The lipoxygenase pathway resulted in the highest release of GLVs in comparison to the other biochemical pathways of volatile production. As a result of Fusarium infestation, the amounts of VOCs varied between tested cereals. We also subjected uninfested wheat, barley, and oat plants to infested wheat plants, and found that these cereals released larger amounts of VOCs compared to control plants. Emitted amounts of VOCs were significantly higher the shorter the distance between uninfested and infested plants.     

Degradation of mecoprop at different concentrations in surface and sub-surface soil

Biodegradation of [ring-¹⁴C] mecoprop (2-(4-chloro-2-methylphenoxy)propionic acid) was determined in surface and sub-surface soil at concentrations of 0·0005, 0·05, 0·5, 5, 50, 500, 5000 and 25000 mg kg^-1. The kinetics of mineralisation were evaluated from the mineralisation rates as a function of time and by non-linear regression analysis. In the sub-surface soil, degradation was 6–8 times slower than in surface soil, but the shape of the curves was the same in both layers. At concentrations between 0·0005 and 0·5 mg kg^-1, in both surface and sub-surface soil, degradation was initially zero-order followed by first-order kinetics. At 5 to 500 mg kg^-1 in surface soil and 5 to 50 mg kg^-1 in sub-surface soil the degradation rate was initially either constant or decreasing followed by exponential degradation indicating increasing populations of mecoprop decomposers in the soil. At 5000 and 25000 mg kg^-1 in the surface soil and at 500, 5000 and 25000 mg kg^-1 in the sub-surface soil, the degradation was negligible, as determined by the percentage [¹⁴C] carbon dioxide evolved. By non-linear regression, the three-half order model was found to describe the mineralisation. © 1998 SCI     

Stereochemistry and active conformation of a novel insecticide,acetamiprid

Acetamiprid, (NI-25; (E)-N¹-[(6-chloro-3-pyridyl)methyl]-N²-cyano-N¹-methylacetamidine), is a novel neonicotinoid insecticide having an N-cyanoacetamidine structure as its characteristic feature. The [¹H] and [¹³C]-NMR spectra indicated the existence of two different structures in acetamiprid at room temperature in solution. The measurement of CH-NOE and C–C coupling constants proved the E-configuration at the cyanoimino group in both existing structures. The [¹³C] chemical shifts of N-CH₃ and the long range C–H coupling in the formamidine analogue of acetamiprid suggested that there exist two conformers generated by the rotation of C–C single bond in the amidine moiety. Dynamic NMR spectra of acetamiprid and the computer simulation of the two-site exchange demonstrated that the two conformers change slowly to each other at room temperature. The conformational analysis by semi-empirical molecular orbital calculations using MNDO-PM3 method predicted four conformers as energy-minimum structures, among which two E-conformers were more stable than Z-conformers. One of the E-conformers in which two methyl groups are in cis configuration was superimposable onto the structure of imidacloprid, which is a known neonicotinoid insecticide having more rigid structure. This E-conformer was assumed as the active conformation of acetamiprid on the basis of the molecular similarity in terms of steric and electrostatic properties. © 1997 SCI