Permethrin treatments in canadian forests. Part 1: Impact on stream fish

The effects of permethrin on native and caged fish when aerially applied directly to forest streams at dosages between 8.8 and 70 g ha^?1 were studied between 1976 and 1981. None of the applications caused mortality of caged or native fish in streams. Trout and salmon diets were altered by the treatments due to effects on fish food organisms. The duration of the effects varied from several months to over a year with increasing dosage. Reductions in salmonid growth rates and reductions in fish densities in treated areas, presumably due to emigration, were documented following severe impacts on aquatic invertebrates in salmon nursery streams. Growth rates and population densities both recovered within four months after treatment.     

Studies on octylphenoxy surfactants. Part 2: Effects on foliar uptake and translocation

The effects of octylphenol (OP) and four of its ethoxylated derivatives on uptake into, and distribution within, maize leaf of 2-deoxy-glucose (2D-glucose), atrazine and o, p′-DDT are reported. The surfactants and OP (2 g litre^?1 in aqueous acetone) increased the uptake, at both 1.5 and 24 h, of the three model compounds (applied at 1 g litre^?1) having water solubilities in the g, mg and μg litre^?1 ranges. The uptake of 2D-glucose was positively correlated with the hygroscopicity of the surfactants. The uptake of DDT and atrazine increased with the uptake of the surfactants, being inversely related to their hydrophile:lipophile balance (HLB). Uptake of 2D-glucose and atrazine was enhanced at high humidity, the relative enhancement for atrazine increasing with increasing ethylene oxide (EO) content of the surfactants. A significant proportion of the atrazine and DDT entering the leaf was recovered from the epicuticular wax, the amount of atrazine recovered from the wax increasing with the EO content of the surfactants. The proportion of the surfactants taken up which was recovered from the epicuticular wax was minimal at an EO content of 12.5–16 mole equivalents. The appearance of the deposits on the leaf surface differed markedly among the surfactants, with similar trends for all three chemicals and without visible evidence for infiltration of the stomatal pores. The total quantities of glucose and atrazine translocated were increased by all surfactants but that of DDT was not, despite increases in uptake of up to 7.5-fold. Relative translocation (export from treated region of leaf as a percentage of chemical penetrating beyond the epicuticular wax) was reduced in all cases in the presence of surfactant. Up to 30% of the applied [¹⁴C]chemicals was not recovered from the treated leaf after 24 h. The reduced recovery of 2D-glucose, but not that of atrazine and DDT, was largely attributable to movement out of the treated leaf, with approximately 70% of the chemical taken up being translocated basipetally. Loss of atrazine and DDT was a result of volatilisation. There was no evidence that either [14C]2 D-glucose or [¹⁴C]atrazine was metabolised to [¹⁴C]carbon dioxide.     

Benchmark study on glyphosate-resistant crop systems in the United States. Part 2: Perspectives

A six-state, 5 year field project was initiated in 2006 to study weed management methods that foster the sustainability of genetically engineered (GE) glyphosate-resistant (GR) crop systems. The benchmark study field-scale experiments were initiated following a survey, conducted in the winter of 2005-2006, of farmer opinions on weed management practices and their views on GR weeds and management tactics. The main survey findings supported the premise that growers were generally less aware of the significance of evolved herbicide resistance and did not have a high recognition of the strong selection pressure from herbicides on the evolution of herbicide-resistant (HR) weeds. The results of the benchmark study survey indicated that there are educational challenges to implement sustainable GR-based crop systems and helped guide the development of the field-scale benchmark study. Paramount is the need to develop consistent and clearly articulated science-based management recommendations that enable farmers to reduce the potential for HR weeds. This paper provides background perspectives about the use of GR crops, the impact of these crops and an overview of different opinions about the use of GR crops on agriculture and society, as well as defining how the benchmark study will address these issues.     

Development of novel pesticides based on phytoalexins: Part 2. Quantitative structure-activity relationships of 2-heteroaryl-4-chromanone derivatives

Phytoalexins are low-molecular-weight chemicals that immune systems of plants produce and accumulate in response to infections, especially those of fungal origin. Although their content is not high in plants, yet they have shown unique fungicidal activity and played an important role in the defence system of plants. In searching for novel environmentally benign fungicides with high activity, the structures of flavanone derivatives, one of the most important phytoalexins groups, have been modified via bioisosteric substitution and a series of 2-heteroaryl-4-chromanones were designed and synthesized. They showed good fungicidal activities against rice blast disease, Pyricularia grisea (Sacc). Their IC50 values were tested in vitro and the relationship between structure and fungicidal activity was analyzed quantitatively using a Hansch-Fujita approach. The results showed that hydrophobicity was very important for fungicidal activity and there is apparently an optimum hydrophobic property for the molecules at a log Pow value of about 2.7. In addition, the results indicated that electronic effects played an important role in binding with the receptor and that the C=O group was probably a electron-accepting site. The quantitative structure-retention correlative equation of the title compounds was also established.     

A survey for Bursaphelenchus spp. in pine forests in Norway

Wood samples from pine trees were taken from 429 sites throughout Norway. The samples were selected as being either from (1) healthy trees, (2) trees suffering from stress, either physical or pathological or (3) dead trees. Nematodes were recovered from 39% of samples, most from dead wood and least from healthy trees. Species of Bursaphelenchus were recovered from 12% of dead trees and 5% of stressed trees, but were never found in healthy wood. B. mucronatus was found at just one site and in this sample it was associated with Monochamus sutor , only one of two sites at which the beetle was detected. Based on the information gained from the survey and from other sources, an assessment is made of the risk of introduction of B. xylophilus from outside Europe on imported wood and its survival, spread and disease potential in European forests.     

Sorption of lonisable organic compounds by field soils. Part 2: Cations,bases and zwitterions

Sorption of a range of permanent cations, bases and zwitterionic compounds was measured as a function of pH in two soil types. Pyridinium cations were more strongly sorbed (K_d 10– > 1000) than aliphatic cations (K_d < 5). At very low pH, sorption of the aliphatic cations sharply decreased, probably because they are displaced by protons. Most weak bases, including carbendazim andpyridines, were strongly sorbed (K_d 9–35) at low pH, where they would be appreciably protonated, sorption becoming much weaker at soil pH values > 6. However, an additional mechanism of sorption was observed for those zwitterions capable of chelation (e.g. picolinic acid and alanine) which gave rise to high K_d values at pH values near neutral. Inorganic phosphate was strongly sorbed (K_d > 140) save at very low pff. Glyphosate and inorganic phosphate were sorbed very strongly at pH values near to 4 (K_d > 200). The very strong sorption was attributed to ligand exchange interaction. Sorption of picolinic acid was similar when measured in water or calcium chloride solution (0.01 M). However, sorption decreased with increasing concentration of calcium chloride up to 1 M, probably because the protonated form of picolinic acid was displaced by calcium ions.     

Substituted alpha-(phenylhydrazono)phenylacetonitrile derivatives. Part 2: Synthesis and biological activity of pro-pesticides

Pro-pesticides of alpha-(2,6-dichloro-4-trifluoromethylphenylhydrazono)-4-nitrophenylacetonitrile have been prepared and tested against mite and insect pests. Variations in potency and spectrum were observed depending on the choice of cleavable pro-moiety. Cleavage of the pro-moiety was demonstrated in one case by measuring the rate of increase in the uncoupling activity using a mitochondrial preparation. Irradiation experiments have demonstrated a rapid isomerisation of the planar Z isomer to the E isomer, which is reversible.     

The efficacy of a petroleum spray oil against Aphis gossypii Glover on cotton. Part 2: indirect effects of oil deposits

The primary mode of action of petroleum spray oils (PSOs) on pest insects is through direct contact. Indirect effects are, however, also possible, and deposits of the oils may influence pest populations by killing insects and/or by influencing their behaviour. The indirect effects of deposits of a new nC24 oil against the cotton aphid, Aphis gossypii Glover, were therefore determined. The effects of oil deposits on the acceptance of cotton as host plant by the aphids were assessed, as well as aphid mortality rates and their success in the establishment of colonies. The efficacy of deposits of a heavier oil (nC27) was also evaluated. Deposits of PSO were toxic to A. gossypii and remained effective until 8 days after spraying. Mortality decreased with time, so that, the older the deposit, the lower was the mortality. Significantly higher aphid mortalities were achieved on younger leaves than on mature ones. Thus, leaf age proved a significant factor in the efficacy of the deposits. Consecutive prophylactic applications (at 9 day intervals) did not have a cumulative effect, and their killing power proved to be independent of one another. Thus, applying the oil prior to aphid infestations would confer only minimal protection. The mortality inflicted by the deposits was not improved by increasing the molecular mass of the oil used (nC27 oil), but the toxic life of the oil deposit was increased. Oil deposits did not deter alates from landing on oil-sprayed plants. Oil deposits did, however, affect subsequent alate and nymphal survival, and thus the establishment of aphid colonies. The impact that the oils could have on the longer-term development of aphid populations in the field was thus demonstrated. First- and second-instar nymphs were the most susceptible life stages, with > 50% mortality compared with < 10% for the other stages. These nymphs did not show the typical signs of oil-induced mortality observed in aphids killed by direct oil applications, which suggests an alternative mode of action to that of the directly applied oil. Anoxia does not seem to be involved in either process, and alternative modes of action of the oil deposits are discussed. The implications of these findings for cotton aphid control are also considered, primarily in relation to the timing and frequency of oil application.     

Synthesis of endrin metabolites. Part 2: Total synthesis and confirmation of the structure of 3-hydroxyendrin

3-Hydroxyendrin, a minor metabolite of endrin in several mammals, has been synthesised for the first time in a three-step procedure. The synthesis is based on the two-step commercial manufacture of endrin, with cyclopenta-1,3-dienyl acetate replacing cyclopentadiene in the Diels-Alder adduction step to isodrin formation. The adduct formed from cyclopenta-1,3-dienyl acetate and 1,2,3,4,7,7-hexachlorobicyclo-[2.2.1]hepta-2,5-diene, 3-acetoxyisodrin, was purified by chromatography and sequentially deacetylated (to 3-hydroxyisodrin) and epoxidised to yield 3-hydroxyendrin. A comparison of this material with a sample of a metabolite, isolated from endrin-dosed rates in 1970, showed that they were identical in all spectral properties (m.s., i.r. and n.m.r.). This has provided confirmation of the original structural assignment and has made available sufficient quantities of the metabolite as a reference material for any future metabolism or residue studies.     

Dimethoxypyrimidines as Novel Herbicides. Part 2. Synthesis and Herbicidal Activity of O-Pyrimidinylsalicylates and Analogues

A new series of the O-pyrimidinylsalicylates was synthesized and their herbicidal activity was examined. Some of these compounds showed very strong herbicidal activity under pre- and post-emergent treatment conditions against various kinds of grass and broadleaf weeds. Among these compounds, O-(4, 6-dimethoxypyrimidin-2-yl) salicylic acid and its methyl ester were found to exhibit the highest activity. The herbicidal symptoms observed after the treatments included early cessation of plant growth followed by chlorosis, necrosis and plant death. The symptoms were similar to those caused by sulfonylureas and imidazolinones, which inhibit branched-chain amino acid biosynthesis.     

Studies on the biology of black mould (Aspergillus niger) on temperate and tropical onions. 2. The effect of treatments on the control of seedborne A. niger

Treatment of A. niger -inoculated onion seed with benomyl dust (1 g a.i./kg), or a foliar spray of thiram (0·4% a.i./ha) applied to plants grown from inoculated seed under temperate (UK) conditions reduced the incidence of A. niger in harvested crops. Treatment of naturally contaminated Sudanese onion seed with a benomyl + thiram mixture at a rate of 2·5 + 2·5 g a.i./kg or soaking the seed in hot water (15 min at 60°C) reduced the incidence of black mould on bulbs grown in the Sudan in field soil that had not previously been used for onion production. The seed treatments were less effective in crops produced in fields regularly used for onion production. However, incubation of harvested bulbs in moist chambers showed that damage to the internal storage tissue of onion bulbs caused by A. niger was reduced by seed treatment.     

The pyrethrins and related compounds. Part xxxi: Alkoxyimino-substituted esters

Esters derived from pyrethroidal acids and benzyl and furylmethyl alcohols bearing a wide range of side-chains each containing at least one oxime ether group, and related derivatives of allethrin and benzylnorthrin, were synthesised and tested for insecticidal activity. Of the benzyl esters, the most insecticidal were those with the methoxyimino-methyl or -ethyl side-chains at C-3 or C-4, and with E configuration. Changing the alkoxy group, the configuration or the chain length resulted in lower activity. Introducing an occyano group increased activity if the side-chain was at C-3, but lowered it drastically if the substituent was at C-4. In the case of allethrin, the methoxime derivative was less active than the parent ketone, but with benzylnorthrin conversion to the methoxime markedly increased activity against one of the test species.     

The pyrethrins and related compounds. Part XXIX: Haloallylbenzyl esters

Synthesis and bioassay of a series of esters based on pyrethroidal acids established that the activity of halosubstituted allylbenzyl esters depends on the position and stereochemistry of substitution in the allyl side-chain, on the substitution pattern on benzyl, on the esterifying acid, and, to a lesser extent, on the nature of the halogen substituent itself. The most powerful combination of the first four parameters for activity against houseflies is in (Z)-3-haloallylbenzyl esters of the (1R)-cis 3-(2,2-dibromovinyl) acid. Other combinations have moderate to low activity. Some aspects of the variation conform to previously recognised patterns, others define more precisely the requirements for the side-chain to confer activity. The pattern of response of activity to cyano-substitution at the α-position, noted earlier, persists in the current compounds, and is here analysed quantitatively.     

Aryldiones incorporating a [1,4,5]oxadiazepane ring. Part 2: chemistry and biology of the cereal herbicide pinoxaden

BACKGROUND: Pinoxaden is a new cereal herbicide that provides outstanding levels of post‐emergence activity against a broad spectrum of grass weed species for worldwide selective use in both wheat and barley. RESULTS: Factors influencing activity and tolerance to pinoxaden were in part linked to distinct structural parts of the active ingredient. Three complementary contributions that decisively impact upon the herbicidal potency against grasses were identified: a preferred 2,6‐diethyl‐4‐methyl aromatic substitution pattern, a dione area suitable for proherbicide formation and beneficial adjuvant effects. The uptake and translocation pattern of pinoxaden when coapplied with its tailored adjuvant were analysed by autoradiography, indicating extensive and rapid penetration, followed by effective distribution throughout the plant. Crop injury reduction on incorporation of the [1,4,5]oxadiazepane ring into the aryldione template was reinforced with safener technology. Comparative studies on the behaviour of pinoxaden applied either alone or in combination with the safener cloquintocet‐mexyl demonstrated that addition of the safener resulted in significant enhancement of metabolic degradation in wheat and barley, providing excellent crop tolerance and a substantial selectivity margin without adverse effects on weed control. CONCLUSION: The biological potential of pinoxaden and its active principle pinoxaden dione in terms of grass weed control and tolerance in cereals was fully exploited by inclusion of the safener cloquintocet‐mexyl in the formulation in combination with a specific and tailor‐made tank‐mix adjuvant based on methylated rape seed oil. Copyright © 2011 Society of Chemical Industry     

Residues of chlorpyrifos in various crops II. Residues after field treatments

Five agricultural crops were treated with OO-diethyl O-(3,5,6-trichloro-2-pyridyl) phosphorothioate (chlorpyrifos) granular or emulsifiable concentrate formulations at dosages from 0.5 to 6.0 kg (a.i.)/ha and at different periods before harvest. Chlorpyrifos residues were determined by gas chromatography after extraction and sweep co-distillation clean-up. Low residue levels were found. The average values in lettuce were 0.046 and 0.070 part/million, in sugar beet leaves 0.037 to 0.128 part/million and roots <0.005 to 0.038 part/million; no chlorpyrifos was detected in carrots, potatoes and cured tobacco leaves at the limit of the method (0.005 part/million).     

Pathogens of bark beetles (Coleoptera: Curculionidae) in Bulgarian forests

The occurrence and prevalence of bark beetle pathogens in forest stands in Bulgaria were investigated in 944 specimens belonging to 21 bark beetle species. Protozoa, microsporidia, fungi and nematodes occurred in 19 of all investigated species. The infections were found in the gut (nematodes, gregarines, microsporidia), gonads (microsporidia) and hemolymph (nematodes) of the infected insects. Protozoan species (Gregarina typographi, Gregarina spp.) were detected in eight bark beetle species. Morphometric data about G. typographi and Gregarina spp. are presented. The prevalence of the gregarines varied between 1.4% and 64.2%. Microsporidia of the genera Nosema and Chytridiopsis were revealed in three bark beetle species. The prevalence of microsporidia ranged between 1.5% and 11.8%. This is the first report of a microsporidium in Taphrorychus villifrons and of gregarines in T. villifrons, Pityogenes bistridentatus, P. conjunctus, and Orthotomicus erosus. The fungus Beauveria bassiana was found in 3.4% of Hylurgops palliatus specimens. Nematodes (in gut and haemolymph) were revealed in 19 bark beetle species and their prevalence varied between 10% and 98.5%.     

Fungal endophytes in Mediterranean oak forests: a lesson from Discula quercina

Fungal endophytes that colonize forest trees are widespread, but they are less well known than endophytes infecting grasses. The few studies on endophytes in trees mainly concern the tropical areas and the northernmost latitudes, while similar investigations in the Mediterranean region have so far been scarce and incidental. Endophytes are studied mostly in economically important forests suffering from diseases, such as oak forests. One common endophyte that has received some study on oak is the mitosporic Discula quercina. This paper, after first addressing some basic problems on tree endophytes, examines the ecology of D. quercina in Mediterranean oak stands. D. quercina is usually viewed as a symptomless colonizer of healthy Quercus cerris, infecting new leaves early in the growing season, in an unstable equilibrium between transient mutualism/neutralism and latent pathogenesis. It is postulated here that climatic factors can change the endophytic nature of D. quercina, turning it into a weak pathogen or an opportunistic invader of senescing and indeed healthy trees. It is argued more generally that stochastic events can cause the lifestyle of an endophyte to switch from beneficial/neutral to pathogenic, transforming the tree-endophyte interaction, an interaction that depends in part on the matching genomes of the tree and endophyte, and on the environmental context.