Diel rhythm of volatile emissions of males and females of the peach fruit fly Bactrocera zonata.

Fruit flies in the genus Bactrocera are among the most destructive insect pests of fruits and vegetables throughout the world. A number of studies have identified volatiles from fruit flies, but few reports have demonstrated behavioral effects or sensitivities of fly antennae to these compounds. We applied a recently developed method of automated headspace analysis using SPME (Solid Phase Microextraction) fibers and GC-MS (gas chromatography mass spectrometry), termed SSGA, to reveal volatiles specific to each sex of B. zonata that are emitted in a diel periodicity. The volatiles released primarily at dusk were identified by GC-MS and chemical syntheses as several spiroacetals, pyrazines, and ethyl esters. Solvent extraction of male rectal glands or airborne collections from each sex, followed by GC-MS, showed that certain of the volatiles increase or decrease in quantity sex-specifically with age of the flies. Electroantennographic (EAG) analysis of dose-response indicates differences in sensitivities of male and female antenna to the various volatiles. Our study provides a comprehensive analysis of the volatile chemicals produced and released by B. zonata and their antennal responses. The possible pheromone and semiochemical roles of the various volatiles released by each sex and the difficulties of establishing behavioral functions are discussed.

Adding diffusion ordered NMR spectroscopy (DOSY) to the arsenal for characterizing paramagnetic complexes.

Herein we report the development of diffusion ordered NMR spectroscopy (DOSY) for its use to characterize metal complexes containing paramagnetic first row transition metal elements. This technique is capable of assessing the purity and speciation of paramagnetic complexes, and also provides a convenient method to provide qualitative and sometimes quantitative molecular weight data.

Monitoring and mass-trapping methodologies using pheromones: the lesser date moth Batrachedra amydraula.

The lesser date moth (LDM) Batrachedra amydraula is a significant pest of date palm fruits. Previously, detection and monitoring of the pest was inaccurate due to high costs of sampling with lifting machines. We report a practical system for detection and monitoring of LDM based on pheromone traps and relevant models. Dose-response experiments with LDM pheromone traps indicated a 1 mg lure is optimal for monitoring. Delta traps with adhesive covering their entire inner surface gave the highest captures while trap colour was unimportant. Sampling pheromone traps throughout the night indicated male flight began at 1:00-2:00 and reached a peak 2 h before sunrise. Monitoring traps exposed all year long in Israel revealed three generations with different abundance. Trapping transects in a date plantation indicated interference from a monitoring trap became minimal at distances >27 m away. Inter-trap distances closer than this may lower efficiency of monitoring and mass trapping in control programs. Our estimate of the circular effective attraction radius (EARc) of a 1 mg delta trap for LDM (3.43 m) shows this bait is among the most attractive compared with baits for other insects. We developed encounter-rate equations with the pheromone trap EARc to model the interplay between population levels, trap density and captures that are useful for detection of invasive LDM and its control by mass trapping. The integrated methodologies are applicable to many pest species.

The role of ligand redox non-innocence in ring-opening polymerization reactions catalysed by bis(imino)pyridine iron alkoxide complexes.

The reactivity of iron-based ring opening polymerization catalysts is compared when the catalyst is in three different oxidation states. Formally iron(i) monoalkoxide complexes 3a (p-methoxyphenoxide) and 3b (neopentoxide) supported by bis(imino)pyridine ligands were synthesized and investigated as catalysts for the ring opening polymerization and copolymerization of various monomers. For most monomers, 3a and 3b were superior catalysts compared to analogous, formally iron(ii) and iron(iii) complexes (1a/1b and 2a/2b, respectively) for the ring opening polymerization of various cyclic ester and cyclic carbonate monomers. Experimental and computational investigation into the electronic structures of 3a and 3b revealed that they are most accurately described as containing a high spin iron(ii) center that is antiferromagnetically coupled to a singly reduced bis(imino)pyridine ligand. This electronic structure leads to increased electron density near the metal center without modulating the apparent metal oxidation state, which results in superior catalytic performance for the more highly reduced 3a and 3b compared to the increasingly more oxidized complexes (i.e.1a/1b and 2a/2b, respectively) in ring opening polymerization reactions. These findings have significant ramifications for the emerging field of redox-switchable polymerization catalysis.

Potential of "lure and kill" in long-term pest management and eradication of invasive species.

"Lure and kill" technology has been used for several decades in pest management and eradication of invasive species. In lure and kill, the insect pest attracted by a semiochemical lure is not "entrapped" at the source of the attractant as in mass trapping, but instead the insect is subjected to a killing agent, which eliminates affected individuals from the population after a short period. In past decades, a growing scientific literature has been published on this concept. This article provides the first review on the potential of lure and kill in long-term pest management and eradication of invasive species. We present a summary of lure and kill, either when used as a stand-alone control method or in combination with other methods. We discuss its efficacy in comparison with other control methods. Several case studies in which lure and kill has been used with the aims of long-term pest management (e.g., pink bollworm, Egyptian cotton leafworm, codling moth, apple maggot, biting flies, and bark beetles) or the eradication of invasive species (e.g., tephritid fruit flies and boll weevils) are provided. Subsequently, we identify essential knowledge required for successful lure and kill programs that include lure competitiveness with natural odor source; lure density; lure formulation and release rate; pest population density and risk of immigration; and biology and ecology of the target species. The risks associated with lure and kill, especially when used in the eradication programs, are highlighted. We comment on the cost-effectiveness of this technology and its strengths and weaknesses, and list key reasons for success and failure. We conclude that lure and kill can be highly effective in controlling small, low-density, isolated populations, and thus it has the potential to add value to long-term pest management. In the eradication of invasive species, lure and kill offers a major advantage in effectiveness by its being inverse density dependent and it provides some improvements in efficacy over related control methods. However, the inclusion of insecticides or sterilants in lure and kill formulations presents a major obstacle to public acceptance.

Floral scent of Canada thistle and its potential as a generic insect attractant.

The flowers of Canada thistle, Cirsium arvense (L.), attract a wide range of insects, including pollinators and herbivorous species. This attraction is primarily mediated by floral odor, which offers potential for developing generic insect attractants based on odor. In this study, we have analyzed the chemical composition of the volatiles produced by Canada thistle flowers. Nineteen floral compounds were identified in the headspace, including phenylacetaldehyde (55%), methyl salicylate (14%), dimethyl salicylate (8%), pyranoid linalool oxide (4.5%), and benzaldehyde (3.5%). Other minor compounds include benzyl alcohol, methylbenzoate, linalool, phenylethyl alcohol, furanoid linalool oxide, p-anisaldehyde, 2,6-dimethyl-1,3,5,7-octatetraene, benzylacetate, benzyl tiglate, (E,E)-alpha-farnesene, benzyl benzoate, isopropyl myristate, and 2-phenylethyl ester benzoic acid. The relative attractiveness of various doses of the main floral volatile compound phenylacetaldehyde (i.e., 10, 100, 200, and 400 mg) was tested for insect attraction. Both the total catch and the biodiversity of insect species trapped increased as the loading of phenylacetaldehyde increased. Volatiles were chosen from the odors from the flowers of Canada thistle and formulated and tested in the field. An 11-component blend was the most attractive of several floral blends tested. These findings indicate that chemical components of flower odors of Canada thistle can serve as a generic insect attractant for monitoring of invasive pest species.

Potential of mass trapping for long-term pest management and eradication of invasive species.

Semiochemical-based pest management programs comprise three major approaches that are being used to provide environmentally friendly control methods of insect pests: mass trapping, "lure and kill," and mating disruption. In this article, we review the potential of mass trapping in long-term pest management as well as in the eradication of invasive species. We discuss similarities and differences between mass trapping and other two main approaches of semiochemical-based pest management programs. We highlight several study cases where mass trapping has been used either in long-term pest management [e.g., codling moth, Cydia pomonella (L.); pink bollworm, Pectinophora gossypiella (Saunders); bark beetles, palm weevils, corn rootworms (Diabrotica spp.); and fruit flies] or in eradication of invasive species [e.g., gypsy moth, Lymantria dispar (L.); and boll weevil, Anthonomus grandis grandis Boheman). We list the critical issues that affect the efficacy of mass trapping and compare these with previously published models developed to investigate mass trapping efficacy in pest control. We conclude that mass trapping has good potential to suppress or eradicate low-density, isolated pest populations; however, its full potential in pest management has not been adequately realized and therefore encourages further research and development of this technology.

Behavioral response of Lygus hesperus to conspecifics and headspace volatiles of alfalfa in a Y-tube olfactometer.

The western tarnished plant bug, Lygus hesperus Knight, feeds and develops on a variety of weeds in the spring, with later generations moving to alfalfa and cotton where severe damage to reproductive structures can occur. A synthetic attractant for monitoring or mass-trapping L. hesperus, or the identification of potential attractants for natural enemies, would be useful tools for integrated pest management programs. Studies investigated the response of naive and experienced fifth-instar and adult L. hesperus to odors associated with conspecifics and alfalfa, Medicago sativa L. Fifth-instar L. hesperus responded to all plant/insect combinations, whereas female L. hesperus only responded preferentially to vegetative and flowering alfalfa where conspecifics had fed for 24-72 hr, and to vegetative alfalfa where conspecifics were added approximately 30 min before the test began. Males were not attracted to headspace volatiles from any of the alfalfa treatments. Analysis of headspace volatiles showed that (E)-2-hexanal, (Z)-3-hexen-l-ol, alpha-pinene, (Z)-3-hexenyl acetate, (E)-2-hexenyl acetate, limonene, (Z)-ocimene, (E)-beta-ocimene, linalool, (3E)-4,8-dimethyl-1,3,7-nonatriene, and (E, E)-alpha-farnesene are emitted from both vegetative and flowering alfalfa. Indole and (3E, 7E)-4,8,12-trimethyl-1,3,7,11-tridecatetraene were only detected in flowering alfalfa. Damage to alfalfa by L. hesperus increased emissions of (Z)-ocimene, (E)-beta-ocimene, (E)-beta-caryophyllene, and (E, E)-alpha-farnesene, while beta-pinene, myrcene, methyl salicylate, and (3E, 7E)-4,8,12-trimethyl-1,3,7,11-tridecatetraene were only detected from damaged plants. Thus, individual or mixtures of these alfalfa volatiles may be useful as attractants for capturing nymphs and adult females of L. hesperus in the field.

Strategies of a bark beetle, Pityogenes bidentatus, in an olfactory landscape.

Volatiles from leaves or bark of nonhost birch (Betula pendula) and Norway spruce (Picea abies) dramatically reduced the attraction of the bark beetle, Pityogenes bidentatus (Coleoptera: Scolytidae), to their aggregation pheromone components (cis-verbenol and grandisol) in the field. In addition, odors from both the needles and bark of the host Scots pine (Pinus sylvestris) similarly inhibited attraction. Monoterpenes of pine and spruce (alpha-pinene, beta-pinene, terpinolene, and 3-carene) as well as ethanol, chalcogran and some nonhost green leaf alcohols [(Z)-3-hexen-1-ol, (E)-2-hexen-1-ol, and 1-hexanol], also reduced catches. Collections of volatiles from the field-tested plant tissues indicated they released monoterpenes in amounts similar to the synthetics that inhibited responses. The various plant and insect sources of these inhibitory compounds indicate that P. bidentatus bark beetles have evolved several strategies to increase their fitness by avoiding nonhost and unsuitable host trees in a complex olfactory landscape.

TAXOKEY: a universal taxonomic key program using DOS text files and graphics.

A program (TAXOKEY.EXE), requiring only a few keystrokes to use, is described as a universal taxonomic key in the identification of plant and animal species by IBM-compatible personal computers. A DOS text file serves as the database for a key that can be dichotomous or with multiple choices. TAXOKEY can optionally display colour or monochrome screen pictures to illustrate the keys. Additional programs are described that are used to make the keys and check for errors, as well as convert .PCX graphic images for use with TAXOKEY. A second text file can be searched by TAXOKEY for information on particular species descriptions, notes and references.

Random selection algorithms for spatial and temporal sampling.

Seven BASIC programs are presented that use algorithms for selection of treatments and samples in spatial and temporal contexts. Program (1) takes a natural sequence of samples (such as logs cut from a tree trunk) and divides them into groups (equal to the number of samples divided by treatments), and then selects non-redundantly from each group a sample at random for each treatment. Program (2) matches items from different categories equally to any number of treatments in proportion to the numbers of items of each category. Program (3) selects sampling times or segment lengths of specified interval and number from within a time period or perimeter distance. These samples can be spaced apart by at least a specified amount of time or distance but otherwise are chosen at random. In program (4), a series of sample coordinates (x,y) are chosen at random from a rectangular area so that no points are closer than a specified minimum distance to any other. For each of the sample points, the Cartesian and polar coordinates are given. Program (5) generates any possible Latin square, while program (6) generates Latin cubes, and program (7) makes Graeco-Latin cubes. Examples of program use and output are presented for experiments with bark beetles (Coleoptera: Scolytidae) responding to pheromone blends and colonizing host trees.

Temporal clumping of bark beetle arrival at pheromone traps: Modeling anemotaxis in chaotic plumes.

The sequence of arrival of the bark beetlesIps typographus andPityogenes chalcographus (Coleoptera: Scolytidae) at traps baited with their synthetic pheromones was monitored with a portable fraction collector. Histograms of the natural arrival patterns of both species were nonrandom and clumped at shorter time scales (1-, 2-, 4-, 5-, or 6-min cells) but appeared random at larger time scales (10, 20 or 30 min). Monte Carlo generation of similar histograms showed them to be random at all of these time scales. A stochastic computer model could graphically simulate insect orientation to odor sources based on present theories of odor-modulated anemotaxis and casting. Although this model was used throughout, since it assumes only that insects cast perpendicular to the current wind direction, a second model could slightly improve orientation success. However, the second model requires that the insect remember its ground path (upwind) prior to losing the plume (after an abrupt wind direction change). The effects of casting and flight parameters on orientation success and randomness of arrival sequence within various plumes were determined by simulation. Similarly, the effects of random walks in plume direction, plume width, and wind speed were explored. The results showed that dynamic random variations in plume direction and especially wind speed could cause an otherwise random arrival sequence (e.g., under constant wind) to become clumped and nonrandom. Therefore, the clumped arrival patterns of bark beetles and other insects, includingSpodoptera litura, at pheromone sources could result from random-walk fluctuations in wind speed and wind direction.

Randomization algorithms in BASIC for experimental design.

Six BASIC programs for randomization of treatments with respect to space and time are presented. Program 1 is used to obtain randomization of several treatments in an equal number of positions for any number of replicates such that identical treatments are not replicated successively in the same position. Program 2 randomly assigns different treatments as specified in a grid of any size either (a) without constraints or (b) so that similar treatments do not occur next to each other either horizontally or vertically, or (c) horizontally, vertically, or diagonally. Program 3 assigns from five to 100 different treatments in equal proportions to a grid of specified size with treatments separated as in Program 2 (c) above. Program 4 randomly assigns any number of different treatments in equal proportions to a Latin square-like grid containing row and column cells with a multiple number of the treatments such that no identical treatments are replicated successively in the same row, column, or both row and column. Program 5 produces Latin squares of letters with unique numbered subscripts randomized. Program 6 makes Greco-Latin squares with an odd number of letters per side. These programs will aid in randomization of treatments within positions and replicates when a degree of uniformity or spacing of treatments is desired in order to increase the power of statistical tests. Examples of program output are discussed for tests with bark beetle pheromone components.

Orientation of bark beetlesPityogenes chalcographus andIps typographus to pheromonebaited puddle traps placed in grids: A new trap for control of scolytids.

A puddle trap was designed that is simple to build and efficient in catching bark beetles (Coleoptera: Scolytidae). The trap is insensitive to wind and should be much easier to manufacture than the more complicated perforated pipe and barrier traps commercially available. A 7 × 7 grid of 49 puddle traps baited with aggregation pheromone components ofPityogenes chalcographus (chalcogran and methyl decadienoate) was placed at either 1.5-, 3-, 6-, or 12-m spacing between traps in the field for two or more replicates of one day length (June 1989, Torsby, Sweden). The resulting catches showed that beetles were trapped as they flew into the grid since the inner square-ring of 24 traps caught less beetles per trap than the outer square-ring trap average (36 traps) in most experiments.Ips typographus also landed in puddle traps primarily on the periphery of the grid (6-m spacing only) when traps were baited with its pheromone components, (S)-cis-verbenol and methyl butenol. Computer simulation of flying bark beetles in grids of traps of various spacings and catch radii estimated that the experimental pheromone traps had an effective catch radius of 1.3 m or less forP. chalcographus, depending on the spacing between traps. An effective catch radius of 2 m forI. typographus was found for the 6-m grid spacing.P. chalcographus beetles were increasingly disrupted in their orientation to pheromone at the closer trap spacings since the effective catch radius declined linearly with closer trap spacing. However, landing was still precise since unbaited puddle traps within the grid did not catch any bark beetles.

Simulation and equation models of insect population control by pheromone-baited traps.

A spatial-temporal model for personal computers is developed that simulates trapping of an insect population based on trap and population parameters that can be varied independently. The model allows individual "insects" to move forward at any step size with right or left turns within any specified angle taken at random. Thex andy axes of the area within which insects move can be varied as well as the number of insects, their flight speed, and the duration of the control period. In addition, the number of pheromonebaited traps, their placement in a grid or at random (with a variable degree of spacing), and their effective catch radius (proportional to pheromone release rate) can also be varied. Simulations showed that catch was similar regardless of whether traps were placed in a grid or practically at random (random placement but no traps were allowed to overlap in their effective catch radii). Iterative equations were developed for computer that can rapidly obtain values that correspond to the mean results from the slower simulation model. Based on a set of input parameters, the equations determine the percentage of the population that should be caught during a specified time, the time required to catch a specified proportion of the insects, and the number of traps necessary to catch the population proportion in the time period. The effects of varying the number of insects, flight speed, trap radius, and number of traps on the percent control or time to catch all insects are presented. Population control of the bark beetleIps typographus was simulated using realistic pheromone trap and population parameters. A discussion of insect and bark beetle (Coleoptera: Scolytidae) population control using pheromone traps is presented.

REF-LIST: program to list references found in DOS text files of scientific manuscripts.

A computer program, coded in QuickBASIC language, is used to make a non-redundant list of references, in alphabetical order, that are found in a scientific manuscript (formatted as a DOS text file). The program can extract either direct or indirect citations as in the following: Byers (1983a, b, 1984) and Miller and Keen, 1960; Byers et al., 1984; Byers 1984) An IBM-compatible personal computer is required to run the executable program.

Trends in chemical ecology revealed with a personal computer program for searching data bases of scientific references and abstracts.

A compiled program, JCE-REFS.EXE (coded in the QuickBASIC language), for use on IBM-compatible personal computers is described. The program converts a DOS text file of current B-I-T-S (BIOSIS Information Transfer System) or BIOSIS Previews references into a DOS file of citations, including abstracts, in a general style used by scientific journals. The latter file can be imported directly into a word processor or the program can convert the file into a random access data base of the references. The program can search the data base for up to 40 text strings with Boolean logic. Selected references in the data base can be exported as a DOS text file of citations. Using the search facility, articles in theJournal of Chemical Ecology from 1975 to 1991 were searched for certain key words in regard to semiochemicals, taxa, methods, chemical classes, and biological terms to determine trends in usage over the period. Positive trends were statistically significant in the use of the words: semiochemical, allomone, allelochemic, deterrent, repellent, plants, angiosperms, dicots, wind tunnel, olfactometer, electrophysiology, mass spectrometry, ketone, evolution, physiology, herbivore, defense, and receptor. Significant negative trends were found for: pheromone, vertebrates, mammals, Coleoptera, Scolytidae,Dendroctonus, lactone, isomer, and calling.

Optimal fractionation and bioassay plans for isolation of synergistic chemicals: The subtractive-combination method.

Studies of chemical ecology of an organism are founded on the isolation and identification of a semiochemical, often comprised of two or more synergistic compounds (each Synergist alone has little activity, but presented together they are bioactive). Chromatographie fractionation and bioassay methods of binary splitting, additive combination, and subtractive combination are compared for efficiency in isolating synergists. Formulas are derived for the latter two methods that calculate the expected number of bioassay tests required for isolation of from two to five synergists from biological extracts with any number of compounds, depending on the number of initial (major) Chromatographic fractions. A computer program based on the formulas demonstrates the superiority of the subtractive-combination method. Simulations with the program were used to determine the optimal number of initial fractions for the additive- and subtractive-combination methods when isolating two to five synergists from extracts of from 25 to 1200 compounds. Methods of bioassay, isolation, identification, and field testing of semiochemicals are discussed.

Attraction of bark beetles,Tomicus piniperda,Hylurgops palliatus, andTrypodendron domesticum and other insects to short-chain alcohols and monoterpenes.

Several Scandinavian forest insects,Hylurgops palliatus, Tomicus piniperda, andTrypodendron domesticum (Coleoptera: Scolytidae),Rhizophagus ferrugineus (Coleoptera: Rhizophagidae) andPollenia spp. (Diptera: Calliphoridae) were attracted to window traps baited with ethanol and placed on Scots pine trees (Pinus sylvestris) in May-June, 1986. Release of ethanol at increasing relative rates of 0, 0.01, 0.1 and 1.0 (800 mg/day) from the window traps on trees in 1987 causedH. palliatus, T. domesticum, andR. ferrugineus to be increasingly attracted, whileT. piniperda was equally attracted at both 0.1 and 1.0 rates. The attraction ofT. piniperda to ethanol was weak compared to attraction to a monoterpene mix, (±)-α-pinene, (+)-3-carene, terpinolene. The terpene mix plus ethanol was significantly more attractive toH. palliatus than ethanol alone, but terpenes significantly reduced the attraction ofT. domesticum to ethanol. Baiting of pipe traps with a series of short-chain alcohols (methanol to hexanol) each alone showed that ethanol was greatly preferred byH. palliatus, T. domesticum, andR. ferrugineus over alcohols of one more or one less carbon, while longer-chain alcohols were not attractive. However,Glischrochilus hortensis (Col.: Nitidulidae) was attracted only to propanol. A series of 10-fold increasing release rates of ethanol (0.0001-1.0, where 1.0=800 mg/day) with either a "low" or "high" release of the terpene mix had various effects on the sexes during their attraction to pipe traps and subsequent entering of holes. Release of (-)-verbenone at 0.25 mg/day had no significant effect onH. palliatus orR. ferrugineus attraction to ethanol, but the response ofT. domesticum to ethanol was reduced. Several theories on olfactory mechanisms of host selection byT. piniperda are integrated and placed in ecological perspective.

Basic algorithms for random sampling and treatment randomization.

Five BASIC programs to select random samples from populations or to randomize treatments are presented. Program 1 is used to obtain randomization of any number of treatments in an equal number of positions or test units for any number of replicates. Program 2 produces latin squares of any size for treatment randomization. Program 3 is used to obtain a specific number of randomly selected samples from a population without replacement. Program 4 produces quasi-latin squares that have treatments repeated equally in all rows and columns, with identical treatments either spaced or not. Program 5 can be used with any size grid to place 3-100 treatments in equal proportions and with spacing of identical treatments. Both programs 4 and 5 allow for horizontal and vertical separation between identical treatments at sampling places while still retaining the quality of randomness. These programs should facilitate random sampling and randomization procedures which are required to correctly analyze experiments by the methods of statistical probability.