Limoniic Acid - Major Component of the Sex Pheromones of the Click Beetles Limonius canus and L. californicus

Abstract

Wireworms, the larvae of click beetles (Coleoptera: Elateridae), are soil-dwelling insect pests inflicting major economic damage on many types of agricultural crops worldwide. The objective of this work was to identify the female-produced sex pheromones of the Pacific Coast wireworm, Limonius canus LeConte, and the sugarbeet wireworm, L. californicus (Mannerheim) (Coleoptera: Elateridae). Headspace volatiles from separate groups of female L. canus and L. californicus were collected on Porapak Q and analyzed by gas chromatography with electroantennographic detection (GC-EAD) and GC-mass spectrometry. GC-EAD recordings revealed strong responses from male L. canus and male L. californicus antennae to the same compound, which appeared below GC detection threshold. The structure of this candidate pheromone component was deduced from the results of micro-analytical treatments of extracts, retention index calculations on four GC columns, and by syntheses of more than 25 model compounds which were assessed for their GC retention characteristics and electrophysiological activity. The EAD-active compound was identified as (E)-4-ethyloct-4-enoic acid, which we name limoniic acid. In field experiments in British Columbia and Alberta, Canada, traps baited with synthetic limoniic acid captured large numbers of male Limonius click beetles, whereas unbaited control traps captured few. Compared to traps baited with the analogue, (E)-5-ethyloct-4-enoic acid, traps baited with limoniic acid captured 9-times more male L. californicus, and 6.5-times more male western field wireworms, L. infuscatus Motschulsky, but 2.3-times fewer male L. canus. Limoniic acid can now be developed for detection, monitoring and possibly control of L. californicus, L. infuscatus and L. canus populations.

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Data Availability

Data are reported in the manuscript and in the electronic Supplementary Information.

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Acknowledgements

We thank Jocelyn Millar for a most valuable suggestion regarding the interpredation of DMDS treatment results, Associate Editor David Hall for his meticulous review of the manuscript, Sharon Oliver for word processing and comments, Russ Alcock and Blaine Dunlop for permitting access to their farms, David Shack, Emmanuel Hung, and Sebastian Damin for assistance with processing beetles, Stephen Takács for help with graphical illustrations, and two anonymous reviewers for complimentary comments. The research was supported by an AAFC Canadian Agricultural Partnership Cluster Project (Developing IPM tools for wireworm management in Canada) administered by the Canadian Horticulture Council and supported by the Potato Growers of Alberta, the B.C. Potato Industry Development Committee, the B.C. Lower Mainland Horticultural Improvement Association, and by a Natural Sciences and Engineering Research Council of Canada (NSERC) – Industrial Research Chair to GG, with BASF Canada Inc. and Scotts Canada Ltd. as the industrial sponsors.

Funding

The research was supported by an AAFC Canadian Agricultural Partnership Cluster Project (Developing IPM tools for wireworm management in Canada) administered by the Canadian Horticulture Council and supported by the Potato Growers of Alberta, the B.C. Potato Industry Development Committee, the B.C. Lower Mainland Horticultural Improvement Association, and by a Natural Sciences and Engineering Research Council of Canada (NSERC) – Industrial Research Chair to GG, with BASF Canada Inc. and Scotts Canada Ltd. as the industrial sponsors.

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WvH & GG conceived the study; WvH and HC captured beetles for pheromone analyses; RG captured headspace odorants, and analyzed odorant extract as well as model compounds by GC-EAD and GC-MS; SA synthesized chemicals; WvH, HC, SM and EL ran field experiments; EL and WvH identified and determined the sex of beetles captured in traps; WvH analyzed capture data statistically; RG and GG wrote the first draft, and all authors reviewed and approved of the final draft.

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Correspondence to Gerhard Gries.

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Regine Gries and Gerhard Gries are dedicating this article to Prof. Dr. Dr. h.c. mult. Wittko Francke, in memoriam.

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Gries, R., Alamsetti, S.K., van Herk, W.G. et al. Limoniic Acid - Major Component of the Sex Pheromones of the Click Beetles Limonius canus and L. californicus. J Chem Ecol 47, 123–133 (2021). https://doi.org/10.1007/s10886-020-01241-y

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Keywords

  • Wireworms
  • Elaterid beetles
  • (E)-4-Ethyloct-4-enoic acid
  • (E)-5-Ethyloct-4-enoic acid
  • GC-EAD
  • GC-MS
  • Limonius infuscatus