Weeds are one of the major constraints in crop production affecting both yield and quality. The excessive and exclusive use of synthetic herbicides for their management is increasing the development of herbicide-resistant weeds and is provoking risks for the environment and human health. Therefore, the development of new herbicides with multitarget-site activity, new modes of action and low impact on the environment and health are badly needed. The study of plant–plant interactions through the release of secondary metabolites could be a starting point for the identification of new molecules with herbicidal activity. Essential oils (EOs) and their components, mainly terpenoids, as pure natural compounds or in mixtures, because of their structural diversity and strong phytotoxic activity, could be good candidates for the development of new bioherbicides or could serve as a basis for the development of new natural-like low impact synthetic herbicides. EOs and terpenoids have been largely studied for their phytotoxicity and several evidences on their modes of action have been highlighted in the last decades through the use of integrated approaches. The review is focused on the knowledge concerning the phytotoxicity of these molecules, their putative target, as well as their potential mode of action.

The essential oil composition of Cistus ladanifer grown in central Spain was analysed by gas chromatography and gas chromatography/mass spectrometry, revealing it to be rich in oxygenated compounds, with trans-pinocarveol (20.00%), bornyl acetate (7.03%) and terpinen-4-ol (6.37%) as the main monoterpene compounds. Viridiflorol (13.59%) and ledol (4.36%) were the main constituents of the oxygenated sesquiterpene fraction. Large amounts of α-pinene (4.70%) were found in the hydrocarbonated fractions. To study its possible use as a natural herbicide, the oil was tested in vitro against Amaranthus hybridus, Portulaca oleracea, Chenopodium album, Conyza canadensis and Parietaria judaica, completely inhibiting A. hybridus germination, and nearly blocking C. canadensis and P. judaica germination at all concentrations assayed. In P. oleracea, the oil showed less effect, inhibiting its germination at the higher doses studied. It did not control C. album germination. Regarding seedling length, the oil had strong phytotoxic activity, being effective at all concentrations tested.

Weeds and herbicides are important stress factors for crops. Weeds are responsible for great losses in crop yields, more than 50% in some crops if left uncontrolled. Herbicides have been used as the main method for weed control since their development after the Second World War. It is necessary to find alternatives to synthetic herbicides that can be incorporated in an Integrated Weed Management Program, to produce crops subjected to less stress in a more sustainable way. In this work, three natural products: pelargonic acid (PA), carvacrol (CV), and cinnamic aldehyde (CA) were evaluated, under greenhouse conditions in postemergence assays, against problematic weeds in Mediterranean crops Amaranthus retroflexus, Avena fatua, Portulaca oleracea, and Erigeron bonariensis, to determine their phytotoxic potential. The three products showed a potent herbicidal activity, reaching high efficacy (plant death) and damage level in all species, being PA the most effective at all doses applied, followed by CA and CV. These products could be good candidates for bioherbicides formulations.

The essential oil composition of Peumus boldus and Drimys winterii was analyzed by means of capillary GC-FID and GC-MS. More than 96% of the total oil components (43 and 54 compounds, respectively) were identified, with ascaridole (51.17 ± 9.51), p-cymene (16.31 ± 2.52) and 1,8-cineole (14.45 ± 2.99) as the main compounds in P. boldus and g-eudesmol (21.65 ± 0.41), followed of elemol (12.03 ± 0.34) and terpinen-4-ol (11.56 ± 1.06) in D. winterii. The herbicidal activity was tested against Amaranthus hybridus and Portulaca oleracea. P. boldus essential oil was the most phytotoxic against both weeds, inhibiting seed germination and seedling growth at all concentrations assayed (0.125–1 µL/mL). D. winterii essential oil did not show any effect on A. hybridus germination and only affected P. oleracea germination at the highest concentration. The results suggest the possible use of the essential oil from P. boldus as a natural herbicide.

Essential oils (EOs), extracted from aromatic plants, have been proposed as candidates to develop natural herbicides. This study aimed to evaluate the herbicidal potential of Thymbra capitata (L.) Cav., Mentha × piperita L. and Santolina chamaecyparissus L. essential oils (EOs) on Avena fatua L., Echinochloa crus-galli (L.) P. Beauv, Portulaca oleracea L. and Amaranthus retroflexus L. and their effects on soil microorganisms. A pot experiment was set up and three EOs at three doses were applied by irrigation. Efficacy and effects of EOs on weed growth were determined. Soil microbial biomass carbon and nitrogen, microbial respiration, and the main microbial groups were determined at days 7, 28 and 56. EOs demonstrated herbicidal activity, increasing their toxicity with the dose. T. capitata was the most effective against all weeds at the maximum dose. P. oleracea was the most resistant weed. Soil microorganisms, after a transient upheaval period induced by the addition of EOs, recovered their initial function and biomass. T. capitata EO at the highest dose did not allow soil microorganisms to recover their initial functionality. EOs exhibited great potential as natural herbicides but the optimum dose of application must be identified to control weeds and not negatively affect soil microorganisms.

The bioherbicidal potential of Thymbra capitata (L.) Cav. essential oil (EO) and its main compound carvacrol was investigated. In in vitro assays, the EO blocked the germination and seedling growth of Erigeron canadensis L., Sonchus oleraceus (L.) L., and Chenopodium album L. at 0.125 µL/mL, of Setaria verticillata (L.) P.Beauv., Avena fatua L., and Solanum nigrum L. at 0.5 µL/mL, of Amaranthus retroflexus L. at 1 µL/mL and of Portulaca oleracea L., and Echinochloa crus-galli (L.) P.Beauv. at 2 µL/mL. Under greenhouse conditions, T. capitata EO was tested towards the emergent weeds from a soil seedbank in pre and post emergence, showing strong herbicidal potential in both assays at 4 µL/mL. In addition, T. capitata EO, applied by spraying, was tested against P. oleracea, A. fatua and E. crus-galli. The species showed different sensibility to the EO, being E. crus-galli the most resistant. Experiments were performed against A. fatua testing T. capitata EO and carvacrol applied by spraying or by irrigation. It was verified that the EO was more active at the same doses in monocotyledons applied by irrigation and in dicotyledons applied by spraying. Carvacrol effects on Arabidopsis root morphology were also studied.