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The ubiquitous use of mosquito repellents in homes across Asia, Africa, and South America is related with human exposure to indoor volatile organic compounds (VOCs). There are three primary types of mosquito repellents: those in the form of coils, mats, and liquids. The repellent mechanisms of these products are distinct, resulting in the generation of varying types of VOCs during the repellent process. In this study, the emission characteristics of commercial coil-, mat-, and liquid-type mosquito repellents were observed in a laboratory chamber using real-time measurement. A previously developed personal passive sampler, ePTFE PS, was used to quantify personal exposure to indoor VOCs while 86 volunteers habitually used those three representative types for 3 h in their residence. Notable increase of indoor benzene was observed for coil- and mat-type mosquito repellents, while α-pinene concentration increased significantly following the use of liquid-type mosquito repellent. The average incremental cancer risks for benzene were 10 -6 to 10 -4 for adults following the use of coil- and mat-type mosquito repellents. The average non-cancer risks for all chemicals were <1 after the use of three types of mosquito repellents. Considering the potential human health risks associated with byproducts (e.g., particulate matter or carbon monoxide from incomplete combustion) emitted after mosquito coil use, further research on this topic is warranted., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Volatile secondary metabolites of plants interact with environments heavily. In this work, characteristic components of Michelia yunnanensis essential oils (EOs) were isolated, purified and identified by column chromatography, GC-MS and NMR. Leaves of M. yunnanensis were collected monthly and extracted for EOs to investigate chemical and insecticidal activity variations as well as potential influencing environments. Different organs were employed to reveal distribution strategies of characteristic components. Results of insecticidal activities showed that all EOs samples exerted stronger contact activity to Lasioderma serricorne, but repellent effect was more efficient on Tribolium castaneum. One oxygenated sesquiterpene was isolated from EOs, basically it could be confirmed as (+)-cyclocolorenone (1). It exerted contact toxicity to L. serricorne (LD 50 = 28.8 μg/adult). Chemical analysis showed that M. yunnanensis leaves in reproductive period would produce and accumulate more 1 than in vegetative period. Moreover, reproductive organs (flowers and fruits) contained more 1 than vegetative organs (leaves and twigs). Partial correlation analysis indicated that temperature-related elements positively correlated with the relative content of 1.

Spatial repellents are emerging as a promising approach to reduce vector-disease burden; however, the evolution of genetically resistant mosquitoes decreases repellent efficacy. The development of flight chambers to investigate spatial repellent application techniques is vital for sustainable mosquito control. We present an air-dilution chamber as a novel bioassay to study mosquito flight behavior responses to chemical gradients of the volatile, pyrethroid transfluthrin (TF). Air dilution was used to simulate a larger environment of stable concentration gradients verified with carbon dioxide (CO2) which was homogenously delivered and measured across the chamber to achieve a 5× inlet/outlet [CO2] ratio with 0.17 m/s outlet velocity. Female Aedes (Ae.) aegypti (Diptera: Culicidae, Linnaeus, 1762) were exposed to volatilized TF paired with heat, CO2, and Biogents-Sweetscent host-cues. Tandem solvent extraction-gas chromatography-mass spectrometry (SE-GC-MS) was used to quantify air samples taken during TF emanations with a limit of detection (LOD) and quantification (LOQ) of 2 ± 1 and 5 ± 2 parts-per-trillion (ppt) TF, respectively. Homogenous air diluted emanation of the spatial repellent TF was at least twice that of the 5× CO2 gradient with the same air flow in the chamber. The airborne TF concentrations the mosquitoes were exposed to range from 1 to 170 ppt. Video recordings of mosquito behavior during host-cues exposure revealed increased inlet activity, while exposure to TF protected host resulted in decreased inlet activity over time with inlet-outlet mosquito positional variation. This novel flight chamber design can simulate 'long'-range exposure with simultaneous quantitation of airborne spatial repellent to understand dose-dependent effects on mosquito behavior., (© The Author(s) 2023. Published by Oxford University Press on behalf of Entomological Society of America. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.)

Some people are more attractive to mosquitoes than others, but the mechanistic basis of this phenomenon is poorly understood. We tested mosquito attraction to human skin odor and identified people who are exceptionally attractive or unattractive to mosquitoes. These differences were stable over several years. Chemical analysis revealed that highly attractive people produce significantly more carboxylic acids in their skin emanations. Mutant mosquitoes lacking the chemosensory co-receptors Ir8a, Ir25a, or Ir76b were severely impaired in attraction to human scent, but retained the ability to differentiate highly and weakly attractive people. The link between elevated carboxylic acids in "mosquito-magnet" human skin odor and phenotypes of genetic mutations in carboxylic acid receptors suggests that such compounds contribute to differential mosquito attraction. Understanding why some humans are more attractive than others provides insights into what skin odorants are most important to the mosquito and could inform the development of more effective repellents., Competing Interests: Declaration of interests The authors declare no competing interests., (Copyright © 2022 The Author(s). Published by Elsevier Inc. All rights reserved.)

In recent years, secondary metabolites of plants have attracted researchers' interest as a substitute for synthetic insecticides with many advantages. Elsholtzia kachinensis is an annual herb with medicinal and edible value. In this study, the essential oil (EO) of the aerial part of E. kachinensis was extracted by hydrodistillation, and GC-MS analysed essential oil components. The results show that carvone and dehydroelsholtzia ketone are the main components of the essential oil, accounting for 32.298% and 31.540%, respectively. EO, carvone and dehydroelsholtzia ketone are used to determine the effects against stored-product insects Lasioderma serricorne, Tribolium castaneum, Sitophilus oryzae and Liposcelis bostrychophila. The essential oil showed the most vital contact and fumigation toxicity to L. serricorne, of which LD 50 and LC 50 values were 3.85 μg/adult and 7.74 mg/L air, respectively. S. oryzae did not show repellent activity, but the repellent rate of the other three species reached 90% under EO treatment at a concentration of 78.63 nL/cm 2 . Therefore, the essential oil of E. kachinensis has an insecticidal effect and has the potential to be developed as a new eco-friendly insecticide.

Abstract: Artemisia songarica Schrenk is a dominant sand fixation plant growing in the People's Republic of China. At present, there are rare studies on the chemical composition and biological activity of A. songarica. The chemical composition of the original oil was analyzed by gas chromatography-mass spectrometry, and 16 compounds were determined. The main compounds were bisabolol oxide II (28.7%), nerolidol (18.6%), bisabolol (12.9%), bisaboloxide A (10.0%), and spathulenol (6.0%). The contact toxicity and repellent activity of A. songarica essential oil and four selected compounds (bisabolol, geranyl butyrate, nerolidol, and santalol) were assessed against Tribolium castaneum Herbst and Liposcelis bostrychophila Badonnel. Bioassays showed that the crude essential oil exhibited strong insecticide and repellent activities against both pests. Santalol possessed the strongest contact toxicity (50% lethal dose [LD50] = 1.29 μg per adult) against T. castaneum. Nerolidol, santalol, and geranyl butyrate showed fair contact activity against L. bostrychophila. In particular, geranyl butyrate exhibited outstanding activity (LD50 = 11.53 μg/cm2). In addition, all of the four compounds did not detect a difference between compounds and the positive control (P > 0.05) against two pests at five tested concentrations. These results indicated that A. songarica and its selected compounds could be used as prospective insecticidal and repellent agents for further development and use., (Copyright ©, International Association for Food Protection.)

Plants are known to increase the emission of volatile organic compounds upon the damage of phytophagous insects. However, very little is known about the composition and temporal dynamics of volatiles released by wild plants of the genus Crotalaria (Fabaceae) attacked with the specialist lepidopteran caterpillar Utetheisa ornatrix (Linnaeus) (Erebidae). In this work, the herbivore-induced plant volatiles (HIPV) emitted by Crotalaria nitens Kunth plants were isolated with solid phase micro-extraction and the conventional purge and trap technique, and their identification was carried out by GC/MS. The poly-dimethylsiloxane/divinylbenzene fiber showed higher affinity for the extraction of apolar compounds (e.g., trans -β-caryophyllene) compared to the Porapak™-Q adsorbent from the purge & trap method that extracted more polar compounds (e.g., trans -nerolidol and indole). The compounds emitted by C. nitens were mainly green leaf volatile substances, terpenoids, aromatics, and aldoximes (isobutyraldoxime and 2-methylbutyraldoxime), whose maximum emission was six hours after the attack. The attack by caterpillars significantly increased the volatile compounds emission in the C. nitens leaves compared to those subjected to mechanical damage. This result indicated that the U. ornatrix caterpillar is responsible for generating a specific response in C. nitens plants. It was demonstrated that HIPVs repelled conspecific moths from attacked plants and favored oviposition in those without damage. The results showed the importance of volatiles in plant-insect interactions, as well as the choice of appropriate extraction and analytical methods for their study.

The objective of this study was to establish the chromatographic fingerprints of the essential oil (EO) from Stellera chamaejasme flowers collected from various natural sites by gas chromatography (GC) combined with chemometric methods. The EO was obtained by hydrodistillation, and its chemical composition was analyzed by gas chromatography-mass spectrometry (GC-MS). Most components were identified as ketones and the relatively high-content components were fitone (38.973%), n -hentriacontane (5.807%), myristic acid (4.944%) and phytol (3.988%). In addition, the repellent activities of the EO from S. chamaejasme flowers and its four main chemical compounds were evaluated against three stored product pests ( Tribolium castaneum , Lasioderma serricorne , Liposcelis bostrychophila ) for the first time. In this work, the EO and the four chemical compounds showed a repellent effect against three storage pests after 2 and 4 h exposure. The experimental method and repellent activity of S. chamaejasme flower EO could provide a basis for the development of botanical pesticide and the utilization of the rich plant resources of S. chamaejasme in the future.

Background: Plant-based mosquito control methods may use as a supplementary malaria vector control strategy. This study aimed to evaluate the effect of smoking ethno-medicinal plants on indoor density and feeding activity of malaria vectors at early hours of the night and its residual effect after midnight in southern Ethiopia., Methods: Both field and tent trials were conducted to evaluate the impact of smoking Juniperus procera leaves, Eucalyptus globulus seeds and Olea europaea leaves in Kolla Shara Village from July 2016 to February 2017. For the field trial, five grass-thatched traditional huts (three for ethno-medicinal plants and two as control [only charcoal smoking and non-charcoal smoking]) were used. Indoor host-seeking mosquitoes were collected by CDC light traps. A Latin square design was employed to minimize the bias due to the variation in house location and different sampling nights. For the tent experiment, 25 3-5-day-old starved wild female Anopheles mosquitoes reared from the larvae were released into the tents where a calf was tethered at the mid-point of each tent., Results: A total of 614 Anopheles mosquitoes belonging to 5 species were collected from 5 huts, of which 93.4% was An. arabiensis; O. europaea, E. globulus and J. procera reduced the indoor density of An. arabiensis, with the mean percentage drop of 80%, 73% and 70%, respectively. In the tent trial, smoking of these plants had significant knockdown effects and inhibited feeding on the calves (F = 383.5, DF = 3, P < 0.01). The mean knockdown effect due to O. europaea was relatively high (17.7 ± 0.54; 95% CI 16.8-18.6), while it was only 0.9 ± 0.1 (95% CI 0.29-1.52) in the control tents. All the test plants used in the tent trial caused significantly inhibited feeding activity of An. arabiensis on the host (F = 383.5, DF = 3, P < 0.01). About 94.5%, 89.5% and 86% of mosquitoes were unfed because of the smoking effect of O. europaea, E. globulus and J. procera, respectively, whereas only 19.5% were unfed in the control tent., Conclusions: Smoking ethno-medicinal plant materials reduced indoor density of malaria vectors and inhibited feeding on calves inside the tents. Thus, plant-based mosquito control methods may play a vital role in reducing mosquito bites in the early hours of the night and thereby reduce residual malaria transmission.

The common bed bug, Cimex lectularius L., resurged as an important urban pest in the last 20 yr. Yet, there are no commercial repellent products labeled for bed bugs available in the United States. We evaluated the repellency of two catnip oils from newly developed cultivars, CR3 and CR9, and compared each to 10 and 25% N,N-diethyl-meta-toluamide (DEET). CR3 contains 63.4% E,Z-nepatalactone and 27.5% Z,E-nepatalactone, and CR9 contains 94.9% Z,E-nepatalactone. Arena studies showed that CR3 and CR9 oils were more effective than DEET within a 24-h period. At 10% concentration, both CR3 and CR9 oils exhibited a repellency of over 94% during the first 8 h. At 25% concentration, the repellency of CR3 and CR9 oils increased to 100%, and repellency of DEET was 92% during the first 24 h. Repellency of 25% CR3 and CR9 oils became lower than 25% DEET after being aged for 3 d. After 28-d aging, repellency of 25% CR3, CR9, and DEET reduced to 25, 64, and 92%, respectively. Soiled socks were placed above repellent treated bands to determine if the repellent can protect soiled socks from being infested. The 20% CR3 oil prevented 100% of bed bugs from infesting soiled socks showing that it was more effective than DEET. These results indicate that catnip oils from CR3 and CR9 cultivars are more repellent than DEET over a 24-h period following application, but their longevity is shorter than DEET after 72 h., (© The Author(s) 2020. Published by Oxford University Press on behalf of Entomological Society of America. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.)

Background: Novel malaria vector control approaches aim to combine tools for maximum protection. This study aimed to evaluate novel and re-evaluate existing putative repellent 'push' and attractive 'pull' components for manipulating the odour orientation of malaria vectors in the peri-domestic space., Methods: Anopheles arabiensis outdoor human landing catches and trap comparisons were implemented in large semi-field systems to (i) test the efficacy of Citriodiol ® or transfluthrin-treated fabric strips positioned in house eave gaps as push components for preventing bites; (ii) understand the efficacy of MB5-baited Suna-traps in attracting vectors in the presence of a human being; (iii) assess 2-butanone as a CO 2 replacement for trapping; (iv) determine the protection provided by a full push-pull set up. The air concentrations of the chemical constituents of the push-pull set-up were quantified., Results: Microencapsulated Citriodiol ® eave strips did not provide outdoor protection against host-seeking An. arabiensis. Transfluthrin-treated strips reduced the odds of a mosquito landing on the human volunteer (OR 0.17; 95% CI 0.12-0.23). This impact was lower (OR 0.59; 95% CI 0.52-0.66) during the push-pull experiment, which was associated with low nighttime temperatures likely affecting the transfluthrin vaporisation. The MB5-baited Suna trap supplemented with CO 2 attracted only a third of the released mosquitoes in the absence of a human being; however, with a human volunteer in the same system, the trap caught < 1% of all released mosquitoes. The volunteer consistently attracted over two-thirds of all mosquitoes released. This was the case in the absence ('pull' only) and in the presence of a spatial repellent ('push-pull'), indicating that in its current configuration the tested 'pull' does not provide a valuable addition to a spatial repellent. The chemical 2-butanone was ineffective in replacing CO 2 . Transfluthrin was detectable in the air space but with a strong linear reduction in concentrations over 5 m from release. The MB5 constituent chemicals were only irregularly detected, potentially suggesting insufficient release and concentration in the air for attraction., Conclusion: This step-by-step evaluation of the selected 'push' and 'pull' components led to a better understanding of their ability to affect host-seeking behaviours of the malaria vector An. arabiensis in the peri-domestic space and helps to gauge the impact such tools would have when used in the field for monitoring or control.

Background: Dengue, chikungunya, and Zika viruses are increasingly important public health problems. Burning vegetation, leaves, and other plant products have been shown to be effective mosquito repellents for their vector, Aedes spp., but there has been scant research on whether firewood cooking smoke in households influences mosquito populations or mosquito-borne diseases. About 2.9 billion people worldwide use biomass fuel for household cooking and heating, resulting in an estimated 1.6 million deaths annually from household air pollution (HAP)-related diseases. Global health agencies now encourage households to transition from biomass to clean fuels, but it is unclear whether such interventions may actually increase risk for mosquito-borne diseases. This retrospective case-control study evaluated associations between arboviral infections and cooking with firewood in Santa Rosa, Guatemala., Method: Vigilancia Integrada Comunitaria (VICo) was a prospective public health surveillance system for bacterial, parasitic, and viral causes of diarrheal, neurological, respiratory, and febrile illnesses in hospitals and clinics in the department of Santa Rosa, Guatemala. Enrolled VICo in-patients and out-patients during 2011-2018 were interviewed using standardized questionnaires on demographics and household characteristics. Blood and stool specimens were collected and tested to identify the etiologies presenting symptoms. Cases were defined as laboratory-positive for dengue, chikungunya, or Zika virus infections. Controls were laboratory-positive for bacterial and viral diarrheal illnesses (e.g., Salmonella, Shigella, Campylobacter, Escherichia coli, rotavirus, norovirus, sapovirus, or astrovirus). Cooking with firewood, kitchen location, stove type, and firewood cooking frequency were the independent exposure variables. Logistic regression models were used to analyze unadjusted and adjusted associations between arboviral infections and exposures of interest., Result: There were 311 arboviral cases and 1,239 diarrheal controls. Arboviral infections were inversely associated with cooking with firewood in the main house (AOR: 0.22; 95% CI: 0.08-0.57), cooking with firewood on an open hearth (AOR: 0.50; 95% CI: 0.33-0.78), and cooking with firewood ≥5 times per week (AOR: 0.54; 95% CI: 0.36-0.81), adjusting for age, sex, ethnicity, socioeconomic status index, number of people per household, community population density, community elevation, recruitment location, season, and admission year., Conclusion: Several primary determinants of HAP exposure were inversely associated with arboviral infections. Additional studies are needed to understand whether interventions to reduce HAP might actually increase risk for mosquito-borne infectious diseases, which would warrant improved education and mosquito control efforts in conjunction with fuel interventions., Competing Interests: The authors have declared that no competing interests exist.

In order to develop more environmentally benignant insecticides, the Ligusticum pteridophyllum Franch. rhizomes essential oil and supercritical fluid (SFE-CO 2 ) extract were obtained by two published techniques, hydrodistillation and SFE-CO 2 . The chemical components of this two tested samples were identified by using gas chromatography-mass spectrometry (GC-MS) and gas chromatography-flame ionization detector (GC-FID). Repellent activity and contact toxicity of the obtained samples and myristicin against the adults of Tribolium castaneum (Coleoptera: Tenebrionidae), Lasioderma serricorne (Coleoptera: Anobiidae), and Liposcelis bostrychophila (Psocoptera: Liposcelididae) were compared. Nineteen components were identified in the SFE-CO 2 extract. Twelve components were identified in the L. pteridophyllum rhizomes essential oil. SFE-CO 2 extract exhibited higher contact toxicity against T. castaneum, L. serricorne, and L. bostrychophila (LD 50  = 69.60 μg/adult, 14.58 μg/adult, and 1.69 μg/cm 2 , respectively) than that of L. pteridophyllum rhizomes essential oil (LD 50  = 87.99 μg/adult, 89.82 μg/adult, and 7.87 μg/cm 2 , respectively). Besides, myristicin (LD 50  = 36.46 μg/adult) showed superior contact toxicity against T. castaneum than that of the L. pteridophyllum rhizomes essential oil and SFE-CO 2 extract. It possessed potentially practical significance to develop L. pteridophyllum rhizomes into plant pesticide or repellent agent for these stored insect controls. Graphical abstract .

Marsh rosemary (Ledum palustre, Ericaceae) has been widely used in the traditional medicine of various regions worldwide, and as insect repellent. Little is known on its essential oil insecticidal potential. This study explored the insecticidal effects of the essential oil obtained from L. palustre growing in Poland on selected insect pests and vectors. GC-MS analysis evidenced an uncommon chemotype characterized by ascaridole (35.3% as sum of cis-ascaridole and isoascaridole) and p-cymene (25.5%). The essential oil was effective against Culex quinquefasciatus, Spodoptera littoralis and Musca domestica, showing LC 50 /LD 50 of 66.6 mg L -1 , 117.2 μg larva -1 and 61.4 μg adult -1 , respectively. It was not toxic to non-target Eisenia fetida earthworms and moderately toxic to Daphnia magna microcrustaceans, over the positive control α-cypermethrin. The essential oil cytotoxicity on human keratinocytes and fibroblasts showed high IC 50 values (71.3 and 84.4 μg mL -1 , respectively). Comet assay data highlighted no DNA damages. Based on our findings, this essential oil, characterized by the ascaridole/p-cymene chemotype, could be a candidate for the formulation of botanical insecticides; large-scale production of green insecticides by this rare species may be assured by ex situ cultivation and biotechnological techniques., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

In this work, the essential oil (EO) and supercritical CO 2 fluid extract (SF extract) of four Valerianaceae plants (Valeriana officinalis L., Valeriana officinalis L. var. latifolia Miq., Valeriana jatamansi Jones and Nardostachys chinensis Bat.) were chemically characterized. GC-MS analysis identified 74 compounds, representing 35.2%-82.4% of the total EOs and SF extracts. The EO was dominated by low-molecular-weight components while the SF extract was rich in fatty acids. Bornyl acetate and camphene were the characteristic compounds in EO and SF extracts. The efficacy of six extracts against three stored-product insects was investigated. In contact assays, V. officinalis exhibited strongest toxicity to red flour beetle (LD 50  = 10.0 μg/adult), and V. jatamansi EO was the most active one against the cigarette beetle (LD 50  = 17.6 μg/adult), while V. officinalis var. latifolia EO showed outstanding efficacy against the booklouse (LD 50  = 40.2 μg/cm 2 ). Binary mixtures of two major compounds (camphene and bornyl acetate) were assessed for the contact toxicity to the red flour beetle. Additive effect existed in the natural proportion of V. officinalis, and synergism was observed in that of V. officinalis var. latifolia. This work confirmed the insecticidal efficacy of the species of the Valerianaceae family, and it would offer some information for the development of botanical insecticide., (Copyright © 2019 The Author(s). Published by Elsevier Inc. All rights reserved.)

Three types of mosquito-repellent incenses including disc, electric liquid and electric mat, were selected to investigate the emission of volatile organic compounds in the respiratory zone during the burning. VOCs were analyzed by GC-MS. Results showed that the average concentration of TVOCs released by using the disc, electric liquid and electric mat mosquito repellent incense types were 7.760 ± 4.724, 3.122 ± 0.866 and 1.192 ± 0.062 mg/m 3 , respectively. The TVOCs pollution level produced during the burning of different mosquito-repellent incense types was ranked in the order: disc > electric liquid > electric mat. The concentration of TVOCs produced by Q-liquid, L-liquid, Q-disc and L-disc mosquito-repellent incense types could cause discomfort to the human body. Other types of mosquito-repellent incense induced multiple synergistic effects on human response. About 230 kinds of VOCs including 14 types of VOCs, were found in the smoke of mosquito-repellent incense. The number and content of alkanes was the highest, followed by aromatic hydrocarbons and esters. The level of non-carcinogenic health risk presented by exposure to BTEX (toluene, xylene and ethylbenzene) was acceptable. The chronic daily intake of VOCs decreased with age for both males and females, with male exposure being higher than that of the female, except for children., (Copyright © 2019 Elsevier B.V. All rights reserved.)

N,N-diethyl-meta-toluamide (DEET) is the most widely used active ingredient in commercial insect repellents. In addition to its adverse effects in insects, DEET can affect non-target organisms in surface water systems. Nevertheless, the aquatic life criteria of DEET are not available. This study conducted both acute and chronic toxicity tests on DEET in native Chinese aquatic species, and derived its criterion maximum concentration (CMC) and criterion continuous concentration (CCC). The determined CMC and CCC of DEET were 21.53 and 0.52 mg/L, respectively. The toxicity data indicated that DEET exposure posed a higher toxicity to some algae than other aquatic species. Compared with other insect repellents, DEET exposure posed a moderate toxicity to aquatic species. Therefore, the exposure concentration of DEET in Chinese surface water was collected to assess the potential ecological risk. The preliminary ecological risk assessment showed that DEET posed negligible risk to aquatic ecosystems in China. However, considering its toxic effects on the growth and reproduction to aquatic organisms, the ecological risk posed by DEET is worth further concern., (Copyright © 2019 Elsevier Inc. All rights reserved.)

DEET (N, N-diethyl-m-toluamide) is one of the most frequently detected trace organic contaminants (TOrC) in wastewaters and is used primarily as an insect repellent. It was introduced for use in the general public in 1957. It is ubiquitously present in the environment and DEET concentrations are usually among the highest reported for TOrCs. Due to recent concerns about possible analytical interferences in detection methods being reported, this study focused on possible artifacts caused by seasonal, spatial, and diurnal variations in wastewater influent concentration of DEET. We also compared usage data to observed wastewater concentrations of seven wastewater treatment plants (WWTPs) in four different regions in the US monitored from November 2014 to November 2016. Consumption data obtained reveal patterns of consumption according to climatic regions and season. During the summer DEET usage accounts for almost 60% of all usage during a year, while during the winter months DEET usage accounts for <5%. Concerning spatial distribution, while per capita consumption of DEET in Florida is three times higher than the one observed in Arizona (44 g vs 14 g), DEET concentrations in wastewater tend to be much higher in Arizona. Regardless of WWTPs or monitoring period, concentrations as high as 15,200 ng/L were observed during the month of October 2016. While DEET has a diurnal variation in the wastewater influent, with a maximum at 18:00, the diurnal variability is not enough to explain the great discrepancies between consumption of DEET versus occurrence in wastewaters. Although LC-MS/MS analysis of isobaric and structural mimics suggests some possibility of interferences, NMR spectroscopy analysis of environmental samples does not support the presence of such mimics in real samples., (Copyright © 2019 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Background: African trypanosomosis, primarily transmitted by tsetse flies, remains a serious public health and economic challenge in sub-Saharan Africa. Interventions employing natural repellents from non-preferred hosts of tsetse flies represent a promising management approach. Although zebras have been identified as non-preferred hosts of tsetse flies, the basis for this repellency is poorly understood. We hypothesized that zebra skin odors contribute to their avoidance by tsetse flies., Methodology/principal Findings: We evaluated the effect of crude zebra skin odors on catches of wild savannah tsetse flies (Glossina pallidipes Austen, 1903) using unbaited Ngu traps compared to the traps baited with two known tsetse fly management chemicals; a repellent blend derived from waterbuck odor, WRC (comprising geranylacetone, guaiacol, pentanoic acid and δ-octalactone), and an attractant comprising cow urine and acetone, in a series of Latin square-designed experiments. Coupled gas chromatography-electroantennographic detection (GC/EAD) and GC-mass spectrometry (GC/MS) analyses of zebra skin odors identified seven electrophysiologically-active components; 6-methyl-5-hepten-2-one, acetophenone, geranylacetone, heptanal, octanal, nonanal and decanal, which were tested in blends and singly for repellency to tsetse flies when combined with Ngu traps baited with cow urine and acetone in field trials. The crude zebra skin odors and a seven-component blend of the EAD-active components, formulated in their natural ratio of occurrence in zebra skin odor, significantly reduced catches of G. pallidipesby 66.7% and 48.9% respectively, and compared favorably with the repellency of WRC (58.1%- 59.2%). Repellency of the seven-component blend was attributed to the presence of the three ketones 6-methyl-5-hepten-2-one, acetophenone and geranylacetone, which when in a blend caused a 62.7% reduction in trap catch of G. pallidipes., Conclusions/significance: Our findings reveal fundamental insights into tsetse fly ecology and the allomonal effect of zebra skin odor, and potential integration of the three-component ketone blend into the management toolkit for tsetse and African trypanosomosis control., Competing Interests: The authors have declared that no competing interests exist.

The study reports efficacy of Melissa officinalis L. essential oil (MOEO) as a safe plant-based insecticide against Tribolium castaneum Herbst (TC) by induction of oxidative stress. MOEO nanoencapsulation in chitosan matrix was performed to enhance its bioefficacy. GC-MS analysis of MOEO depicted geranial (31.54%), neral (31.08%), and β-caryophyllene (12.42%) as the major components. MOEO showed excellent insecticidal potential in contact (100% mortality at 0.157 μL/cm 2 ) and fumigant bioassays (LC 50  = 0.071 μL/mL air) and 100% repellency at concentration ≤ 0.028 μL/cm 2 . Increased reactive oxygen species (ROS), superoxide dismutase (SOD), catalase (CAT), and decreased ratio of reduced glutathione (GSH) to oxidized glutathione (GSSG) at the LC 50 dose suggested significant oxidative stress on TC in MOEO treatment sets. The encapsulated MOEO exhibited enhanced activity as fumigant (LC 50  = 0.048 μL/mL air) and showed significant antifeedant activity in situ (EC 50  = 0.043 μL/mL). High LD 50 value (13,956.87 μL/kg body weight of mice) confirmed favorable toxicological profile for non-target mammals. The findings depict potential of nanoencapsulated MOEO as an eco-friendly green pesticide against infestation of stored food by TC.

The antifeedant and contact toxicity of Sphagneticola trilobata L. (Asterales: Asteraceae) extracts and isolated alkane compounds were investigated. Leaves of S. trilobata were sequentially extracted with hexane, dichloromethane, ethyl acetate, and methanol. Each extract and the compounds isolated were evaluated against the third instars of Spodoptera litura (F.) (Lepidoptera: Noctuidae), Spodoptera exigua (Hübner) (Lepidoptera: Noctuidae), and Plutella xylostella L. (Lepidoptera: Yponomeutidae). Ethyl acetate extract and isolated alkanes were feeding deterrents as well as contact toxins against all the three species evaluated (FI50 ~ 0.27-2.34 mg/ml; LD50 ~ 0.88-4.2 µg/larvae for ethyl acetate extract, and FI50 ~ 0.06-4.35 mg/ml; LD50 ~ 0.72-3.54 Ethyl acetate extract for isolated alkane). Impact on detoxifying enzymes was variable. The ethyl acetate crude extract reduced carboxylesterase activity in S. litura and P. xylostella while in S. exigua the enzyme was induced. In contrast, glutathione-S-transferase activity was induced in S. exigua but no significant difference in P. xylostella and S.litura was observed. Our results suggest that the S. trilobata extracts have multiple biological activities that contribute to the toxicity in lepidopterans. Variable enzyme responses to the products evaluated in different lepidopteran species also confirm that some species-specific inductions do occur, suggesting the possibility of resistance development in the future, which cannot be summarily ignored. However, for this detailed biochemical studies are required. Multiple bioefficacies of S. trilobata makes it a potential botanical for further exploitation on larger scale so that field potential can be established in any integrated pest management (IPM) system.

For the first time, the repellent and insecticidal effects of eucalypt essential oil (Eucalyptus globulus) in its free form and associated with different nanostructures (nanoemulsion and nanocapsules) were investigated against Musca domestica (Diptera: Muscidae) and Haemotobia irritans (Diptera: Muscidae) flies. Specimens of M. domestica were collected, separated into groups (n = 10), treated with aspersion of essential oil of eucalypt in its free (1, 5, and 10%) and nanostructured (nanoemulsion or nanoencapsulated at 1, 3, and 5%, respectively) forms. The determination of the insecticidal effect was performed by counting the number of dead flies at intervals of 30, 60, 120, 360 and 750 min after oil aspersion. E. globulus essential oil showed insecticidal effect against M. domestica at concentrations of 1 and 5%. Eucalypt essential oil (10%) caused 100% mortality of M. domestica after 750 min of the treatment. Nanocapsules (3 and 5%) showed efficacy by reducing the number of flies. On the other hand, nanoemulsion did not show insecticidal effect. The repellent action of E. globulus concentrations of 5% was tested against H. irritans on naturally infested cows. The repellent action against H. irritans was verified soon after pulverization. After 24 h, a significant reduction on horn flies' population (83.33 and 66.66%) was observed using free and nanoencapsulated forms tested, respectively. E. globulus essential oil demonstrated insecticidal and repellent effects against M. domestica and H. irritans flies.

We present the use of Raman spectroscopy for determination of functional characteristics of insect repellents and sunscreens by identifying the active ingredients of these products applied topically to the skin. Commercial formulations of insect repellents and sunscreens (SPF 15 and 30) were obtained, and Raman spectra were obtained from the formulations and from volunteers' skins with topical applications of such products compared to controls. The results indicated that, for insect repellents, the peaks at 527 and 1003  cm  -  1 were markers of the presence of the active ingredient diethyl toluamide in the skin, while for sunscreens, the peaks at 1177, 1288, and 1611  cm  -  1, associated to octinoxate, benzophenone-3, and avobenzone, were markers of the presence of solar filters in the skin. The results suggested reliability in the use of Raman spectroscopy to identify the active ingredients of insect repellents and sunscreens topically applied on the skin; the applied methodology can be used to determine the functional characteristics of topical products with similar characteristics., ((2018) COPYRIGHT Society of Photo-Optical Instrumentation Engineers (SPIE).)

In this work, the essential oil (EO) was extracted from the fruits of Evodia lenticellata, and the fumigant toxicity, contact toxicity and repellency against three stored-product insect species were evaluated for the obtained EO and several of its chemical components. The target insects were the adults of Tribolium castaneum (Coleoptera: Tenebrionidae), Lasioderma serricorne (Coleoptera: Anobiidae) and Liposcelis bostrychophila (Psocoptera: Liposcelididae). The EO was obtained with hydrodistillation and its chemical components were analyzed with the gas chromatography-mass spectrometry (GC-MS). Twenty-seven compounds, accounting for 83.1% of the total amount of the oil, were identified from the EO sample. The main compounds included linalool (12.0%), β-pinene (11.5%), 3-carene (9.6%), caryophyllene oxide (8.7%) and β-caryophyllene (7.9%). Among them, the amounts of monoterpenes and sesquiterpenes were as high as 52.7% and 22.7% to the total amount of EO respectively. The results of bioactivity test showed that the EO and its testing compounds had interspecific toxicity and repellent activity. So that, it might be expected that the EO extracted from the fruits of E. lenticellata could be developed to a new type of eco-friendly natural insecticide or repellent for the control of stored-product insects., (Copyright © 2018 Elsevier Inc. All rights reserved.)

The extract from Cinnamomum cassia Presl bark was obtained with supercritical CO 2 fluid extraction (SFE). Chemical components of the SFE extract were characterized by GC-MS spectrometry. The repellency and contact toxicity of the SFE extract were evaluated against the adults of Tribolium castaneum and Lasioderma serricorne along with those of its two main compounds. The results of GC-MS analysis indicated that 33 volatile constituents were identified from the extract. The main components included trans-cinnamaldehyde (32.1%), 3,3-dimethylhexane (10.6%) and 2,4-di-tert-butylphenol (7.9%). Testing results showed that the SFE extract had potent contact toxicity against T. castaneum and L. serricorne with LD 50 values of 3.96 and 23.89 μg/adult, respectively. LD 50 values of trans-cinnamaldehyde against T. castaneum and L. serricorne were 5.78 and 3.24 μg/adult, respectively. Additionally, percentage repellency values of the SFE extract and trans-cinnamaldehyde against T. castaneum and L. serricorne were rather high (PR = 100% and PR > 90%, respectively) at 78.63 and 15.73 nL/cm 2 at 2 h post-exposure. 2,4-Di-tert-butylphenol showed some repellency against both beetle species. Considering its insecticidal and repellent effects, the SFE extract from C. cassia bark might be used in integrated pest management programs for T. castaneum and L. serricorne.

In this work we report a fast and efficient virtual screening protocol for discovery of novel bioinspired synthetic mosquito repellents with lower volatility and, in all likelihood, increased protection time as compared with their plant-derived parental compounds. Our screening protocol comprises two filtering steps. The first filter is based on the shape and chemical similarity to known plant-derived repellents, whereas the second filter is based on the predicted similarity of the ligand's binding mode to the Anopheles gambiae odorant binding protein (AgamOBP1) relative to that of DEET and Icaridin to the same OBP. Using this protocol, a chemical library containing 42,755 synthetic molecules was screened in silico and sixteen selected compounds were tested for their affinity to AgamOBP1 in vitro and repellence against A. gambiae female mosquitoes using a warm-body repellent assay. One of them showed DEET-like repellence (91%) but with significantly lower volatility (2.84 × 10 -6  mmHg) than either DEET (1.35 × 10 -3  mmHg) or its parental cuminic acid (3.08 × 10 -3  mmHg), and four other compounds were found to exhibit repellent indices between 69 and 79%. Overall, a correlation was not evident between repellence and OBP-binding strength. In contrast, a correlation between binding mode and repellence was found., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Insect repellents (IRs) are a group of organic chemicals whose function is to prevent the ability of insects of landing in a surface. These compounds have been found in the environment and may pose a risk to non-target organisms. In this study, an on-line solid phase extraction - high performance liquid chromatography-tandem mass spectrometry multiresidue method was developed using an atmospheric photoionization source (SPE-HPLC-(APPI)-MS/MS). The use of the APPI as an alternative ionization technique to electrospray (ESI) and atmospheric pressure chemical ionization (APCI) allowed expanding the range of analytical techniques suitable for the analysis of IRs, so far relied in gas chromatography. High sensitivity and precision was reached with method limits of quantification between 0.2 and 4.6 ng l -1 and interday and intraday precision equal or below 15%. The validated method was applied to the study of surface water samples from three European river basins with different flow regime (Adige River in Italy, Sava River in the Balkans, and Evrotas River in Greece). The results showed that two IRs (DEET and Bayrepel) were ubiquitous in the Sava and Evrotas basins, reaching concentrations as high as 105 μg l -1 of Bayrepel in the Sava River, and 5 μg l -1 of DEET in the Evrotas River. Densely populated areas and effluent waste waters are pointed out as the responsible for this pollution. In the alpine river Adige, only three samples showed low levels of IRs (6.01-37.8 ng l -1 ). The concentrations measured were used to perform an environmental risk assessment based on the hazard quotients (HQs) estimation approach by using the chronic and acute eco-toxicity data available. The results revealed that despite the high frequency and eventually high concentrations of these IRs determined in the three basins, only few sites were at risk, with 1 < HQs < 3.3., (Copyright © 2018 The Author(s). Published by Elsevier B.V. All rights reserved.)

Plants naturally produce bioactive compounds along with many secondary metabolites which serve as defensive chemical against herbivorers including insect pests. One group of these phytochemicals are the 'Essential Oils' (EO's), which possess an extensive range of biological activity especially insecticidal and insect repellents. This review provides a comprehensive viewpoint on potential modes of action of biosafety plant derived Essential Oils (EO's) along with their principal chemical derivatives against larvae and adult mosquito vectors of dengue virus. The development and use of Essential Oils (EO's) effectively applied in small rural communities provides an enormous potential for low cost effective management of insect vectors of human pathogens which cause disease., (Copyright © 2017. Published by Elsevier Ltd.)

Fingerprints, specifically the ridge details within the print, have long been used in forensic investigations for individual identification. Beyond the ridge detail, fingerprints contain useful chemical information. The study of fingerprint chemical information has become of interest, especially with mass spectrometry imaging technologies. Mass spectrometry imaging visualizes the spatial relationship of each compound detected, allowing ridge detail and chemical information in a single analysis. In this work, a range of exogenous fingerprint compounds that may reveal a personal lifestyle were studied using matrix-assisted laser desorption/ionization mass spectrometry imaging (MALDI-MSI). Studied chemical compounds include various brands of bug sprays and sunscreens, as well as food oils, alcohols, and citrus fruits. Brand differentiation and source determination were possible based on the active ingredients or exclusive compounds left in fingerprints. Tandem mass spectrometry was performed for the key compounds, so that these compounds could be confidently identified in a single multiplex mass spectrometry imaging data acquisition.

The rise of the mosquitoes-transmitted diseases, like dengue, zika and chikungunya in Brazil in the last years has increased concerns on protection against mosquitoes bites. However, the prohibitive prices of the commercially available repellents for the majority of the Brazilian population has provoked a search for cheaper solutions, like the use of the homemade ethanolic extract of Indian clove (Syzygium aromaticum L.) as repellent, which has been reported as quite efficient by the local press. In order to verify this, we performed here the quantification of the main components of this extract through high-performance thin-layer chromatography (HPTLC)-densitometry and evaluated its efficiency as a repellent and its acetylcholinesterase (AChE) inhibition capacity. Our results have proved HPTLC-densitometry as an efficient and appropriate method for this quantification and confirmed the repellency activity, as well as its capacity of AChE inhibition., (Copyright © 2017 John Wiley & Sons, Ltd.)

Mosquito-repellent incense is one of the most popular products used for dispelling mosquitos during summer in China. It releases large amounts of particulate and gaseous pollutants which constitute a potential hazard to human health. We conducted chamber experiment to characterize major pollutants from three types of mosquito-repellent incenses, further assessed the size-fractionated deposition in human respiratory system, and evaluated the indoor removing efficiency by fresh air. Results showed that the released pollutant concentrations were greater than permissible levels in regulations in GB3095-2012, as well as suggested by the World Health Organization (WHO). Formaldehyde accounted for 10-20% of the total amount of pollutants. Fine particles dominated in the total particulate concentrations. Geometric standard deviation (GSD) of particle number size distributions was in the range of 1.45-1.93. Count median diameter (CMD) ranged from 100 to 500 nm. Emission rates, burning rates and emission factors of both particulate and gaseous pollutants were compared and discussed. The deposition fractions in pulmonary airway from the disc solid types reached up to 52.7% of the total deposition, and the largest deposition appeared on juvenile group. Computational Fluid Dynamics (CFD) modellings indicated air-conditioner on and windows closed was the worst case. The highest concentration was 180-200 times over the standard limit., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Five flavonoids from hops, two of their derivatives, along with naringenin used as a model compound, were tested for their antifeedant activity against three coleopteran stored product pests: Sitophilus granarius L., Tribolium confusum Duv. and Trogoderma granarium Everts. The introduction, into the tested flavonoid molecules, of additional structural fragments such as prenyl or dimethylpyran moiety, is proposed to significantly alter the deterrent activity of the compounds. The prenyl moiety in flavonoids increased the deterrent activity of these compounds in all three of the grain feeding species used in the tests. It is also concluded that the introduction of dimethylpyran moiety to the flavonoid structure increases its deterrent activity in S. granarius and T. confusum, but in one of the test insects, T. granarium, an increased feeding was observed in response to the introduction of dimethylpyran moiety to the flavonoid structure.

Introduction: Unintentional mothball ingestions may cause serious toxicity in small children. Camphor, naphthalene, and paradichlorobenzene mothballs are difficult to distinguish without packaging. Symptoms and management differ based on the ingested compound. Previous studies have used a variety of antiquated, impractical and potentially dangerous techniques to identify the mothballs. The goal of this study is to discover a simplified identification technique using materials readily available in an emergency department., Methods: Mothballs made of naphthalene and paradichlorobenzene along with camphor tablets were tested. Each material was tested both intact and after being fragmented to simulate a partially ingested mothball. Each of these six sample types were then immersed in 40 ml each of 11 fluids: water, 0.45% NaCl, 0.9% NaCl, lactated Ringer's, 5% dextrose in water, 5% dextrose in 0.9% NaCl, 50% dextrose in water, 8.4% NaHCO 3 , 3% H 2 O 2 , 70% isopropanol, and 91% isopropanol. All tests were conducted in standard urinalysis sample cups to replicate available materials. Three toxicologists blinded to the identities of samples and solutions visually evaluated each sample. Observations included assessing response to immersion: sink, float, or dissolve., Results: All evaluators agreed in their description of 62/66 (94%) of the samples, with all four disagreements being on sinking and dissolving versus sinking only. A two-fluid algorithm utilizing 50% dextrose and water was sufficient to distinguish the sample types. Camphor will float in water while both paradichlorobenzene and naphthalene will sink. In 50% dextrose, both naphthalene and camphor will float while paradichlorobenzene will sink., Conclusion: Mothball materials can be distinguished by immersion in water and 50% dextrose. Limitations of this study include using camphor tablets as a substitute for mothballs given lack of availability.

Concentrations of four monoterpenes were determined in needles of Pinus radiata (D.Don) (Pinales: Pinaceae) trees that were attacked or nonattacked by Tomicus piniperda (L.) (Coleoptera: Scolytinae). Compounds were identified and quantified by gas chromatography-mass spectrometry. The mean ambient temperature was obtained using climate-recording data loggers. The effect of limonene on field aggregation was also evaluated at three limonene release rates using Lindgren attractant-baited traps and trap logs. Attacked trees produced less α-pinene in March, July, and November than nonattacked trees, less β-pinene in July and November, and less limonene from May to November. Limonene reduced the attraction of T. piniperda to attractant-baited traps and trap logs. Results were linked to better responses to high temperatures, with respect to terpene contents, by the nonattacked trees after the spring attack., (© The Author 2017. Published by Oxford University Press on behalf of Entomological Society of America.)

The diversity of phytophagous insects is largely attributable to speciation involving shifts between host plants. These shifts are mediated by the close interaction between insects and plant metabolites. However, there has been limited progress in understanding the chemical signatures that underlie host preferences. We use the pea aphid (Acyrthosiphon pisum) to address this problem. Host-associated races of pea aphid discriminate between plant species in race-specific ways. We combined metabolomic profiling of multiple plant species with behavioural tests on two A. pisum races, to identify metabolites that explain variation in either acceptance or discrimination. Candidate compounds were identified using tandem mass spectrometry. Our results reveal a small number of compounds that explain a large proportion of variation in the differential acceptability of plants to A. pisum races. Two of these were identified as L-phenylalanine and L-tyrosine but it may be that metabolically-related compounds directly influence insect behaviour. The compounds implicated in differential acceptability were not related to the set correlated with general acceptability of plants to aphids, regardless of host race. Small changes in response to common metabolites may underlie host shifts. This study opens new opportunities for understanding the mechanistic basis of host discrimination and host shifts in insects.

A simple, accurate and sensitive reversed-phase high-performance liquid chromatographic (RP-HPLC) method has been developed for the estimation of ethyl 2-aminobenzoate (EAB) in a matrix type monolithic polymeric device and validated as per the International Conference on Harmonization guidelines. The analysis was performed isocratically on a ZORBAX Eclipse plus C18 analytical column (250 × 4.4 mm, 5 μm) and a diode array detector (DAD) using acetonitrile and water (75:25 v/v) as the mobile phase by keeping the flow-rate constant at 1.0 mL/min. Determination of EAB was not interfered in the presence of excipients. Inter- and intra-day relative standard deviations were not higher than 2%. Mean recovery was between 98.7 and 101.3%. Calibration curve was linear in the concentration range of 0.5-10 µg/mL. Limits of detection and quantification were 0.19 and 0.60 µg/mL, respectively. Thus, the present report put forward a novel method for the estimation of EAB, an emerging insect repellent, by using RP-HPLC technique., (© The Author 2017. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.)

We evaluated the repellent activity of 12 Apiaceae plant essential oils and their components against male and female adult German cockroaches, Blattella germanica L., to find new natural repellents. Of all the plant essential oils tested, ajowan (Trachyspermum ammi Sprague) and dill (Anethum graveolens L.) essential oils showed the most potent repellent activity against male and female adult German cockroaches. Repellent activities of chemicals already identified in active oils were also investigated. Of the compounds identified, carvacrol, thymol, and R-(-)-carvone showed >80% repellent activity against male and female adult German cockroaches at 2.5 µg/cm2. S-(+)-Carvone, (+)-dihydrocarvone, and terpinen-4-ol showed >70% repellent activity against male and female adult German cockroaches at 10 µg/cm2. Our results indicated that Apiaceae plant essential oils and their constituents have good potential as natural repellents against adult German cockroaches., (© The Authors 2016. Published by Oxford University Press on behalf of Entomological Society of America. All rights reserved. For Permissions, please email: journals.permissions@oup.com.)

Although host-plant selection is a central topic in ecology, its general underpinnings are poorly understood. Here, we performed a case study focusing on the publicly available data on Japanese butterflies. A combined statistical analysis of plant-herbivore relationships and taxonomy revealed that some butterfly subfamilies in different families feed on the same plant families, and the occurrence of this phenomenon more than just by chance, thus indicating the independent acquisition of adaptive phenotypes to the same hosts. We consequently integrated plant-herbivore and plant-compound relationship data and conducted a statistical analysis to identify compounds unique to host plants of specific butterfly families. Some of the identified plant compounds are known to attract certain butterfly groups while repelling others. The additional incorporation of insect-compound relationship data revealed potential metabolic processes that are related to host plant selection. Our results demonstrate that data integration enables the computational detection of compounds putatively involved in particular interspecies interactions and that further data enrichment and integration of genomic and transcriptomic data facilitates the unveiling of the molecular mechanisms involved in host plant selection.

The insect repellent diethyltoluamide (DEET) is among the most frequently detected organic chemical contaminants in water across a wide range of geographies from around the world. These observations are raising critical questions and increasing concerns regarding potential environmental relevance, particularly when the emergence of severe neurological conditions attributed to the Zika virus has increased the use of insect repellents. After dermal application, DEET is washed from the skin when bathing and enters the municipal sewer system before discharge into the environment. Mainly measured by gas chromatography or liquid chromatography coupled to mass spectrometry (GC-MS or LC-MS), more than 200 peer-reviewed publications have already reported concentrations of DEET ranging ng/L to mg/L in several water matrices from North America, Europe, Asia, Oceania, and more recently Africa and South America. While conventional wastewater treatment technology has limited capacity of removal, advanced technologies are capable of better attenuation and could lower the environmental discharge of organic contaminants, including DEET. For instance, adsorption on activated carbon, desalinating membrane processes (nanofiltration and reverse osmosis), ozonation, and advanced oxidation processes can achieve 50% to essentially 100% DEET attenuation. Despite the abundant literature on the topic, the ubiquity of DEET in the environment still raises questions due to the apparent lack of obvious spatio-temporal trends in concentrations measured in surface water, which does not fit the expected usage pattern of insect repellents. Moreover, two recent studies showed discrepancies between the concentrations obtained by GC-MS and LC-MS analyses. While the occurrence of DEET in the environment is well established, the concentrations reported should be interpreted cautiously, considering the disparities in methodologies applied and occurrence patterns observed. Therefore, this manuscript provides a critical overview of the origin of DEET in the environment, the relevant analytical methods, the occurrence reported in peer-reviewed literature, and the attenuation efficacy of water treatment processes., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

In this study, 10 mosquito coils manufactured in China were obtained in Suriname, South America, where they are used extensively. The coils were analyzed for organics (allethrin, permethrin, and butylated hydroxytoluene) and heavy metals (Cr, Co, As, Cd, and Pb) by GC-MS and ICP-MS, respectively. Allethrin was the only target organic compound detected in all mosquito coils with concentrations ranging from ~1900 to ~4500 µg/g. The concentrations of heavy metals varied as follows (in µg/g): Cr: 2.9-9.4, Co: 0.1-1.2, Cu: 0.7-16.1, Se: 0.10-0.4, Ni: 2.1-5.8, As: 0.10-2.2, Cd: 0.10-0.2, and Pb: 1.1-3.6.

Two essential oil samples were obtained from the pericarp of Zanthoxylum bungeanum with the methods of hydrodistillation (HD) and supercritical fluid CO 2 extraction (SFE), their chemical components were identified, and their bioactivities against Lasioderma serricorne adults were evaluated. In the process of testing, the two samples showed significant bioactivities against Lasioderma serricorne adults. For an example, the SFE-sample expressed relatively stronger fumigant toxicity on Lasioderma serricorne adults (LC 50 = 3.99 μg/mL air) than that of the HD-sample (LC 50 = 12.54 μg/mL air). According to GC-MS analysis, the chemical components between two samples were different. The major chemical components for HD included linalool (25.99%), limonene (19.34%), linalyl anthranilate (12.22%), 4-terpinenol (10.49%), eucalyptol (6.53%) and α-terpineol (5.02%), while for SFE included nonanoic acid (21.43%), γ-terpinene (14.51%), eucalyptol (13.45%), α-terpineol (5.83%) and caryophyllene oxide (5.48%). The results showed that different chemical components result in different bioactivities. This work provides theoretical basis for traditional Chinese concept of antagonistic storage, and it also provides important information for the development and comprehensive utilization of Zanthoxylum bungeanum.

N,N-diethyl-m-toluamide (DEET), the active component of many insect repellents, is among the most frequently detected compounds in aqueous environments with concentrations reported in the ng L(-1) to μg L(-1) range. However, DEET is often detected in blanks and reported concentrations differ significantly depending on the analytical technique employed. In addition, relatively sparse data are available regarding the seasonal variability of DEET concentrations in water and there are apparent inconsistencies with expected use patterns. Therefore, the present study investigates potential interferences affecting the detection and quantification of DEET then the geographical and seasonal variations of DEET concentrations. To examine potential analytical interferences, DEET was analyzed in five geographically-diverse wastewater effluents using both gas chromatography and liquid chromatography coupled to mass spectrometric detectors. At times, the concentrations quantified by the employed analytical methods varied significantly. Five compounds with similar molecular weights and structures as DEET were investigated as potential mimics and some were shown to induce an overestimation of DEET. Further experimentation suggested that the solvents used in sample preparation and HPLC analysis are another possible source of interference. Besides potential interferences, the seven-month weekly monitoring of DEET in the primary effluent of a wastewater treatment plant demonstrated a clear seasonal trend with decreasing concentration from summer to winter. These data collectively demonstrate that there are many challenges in the quantification of DEET in complex environmental samples and that co-occurrence of similarly structured substances present in the water sample and/or the solvents used for the analysis could induce analytical bias., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Mosquitoes are the most deadly vectors of parasites that cause diseases such as malaria, yellow fever, and filariasis. In view of the recent increased interest in developing plant origin insecticides as an alternative to chemical insecticides, the objective of this study was to determine the repellent activity of creams formulated with methanol crude extract (MCE), hexane fraction (HF), and ethyl acetate fractions (EAFs) of Ocimum gratissimum and Lantana camara leaves in single and combined actions against female Aedes aegypti. Evaluation was carried out in the net cages (30 by 30 by 30 cm) containing 60 blood-starved female mosquitoes each and were assayed in the laboratory condition following World Health Organization 2009 protocol. All formulations (single and mixture) were applied at 2, 4, 6, and 8 mg/cm(2) in the exposed area of human hands. Only acetone + white soft paraffin served as negative control and odomos (12% DEET) as positive control. All the formulations presented good protection against mosquito bites without any allergic reaction by the human volunteers. The repellent activity was dependent on the strength of the extracts and fractions. Among the tested formulations, the maximum protection time was observed in MCE (120 min) and EAF (150 min) of O. gratissimum; MCE:MCE (150 min) and HF:HF (120 min) mixtures of both plants. In addition, MCE:MCE and HF:HF mixtures from both plants showed possible synergistic effect. From the results, the combination of O. gratissimum and L. camara to formulate natural mosquito repellent using small amount of extracts can be encouraging to be an alternative to conventional DEET., (© The Author 2015. Published by Oxford University Press on behalf of the Entomological Society of America.)

An observational biomonitoring study was conducted involving adults and children in households that purchased and applied a cyphenothrin-containing spot-on product for dogs as part of their normal pet care practices. The 3- to 6-yr-old children had greater exposure than the adult applicators in the same house, 3.8 and 0.6 μg/kg body weight, respectively. The mean measured values in children were 13-fold lower than those estimated using the U.S. Environmental Protection Agency (EPA) current standard operating procedures (SOP) for pet products (assuming 5% dermal absorption), although the maximum absorbed dosage of one child on one day was equivalent to the default value derived from the SOPs. With regard to potential human health risks, it can be concluded that despite the inherent conservatism in both the exposure and toxicology data, the margins of exposure (MOE) were consistently greater than 100 for average, 95th percentile, and maximum exposures. More specifically, the results of this study demonstrated that the MOE were consistently greater than 1,000 for mean exposures and exceeded 100 for 95th percentile and maximum measured exposures, which clearly indicates a reasonable certainty of no harm when using the cyphenothrin spot-on products. It is also noteworthy that Sergeant's spot-on products containing cyphenothrin currently sold in the United States have lower weight percentages of active ingredient and lower applied amounts than those used by all but two of the participant households in this study.

The essential oils of two representatives of the Lamiaceae, Dracocephalum heterophyllum Benth. and Hyssopus officinalis L., are described for their antifungal, antibacterial, larvicidal and inect biting deterrent activities. Additionally, the chemical compositions of the essential oils, analyzed by simultaneous GC-MS and GC-FID, and odor descriptions are given. The main components of H. officinalis oil were pinocarvone, cis-pinocamphone, and β-pinene. Citronellol was found as the main compound of D. heterophyllum essential oil. Antibacterial testing by agar dilution assay revealed greater activity of D. heterophyllum against Staphylococcus aureus compared with H. officinalis. D. heterophyllum essential oil also showed promising antifungal activity against Colletotrichum species and was more toxic to Aedes aegypti larvae in a larvicial bioassay. Both essential oils showed high activity in the biting deterrent bioassay.

Dendranthema indicum (L.) Des Moul. is a perennial herb commonly used as a traditional Chinese medicine for a long time. In this work, we took Dendranthema indicum as a target plant and two stored insects which include Tribolium castaneum and Stegobium paniceum adults as target insects. Essential oil obtained from Dendranthema indicum was analyzed by gas chromatography-mass spectrometry (GC-MS). A total of 31 components representing 92.44% of the oil were identified and the main compounds were found to be chamazulene (15.93%), β-caryophyllene (13.78%), germacrene D (9.11%), and b-cis-farnesene (6.59%). With a further isolation, three constituents were obtained from the essential oil and identified as chamazulene, β-caryophyllene and eucalyptol. Significantly, in the progress of assay, it showed that the essential oil and chamazulene exhibited stronger insecticidal and repellent activities against Stegobium paniceum than Tribolium castaneum. The results indicate that additional to its traditional use as Chinese medicinal herb, the essential oil of Dendranthema indicum aerial parts and isolated compounds have potential to be developed into natural insecticides or repellents for control of insects in stored grains.

Background: A plant-based 'push-pull' strategy for Ectropis obliqua (Prout) (Lepidoptera: Geometridae) is being developed using semiochemicals in the volatiles of Rosmarinus officinalis (Lamiaceae). The aim of this study was to identify and quantify the bioactive components within R. officinalis by gas chromatography-electroantennographic detection (GC-EAD) and gas chromatography-mass spectrometry (GC-MS), and to test the antennal and behavioural responses of E. obliqua to these chemicals. The emission dynamics of bioactive chemicals was also monitored., Results: GC-EAD experiments indicated that E. obliqua antennae responded to the following volatile compounds from R. officinalis: myrcene, α-terpinene, γ-terpinene, linalool, cis-verbenol, camphor, α-terpineol and verbenone, which were the minor constituents. Based on the dose-dependent antennal and behavioural responses of E. obliqua to these bioactive compounds, myrcene, γ-terpinene, linalool, cis-verbenol, camphor and verbenone were found to play a key role in repelling the moths, and the mixture that included all eight compounds was significantly more effective. The maximum emissions of these semiochemicals occurred at nightfall., Conclusions: The specifically bioactive compounds in R. officinalis volatiles are responsible for repelling E. obliqua adults. Results indicate that R. officinalis should be considered as a potential behaviour-modifying stimulus for 'push' components when developing 'push-pull' strategies for control of E. obliqua using semiochemicals., (© 2014 Society of Chemical Industry.)

The aim of this research was to determine chemical composition and repellent and insecticidal activities of the essential oil of Kaempferia galanga L. rhizomes against the booklouse, Liposcelis bostrychophila Badonnel, and to isolate insecticidal or repellent constituents from the oil. The essential oil was obtained by hydrodistillation and analyzed by gas chromatography-mass spectrometry. Twenty-eight components of the oil were identified. The major compounds in the oil were ethyl-rho-methoxycinnamate (38.6%), ethyl cinnamate (23.2%), 1,8-cineole (11.5%), trans-cinnamaldehyde (5.3%), and borneol (5.2%). Based on bioactivity-guided fractionation, four active constituents were isolated from the oil and identified as 1,8-cineole, ethyl cinnamate, ethyl rho-methoxycinnamate, and trans-cinnamaldehyde. The essential oil exhibited contact toxicity against the booklouse with an LC50 value of 68.6 microg/cm2. Ethyl cinnamate (LC50 = 21.4 microg/cm2) exhibited stronger contact toxicity than ethyl rho-methoxycinnamate and trans-cinnamaldehyde (LC50 = 44.6 and 43.4 microg/cm2, respectively) while 1,8-cineole showed weak acute toxicity. The essential oil also possessed fumigant toxicity against the booklouse with a LC50 value of 1.5 mg/liter air. 1,8-Cineole and trans-cinnamaldehyde (LC50 = 1.1 and 1.3 mg/liter, respectively) possessed stronger fumigant toxicity against the booklouse than ethyl cinnamate and ethyl rho-methoxycinnamate (LC50 = 10.2 and 10.2 mg/liter air, respectively). trans-Cinnamaldehyde was strongly repellent to booklice, whereas ethyl cinnamate and ethyl rho-methoxycinnamate were weakly repellent and 1,8-cineole did not repel booklice. The results indicate that the essential oil and its constituent compounds have potential for development into natural insecticides or fumigants and repellents for control of insects in stored grains.

Water-distilled essential oils from dried aerial parts of Tanacetum argenteum (Lam.) Willd. subsp. argenteum (Lam.) and T. argenteum (Lam.) Willd. subsp. canum (C. Koch) Grierson were analyzed by gas chromatography and gas chromatography-mass spectrometry. In total, 27 and 32 components were identified representing 97.2 and 98.7% of essential oils of subsp. argenteum and canum, respectively. Main compounds of T. argenteum subsp. argenteum were alpha-pinene (67.9%) and beta-pinene (4.8%), whereas alpha-pinene (53.6%), 1, 8-cineole (14.8%), and camphor (4.7%) were the major constituents of subsp. canum. Essential oil of T. argenteum subsp. canum at 10 microg/cm2 with Biting Deterrent Index (BDI) value of 0.73 showed activity similar to N,N-Diethyl-meta-toluamide (DEET) at 25 mol/cm2, whereas the activity of essential oil of subsp. argenteum was lower (BDI = 0.47) than subsp. canum and DEET. Based on 95% CIs, activity of beta-caryophyllene (BDI value = 0.54) and caryophyllene oxide (BDI = 0.66) were significantly lower than DEET. In larval bioassays, essential oil of T. argenteum subsp. argenteum showed LC50 value of 93.34 ppm, whereas T. argenteum subsp. canum killed only 40% of the larvae at the highest dose of 125 ppm. Among the pure compounds, beta-caryophyllene (LC50 = 26 ppm) was the most potent compound followed by caryophyllene oxide (LC50 = 29 ppm), which was also similar to (-)-beta-pinene (LC50 = 35.9 ppm) against 1-d-old Ae. aegypti larvae at 24-h post treatment. Compounds (-)-alpha-pinene and (+)-beta-pinene showed similar larvicidal activity. Activity of (+)-alpha-pinene with LC50 value of was similar to the essential oil of T. argenteum subsp. argenteum.

The fumigant, contact, and repellent activities of four essential oils extracted from Citrus limonum (Sapindales: Rutaceae), Litsea cubeba (Laurales: Lauraceae), Cinnamomum cassia, and Allium sativum L. (Asparagales: Alliaceae) against 6th instars and adults of the darkling beetle, Alphitobius diaperinus (Panzer) (Coleoptera: Tenebrionidae), one of the main pests of materials and products of Juncus effuses L. (Poales: Juncaceae) during the storage period, were assayed, and chemical ingredients were analyzed with gas chromatography-mass spectrometry in this study. While the major ingredients found in C. limonum and C. cassia were limonene and (E)-cinnamaldehyde, the main constituents of L. cubea were D-limonene, (E)-3,7-dimethyl-,2,6-octadienal, (Z)-3,7-dimethyl,2 ,6-octadienal, and diallyl disulphide (18.20%), while the main constituents of and A. sativum were di-2-propenyl trisulfide and di-2-propenyl tetrasulfide. The fumigation activities of A. sativum and C. limonum on A. diaperinus adults were better than those of the other two essential oilss. The toxicities of A. sativum and C. limonum were almost equitoxic at 96 hr after treatment. Essential oils from Allium sativum and L. cubeba also showed good contact activities from 24 hr to 48 hr, and toxicities were almost equitoxic 48 hr posttreatment. The repellent activities of A. sativum and L. cubeba oils on 6th instars were also observed, showing repellence indexes of 90.4% and 88.9% at 12 hr after treatment, respectively. The effects of A. sativum on AChE activity of 6th instars of A. diaperinus were strongest compared to the other essential oils, followed by C. limonum, L. cubeba, and C. cassia. These results suggest that the essential oils of C. limonum and A. sativum could serve as effective control agents of A. diaperinus., (This is an open access paper. We use the Creative Commons Attribution 3.0 license that permits unrestricted use, provided that the paper is properly attributed.)