Neem extract is an alternative insecticide for organic farming and is an allowed component for commercial biopesticide in Korea. However, crop protection properties are not consistent in commercial products. In this report, quantitative analysis of commercial biopesticides for the four insecticidal limonoids of neem extract-azadirachtin A, azadirachtin B, deacetylsalannin and salannin, was conducted through solid phase extraction method with lipophilic-hydrophilic balanced material. The recoveries of the four limonoids ranged from 80.5% to 105%, and their limit of quantitation ranged from 0.028 mg/L to 0.356 mg/L. On the five imported neem extracts, the total contents of the four bioactive limonoids extracted were from 321 mg/L to 5810 mg/L, but there were big variations in the relative composition of the limonoids. The total limonoidal concentrations in 23 commercial bio-pesticides made from neem showed from below LOQ to 7190 mg/L with significant differences in the relative composition. These differences determine the biopesticide's efficacy on pests, therefore, tracking the active ingredients is necessary for the quality control of commercial bio-pesticides.

The stabilities of four limonoidal substances including azadirachtin A, azadirachtin B, deacetylsalannin and salannin were investigated both in controlled aquatic and soil conditions. The half-life of the total limonoid for neem extracts and its two commercial biopesticides was estimated 86.6-173 days in water under air, while degradation of the compounds was detected below 10% after eight weeks in deoxygenated water. The half-life in dry soil was estimated 43.3-57.7 days, and there was a similar degradation pattern with in aerobic water condition. In case of wet soil condition, the total bacteria of the soils ranged 6-8 log CFU/g soil for during the experiment, and the half-life of the total limonoid was 6.4-12.3 days. From the result, the fast limonoid degradation in wet soil environment was the result of both chemical oxidation and microbial degradation.

. The selected bioactive compounds were cinnamaldehyde, and cinnamyl alchol in cinnamon extract and deguelin, and rotenone in derris extract. Half-lives of the total cinnamyl derivatives in biopesticide (A, B, C, and D) ranged from 15.1 to 46.2 days on the different temperature and cinnamaldehyde was more stable than cinnamyl alcohol in the biopesticide. The half-lives of total rotenoid ranged from 1.7 to 173 days on the different temperature in the tested biopesticide (E, F, and G) containing derris extract. The stabilities of deguelin, and rotenon in the biopesticide showed similar values in the same condition.

The current official perfluorochemicals (PFCs) analysis method is established with hydrophiliclipophilic balance (HLB) solid phase extraction (SPE) clean-up method with LC-tandem mass spectrometry (MS n ). Herein the HLB clean-up method from the official method by Korean government was modified with Envi-Carb TM to improve the clean-up efficiency for agricultural water and the unexpected UV disturbance in the water was effectively removed by the adsorbent treatment without a significant disturbance of quantitation. And quadrupole time of flight mass spectrometry (qTOFMS) was suggested to the available MS n instruments for the residue analysis of PFCs based on the ng/L of quantitation limits in water as well.

BACKGROUND:Castor oil and wormseed extract are important active ingredients for biopesticide, and ricinoleic acid in castor oil and three monoterpenes (ascaridole, carvacrol and p-cymene) in wormseed extract are known bioactive substances. However, their stabilities had not been studied, even though the stability was the core property for estimation of shelf-life of biopesticide. Aimed to investigate the thermal stabilities of the bioactive substances in castor oil and wormseed extracts. METHODS AND RESULTS:The contents of ricinoleic acid and three monoterpenes (ascaridole, carvacrol and p-cymene) were analyzed by gas chromatography (GC). The thermal stabilities of the bioactive substance were measured at 0 , 23 , 30 , 40 , 45 and 54 for 84 ℃ ℃ ℃ ℃ ℃ ℃ d. The half-lives of ricinoleic acid in biopesticides was ranged from 28.9 d to 57.8 d at 30 , and the stability of ℃ pure castor oil were located in the range (t 1/2 =46.2 d for Indian product and 27.7 d for Korean product) at the same temperature. The half-lives of the total monoterpenes in biopesticides were ranged from 3.9 d to 27.7 d at 30 . ℃ Among the monoterpenes, the stability ascaridole and p-cymene were decreased in acidic condition. All the bioactive substances showed similar stability on the different thermal conditions. CONCLUSION: The half-lives of most bioactive substance from castor oil and wormseed extracts were less than 100 d. To increase the stability of bioactive substance in biopesticide, stabilizing additives like antioxidant and oxygen remover should be considered to extend of the shelf-life.