Rotenone residues on olives and in olive oil

The disappearance of rotenone on olives under field conditions was studied. The field data showed that rotenone residues on olives decreased with a half-life (t(1/2)) of 4.0 days. After pre-harvest time (10 days) the residues were higher than the maximum residue level fixed in Italy (0.04 mg/kg). Experiments with model systems showed that the mechanism of disappearance of rotenone is not related to evaporation, thermodegradation, or co-distillation, but only to photodegradation. When the olives were processed for oil, the residues in the oil were higher than the residues on the olives by a factor of 2.4-4.8.     

Degradation of pyrethrin residues on stored durum wheat after postharvest treatment

In this paper, pyrethrin levels during a postharvest treatment on stored durum wheat were studied. Two experiments were carried out at single and double the dose recommended by the manufacturer. In all trials, the initial deposition of pyrethrins levels was below the fixed maximum residue level of 3 mg/kg. The fate of pyrethrins in the two experiments was similar, and the total content of pyrethrins remained unchanged for 22 days with a complete dissipation in 8 months. In the single dose experiment, half-life times of pyrethrins I and II were 46 and 72 days, while for the double dose, pyrethrins I and II were 41 and 53 days, respectively.     

Influence of harvesting method and washing on the presence of pesticide residues in olives and olive oil

The influence of the preliminary steps in olive oil production (harvesting and washing) on pesticide residues in olives and olive oil has been investigated. Analyses were performed by GC-MS/MS and revealed that endosulfan sulfate and two herbicides (diuron and terbuthylazine) were the most frequently found residues in olives and olive oil. The harvesting method has a decisive influence on herbicide concentrations found in olives. Thus, 16 and 48% of the olive samples harvested on the ground after falling from the tree presented concentrations higher than the maximum residue limit (MRL) for diuron and terbuthylazine, respectively. In olives harvested directly from the tree, diuron was not found at concentrations higher than MRL and terbuthylazine was found in only 10% of the samples. The washing step performed routinely in olive mills was effective in removing the superficial contamination by herbicides present in olives harvested on the ground. Nevertheless, even after washing, the olive oil obtained from ground olives showed herbicide residue concentrations higher than those obtained from tree olives.     

LC/DAD/ESI/MS method for the determination of imidacloprid, thiacloprid, and spinosad in olives and olive oil after field treatment

The behavior in the field and the transfer from olives to olive oil during the technological process of imidacloprid, thiacloprid, and spinosad were studied. The extraction method used was effective in extracting the analytes of interest, and no interfering peaks were detected in the chromatogram. The residue levels found in olives after treatment were 0.14, 0.04, and 0.30 mg/kg for imidacloprid, thiacloprid, and spinosad, respectively, far below the maximum residue levels (MRLs) set for these insecticides in EU. At the preharvest interval (PHI), no residue was detected for imidacloprid and thiacloprid, while spinosad showed a residue level of 0.04 mg/kg. The study of the effect of the technological process on pesticide transfer in olive oil showed that these insecticides tend to remain in the olive cake. The LC/DAD/ESI/MS method showed good performance with adequate recoveries ranging from 80 to 119% and good method limits of quantitation (LOQs) and of determination (LODs). No matrix effect was detected.     

印楝素对植物病原菌抑菌作用初步研究

印楝(Azadirachta indica A.Juss)系楝科楝属乔木,原产于印度与缅甸,广泛种植于热带、亚热带地区,在亚洲南部、非洲和南美洲的70多个国家已有分布[J].印楝是一种多用途树种,并含有以印楝素为主的多种能防虫、杀虫、杀菌的活性物质[2],在我国云南、四川、海南、广西、广东等地均有种植,其中云南省的种植面积最大.     

Residues and persistence of neem formulations on strawberry after field treatment

Azadirachtoids were determined by liquid chromatography/mass spectrometry (LC/MS) in five methanolic seed extracts of the neem tree and in a commercial formulation. On average, seed extracts contain azadirachtin A (10.9%), azadirachtin B (3.5%), nimbin (10.4%), and large quantities of salannin (19.0%). The composition of the commercial formulations may present different azadirachtoids contents depending on the natural extracts used in the preparation. Because these compounds may also show insecticide activity, the efficacy on field of these formulations may be very different. Photodegradation of pure azadirachtoids was also studied. Azadirachtins and related compounds are very sensitive to sunlight, degrading rapidly, with half-lives of the order of 11.3 h for azadirachtin A and 5.5 h for azadirachtin B and few minutes for the other limonoids compounds studied. The residues of azadirachtins and the main constituents, e.g., salannin, nimbin, deacetylnimbin, and deacetylsalannin, of the neem seed extract were determined on strawberries after field treatment using two different formulations. This residue study on strawberry was carried out to assess not only the azadirachtin content but also the main azadirachtoids contents. Three days after field application at five times the dose recommended by the manufacturer, residues of azadirachtin A and B were 0.03 and 0.01 mg/kg, respectively, while residues of salannin (LOQ 0.01 mg/kg) and nimbin (LOQ 0.5 mg/kg) were not detectable.     

Relatively rapid loss of lampricide residues from fillet tissue of fish after routine treatment

The selective sea lamprey (Petromyzon marinus) larvicide 3-trifluoromethyl-4-nitrophenol (TFM) is currently used to control parasitic sea lampreys in tributaries to the Great Lakes basin. The concentration and persistence of TFM and its major metabolite, TFM glucuronide (TFM-glu), was determined in fillet tissue of fish after a typical stream application. Rainbow trout (Oncorhynchus mykiss) and channel catfish (Ictalurus punctatus) were exposed to a nominal concentration of 12.6 nmol/mL TFM for about 12 h during a sea lamprey control treatment of the Ford River in Michigan. Concentrations of TFM and TFM-glu were greatest in the fillet tissues during the exposure period, with greater residues in channel catfish (wet wt; mean, 6.95 nmol/g TFM; mean, 2.40 nmol/g TFM-glu) than in rainbow trout (wet wt; mean, 1.45 nmol/g TFM; mean, 0.93 nmol/g TFM-glu). After the exposure period, residues in both species decreased by 90-99% within 6-12 h and were less than the quantitation limit (<0.03 nmol/g) within 36 h.     

Analytical study of azadirachtin and 3-tigloylazadirachtol residues in foliage and phloem of hardwood tree species by liquid chromatography-electrospray mass spectrometry

A rapid and sensitive LC-ESI-MS method has been developed and validated for the quantitation of azadirachtin and 3-tigloylazadirachtol in deciduous tree matrices. The method involves automated extraction and simultaneous cleanup using an accelerated solvent technique with the matrix dispersed in solid phase over a layer of primary-secondary amine silica. The limits of quantification were 0.02 mg/kg for all matrices with the exception of Norway maple foliage (0.05 mg/kg). Validation at three levels (0.02, 0.1, and 1 mg/kg), demonstrated satisfactory recoveries (71-103%) with relative standard deviation <20%. Two in-source fragment ions were used for confirmation at levels above 0.1 mg/kg. Over a period of several months, quality control analyses showed the technique to be robust and effective in tracking the fate of these natural botanical insecticides following systemic injection into various tree species for control of invasive insect pest species such as the emerald ash borer and Asian longhorned beetle.     

Flunixin residues in milk after intravenous treatment of dairy cattle with (14)C-flunixin

Flunixin meglumine is used in veterinary medicine as an alternative to narcotic analgesics and as an antiinflammatory agent. Eight Holstein dairy cows were dosed intravenously once daily on three consecutive days with (14)C-flunixin meglumine at approximately 2.2 mg of flunixin free acid/kg of body weight. Milk was collected twice daily to determine the decline of the total radioactive residues (TRR) in milk and to identify or characterize residue components. TRR in milk declined rapidly and averaged 66, 20, and 14 ppb, respectively, for the first, second, and third milkings after administration of the last dose. Milk was extracted, and the extracts were examined for radioactive residues. Mean extractability of milk TRR was always greater than 80%. Flunixin and 5-hydroxyflunixin were identified by coelution with analytical standards using reverse phase HPLC. These two residues were the main radioactive residues found in milk and together accounted for 64, 37, and 44% of the extractable residues, for the first, second, and third milkings, respectively, after administration of the last dose. The presence of 5-OH flunixin in milk was confirmed by HPLC/MS/MS.     

Effect of assay conditions and field exposure on urease activity associated with cereal residues

Abstract

Urea fertilisers are often applied to soil with cereal residues on the surface. Although the urease properties of soils have been investigated, the urease activities associated with cereal residues have not been thoroughly studied. Two experiments were performed to develop an acceptable urease assay for cereal residues, and to determine the effect of field exposure and concomitant saprophytic colonization on urease levels.

Two acceptable assays were found: 1) incubation in the presence of THAM‐H₂SO₄ buffer (pH 8), toluene, and urea, and 2) incubation only in the presence of urea. In both assays substrate concentration was 0.05 M, incubation temperature was 37°C, incubation length was 2 hours, and urea hydrolysis was determined by ammonium production. Although both assays were highly correlated (r² = 0.992), the buffer method gave higher values. Subsequent investigations illustrated that urease activity associated with cereal residues is dramatically increased by saprophytic colonization after harvest. Freshly‐harvested winter wheat (Triticum aestivum, L.), winter rye (Secale cereale, L.), and spring wheat residues had urease activities (by the buffer method) of 4.3, 6.9, and 3.1 μmol urea g^‐1 h^‐1, respectively. After field exposure of 67–77 days, the urease activities had increased to 69.1, 101.9, and 74.3, respectively. The latter are far higher than literature values for U.S. mineral soils or the dried green leaves of plants.     

Persistence of CaCl2 washing effect for amelioration of a Cd-contaminated paddy field soil

Abstract

Soil washing is one of the methods used to remediate soil contaminated with heavy metals, and when the contaminated elements have been effectively removed the washed soil can be used for agriculture. Soil washing was conducted using 0.5 mol L^?1 CaCl₂ solution at pH 4 as an extracting agent to remediate a paddy field soil contaminated with Cd. Dolomite powder was applied to neutralize the soil to the original pH 6.2. After CaCl₂ washing, the content of Cd extractable in 0.1 mol L^?1 HCl decreased from 2.4 to 0.8 mg kg^?1. Subsequently, a pot experiment was carried out to evaluate the effect of soil washing on Cd concentration in polished rice (Cd_pr) for three successive years. Using the washed soil, Cd_pr was ≤ 0.2 mg kg^?1 with and without a treatment that simulates midseason drainage, whereas it was > 0.5 mg kg^?1 in the unwashed soil with the midseason drainage treatment. The reasons for low Cd_pr growth in the washed soil were the low content of exchangeable Cd in the soil and the resultant high soil pH (> 7). To evaluate the effect of soil pH on Cd_pr in the fourth year, we adjusted soil pH to 5 with H₂SO₄ before transplanting rice seedlings. The Cd_pr in the washed soil with the midseason drainage treatment increased to 0.47 mg kg^?1, whereas it was less than 0.2 mg kg^?1 under continuous flooding. Thus, high pH or whole season flooding are important to keep Cd_pr at ≤ 0.2 mg kg^?1 even after soil washing. With the application of dolomite and other ordinary fertilizers, soil properties were little affected by the present soil washing procedure because the difference in rice yield between the washed and unwashed plots was not significant within each year.     

Influence of processing conditions on acrylamide content in black ripe olives

The presence of acrylamide was investigated in different presentations of commercial black ripe olives, a well-known sterilized alkali-treated product. The analysis was performed by gas chromatography-mass spectrometry (GC-MS) after bromination of acrylamide, using (13C3)acrylamide as internal standard. In-house validation data for commercial ripe olives showed good precision and accuracy of the method, with repeatability below 3% and recoveries between 94 and 105%. Acrylamide was detected in all samples, but its concentration varied significantly from 176 to 1578 microg/kg of pulp. The effects of different processing conditions (two preservation methods and three darkening methods), cultivar (Hojiblanca or Manzanilla), and presentation form (pitted or sliced olives) on acrylamide content were evaluated in experiments performed in an olive-processing plant. All canned samples were sterilized at 121 degrees C for 30 min. Statistical analysis of the data indicated that the effects of darkening method and olive cultivar were the most pronounced. Acrylamide contents did not significantly differ after 6 months of storage. The small amounts of free amino acids and reducing sugars found in olives before sterilization did not significantly correlate with the acrylamide formed.     

Polyphenol changes during fermentation of naturally black olives

The individual evolution of phenolic compounds has been studied during the natural fermentation of black olives for the first time. Cyanidin 3-rutinoside and cyanidin 3-glucoside were the main anthocyanins identified in fresh olives, and they were not detected after 1 month of storage either in brine or in olive. The fruit colors were different when aerobic or anaerobic conditions were used and as a consequence of the different anthocyanin polymerizations that took place. At time zero, the polyphenols observed in the olive juice were hydroxytyrosol-4-beta-glucoside, oleuropein, hydroxytyrosol, tyrosol, salidroside, and verbascoside and, after 12 months, the main phenol was hydroxytyrosol. The polyphenol content in the oil phase of olives was also analyzed. The dialdehydic form of elenolic acid linked to hydroxytyrosol and tyrosol, oleuropein aglycon, and ligstroside aglycon were the main compounds found at the beginning of fermentation but were not detected after 3 months. In contrast, hydroxytyrosol, hydroxytyrosol acetate, tyrosol, and tyrosol acetate were the main polyphenols detected in the oil phase of the final product. The acid hydrolysis of the initial glucosides (in olive juice) and the aglycons (in oil phase) was, therefore, the main reaction that took place during fermentation.     

Persistence of introduced Glomus intraradices in the field as influenced by repeated inoculation and cropping system

We studied the persistence of an introduced vesicular-arbuscular mycorrhizal (VAM) fungus in the field under the influence of a mycorrhizal host, a non-mycorrhizal host, and when the field was left fallow. There was a significantly greater, build-up of the mycorrhizal fungus in plots cropped with mycorrhizal hosts (finger millet or field beans) compared to plots cropped with a nonmycorrhizal host (mustard) or left fallow. Glomus intraradices, the introduced fungus, was further monitored by the electrophoretic mobility of the isozymes of malate dehydrogenase extracted from the resting spores of the fungus. The zymogram from G. intraradices spores showed three distinct isozyme bands: 1,3 and 7. A zymogram of malate dehydrogenase spores isolated from plots inoculated with G. intraradices for three seasons exhibited similar bands. Spores isolated from plots inoculated with G. intraradices for one or two seasons showed only one weak band, corresponding to isozyme band 7. The results indicated that the introduced fungus persisted in the field for only one season.     

Persistence of volatile compounds in the breath after their consumption in aqueous solutions

The persistence of volatile compounds in the breath was monitored after their consumption in aqueous solutions. Factors studied were variation in volatile release patterns between panelists, effect of adding hydroxy propyl methyl cellulose (HPMC), and differences among compounds. For any given compound, the extent of volatile persistence was broadly similar for all panelists. Adding HPMC at concentrations in excess of c did not substantially affect persistence. The largest differences in persistence were observed when compounds were compared (>20-fold). The differences were modeled using a quantitative structure property relationship approach, based on the persistence data from 41 compounds. Major components of the model were terms that described the hydrophobicity and vapor pressure of a molecule. The model was validated with a test set, which showed that there was a significant correlation between persistence predicted by the model and the actual values observed.     

Nitrous oxide emission from soils after incorporating crop residues

Abstract. Emissions of N₂O were measured from different agricultural systems in SE Scotland. N₂O emissions increased temporarily after fertilization of arable crops, cultivation of bare soil, ploughing up of grassland and incorporation of arable and horticultural crop residues, but the effect was short-lived. Most of the emission occurred during the first two weeks, returning to 'background' levels after 30–40 days. The highest flux was from N-rich lettuce residues, 1100 g N₂O-N ha⁻¹ being emitted over the first 14 days after incorporation by rotary tillage. The magnitude and pattern of emissions was strongly influenced by rainfall, soil mineral N, cultivation technique and C:N ratio of the residue. Comparatively large emissions were measured after incorporation of material with low C:N ratios. Management practices are recommended that would increase N-use efficiency and reduce N₂O emissions from agricultural soils.