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Volatiles from apple (Malus domestica) eliciting antennal responses in female codling moth Cydia pomonella (L.) (Lepidoptera: Tortricidae): effect of plant injury and sampling technique.

The antennal responses of codling moth females, Cydia pomonella, to volatiles from apple branches with green fruits were recorded by electroantennography coupled to gas chromatography. The antennae strongly responded to 4,8-dimethyl-1,3(E),7-nonatriene, linalool, beta-caryophyllene, (E)-beta-farnesene, germacrene D, (Z,E)-alpha-farnesene, (E,E)-alpha-farnesene and methyl salicylate. These compounds were all present in volatile collections on Porapak Q from both living and cut branches. Analysis by the solid phase microextraction technique (SPME) showed that the emission of some electrophysiologically active compounds increased after branches had been cut, especially 4,8-dimethyl-1,3(E),7-nonatriene, linalool and (E,E)-alpha-farnesene. The identification of apple volatiles eliciting antennal responses is the first step towards the identification of compounds mediating host-finding and oviposition in codling moth females.

Acyclic Monoterpenes↗

Rapid determination of volatile compounds emitted from Chimonanthus praecox flowers by HS-SPME-GC-MS.

A novel rapid, simple and solvent-free method was developed for determination of the volatile compounds from the flowers of Chimonanthus praecox Link using headspace solid-phase microextraction (HS-SPME) and gas chromatography-mass spectrometry (GC-MS). The SPME conditions were firstly optimized and applied to sampling of the volatile compounds emitted from living Chimonanthus praecox L. flowers and excised Chimonanthus praecox L. flowers. Thirty-one compounds emitted from living flowers were identified for the first time, which mainly included 4-methyl-1,3-pentadiene (2.0%), a-phellandrene (4.7%), benzyl methanol (11.1%), trans-linalool oxide (furanyl ring) (5.3%), a-linalool (36.0%), methyl salicylate (24.5%) and acetic acid benzyl ester (5.9%). Comparing the emission from living flowers and excised flowers, twenty-eight compounds were found to be detected in the two emissions, and three compounds, n-pentadecane, n-cetane and n-heptadecane, were only found in the emission from the living flowers, which shows that they might be biomarker compounds.

China↗

Demonstration of 2-unsaturated C19-steroids in the urine of female Asian elephants, Elephas maximus, and their dependence on ovarian activity.

Air-borne volatile substances have been demonstrated to signal oestrus, induce ovulation and synchronize ovarian activity in different mammals. An oestrous-related pheromone of the female Asian elephant (Elephas maximus) is known to induce behavioural responses in elephant bulls. Additional data revealed that timing of oestrus in females with close social relationships tends to be synchronized. Therefore, urine from female Asian elephants might be expected to contain luteal phase-dependent volatile substances, which may function as additional chemical signals in this species. The aim of the present study was to identify such compounds and to investigate their pattern of excretion throughout the ovarian cycle. Urine samples were collected three times a week during the follicular phase and one to three times a week during the luteal phase from five adult female Asian elephants from a total of 13 non-conception cycles and one conception cycle, including the first 72 weeks of pregnancy. A simple headspace solid-phase microextraction method has been developed for quantification of urinary volatile substances and analysis was performed by gas chromatography. The comparison of urine collected during the follicular and the luteal phase indicated the presence of two luteal phase-dependent substances. Mass spectrometry was used to identify one substance as 5alpha-androst-2-en-17-one and a second substance as the corresponding alcoholic compound 5alpha-androst-2-en-17beta-ol. The 5alpha-androst-2-en-17beta-ol and -17-one profiles reflected cyclic ovarian activity with clear (10-20-fold) luteal phase increases. Furthermore, measurements of both compounds were correlated positively with the concentration of urinary pregnanetriol and indicated cycle duration (15.1 +/- 1.2 weeks) similar to that obtained from pregnanetriol measurements (15.2 +/- 1.6 weeks). The results demonstrate the presence of two luteal phase-specific steroidal volatile compounds in elephant urine. One of the substances, 5alpha-androst-2-en-17-one, has been demonstrated in human axillary bacterial isolates. The measurement of both volatile substances in elephant urine can be used for rapid detection of the stage of the ovarian cycle, as the analysis can be completed within 2 h.

Androstenes↗

Effect of aging on pheromone emission from a commercial beet armyworm (Lepidoptera: Noctuidae) lure and trap efficiency.

The effect of aging on a commercial pheromone-based lure for attractiveness to male adult beet armyworms, Spodoptera exigua (Hübner), was assessed in terms of trapping efficiency and volatile emissions of two key components: (Z,E)-9,12-tetradecadienyl acetate and (Z)-9-tetradecen-1-ol. In field assays conducted in the Lower Rio Grande Valley, Texas, for 9 wk (June-August 2000) and for 8 wk (March-May) in Tamaulipas, Mexico, 0-1-wk-old lures collected greater than four-fold more male beet armyworm adults than lures that had been aged for 3-4 wk. Using solid phase microextraction and gas chromatographic analysis of the volatiles, mean (Z,E)-9,12-tetradecadienyl acetate emission declined by 32% after 5 wk of aging in a ventilated environmental chamber at 29.4 degrees C, 3.5% RH, to simulate subtropical summers. Mean (Z)-9-tetradecen-1-ol emission was reduced by 62% after 4 wk of aging. Under the tropical and subtropical conditions of this study, the capacity of the lure to attract moths into the trap declined after aging for 3 wk. The blend ratio (Z,E) -9,12-tetradecadienyl acetate: (Z)-9-tetradecen-1-ol declined 29% when the lure was aged for 5 wk. This study will assist in the development of a standard trapping system for assessing adult beet armyworm populations in the tropical and subtropical conditions to which the species is endemic.

Animals↗

Chronic toxicity and body residues of the nonpolar narcotic 1,2,3,4-tetrachlorobenzene in Chironomus riparius.

The use of internal concentrations as a dose parameter for baseline toxicity requires an understanding of the relationship between accumulation level and toxic effects, not only for acute but also for chronic exposure. In this study of chronic toxicity of the nonpolar narcotic 1,2,3,4-tetrachlorobenzene (TeCB) to Chironomus riparius, the chronic median lethal concentration (LC50) was determined to be 0.99 (0.54-1.82) microM, the median sublethal effect concentration (EC50) for growth was 0.76 (0.73-0.97) microM, and the chronic (sublethal) no-observed-effect concentration (NOEC) was 0.24 +/- 0.01 microM. An acute-to-chronic ratio of 9.8 was calculated from a previously determined acute LC50 value and this NOEC. The chronic critical body residue (CBR), 136 mmol/kg lipid, was the same as the acute CBR, previously determined. The similarity of the chronic and acute CBRs lends support to the exposure time independent aspect of baseline toxicity theory. An implication of this is that internal concentrations estimated by biomimetic sampling devices may be compared to acute CBR data to determine chronic baseline toxicity risk. Such sampling devices, solid-phase microextraction (SPME) fibers, were simultaneously exposed during the toxicity test. The results of this study suggest that body residues estimated with SPME may be used to predict baseline toxicity for various exposure durations.

Animals↗

A perspective on the environmental risk of halogenated by-products from uses of hypochlorite using a whole effluent toxicity based approach.

An assessment has been made of the potential for toxic effects to aquatic life that may arise from halogenated organic by-products formed by reaction of hypochlorite with organic matter in various use scenarios as a contribution to the risk assessment of sodium hypochlorite under the European Union Existing Chemicals legislation. In the study, samples that would represent worst-case models for effluents containing halogenated by-products from a range of uses of hypochlorite were prepared by chlorinating and then dechlorinating (removing residual chlorine) raw settled sewage (C/D-RSS). This sample was then compared to raw settled sewage that had not been treated (RSS) to assess whether halogenated by-products formed in the chlorination process were toxic or bioaccumulable and persistent. The relative toxicity of the samples was assessed using a series of tests with representatives of different taxonomic groups (bacteria, algae, and invertebrates). The persistence and potential for bioaccumulation of chlorinated by-products was assessed by exposing solid-phase microextraction fibers to samples of RSS and C/D-RSS before and after degradation in a Zahn-Wellens test. For all the taxa tested in the study, the mixture of by-products formed in the C/D-RSS sample did not increase toxicity relative to that measured in the RSS sample. Chlorination of the raw settled sewage did produce additional potentially bioaccumulable halogenated substances compared to the raw settled sewage. However, after degradation, the amount of potentially bioaccumulable halogenated substances in the RSS and C/D-RSS samples was comparable, indicating that these substances were degradable. The results are discussed in the context of the overall risk assessment for sodium hypochlorite.

Adsorption↗

Inhibition of aquatic toxicity of pyrethroid insecticides by suspended sediment.

The use of pyrethroid insecticides is increasing in both agricultural and urban environments. Although pyrethroids display very high acute toxicities to water column organisms in laboratory tests, environmental water samples typically contain suspended sediment (SS) that can reduce the freely dissolved concentration of pyrethroids, hence their bioavailability. Consequently, phase distribution could play an important role in pyrethroid aquatic toxicology. In this study, we evaluated the effect of SS on the acute toxicity of four widely used pyrethroid insecticides to Ceriodaphnia dubia. In all assays, median lethal concentrations (LC50s) consistently increased with increasing SS, demonstrating the pronounced inhibitory effects of SS on pyrethroid toxicity. The LC50s in the 200 mg/L SS solutions were 2.5 to 13 times greater than those measured in sediment-free controls. Solid-phase microextraction (SPME) was used to determine the apparent distribution coefficient Kd for the pyrethroids in the water samples. Under the assumption that only the freely dissolved fraction is bioavailable, the measured Kd was used to predict C. dubia LC50s in the water samples. The predicted LC50s were within a factor of two of the measured values for 95% of the treatments. Results from this study suggest that the inhibitory effect of SS can be highly significant and must be considered in estimating exposures to pyrethroids in aquatic systems. The SPME methodology could be used effectively to measure bioavailable concentration and to predict the actual ecotoxicologic effects of pyrethroids.

Animals↗

Time dependence of phase distribution of pyrethroid insecticides in sediment.

Synthetic pyrethroids are strongly hydrophobic compounds, and their toxicity in sediment is regulated by phase distribution among the sediment, dissolved organic matter, and water phases. In the present study, we spiked and equilibrated four pyrethroids in two sediments, and we characterized their phase distribution as a function of contact time. The freely dissolved concentration measured by solid-phase microextraction was only a small fraction (<16.3%) of the total pore-water concentration as determined by liquid-liquid extraction. The fraction of the freely dissolved concentration was significantly greater in the freshwater sediment (1.7-16.3%) than in the marine sediment (1.1-4.2%) following 9 d of equilibration, and it decreased substantially with contact time to less than 5% at 30 d after sediment dosing. Consequently, the apparent organic carbon partition coefficient (Koc) and dissolved organic carbon partition coefficient (Kdoc) values increased significantly over the contact time, especially in the freshwater sediment, suggesting that phase distribution was not at equilibrium after 9 d of equilibration. If only the freely dissolved concentration is bioavailable, these observations suggest that contact time after sediment dosing may greatly affect the bioavailability and, hence, the toxicity of pyrethroids. Therefore, a long contact time (> or = 30 d) is recommended for sediment toxicity testing of this class of compounds. The dependence of bioavailability on contact time also implies that test conditions must be standardized to allow comparison between laboratory-dosed samples and field samples.

Carbon↗

A new PVC-activated charcoal fiber coated on silver wire; application in determination of n-alkanes in the headspace of soil samples by SPME-GC.

In this study, a new solid phase microextraction (SPME) fiber based on activated charcoal and polyvinyl chloride (PVC) coated on silver wire is presented. This fiber is very mechanically and thermally stable. Unlike commercial fiber, which is coated on fused silica, this fiber has a metallic base to which the coating adheres very strongly. On the other hand, producing this fiber is very fast, and can be completed in less than 30 min. This compares favorably with the time to make a fiber based on fused silica, which may last several days, due to many steps, such as conditioning in HCl, drying, deactivation, impregnation with a binder and coating. Also, this fiber is stable up to 250 degrees C. It has been successfully used for the analysis of n-alkanes in the gaseous phase and headspace of soil samples after optimization of the experimental parameters by capillary gas chromatography. The relatively high capacity of the sorbent allows 20-30% of the analytes to be transferred to a separative system during first extraction.

Alkanes↗

Separation and determination of methyl tert-butyl ether and its degradation products by a laboratory-constructed micro-cryogenic chromatographic oven.

A laboratory-made micro-cryogenic chromatographic oven was mainly improved in size, which was controlled at 6 x 6 x 2.5 cm. A thermoelectric system was used to cool the capillary column instead of the traditional liquid cryogen. A cold block connected to the cryogenic module was directly solidified at room temperature with thermally conductive adhesive so that the uniformity of transferring heat was greatly improved, and the size of the system was reduced. Moreover, this system was inexpensive and convenient for both operation and control. The newly developed device coupled with headspace solid-phase microextraction (SPME) was successfully applied to the determination of methyl tert-butyl ether (MTBE) and its degradation products. During the analysis procedure, a 65 microm polydimethylsiloxane/divinylbenzene (PDMS/DVB) fiber was used to extract MTBE and its degradation products. The extraction was controlled at 50 degrees C for 30 min and the NaCl content in the sample was maintained at 35%. The limits of detection (LODs) ranged from 0.006 microg mL(-1) (for MTBE) to 0.206 microg mL(-1) (for methyl acetate) and the relative standard deviations (RSD%) were below 4%. The spiked recoveries for the developed method were evaluated using various water samples as a matrix.

Chromatography↗

Evaluation of zeolite for control of odorants emissions from simulated poultry manure storage.

Poultry operations are associated with emissions of aerial ammonia (NH3), volatile organic compounds (VOCs), and odor, and the magnitude of emissions is influenced by manure management practices. As a manure treatment additive, zeolites have been shown to have the potential to control NH3. Because of their properties it is also expected that zeolites could effectively adsorb VOCs and odor. The effectiveness of zeolite in controlling odor and VOCs was qualitatively evaluated in this controlled laboratory study involving simulated poultry manure storage. In the first two trials, zeolite was topically applied on nearly fresh laying hen manure at the rates of 0, 2.5, 5, and 10% (by weight). In the third trial, zeolite was topically applied at 5% with each addition of fresh manure into the storage vessel. Headspace samples from the emission vessels were collected with solid phase microextraction (SPME) and analyzed on a multidimensional-gas chromatograph-mass spectrometry-olfactometry (MDGC-MS-O) system for identification and prioritization of poultry manure odorants. Acetic acid, butanoic acid, isovaleric acid, indole, and skatole were consistently controlled in the headspace, with the reduction rate being proportional to the zeolite application rate. Dimethyl trisulfide and phenol were consistently generated, and with a few exceptions, the rate of generation was proportional to the application rate. Average reduction of the odor caused by all odorants evaluated with SPME-GC-O was 67% (+/-12%) and 51% (+/-26%) for the two topical applications, respectively, while no significant reduction of VOCs and odor was detected for the layered application.

Animals↗

Relative efficacy of intrinsic and extant parameters for modeling biodegradation of synthetic organic compounds in activated sludge: steady-state systems.

The performance of intrinsic and extant kinetic parameters as predictors of synthetic organic compound (SOC) concentration in biotreatment systems operated at steady state was evaluated. Two laboratory-scale, completely mixed activated-sludge systems were sampled on a routine basis, and SOC concentrations were quantified using gas chromatography with flame-ionization detection coupled with solid-phase microextraction for analyte concentration. At the same time, intrinsic and extant respirometric tests were performed periodically, and the kinetic parameter estimates obtained were used to predict effluent SOC concentrations for comparison with the measured values. Out of 28 comparisons that could be made between intrinsic and extant predictions, extant parameters were superior in 27 cases and intrinsic parameters were comparable, at best, to extant parameters in the remaining case. Given their superior performance and relative ease of measurement, extant parameters are preferable for use in design and operational decision-making.

Biodegradation, Environmental↗

A laboratory batch reactor test for assessing nonspeciated volatile organic compound biodegradation in activated sludge.

The relative rates of biodegradation and stripping and volatilization of nonspeciated volatile organic compounds (VOCs) in wastewater treated with aerobic activated-sludge processes can be quantified using a newly developed procedure. This method was adapted from the original aerated draft tube reactor test that was developed to measure biodegradation rate constants for specific volatile pollutants of interest. The original batch test has been modified to include solid-phase microextraction (SPME) fibers for sampling in the gas phase. The experimental procedure using SPME fibers does not require specific identification and quantitation of individual pollutants and can be used to evaluate wastewater with multiple VOCs. To illustrate use of this procedure, laboratory experiments were conducted using biomass and wastewater or effluent from three activated-sludge treatment systems. Each experiment consisted of two trials: a stripping-only trial without biomass and a stripping plus biodegradation trial using biomass from the activated-sludge unit of interest. Data from the two trials were used to quantify the rates of biodegradation by difference. The activated-sludge systems tested were a laboratory diffused-air reactor treating refinery wastewater, a full-scale surface aerated reactor treating a petrochemical wastewater, and a full-scale diffused-air reactor treating a variety of industrial effluents. The biodegradation rate constant data from each laboratory batch experiment were used in model calculations to quantify the fraction emitted (fe) and the fraction biodegraded (fbio) for each system. The fe values ranged from a maximum of 0.01 to a maximum of 0.32, whereas fbio values ranged from a minimum of 0.40 to a minimum 0.95. Two of these systems had been previously tested using a more complicated experimental approach, and the current results were in good agreement with previous results. These results indicate that biodegradation rate constant data from this laboratory method can be successfully used to predict the fate of VOCs in field-scale treatment units, and thus could potentially be used for demonstration of compliance with wastewater VOC emission regulations.

Biodegradation, Environmental↗

Effects of milk fat, cocoa butter, or selected fat replacers on flavor volatiles of chocolate ice cream.

Selected volatile compounds of chocolate ice creams containing 0.6, 4.0, 6.0, or 9.0% milk fat or containing 2.5% milk fat, cocoa butter, or one of three fat replacers (Simplesse, Dairy Lo, or Oatrim) were analyzed by gas chromatography and gas chromatography-mass spectrometry using headspace solid-phase microextraction. The headspace concentration of most of the selected volatile compounds increased with decreasing milk fat concentration. Fat replacers generally increased the concentration of volatiles found in the headspace compared with milk fat or cocoa butter. Few differences in flavor volatiles were found between the ice cream containing milk fat and the ice cream containing cocoa butter. Among the selected volatiles, the concentration of 2,5-dimethyl-3(2-methyl propyl) pyrazine was the most highly correlated (negatively) with the concentration of milk fat, and it best discriminated among ice creams containing milk fat, cocoa butter, or one of the fat replacers.

Animals↗

Determining flavor and flavor variability in commercially produced liquid cheddar whey.

Dried whey and whey protein are important food ingredients. Functionality of whey products has been studied extensively. Flavor inconsistency and flavors which may carry through to the finished product can limit whey ingredient applications in dairy and nondairy foods. The goal of this research was to determine the flavor and flavor variability of commercially produced liquid Cheddar cheese whey. Liquid Cheddar cheese whey from five culture blends from two different stirred-curd Cheddar cheese manufacturing facilities was collected. Whey flavor was characterized using instrumental and sensory methods. Wide variation in whey headspace volatiles was observed between different manufacturing facilities (P < 0.05). Hexanal and diacetyl were two key volatiles that varied widely (P < 0.05). FFA profiles determined by solid-phase microextraction and degree of proteolysis of the whey samples were also different (P < 0.05). Differences in whey flavor profiles were also confirmed by descriptive sensory analysis (P < 0.05). Differences in liquid whey flavor were attributed to differences in milk source, processing and handling and starter culture blend. The flavor of liquid Cheddar cheese whey is variable and impacted by milk source and starter culture rotation. Results from this study will aid future studies that address the impact of liquid whey flavor variability on flavor of dried whey ingredients.

Amino Acids↗

Composition and aroma compounds of Ragusano cheese: native pasture and total mixed rations.

Raw milk from 13 cows fed TMR supplemented with native pasture and from 13 cows fed only TMR on one farm was collected separately 4 times with an interval of 15 d between collections. Two blocks (14 kg each) of cheese were made from each milk. The objective was to determine the influence of consumption of native plants in Sicilian pastures on the aroma compounds present in Ragusano cheese. Milk from cows that consumed native pasture plants produced cheeses with more odor-active compounds. In 4-mo-old cheese made from milk of pasture-fed cows, 27 odor-active compounds were identified, whereas only 13 were detected in cheese made from milk of total mixed ration-fed cows. The pasture cheeses were much more rich in odor-active aldehyde, ester, and terpenoid compounds than cheeses from cows fed only total mixed ration. A total of 8 unique aroma-active compounds (i.e., not reported in other cheeses evaluated by gas chromatography olfactory) were detected in Ragusano cheese made from milk from cows consuming native Sicilian pasture plants. These compounds were 2 aldehydes ([E,E]-2,4-octadienal and dodecanal), 2 esters (geranyl acetate and [E]-methyl jasmonate), 1 sulfur compound (methionol), and 3 terpenoid compounds (1-carvone, L(-) carvone, and citronellol). Geranyl acetate and (E)-methyl jasmonate were particularly interesting because these compounds are released from fresh plants as they are being damaged and are part of a possible plant defense mechanism against damage from insects. Most of the odor-active compounds that were unique in Ragusano cheese from pasture-fed cows appeared to be compounds created by oxidation processes in the plants that may have occurred during foraging and ingestion by the cow. Some odor-active compounds were consistently present in pasture cheeses that were not detected in the total mixed ration cheeses or in the 14 species of pasture plants analyzed. Either these compounds were present in other plants not analyzed, created in the rumen or in cheese after the pasture-plant material had been consumed, or the compounds were lost in the method of sample extraction used for the plant analysis (i.e., steam distillation) versus the solid-phase microextraction method used for the cheeses. This research has demonstrated clearly that some unique odor-active compounds found in pasture plants can be transferred to the cheese.

Animal Feed↗

Comparison of the compositional, microbiological, biochemical, and volatile profile characteristics of nine Italian ewes' milk cheeses.

Nine Italian ewes' milk cheeses were compared for compositional, microbiological, biochemical, and volatile profile characteristics. Mean values for the gross composition were rather similar among cheeses. The lowest pH values were found for cheeses that used primary starters. At the end of ripening, cheeses made from raw milk contained >6.0 log10 cfu/g of nonstarter lactic acid bacteria. Several species of lactobacilli were identified, but Lactobacillus plantarum and Lactobacillus paracasei were dominant. Random amplified polymorphic DNA-PCR analysis showed the biodiversity among the strains, and in several cases a relationship with the cheese of provenance. Cheeses differed mainly for secondary proteolysis, as shown by the principal component analysis applied to reversed-phase fast protein liquid chromatography data of the pH 4.6-soluble fractions and by determination of the free AA. A total of 113 volatile components were identified in the Italian Pecorino cheeses by solid-phase microextraction coupled with gas chromatography-mass spectrometry analysis. The volatile profiles of the 9 cheeses differed significantly. Quantitatively, alcohols were the most abundant chemical class for some cheeses, whereas ketones were the most abundant for other cheeses. Esters and carboxylic acids were largely found. Specific volatile components seemed to distinguish specific cheeses.

Amino Acids↗