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Nitrogen metabolism and excretion in the mangrove killifish Rivulus marmoratus II. Significant ammonia volatilization in a teleost during air-exposure.

The mangrove killifish Rivulus marmoratus can tolerate prolonged periods of air-exposure (>1 month). During these periods of emersion, we hypothesized that R. marmoratus would convert potentially toxic ammonia into urea and free amino acids (FAAs). In air-exposed fish, both ammonia (J(Amm)) and urea (J(Urea)) excretion continued at approximately 57 % and 39 %, respectively, of submerged rates. Remarkably, approximately 42 % of the total ammonia excreted during air-exposure was through NH(3) volatilization. Ammonia did not accumulate in whole-body tissues of air-exposed fish, but levels of both urea and some FAAs (primarily alanine and glutamine) were up to twofold higher after 10 days. The activities of the ornithine-urea cycle enzymes carbamoyl phosphate synthetase III and ornithine transcarbamylase increased (by approximately 30 % and 36 %, respectively) in whole-body tissues of air-exposed fish, while levels of arginase remained unchanged. The activities of enzymes involved in amino acid and oxidative metabolism were not significantly different between control and air-exposed fish. Partitioning of the anterior and posterior ends of immersed fish revealed that just over half (57 %) of the total nitrogen (ammonia+urea) was excreted through the anterior end of the fish, presumably via the branchial tissues, while emersed fish increased excretion via the posterior end (kidney+skin). R. marmoratus do not undergo a shift towards ureotelism during air-exposure. Rather, we propose that R. marmoratus are able to survive on land for extended periods without significant ammonia accumulation because they continuously release ammonia, partially by NH(3) volatilization.

Air↗

Biogenesis of volatile methyl esters in snake fruit (Salacca edulis, Reinw) cv. Pondoh.

The methyl esters of carboxylic acids are characteristic olfactory volatile compounds for the sweet aroma of snake fruit, (Salacca edulis, Reinw) cv. Pondoh. Although methanol was not detected as a volatile constituent, the crude enzymes showed activity to synthesize the methyl esters in the presence of acyl-CoA and methanol. Therefore, the biosynthetic origin of methanol was investigated, resulting in the detection of pectin methyl transferase activity in the flesh. This pectin methyl transferase activity increased during fruit maturation, in parallel with the level of methanol originating from hand-squeezed juice and with the methyl esters extracted from flesh of the fruit. Based on these results, the origin of methanol was confirmed to be the methyl esters of pectins. The crude enzyme also catalyzed the formation of methyl hexanoate, one of the esters of the fruit, in the presence of methyl pectins and hexanoyl-CoA that were used as precursors for a model reaction.

Acyl Coenzyme A↗

Measurement of volatile organic compounds in human blood.

Volatile organic compounds (VOCs) are an important public health problem throughout the developed world. Many important questions remain to be addressed in assessing exposure to these compounds. Because they are ubiquitous and highly volatile, special techniques must be applied in the analytical determination of VOCs. The analytical methodology chosen to measure toxicants in biological materials must be well validated and carefully carried out; poor quality assurance can lead to invalid results that can have a direct bearing on treating exposed persons. The pharmacokinetics of VOCs show that most of the internal dose of these compounds is quickly eliminated, but there is a fraction that is only slowly removed, and these compounds may bioaccumulate. VOCs are found in the general population at the high parts-per-trillion range, but some people with much higher levels have apparently been exposed to VOC sources away from the workplace. Smoking is the most significant confounder to internal dose levels of VOCs and must be considered when evaluating suspected cases of exposure.

Benzene↗

Recovery of volatile products from dilute high-fouling process streams.

As biomass hydrolysis and fermentation technologies approach commercial viability, advancements in product recovery technologies will be required. For cases in which fermentation products are more volatile than water, recovery by distillation is often the technology of choice. Distillation technologies that will allow the economic recovery of dilute volatile products from streams containing a variety of impurities have been developed and commercially demonstrated. Distillation tower and tray designs, along with specialized heat-exchanger designs, allowing for extended processing intervals on solutions containing lignocellulosic residues, organic acids, and inorganic salts concentrations > 100 g/L are in commercial operation. In the case of ethanol, distillation energy consumption efficiencies for processing solutions containing < 40 g/L of desired product can approach demonstrated energy consumption efficiencies for solutions containing concentrations > 120 g/L. These proprietary technologies have been applied individually at commercial scale, and designs have been developed that incorporate the combined technologies with only a marginal increase in capital investment compared to traditional methods.

Biomass↗

GC profiles of volatile constituents from human urine obtained by closed loop stripping, purge and trap technique and simultaneous stem distillation-extraction.

Different techniques like "closed loop stripping" [CLSA], "purge and trap" [PTI], and continuous steam distillation extraction [SDE] were used to establish GC profiles of major histocompatibility complex-associated volatile constituents of human urine and statistically evaluated for reliability. Of the three methods investigated, PTI appeared to be superior for the detection of very volatile substances, whereas SDE was the most efficient one with respect to yield. A number of short to medium-chain ketones, 4-hydroxy-3-methoxy-styrene, menthol and nicotine were identified in preliminary analyses.

Chromatography, Gas↗

Comparative analysis of the composition of flower volatiles from Lamium L. species and Lamiastrum galeobdolon Heist. ex Fabr.

The volatiles of fresh flowers from nine natural populations of four Lamium species and Lamiastrum galeobdolon were analyzed by GC/MS. 49 compounds, 43 of them new for Lamium and Lamiastrum, were identified. The studied samples showed similarity of the volatile profiles and dependence of the oil-composition on the collection site. Significant amounts of squalene were found in all samples. The presence of homological series of straight chain alkanes from C12 to C31 was shown. Phenethyl alcohol was found only in L. maculatum f. alba.

Acids↗

Volatile substances of the green alga Scenedesmus incrassatulus.

Volatile substances of the green microalga Scenedesmus incrassatulus, cultivated in fresh and salt water, were studied. Cultivation in fresh water diversifies volatile secondary metabolites. Hydrocarbons and derivatives of the acetate pathway predominate when algae are grown in salt water; isoprenoids and aromatics are more abundant after fresh water cultivation.

Alcohols↗

Chemical composition and phytotoxicity of volatile essential oil from intact and fallen leaves of Eucalyptus citriodora.

A total of 23 volatile constituents was identified and characterized by GC and GC-MS in the volatile essential oil extracted from intact (juvenile and adult) and fallen (senescent and leaf litter) leaves of lemon-scented eucalyptus (Eucalyptus citriodora Hook.). The leaves differed in their pigment, water and protein content, and C/N ratio. The oils were, in general, monoterpenoid in nature with 18 monoterpenes and 5 sesquiterpenes. However, a great variability in the amount of essential oils and their individual constituents was observed in different leaf tissues. The amount was maximum in the senescent leaves collected from the floor of the tree closely followed by that from juvenile leaves. In all, 19 constituents were identified in oil from juvenile and senescent leaves compared to 23 in adult leaves and 20 in leaf litter, respectively. Citronellal, a characteristic monoterpene of the oil reported hitherto was found to be more (77-78%) in the juvenile and senescent leaves compared to 48 and 54%, respectively, in the adult leaves and leaf litter. In the adult leaves, however, the content of citronellol--another important monoterpene-- was very high (21.9%) compared to other leaf types (7.8-12.2%). Essential oil and its two major monoterpenes viz. citronellal and citronellol were tested for their phytotoxicity against two weeds (Amaranthus viridis and Echinochloa crus-galli) and two crops (Triticum aestivum and Oryza sativa) under laboratory conditions. A difference in the phytotoxicity, measured in terms of seedling length and dry weight, of oil from different leaves and major monoterpenes was observed. Oil from adult leaves was found to be most phytotoxic although it occurs in smaller amount (on unit weight basis). The different toxicity of different oil types was due to the relative amount of individual monoterpenes present in the oil, their solubility and interactive action. The study concludes that oil from senescent and juvenile leaves being rich in citronellal could be used as commercial source of citronellal whereas that from adult leaves for weed management programmes as it was the most phytotoxic.

Aging↗

Concentration effects of volatile anesthetics on the properties of model membranes: a coarse-grain approach.

To gain insights into the molecular level mechanism of drug action at the membrane site, we have carried out extensive molecular dynamics simulations of a model membrane in the presence of a volatile anesthetic using a coarse-grain model. Six different anesthetic (halothane)/lipid (dimyristoylphosphatidylcholine) ratios have been investigated, going beyond the low doses typical of medical applications. The volatile anesthetics were introduced into a preassembled fully hydrated 512-molecule lipid bilayer and each of the molecular dynamics simulations were carried out at ambient conditions, using the NPT ensemble. The area per lipid increases monotonically with the halothane concentration and the lamellar spacing decreases, whereas the lipid bilayer thickness shows no appreciable differences and only a slight increase upon addition of halothane. The density profiles of the anesthetic molecules display a bimodal distribution along the membrane normal with maxima located close to the lipid-water interface region. We have studied how halothane molecules fluctuate between the two maxima of the bimodal distribution and we observed a different mechanism at low and high anesthetic concentrations. Through the investigation of the reorientational motions of the lipid tails, we found that the anesthetic molecules increase the segmental order of the lipids close to the membrane surface.

Anesthetics, Inhalation↗

Occupational exposure to volatile organic compounds and mitigation by push-pull local exhaust ventilation in printing plants.

The extensive use of multiple organic solvents in offset lithographic printing causing high emissions of volatile organic compounds (VOCs) indeed poses a serious risk to printing workers' health. In this study, indoor air quality (IAQ) assessments were carried out in seven printing plants and the main objectives were to understand the effect of VOC emissions on IAQ and develop effective mitigation measures to protect workers. The thorough gas chromatography/mass spectrometry (GC/MS) measurements showed that although a variety of VOCs were presented in the indoor air, none of them was found close to individual 8-h time-weighted average (TWA) of the occupational exposure limit (OEL). The additive effect was also found below the critical value of unity. However, short-term personal exposure to total volatile organic compounds (TVOCs) was exceedingly high when a print worker carried out blanket and ink roller cleaning procedures. Therefore, the occupational health risk was mainly due to repeated short-term exposures during intermittent VOC-emitting procedures rather than long-term exposure to background VOCs. Push-pull local exhaust ventilation (LEV) was identified as an effective mitigation measure. Computational fluid dynamics (CFD) analysis was conducted to study the push-pull LEV operation. It was found that there existed a threshold LEV air flow rate for an abrupt reduction in the worker's exposure to VOCs. The reduction was less sensitive when the LEV airflow was further increased beyond the threshold. These phenomena, consistent with experimental results reported by other investigators, were explained by detailed CFD analysis showing the competition between the general ventilation and the push-pull LEV to become the dominating driving force for the resultant local flow pattern.

Air Pollutants, Occupational↗

Toxicity study of the volatile constituents of Myoga utilizing acute dermal irritation assays and the Guinea-pig Maximization test.

Myoga is a fragrant plant which is the special product of Japan and is cultivated throughout Japan. According to our earlier investigation (unpublished data) of myoga cultivators in Japan, 8 of 35 cultivators experienced contact dermatitis in the harvest season. The purpose of this study was to assess the allergenicity of myoga and its major volatile components. The volatile components of myoga were analyzed by gas chromatograph (GC). They included a-pinene, beta-pinene and R-(+)-limonene. We performed a toxicity study of each of the major fragrant components of myoga using acute dermal irritation assays and the Guinea-Pig Maximization test (GPMT) in order to probe the mechanism of allergic contact dermatitis. In acute dermal irritation assays, alpha-pinene, beta-pinene and limonene showed positive responses at concentrations of 4%; limonene oxide at 20% and myoga showed a positive response at concentrations of 100%. From the results of the GPMT, according to Kligman scores, limonene oxide was identified as an extreme skin sensitizer and myoga as a mild skin sensitizer. The results of the present study show that R-(+)-limonene is the most important allergen amongst the chemical components of myoga, and we consider it to be the reason why myoga cultivators experience allergic contact dermatitis.

Agricultural Workers' Diseases↗

Longitudinal evaluation of repellent activity of Ocimum gratissimum (Labiatae) volatile oil against Simulium damnosum.

To determine the repellent activity of Ocimum gratissimum volatile oil against Simulium damnosum (blackflies), a 12 month (January-December 2003) field study was conducted in three onchocerciasis endemic communities (Idomido, Obio camp, and Ikot Adaha) in Ini Local Government Area of Akwa Ibom State, Nigeria. The result revealed that topical application of 20% (v/v) concentration of the oil with liquid paraffin as a base, reduced the biting rate of S. damnosum by 90.2, 81.6, and 79.7%, in Idomido, Obiocamp, and Ikot Adaha respectively. The oil gave protection against the bite of S. damnosum for at least 3 h. A total of 710 adults S. damnosum were caught by individuals treated with Ocimum oil, as against 4296 caught by the control group. When the flies caught by the treated individuals were dissected none of them was infected with microfilariae of Onchocerca volvulus. Human-vector contact and onchocerciasis transmission could be reduced by the topical application of the volatile oil during the peak biting periods of the vector

Analysis of Variance↗

Source apportionment modeling of volatile organic compounds in streams.

It often is of interest to understand the relative importance of the different sources contributing to the concentration c(w) of a contaminant in a stream; the portions related to sources 1, 2, 3, etc. are denoted c(w,1), c(w2), c(w3), etc. Like c(w), the fractions alpha1 = c(w,1)/c(w), alpha2 = c(w,2)/c(w), alpha3 = c(w,3)/c(w), etc. depend on location and time. Volatile organic compounds (VOCs) can undergo absorption from the atmosphere into stream water or loss from stream water to the atmosphere, causing complexities affecting the source apportionment (SA) of VOCs in streams. Two SA rules are elaborated. Rule 1: VOC entering a stream across the air/water interface exclusively is assigned to the atmospheric portion of c(w). Rule 2: VOC loss by volatilization, flow loss to groundwater, in-stream degradation, etc. is distributed over c(w,1), c(w,2), c(w3), etc. in proportion to their corresponding alpha values. How the two SA rules are applied, as well as the nature of the SA output for a given case, will depend on whether transport across the air/water interface is handled using the net flux F convention or using the individual fluxes J convention. Four hypothetical stream cases involving acetone, methyl-tert-butyl ether (MTBE), benzene, chloroform, and perchloroethylene (PCE) are considered. Acetone and MTBE are sufficiently water soluble from air for a domestic atmospheric source to be capable of yielding c(w) values approaching the common water quality guideline range of 1 to 10 microg/L. For most other VOCs, such levels cause net outgassing (F > 0). When F > 0 in a given section of stream, in the net flux convention, all of the alpha(j) for the compound remain unchanged over that section while c(w) decreases. A characteristic time tau(d) can be calculated to predict when there will be differences between SA results obtained by the net flux convention versus the individual fluxes convention. Source apportionment modeling provides the framework necessary for comparing different strategies for mitigating contamination at points of interest along a stream.

Acetone↗

Atmospheric ammonia, volatile fatty acids, and other odorants near beef feedlots.

Intensive livestock operations can release odorous gases from stored or land-applied manure. We measured concentrations of dust and 14 odor-causing gases at increasing distances from four feedlots near Lethbridge, southern Alberta, Canada. Concentration was determined from the amount of total dust or gas accumulated in the sampIers, and the volume of air sampled. Adjacent the feedlots, the maximum concentration of many volatile fatty acids exceeded reported odor detection thresholds; the maximum ammonia concentration was close to the threshold. Ammonia and butyric acid approached or exceeded their individual odor thresholds as far as 200 m downwind of the feedlots. Highest concentrations were measured adjacent to land where manure was being applied. None of the odorant concentrations exceeded their irritation threshold. There was a positive relationship between ammonia concentration and odor intensity as well as dry deposition. Much of the emitted ammonia was deposited to soil immediately downwind, enough to supply all the nitrogen needed for crop growth. Odorant concentrations declined sharply with distance, though measurable odor occasionally persisted to 1 km from the feedlot, beyond the minimum separation guidelines (Alberta) for a single residential dwelling. The weekly averaged total suspended particulates (> 5 microm) were below the Alberta guideline criterion except for one period. Differences among feedlots in odorant plume concentrations were partly related to the stocking density of feedlots, which presumably affects manure moisture and amount of volatiles within the pens.

Air Movements↗

Attenuation of methane and volatile organic compounds in landfill soil covers.

The potential for natural attenuation of volatile organic compounds (VOCs) in landfill covers was investigated in soil microcosms incubated with methane and air, simulating the gas composition in landfill soil covers. Soil was sampled at Skellingsted Landfill at a location emitting methane. In total, 26 VOCs were investigated, including chlorinated methanes, ethanes, ethenes, fluorinated hydrocarbons, and aromatic hydrocarbons. The soil showed a high capacity for methane oxidation resulting in very high oxidation rates of between 24 and 112 microg CH4 g(-1) h(-1). All lower chlorinated compounds were shown degradable, and the degradation occurred in parallel with the oxidation of methane. In general, the degradation rates of the chlorinated aliphatics were inversely related to the chlorine to carbon ratios. For example, in batch experiments with chlorinated ethylenes, the highest rates were observed for vinyl chloride (VC) and lowest rates for trichloroethylene (TCE), while tetrachloroethylene (PCE) was not degraded. Maximal oxidation rates for the halogenated aliphatic compounds varied between 0.03 and 1.7 microg g(-1) h(-1). Fully halogenated hydrocarbons (PCE, tetrachloromethane [TeCM], chlorofluorocarbon [CFC]-11, CFC-12, and CFC-113) were not degraded in the presence of methane and oxygen. Aromatic hydrocarbons were rapidly degraded giving high maximal oxidation rates (0.17-1.4 microg g(-1) h(-1)). The capacity for methane oxidation was related to the depth of oxygen penetration. The methane oxidizers were very active in oxidizing methane and the selected trace components down to a depth of 50 cm below the surface. Maximal oxidation activity occurred in a zone between 15 and 20 cm below the surface, as this depth allowed sufficient supply of both methane and oxygen. Mass balance calculations using the maximal oxidation rates obtained demonstrated that landfill soil covers have a significant potential for not only methane oxidation but also cometabolic degradation of selected volatile organics, thereby reducing emissions to the atmosphere.

Bacteria↗

Odor and volatile organic compound treatment by biotrickling filters: pilot-scale studies at hyperion treatment plant.

A pilot-scale biotrickling filter was installed at the Hyperion Treatment Plant in Los Angeles, California, to study hydrogen sulfide (odor) and volatile organic compound (VOC) removal from headworks waste air. The performance of the reactor was continuously monitored during a 10-month period. At an average empty bed gas residence time of 24 seconds, 10 to 50 ppm of hydrogen sulfide was consistently removed at greater than 98% efficiency, corresponding to an average volumetric elimination capacity of 5.2 g/m3 x h. Concentration profiles over the height of the reactor indicated nearly complete removal in the first section of the reactor, suggesting that elimination capacities up to 30 g/m3 x h could be obtained. The odor reduction (as dilution to threshold) was 98%, which correlated with the efficiency of removal of hydrogen sulfide as the primary pollutant. Volatile organic compounds were present at concentrations up to 225 ppb. Moderate but significant removal of toluene and benzene was observed when the biotrickling filter was operated with pH control to neutralize sulfuric acid production from hydrogen sulfide oxidation. Xylenes and chlorinated VOCs were not removed regardless of experimental conditions in the reactor. The results led to the conclusion that VOC removal is the limiting process in biotrickling filters for the simultaneous removal of hydrogen sulfide and VOCs at publicly owned treatment works.

Bioreactors↗

Investigating the capacity of an activated sludge process to reduce volatile organic compounds and odor emissions.

The effects of hydrogen sulfide (H2S) diffusion into activated sludge (AS) on odor and volatile organic compound (VOC) concentrations in offgas were studied over an 8-week period. Most VOCs detected in the offgas of both aeration tanks were aromatic hydrocarbons. The VOC concentrations generally decreased when H2S was introduced to the AS compared with the control, indicating a negative effect of H2S on VOC removal. Two volatile organic sulfur compounds present in the test AS offgas showed an increase followed by a decrease during H2S peak loads. Six VOCs and odor concentration increased during the introduction of an H2S peak; however no correlation was observed between H2S and odor concentration. The increase in odor concentration resulted from the increase in the concentration of six aromatic VOCs, which had their removal slowed down during a 100-ppmv H2S peak. Activated sludge diffusion provides effective H2S removal with minimal affect on odor emissions.

Gases↗

Gastrointestinal volatile fatty acid concentrations and pH in cats.

OBJECTIVE: To measure volatile fatty acid (VFA) concentrations and pH in the gastrointestinal tracts of healthy adult cats fed a commercial dry cat food. ANIMALS: 14 cats. PROCEDURE: The gastrointestinal tracts were excised immediately after euthanasia and divided into 6 sections (stomach, duodenum, jejunum, ileum, proximal portion of the colon, and distal portion of the colon). Luminal contents were collected from each segment, pH was measured, and contents were centrifuged. The supernatant was analyzed for acetate, proprionate, butyrate, isobutyrate, valerate, and isovalerate concentrations by use of gas chromatography. RESULTS: Mean total VFA concentrations were lowest in the stomach (20 mmol/L); increased through the duodenum, jejunum, and ileum (30, 29, and 41 mmol/L, respectively); and were greatest in the proximal and distal portions of the colon (109 and 131 mmol/L, respectively). Estimated mean total VFA amounts were low (<600 micromol) throughout all segments of the gastrointestinal tract; pH values increased from the stomach through the ileum and subsequently decreased in the colon. CONCLUSIONS AND CLINICAL RELEVANCE: Total VFA concentrations in the colon were comparable to values reported for the forestomach of ruminants and large intestines of monogastric animals, whereas values in the small intestine were higher than reported for other species. Total VFA amounts were low, consistent with the short, nonvoluminous gastrointestinal tract of carnivores. Luminal pH varied throughout the gastrointestinal tract in a pattern similar to other monogastric animals. Volatile fatty acids probably contribute minimal metabolic energy in cats but may be important in the maintenance of local mucosal health.

Animals↗