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A method for monitoring dermal exposure to volatile chemicals.

Absorptive pads of charcoal cloth were developed and tested for monitoring the deposition of volatile toxic materials on skin. The dosimeters can retain over 60% of volatile deposits such as toluene or dichloropropene droplets over an 8-hr workday. Evaporation from liquid deposits and vapor adsorption onto the dosimeters are factors which can complicate the interpretation of exposure data. Evaporation was inversely proportional to the log of the deposit size (volume), vapor pressure, and the air humidity. Vapor adsorption was proportional to the vapor concentration, exposure duration, and the log of air velocity. A procedure is offered for estimating the initial size of the liquid deposit from retained mass. The charcoal cloth dosimeter's accuracy and precision are optimal in situations involving possible dermal exposure to toxic materials with low to moderate volatility or with low vapor concentration, i.e., those where dermal exposure may be equal to or more significant than respiratory exposure.

Adsorption↗

Determination of unique microbial volatile organic compounds produced by five Aspergillus species commonly found in problem buildings.

This study identified unique microbial volatile organic compounds (UMVOCs) produced by five Aspergillus species (A. fumigatus, A. versicolor, A. sydowi, A. flavus, and A. niger) cultivated on malt extract agar and gypsum board. The hypothesis was that UMVOCs can be used to predict the presence of Aspergillus species. During the cultivation humidified air was continually supplied and evenly distributed through each of the culture flasks. Volatile metabolites were collected using Tenax TA tubes on Days 8, 16, and 30 after inoculation. The volatile metabolites were determined by gas chromatography/mass spectroscopy after thermal desorption. Nine compounds recognized as UMVOCs--3-methyl-1-butanol; 2-methyl-1-propanol; terpineol; 2-heptanone; 1-octen-3-ol; dimethyl disulfide; 2-hexanone; 3-octanone; and 2-pentylfuran--were found on the cultures in detectable amounts. The first two compounds were detected at the highest frequency when combining both media. The first four compounds were found to be the dominant UMVOCs on gypsum board, which could be used as chemical markers of the common Aspergillus species grown indoors.

Air Pollution, Indoor↗

Assessing truck driver exposure at the World Trade Center disaster site: personal and area monitoring for particulate matter and volatile organic compounds during October 2001 and April 2002.

The destruction of the World Trade Center (WTC) in New York City on September 11, 2001, created a 16-acre debris field composed of pulverized and burning material significantly impacting air quality. Site cleanup began almost immediately. Cleanup workers were potentially exposed to airborne contaminants, including particulate matter, volatile organic compounds, and asbestos, at elevated concentrations. This article presents the results of the exposure assessment of one important group of WTC workers, truck drivers, as well as area monitoring that was conducted directly on site during October 2001 and April 2002. In cooperation with a local labor union, 54 drivers (October) and 15 drivers (April) were recruited on site to wear two monitors during their 12-hour work shifts. In addition, drivers were administered a questionnaire asking for information ranging from "first day at the site" to respirator use. Area monitoring was conducted at four perimeter locations during October and three perimeter locations during April. During both months, monitoring was also conducted at one location in the middle of the rubble. Contaminants monitored for included total dust (TD), PM10, PM2.5, and volatile organic compounds. Particle samples were analyzed for mass, as well as elemental and organic carbon content. During October, the median personal exposure to TD was 346 microg/m3. The maximum area concentration, 1742 microg/m3, was found in middle of the debris. The maximum TD concentration found at the perimeter was 392 microg/m3 implying a strong concentration gradient from the middle of debris outward. PM2.5/PM10 ratios ranged from 23% to 100% suggesting significant fire activity during some of the sampled shifts. During April, the median personal exposure to TD was 144 microg/m3, and the highest area concentration, 195 microg/m3, was found at the perimeter. During both months, volatile organic compounds concentrations were low.

Air Pollutants↗

[Effect of different types of rations on various characteristics of ruminal and intermediary metabolism in sheep. 1. Formation of volatile fatty acids].

Studies on Ruminal Physiology were made with 15 growing female Merino sheep to investigate the influence of different types of rations on the fermentation of volatile fatty acids. The rations were constructed of green feed, straw and concentrates (type 1) or chemically treated straw pellets + concentrates (type 2). One ration (type 3) consisted of concentrates only. With regard to the total concentration of acids ration 3 was significantly superior to the 2 other types of rations. Moreover, ration 3 produced a specific fermentation pattern of the volatile fatty acids. This was characterized by a significant reduction in the molar proportion of acetate compared with ration 1 and 2 and a significant increase in the level of propionic and valeric acid relative to ration 1. Differences in the fermentation pattern between rations 1 and 2 were mainly limited to differences in the absolute and molar proportions of propionate where the straw pellet rations in each case produced the significant higher values. The acetate to propionate ratio was narrowed in the order of ration 1-3 (4.1 :1, 3.1:1, 2.6-2.9 :1). Statistically wellestablished negative correlations were found to exist between the concentrations of volatile fatty acids and the pH values which were established simultaneously.

Animal Feed↗

Volatile substance and other drug abuse inhalation in Spain.

OBJECTIVE: Inhalant misuse is the intentional inhalation of volatile substances in order to obtain euphoric, disinhibiting, and exciting effects. Solvents, glues, adhesives, paints, varnishes, paint removers, dry cleaning agents, spray paints, nail polish removers, typewriter correction fluids, and aerosol propellants are common sources of volatile substance abuse. In recent years the abuse of inhalant substances, not only among those who abuse other drugs but also in teenagers and younger children, has been reported. We reviewed retrospectively the cases of inhalant misuse reported to the Spanish Poison Control Center. METHODS: Human intoxications from abuse of inhalant substances registered by our service from 1991 to 2000 were studied. Data analyzed were relative to age, gender, signs and symptoms, drug dependence antecedents, and severity of symptoms of the patients. The type of product and composition were also investigated. RESULTS: During the study period 109 cases of patients aged from 8 to 50 years were collected. A percentage of 36.6% was less or equal to 20 years old. Seventy percent corresponded to males. Of the patients, 11% presented dependence antecedents to other abuse drugs and 72.5% were symptomatic. In the symptomatic exposures clinical features affected the following systems: CNS (62.8%), gastrointestinal (8.1%), cardiovascular (8.1%), respiratory (2.9%), peripheral nervous system (1.1%), renal (1.1%), haematological (1.1%), hepatic (1.7%), and other (13.1%). The commercial products more frequently inhaled were solvents (34.9%) and glues/adhesives (22.9%). We noted the use of medicines with ethyl chloride-local anaesthetic (8.3%), three cases with aerosol bronchodilator (with fluorocarbons as propellants), and one case of xylazine inhalation. The composition most often involved was aromatic hydrocarbons (46.9%), halogenated hydrocarbons (16.5%), aliphatic hydrocarbons (11.4%), ketones (10.1%), local anaesthetic (ethyl chloride) (8.4%), ethers (2.5%), nitrous oxides (2.5%), and aliphatic nitrites (1.7%). The calls received were 59.6% from health care units and 22% from general public. Only 14% of cases were at home and 48% had moderate to severe clinical effects. Acute intoxications occurred in 82% of cases. CONCLUSIONS: Inhalation of volatile substance as abuse drugs has been detected in different age groups, including very young people. Although the principal source was industrial products, the use of drugs such as local anaesthetics and aerosol broncodilators was also detected. Based on epidemiological studies in the Spanish population (essentially adolescents and childhood) together with the ability of a Poison Center to detect sentinel-events, the community and authorities should develop strategies to prevent these exposures and the later use of other substances of abuse. In fact, recently a Law on Drug Dependences and Other Addictive Alterations has been approved in Madrid in order to take precautionary measures.

Administration, Inhalation↗

GC/MS analysis of volatile organic selenium species produced during phytoremediation.

The use of plants and microorganisms that can naturally volatilize selenium and remove it from the soil or water has been studied with promising results. It has been shown that selenium can be removed from soils by plant uptake and accumulation, plant volatilization, and removal in the rhizosphere. Preliminary studies indicated that Hydrilla verticillata Royle removed selenium by means of phytovolatilization. Therefore, studies were conducted to examine the volatile products produced during phytoremediation of selenium by hydrilla. Samples were obtained and analyzed by GC/MS. Organoselenium compounds found were dimethyl selenide, dimethyl diselenide, and diethyl diselenide.

Biodegradation, Environmental↗

Dynamic air sampling of volatile organic compounds using solid phase microextraction.

A new dynamic air sampling system was devised and evaluated in conjunction with solid phase microextraction (SPME) fiber materials for extracting odor-causing volatile organic compounds (VOCs) present in swine building environments. Utilizing a standard solution consisting of 11 compounds (i.e., volatile fatty acids, indoles, and phenol), sampling times, volumes, and flow rates were adjusted to establish optimal extraction conditions. Results indicated that the sampling system was effective with the Carboxen/Polydimethylsiloxane (CAR/PDMS) fiber in extracting all 11 standard compounds. The best sampling conditions for the extraction were a 100-mL sampling vial subjected to a continuous flow of 100 mL/min for 60 min. The gas chromatographic analysis showed that the reproducibility was within acceptable ranges for all compounds (RSD=4.24-17.26% by peak areas). In addition, field tests revealed that the sampling system was capable of detecting over 60 VOCs in a swine house whose major components were identified by gas chromatography-mass spectrometry (GC-MS) and by their retention times as volatile fatty acids, phenols, indole, and skatole. The field tests also showed that considerably different levels of VOCs were present in various parts of the swine building.

Air Pollutants↗

Vapor pressure and freezing point osmolality measurements applied to a volatile screen.

This is a report of a rapid and precise screening procedure, developed for the determination of ethanol in serum using osmolality measurements. The osmolality of the patient is determined by freezing point method (freezing point osmometry) and dew point (water vapor pressure osmometry) method. The difference between freezing point osmolality and vapor pressure osmolality (delta osm) is due to the presence of volatiles in the serum, because the volatiles are not measured by vapor pressure osmometry. The amount of ethanol (mg/dL) in serum is estimated by multiplying delta osm by a factor of 4.2. As a comparison method, ethanol also is measured by a spectrophotometric alcohol dehydrogenase method. In addition, a significant difference between an osmometric alcohol assayed value and enzymatic spectrophotometric measurement indicates the presence of volatiles, other than ethanol. In addition to ethanol there is a linear relationship between osmolality and isopropanol or methanol when added in vitro to serum.

1-Propanol↗

Volatile nitrosamines and tobacco-specific nitrosamines in the smoke of Thai cigarettes: a risk factor for lung cancer and a suspected risk factor for liver cancer in Thailand.

In Thailand, smoking of commercial cigarettes and of handmade cigarettes has drastically increased in recent decades. Cancer of the lung and of the upper aero-digestive tract have also increased in Thailand as they have in many other countries. It is our working hypothesis that the increase of primary cancer of the liver, especially of cholangiocarcinoma in the north-eastern provinces of Thailand is associated with the use of tobacco in men infested with the liver fluke Opisthorchis viverrini (OV). Bioassays have shown that volatile nitrosamines and tobacco-specific nitrosamines induce cholangiocarcinoma in laboratory animals and that the hepatocarcinogenic action of nitrosodimethylamine in hamsters is significantly increased by infestation with the liver fluke OV. The endogenous formation of nitrosamines is significantly increased by OV infestation. This report presents analytical data on the concentration of volatile nitrosamines and tobacco-specific nitrosamines in mainstream smoke of nine leading brands of commercially produced Thai cigarettes which represent approximately 85% of the market share in Thailand. Observed ranges (ng/cigarette) were 8.5-31.9 for nitrosodimethylamine, 8.8-49.6 for nitrosopyrrolidine and 4.2-18.9 for nitrosodi-n-butylamine. These values are exceptionally high compared with the smoke of light and blended cigarettes from North America and Western Europe. Among the tobacco-specific nitrosamines, the range was 28-730 for nitrosonornicotine and 16-370 for 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone. There was a correlation between volatile and tobacco-specific nitrosamines, and tar and nicotine deliveries in the mainstream smoke. The analytical data are in line with the rate for lung cancer and support our working hypothesis that nitrosamines, and especially the tobacco-specific nitrosamines, are associated with the increased risk for primary liver cancer among those Thai people who smoke cigarettes and also carry OV infestation.

Bile Duct Neoplasms↗

Headspace sampling and GC analysis of volatile urinary metabolites.

A method requiring only 1 to 3 ml of sample is developed for the analysis of volatile metabolites in urine. Trace volatiles are stripped with helium and concentrated on Porapak Q and activated charcoal traps in series. Volatiles are thermally desorbed into a fused silica capillary column for analysis by gas chromatography. Variables affecting the process are studied. Profiles of untreated and acid hydrolyzed urine are presented.

Adsorption↗

Determination of volatile components in fresh, frozen, and freeze-dried Padrón-type peppers by gas chromatography-mass spectrometry using dynamic headspace sampling and microwave desorption.

"Padrón-type" peppers are a small variety of Capsicum annuum cultivated mainly in Galicia, Spain. To compare the effects of freezing and freeze-drying on the volatile components of Padrón-type peppers, preserved samples are analyzed by means of dynamic headspace sampling on an adsorbent followed by microwave desorption into a gas chromatograph equipped with a mass spectrometric detector. Sixty-five compounds are identified, including hydrocarbons, terpenes, alcohols, phenols, ethers, aldehydes, ketones, esters, pyrroles, pyrazines, and sulfurous compounds. Fresh whole, homogenized, and freeze-dried peppers have characteristic volatile-component profiles, whereas frozen peppers have a highly variable volatile-component profile.

Capsicum↗

Volatile compounds of red and white wines by headspace--solid-phase microextraction using different fibers.

The behavior of four fibers [polydimethylsiloxane (PDMS), PDMS-divinylbenzene (DVB), carboxen (CAR)-PDMS, PDMS-DVB-CAR), is tested for the analysis of volatile compounds of white and red wine. The PDMS-DVB-CAR fiber is the most appropriate to obtain the most wide volatile profile of wines. The better extraction conditions are 40 min at 35 degrees C. Satisfactory data about the reproducibility and uptake are obtained for more than 40 volatile compounds of red and white wine.

Chromatography, Gas↗

Headspace-solid-phase microextraction in the analysis of the volatile fraction of aromatic and medicinal plants.

Headspace (HS)-solid-phase microextraction (SPME) has assumed an ever increasing importance as a technique for HS sampling to study the composition of the HS of medicinal and aromatic plants. HS-SPME has mainly been applied for (a) studying the composition of the volatile fraction, including in addition to or as an alternative to other sampling techniques; (b) monitoring the biological phenomena involved with the volatile fraction of a plant; (c) discriminating between species, subspecies, varieties, cultivars, or chemotypes; and (d) quality control of plant samples. A review of 108 articles published during 2000-2005 is presented covering the use of HS-SPME in the field of aromatic and medicinal plants, selection of the most effective fiber and sampling conditions, comparison of HS-SPME and other volatile fraction sample preparation techniques, and the advantages and limits of HS-SPME when applied to medicinal and aromatic plants.

Chromatography, Liquid↗

The confirmation of volatiles by solid-phase microextraction and GC-MS in the investigation of two traffic fatalities.

A simple, sensitive, and reliable method was developed for the confirmation of nonroutine volatiles in the investigation of two traffic fatalities. Solid-phase microextraction (SPME) fibers were used to extract volatile compounds from the headspace of sample vials; components were subsequently analyzed by gas chromatography-mass spectrometry (GC-MS). In the first case, ethanol and methylene chloride were detected in a urine sample by headspace SPME and GC-MS. The second case involved the analysis of volatile petroleum products from submitted specimens by headspace SPME and GC-MS. In both cases, SPME and GC-MS analyses provided crucial evidence in the investigation of the traffic fatalities.

Accidents, Traffic↗

A GC-MS method for the detection of toluene and ethylbenzene in volatile substance abuse.

The interference of some substances with the gas chromatography-flame ionization detection and gas chromatography-Fourier transform infrared detection of toluene and ethylbenzene in volatile substance abuse poses problems. A gas chromatography-mass spectrometry (GC-MS) method that will overcome such interference has been developed for the detection of toluene and/or ethylbenzene in the headspace of preparations and products containing these substances and in the headspace of blood samples in the cases of volatile substance abuse. The method is based on converting toluene to benzoic acid via the formation of benzotrichloride. The latter compound was obtained upon the reaction of toluene with chlorine gas under direct sunlight conditions. In the presence of water, benzotrichloride was converted to benzoic acid. Ethylbenzene was converted to benzoic acid and two phenylethanols via the formation of side chain chloro-substituted phenylethanes followed by reaction with water. The chloro-substituted phenylethanes were obtained by the reaction of ethylbenzene with chlorine under direct sunlight conditions. The benzoic acid resulting from toluene and/or ethylbenzene and the two phenylethanols resulting from ethylbenzene were detected by GC-MS as their trimethylsilyl (TMS) derivatives. For the method to be viable for the detection of volatile substance abuse, the chlorination reactions were effected in the gaseous state.

Benzene Derivatives↗

A comprehensive screen for volatile organic compounds in biological fluids.

A headspace gas chromatographic (GC) screen for common volatile organic compounds in biological fluids is reported. Common GC phases, DB-1 and DB-WAX, with split injection provide separation and identification of more than 40 compounds in a single 20-min run. In addition, this method easily accommodates quantitation. The screen detects commonly encountered volatile compounds at levels below 4 mg%. A control mixture, providing qualitative and semiquantitative information, is described. For comparison, elution of the volatiles on a specialty phase, DB-624, is reported. This method is an expansion and modification of a screen that had been used for more than 20 years. During its first year of use, the expanded screen has proven to be advantageous in routine forensic casework.

Automation↗

The impact of methionine source on poultry fecal matter odor volatiles.

To determine the impact of Met source on volatile compounds of broiler excreta, 2 trials were conducted using straight-run broiler chicks that were randomly distributed in battery cages with 3 replicate pens of 16 birds each. The treatment groups were 1) dry Met hydroxy analogue (52% Met activity), 2) sodium methioninate aqueous solution (45.9% Met activity), 3) liquid Met hydroxy analogue (88% Met activity), 4) DL-Met, (98% Met activity), and 5) no supplemental Met. All starter diets were formulated to contain 3,135 kcal of ME/kg, 23% crude protein, and 0.8% total Met activity and otherwise met NRC nutrient requirements. Diets were fed ad libitum from d 1 to termination of the study (5 to 6 wk). Feed consumption and feed conversion were measured daily, and all birds were weighed weekly. There were no significant differences in BW, feed consumption, or feed conversion among the treatments in either trial. All excreta were collected in litter pans daily lined with aluminum foil. Litter pans for each pen were individually transferred to a separate room for weekly odor volatile analysis. An electronic nose was used to capture 3 to 4 air samples from various locations for each pan of broiler excreta resulting in a total of 10 air samples from each treatment group. All data taken from the electronic nose were evaluated using analysis of variance. Results indicated that there were significant differences in volatiles in the broiler excreta for all treatment groups. These data indicate that different Met sources may result in the production of different odor-related compounds in broiler excreta.

Animals↗

Effects of volatile anesthetics on light-induced proton uptake of rhodopsin in bovine rod outer segment disk membrane.

The effects of volatile anesthetics upon the function of bovine rhodopsin were estimated from the measurements of light-induced proton uptake. The light-induced pH changes were measured at both 20 degrees C and 37 degrees C with suspensions to which volatile anesthetics were added in the liquid form. Each anesthetic depressed the light-induced proton uptake concentration-dependently. The anesthetic-induced depression was greater at 37 degrees C than at 20 degrees C. For each anesthetic the concentration needed to depress the proton uptake by 10% was roughly identical to that used clinically. Anesthetics also were added to the suspensions in the gaseous form with air. The light-induced proton uptake was decreased in proportion to the partial pressure of the anesthetic. The partial pressures of halothane and methoxyflurane that depressed the proton uptake by 10% at 37 degrees C were 2.0 x 10(-7) and 1.1 x 10(-2) atm., respectively. From these facts it is suggested that volatile anesthetics affect the light-induced conformational changes of rhodopsin molecule during the metarhodopsin I to metarhodopsin II transition and cause inhibition of the light-induced proton uptake of rhodopsin in the rod outer segment disk membrane.

Anesthetics↗