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Characterization of infrared chemical sensors modified with ZnO nanowires for the detection of volatile organic compounds.

In this paper we describe the application and characterization of zinc oxide (ZnO) nanowires in an infrared (IR) chemical sensing system for the detection of volatile organic compounds (VOCs). Under suitable conditions, we grew ZnO nanowires on the surfaces of IR internal reflection elements (IREs) and obtained successful results for the detection of VOCs. ZnO nanowires offer a large surface area to effectively adsorb the examined species; the sensitivity of these IR sensing systems was increased by 3- to 15-fold after surface treatment with the ZnO nanowires. To explore the performance of this type of sensor, we correlated the morphologies of the ZnO nanowires grown on the surfaces of the IREs with the adsorption behavior observed during the sensing of the VOCs. To characterize the properties of the ZnO nanowires during the detection of VOCs having a range of functionalities, we classified the VOCs and examined their enrichment factors by comparing the IR signals detected in the presence and absence of the ZnO nanowires. Our results indicate that the ZnO nanowires exhibited better performance for the detection of aromatic-type VOCs than they did for non-aromatic compounds. For quantitative analyses, we examined several compounds for their responses toward varying quantities of injected VOCs. Our results indicate that the IREs treated with ZnO nanowires display acceptable linearity in their standard curves; the linear regression coefficients were higher than 0.995 for a range of volatile compounds.

Journal Article↗

Gas chromatographic-mass spectrometric characterization of volatile organic compounds in Barcelona tap water.

Barcelona's tap water is supplied by the Llobregat and Ter rivers, which have significant differences in raw water quality. Volatile organic compounds (VOCs) from Barcelona tap water were isolated by closed-loop stripping analysis (CLSA) and identified and determined by gas chromatography-mass spectrometry. The results showed that the Ter river gives the better quality tap water. VOCs, in particular solvents, phosphates, hydrocarbons, C3 and C4 alkylbenzenes and surfactant-related compounds such as C10-C13 alkylbenzenes and non-ionic compounds such as polyethoxylated nonylphenols and their brominated derivatives are present at the ppb level. The last two types of compounds have not previously been reported using the CLSA technique.

Benzene Derivatives↗

Neurobehavioral and sensory irritant effects of controlled exposure to a complex mixture of volatile organic compounds.

Subjective reactions of discomfort, impaired air quality, irritation of mucosal membranes, and impaired memory have been reported in chemically sensitive subjects during exposure to volatile organic compounds (VOCs) found in new buildings. Sixty-six normal healthy male subjects aged 18-39 were exposed for 2.75 hr to a complex VOC mixture at 0 and 25 mg/m3. Each subject completed control and exposure sessions at one-week intervals in counterbalanced order. Measurements included comfort ratings of eye, nose and throat irritation, symptom questionnaire and computerized behavioral tests. Subjects found the odor of VOCs unpleasantly strong and reported that VOC exposure degraded air quality, increased headache and produced general discomfort. VOC exposure did not affect performance on any behavioral tests.

Adult↗

Gas chromatography-mass spectrometry with headspace for the analysis of volatile organic compounds in waste water.

Headspace analysis combined with high-resolution gas chromatography and detection by mass spectrometry was evaluated for the analysis of 53 volatile organic compounds (VOCs) in river waters, waste waters and treated water samples down to 0.1 microgl(-1) concentration levels. The conditions optimised included sample thermostatting time and temperature, autosampler parameters and the nature of salt, added to the sample. The pollutions origin and their seasonal rippling have been done. It was shown that the content of VOCs in river water mainly correlates to the content of these compounds in waste waters, which shows the anthropogenic character of the pollutions.

Calibration↗

Elimination of volatile organic compounds in breath after exposure to occupational and environmental microenvironments.

Breath measurements offer the potential for a direct and noninvasive evaluation of human exposure to volatile organic compounds (VOCs) in the environments in which people live and work. This research study was conducted to further evaluate and develop the potential of this exposure assessment methodology. Several people were exposed to the atmosphere in six microenvironments for several hours. Air concentrations of VOCs were measured during these exposures and breath samples were collected and analyzed at multiple time points after the exposure to evaluate elimination kinetics for 21 VOCs. A new alveolar breath collection technique was applied. Elimination half-lives were estimated using a mono- and bi-exponential model. The alveolar breath collection and analysis methodology proved to be very useful for collecting many samples in short time intervals and this capability was very important for more accurately describing the initial phase of the decay curves. Breath decay curves were generated from samples collected over a four hour period after exposure for 21 of 24 target VOCs. A biexponential function generally provided a better fit for the decay data than did the monoexponential function, supporting a multi-compartment uptake and elimination model for the human body.

Air Pollutants↗

Uptake and decay of volatile organic compounds at environmental concentrations: application of a four-compartment model to a chamber study of five human subjects.

Five subjects were exposed to nine volatile organic compounds (VOCs) at concentrations that can be encountered in everyday life. Breath samples were collected during a 10-h uptake phase and a 24-h decay phase. It was possible to determine four distinct slopes in the decay curve for each chemical. The distribution in the body and residence times in different tissues were calculated using a linear four-compartment mass-balance model. The model was used to predict breath concentrations for two subjects in a second chamber experiment including the same nine VOCs, representing three chemical classes (aromatic, aliphatic, and chlorinated compounds). Predicted values were generally within 25% of those observed, suggesting that the model parameters calculated here could be useful in estimating exposure and body burden to other VOCs in these three classes. Median residence times for the nine VOCs ranged from 3-12 min for compartment 1 (metabolizing); 0.3-2 h for compartment 2; 2-5 h for compartment 3; and 1-4 d for compartment 4. The fraction of the parent compound exhaled at equilibrium was estimated to range from 0.06-0.16 for four aromatic compounds and decane; 0.22-0.23 for trichloroethylene and dichloromethane; 0.35 for hexane; and 0.88 for 1,1,1-trichloroethane. Limited blood measurements were obtained for six of the nine VOCs in two subjects simultaneously with the breath samples over four-hour decay periods. Blood/breath ratios agreed well between the two subjects, but were higher than human blood/air partition coefficients reported in subjects exposed to high concentrations. This observation is consistent with results from other studies at relatively low concentrations.

Adult↗

Volatile organic compounds in foods: a five year study.

A purge and trap procedure was used with gas chromatography-mass spectrometry determination to analyze 70 foods for volatile organic compounds (VOCs). The results from analyses over a 5 year period (1996-2000) are reported. VOCs were found in at least one sample of all foods tested, although no single compound was found in each of the foods. The total amount of VOCs found in a single food item over the 5 year period ranged from 24 to 5328 ppb, with creamed corn (canned) the lowest and cheddar cheese the highest. Benzene was found in all foods except American cheese and vanilla ice cream. Benzene levels ranged from 1 to 190 ppb, with the highest level found in fully cooked ground beef. Benzene was found in 12 samples of cooked ground beef, with an average of 40 ppb. Benzene levels above 100 ppb were also seen in at least one sample each of a cola (138 ppb), raw bananas (132 ppb), and cole slaw (102 ppb). This compares to a maximum contaminant level of 5 ppb set by the U.S. EPA for drinking water.

Benzene↗

State-of-the-art of gas chromatography-based methods for analysis of anthropogenic volatile organic compounds in estuarine waters, illustrated with the river Scheldt as an example.

This review focuses on a number of key procedural steps in the analysis of volatile organic compounds (VOCs) in estuarine waters. The most critical step, from an analytical point of view, is sample preparation. So far, only purge-and-trap and, to some extent, membrane inlet mass spectrometry have successfully been applied in estuarine monitoring of VOCs. The advantages and disadvantages of both techniques are discussed and novel developments are reviewed. Other key elements in VOC analysis and assessment include quality assurance (QA), quality control (QC) and statistical data analysis. This paper gives a brief overview of QA/QC measures of interest in the estuarine monitoring exercise, and provides guidelines for adequate statistical treatment of environmental data. Finally, field measurements of VOCs in estuarine waters are reviewed. Concentrations are reported, and distribution patterns, sources and time-trends are discussed. In addition to data, results of a 3-year monitoring survey (May 1998-November 2000) in the Scheldt estuary are presented.

Belgium↗

Volatile organic compound detection using nanostructured copolymers.

Regioregular polythiophene-based conductive copolymers with highly crystalline nanostructures are shown to hold considerable promise as the active layer in volatile organic compound (VOC) chemresistor sensors. While the regioregular polythiophene polymer chain provides a charge conduction path, its chemical sensing selectivity and sensitivity can be altered either by incorporating a second polymer to form a block copolymer or by making a random copolymer of polythiophene with different alkyl side chains. The copolymers were exposed to a variety of VOC vapors, and the electrical conductivity of these copolymers increased or decreased depending upon the polymer composition and the specific analytes. Measurements were made at room temperature, and the responses were found to be fast and appeared to be completely reversible. Using various copolymers of polythiophene in a sensor array can provide much better discrimination to various analytes than existing solid state sensors. Our data strongly indicate that several sensing mechanisms are at play simultaneously, and we briefly discuss some of them.

Electrochemistry↗

Online sensing of volatile organic compounds in groundwater using mid-infrared fibre optic evanescent wave spectroscopy: a pilot scale test.

A prototype sensing system for in-situ monitoring of volatile organic compounds in contaminated groundwater was tested at a pilot scale plant. The sensor consists of a commercially available Fourier transform infrared spectrometer, connected to a 6 m long infrared transparent silver halide fibre optic cable. A 10 cm long core-only section at the centre of the fibre is mounted on a sensor head and coated with a hydrophobic polymer layer, while the remaining fibre is protected by Teflon tubing and thus not in contact with the surrounding media. The sensor head was immersed into the monitoring wells of the pilot plant testing the sensor system under circumstances close to field conditions and typical for in-situ measurements. The pilot plant consists of a 1 m3 cubic tank filled with gravel. A pump is used to circulate water horizontally through the tank, simulating a natural aquifer. The evolution of the concentration of analytes injected into the system is monitored with time using the developed prototype sensing system. The results are validated by corresponding sampling and analysis with headspace gas chromatography.

Environmental Monitoring↗

Automated gas chromatography with cryogenic/sorbent trap for the measurement of volatile organic compounds in the atmosphere.

An automated gas chromatographic system was constructed to easily adapt either the cryogenic trap or chemical sorbent trap for preconcentrating ambient levels of volatile organic compounds. Remarkable similarity in chromatograms from C3 to C10 was found between these two enrichment methods, except that the sorbent trap did not quantitatively trap the C2-hydrocarbons. In contrast to cryogenic trapping, the chromatographic conditions for more volatile compounds were substantially improved using the sorbent trap. Water interference on the porous-layer open tubular column was also better managed using the sorbent trap for the continuous analysis of humid room air. The similarity in peak profiles between the GC-flame ionization detection (FID) and a commercial GC-MS system, regardless of concentration levels, facilitated compound identification on the FID chromatograms based on a field mission involving analysis of 106 air samples.

Adsorption↗

Headspace/solid-phase microextraction/gas chromatography-mass spectrometry: a screening technique for the recovery and identification of volatile organic compounds (VOC's) in postmortem blood and viscera samples.

This paper describes the application of Headspace/Solid-Phase Microextraction/Gas Chromatography-Mass Spectrometry (HS/SPME/GC-MS) to the recovery and identification of volatile organic compounds in blood and viscera samples from deceased persons. The technique is used as a screening procedure to rapidly obtain information relating to toxicological investigations. The technique is suitable for the detection of volatiles (of wide boiling range) including butane, halothane, toluene, xylenes, and petrol residues in blood and viscera (lung, brain, and body fat).

Adipose Tissue↗

A field comparison of volatile organic compound measurements using passive organic vapor monitors and stainless steel canisters.

Concurrent field measurements of 10 volatile organic compounds (VOCs) were made using passive diffusion-based organic vapor monitors (OVMs) and the U.S. Federal Reference Method, which comprises active monitoring with stainless steel canisters (CANs). Measurements were obtained throughout a range of weather conditions, repeatedly over the course of three seasons, and at three different locations in the Minneapolis/St. Paul metropolitan area. Ambient concentrations of most VOCs as measured by both methods were low compared to those of other large metropolitan areas. For some VOCs a considerable fraction of measurements was below the detection limit of one or both methods. The observed differences between the two methods were similar across measurement sites, seasons, and meteorological variables. A Bayesian analysis with uniform priors on the differences was applied, with accommodation of sometimes heavy censoring (nondetection) in either device. The resulting estimates of bias and standard deviation of the OVM relative to the CAN were computed by tertile of the canister-measured concentration. In general, OVM and CAN measurements were in the best agreement for benzene and other aromatic compounds with hydrocarbon additions (ethylbenzene, toluene, and xylenes). The two methods were not in such good agreement for styrene and halogenated compounds (carbon tetrachloride, p-dichlorobenzene, methylene chloride, and trichloroethylene). OVMs slightly overestimated benzene concentrations and carbon tetrachloride at low concentrations, but in all other cases where significant differences were found, OVMs underestimated relative to canisters. Our study indicates that the two methods are in agreement for some compounds, but not all. We provide data and interpretation on the relative performance of the two VOC measurement methods, which facilitates intercomparisons among studies.

Air Pollutants↗

Measurement of toxic volatile organic compounds in indoor air of semiconductor foundries using multisorbent adsorption/thermal desorption coupled with gas chromatography-mass spectrometry.

A method for the qualitative and quantitative analysis of volatile organic compounds (VOCs) in the air of class-100 clean rooms at semiconductor fabrication facilities was developed. Air samples from two semiconductor factories were collected each hour on multisorbent tubes (including Carbopack B, Carbopack C, and Carbosieve SIII) with a 24-h automatic active sampling system and analyzed using adsorption/thermal desorption coupled with gas chromatography-mass spectrometry. Experimental parameters, including thermal desorption temperature, desorption time, and cryofocusing temperature, were optimized. The average recoveries and the method detection limits for the target compounds were in the range 94-101% and 0.31-0.89 ppb, respectively, under the conditions of a 1 L sampling volume and 80% relative humidity. VOCs such as acetone, isopropyl alcohol, 2-heptanone, and toluene, which are commonly used in the semiconductor and electronics industries, were detected and accurately quantified with the established method. Temporal variations of the analyte concentrations observed were attributed to the improper use of organic solvents during operation.

2-Propanol↗

Relaxed eddy accumulation, a new technique for measuring emission and deposition fluxes of volatile organic compounds by capillary gas chromatography and mass spectrometry.

The possibility afforded by a new relaxed eddy accumulation system in the determination of emission and deposition fluxes of volatile organic compounds (VOCs) by chromatographic techniques will be presented. The system, especially designed to limit sampling artifacts, uses adsorption traps filled with solid sorbents as reservoirs for VOC collection. Enriched compounds were analyzed by capillary GC and positive identification and quantification of eluted compounds was Achieved by mass-spectrometric detection. The method has been used to quantify the emission and deposition of both biogenic and anthropogenic VOCs over a Mediterranean forest ecosystem located in Central Italy. For the first time, both daily and seasonal trends of anthropogenic and biogenic VOCs will be reported. The consistency of monoterpene fluxes with predictions based on the knowledge of VOC emission from the dominant vegetation species will be tested. Data have been used to develop a novel algorithm to predict the seasonality of biogenic emission from the forest ecosystem.

Gas Chromatography-Mass Spectrometry↗

Risk assessment of exposure to volatile organic compounds in different indoor environments.

The lifetime cancer risks of exposure of cooks and food service workers, office workers, housewives, and schoolchildren in Hong Kong to volatile organic compounds (VOCs) in their respective indoor premises during normal indoor activities were assessed. The estimated cancer risk for housewives was the highest, and the second-highest lifetime cancer risk to VOC exposure was for the groups of food service and office workers. Within a certain group of the population, the lifetime cancer risk of the home living room was one to two orders of magnitude higher than that in other indoor environments. The estimated lifetime risks of food service workers were about two times that of office workers. Furthermore, the cancer risks of working in kitchen environments were approximately two times higher than the risks arising from studying in air-conditioned classrooms. The bus riders had higher average lifetime cancer risks than those travelling by Mass Transit Railway. For all target groups of people, the findings of this study show that the exposures to VOCs may lead to lifetime risks higher than 1 x 10(-6). Seven indoor environments were selected for the measurement of human exposure and the estimation of the corresponding lifetime cancer risks. The lifetime risks with 8-h average daily exposures to individual VOCs in individual environments were compared. People in a smoking home had the highest cancer risk, while students in an air-conditioned classroom had the lowest risk of cancer. Benzene accounted for about or more than 40% of the lifetime cancer risks for each category of indoor environment. Nonsmoking and smoking residences in Hong Kong had cancer risks associated with 8-h exposures of benzene above 1.8 x 10(-5) and 8.0 x 10(-5), respectively. The cancer risks associated with 1,1-dichloroethene, chloroform, methylene chloride, trichloroethene, and tetrachloroethene became more significant at selected homes and restaurants. Higher lifetime cancer risks due to exposure to styrene were only observed in the administrative and printing offices and air-conditioned classrooms. Higher lifetime cancer risks related to chloroform exposures were observed at the restaurant and the canteen.

Adult↗

Vehicle occupants' exposure to aromatic volatile organic compounds while commuting on an urban-suburban route in Korea.

This study identified in-auto and in-bus exposures to six selected aromatic volatile organic compounds (VOCs) for commutes on an urban-suburban route in Korea. A bus-service route was selected to include three segments of Taegu and one suburban segment (Hayang) to satisfy the criteria specified for this study. This study indicates that motor vehicle exhaust and evaporative emissions are major sources of both auto and bus occupants' exposures to aromatic VOCs in both Taegu and Hayang. A nonparametric statistical test (Wilcoxon test) showed that in-auto benzene levels were significantly different from in-bus benzene levels for both urban-segment and suburban-segment commutes. The test also showed that the benzene-level difference between urban-segment and suburban-segment commutes was significant for both autos and buses. An F-test showed the same statistical results for the comparison of the summed in-vehicle concentration of the six target VOCs (benzene, toluene, ethylbenzene, and o,m,p-xylenes) as those for the comparison of the in-vehicle benzene concentration. On the other hand, the in-vehicle benzene level only and the sum were not significantly different among the three urban-segment commutes and between the morning and evening commutes. The in-auto VOC concentrations were intermediate between the results for the Los Angeles and Boston. The in-bus VOC concentrations were about one-tenth of the Taipei, Taiwan results.

Air Pollutants↗

Effects of gas flow rate, inlet concentration and temperature on biofiltration of volatile organic compounds in a peat-packed biofilter.

The effects of incoming gas concentration, empty bed residence time (EBRT), and column temperature on the removal efficiency of volatile organic compounds (isoprene, dimethyl sulfide, chloroform, benzene, trichloroethylene, toluene, m-xylene, o-xylene and styrene) were studied for 101 d in a biofilter comprising two glass columns (I.D. 5.0 cm x height 62 cm) packed with peat. At an EBRT of 3 min the removal efficiency increased up to 90% 34 d after start up at both 25 degrees C and 45 degrees C when the incoming gas concentration was raised stepwise to 65 g.m(-3). When the incoming gas concentration increased to 83 g.m(-3), the removal efficiency was 93% at 25 degrees C, but dropped to 74% at 45 degrees C. At an incoming gas concentration of 92 g.m(-3) and an EBRT of 1.5 min, the removal efficiencies were 91% and 94% at 25 degrees C and 32 degrees C, respectively. However, at 1 min of EBRT, the removal efficiencies decreased to 68% and 81% at 25 degrees C and 32 degrees C, respectively. The removal rate per unit time and per unit volume of the biofilter was proportional to the incoming gas rate up to 3483 g VOC.m(-3).h(-1). Further increase of the incoming gas rate lowered the removal rate as compared to that predicted by the proportionality. The maximum removal rate was 3977 g.m(-3).h(-1) at 32 degrees C. At an EBRT of 1.5 min, the removal efficiency was highest for isoprene (93%), and lowest for chloroform (84%). Aromatic compounds (benzene, toluene, and xylene) were removed by 93-94%. The cell concentration increased 100-fold from the initial value, and reached 1.12 x 10(8) cells.(g of dry peat)(-1). At 32 degrees C, 67% of the incoming VOC was removed in the first quarter of the column.

Journal Article↗