A Solid-phase micro extraction(SPME) was evaluated as a tool for headspace sampling of tobacco samples. Several experimental parameters (sampling temperature, pH, and type of SPME fibers) were optimized to improve sampling efficiency in two aspects ; maximum adsorption and selective adsorption of volatile organic acids onto SPME fibers. Among four types of SPME fibers such as PDMS(Polydimethylsiloxane), PA(Polyacrylate), Car/PDMS (Carboxen/Polydimethylsiioxane) and PDMS/DVB(Polydimethylsiioxane/Divinylbenzene) which were investigated to determine the selectivity and adsorption efficiency. A variety of tobacco samples such as flue cured, burley and oriental were used in this study. The effect of these parameters was often dominated by the physical and chemical nature (volatility, polarity) of target compounds. This method allowed us to make important improvements in selectivity and sensitivity. The Car/PDMS fiber was shown to be the most efficient at extracting the 10 selected volatile organic acids. The parameters were optimized: $80^{\circ}C$ adsorption temperature, 30 min of adsorption time, $240^{\circ}C$ desorption temperature, 1 min of adsorption time.
A respirator is useful to protect a worker from the harmful gases and vapors in the workplace, and the evaluation of respirator cartridge service life is important for the worker's health and safety. The performance of cartridge is effected by several factors such as concentration of gas and vapor, humidity, temperature, adsorbents and cartridge packing density. Adsorption model was applied to both sampling tube and respirator cartridge to predict the service life for organic vapors. The variables of the adsorption model were measured from the experiment with the sampling tube, and it was used to predict the service life of respirator cartridge. In the experiment, we used carbon tetrachloride as a organic vapor and activated carbon take out respirator cartridge as activated carbon. As a result, it was possible to predict the service life of respirator cartridge and predicted service life was quite correct. Breakthrough time decreased with increase of CCl4 concentration. In case of sampling tube, adsorbed amount of CCl4 was larger than respirator cartridge due to linear velocity. Also, rate constant of sampling tube was larger than respirator cartridge, because of, effect of flow rate, packing density. In the prediction of service life of respirator cartridge by using sampling tube, the time required for 50% contaminant breakthrough(${\tau}$) is more effective than the rate constant(k').
Polycyclic aromatic hydrocarbons (PAHs) have been of particular concern since they are present both in the vapor and particulate phases in ambient air. In this study, a simple method was applied to determine the vapor phase PAHs, and the performance of the new method was evaluated with a conventional method. The simple method was based on adsorption sampling and thermal desorption with GC/MS analysis, which is generally applied to the determination of volatile organic compounds (VOCs) in the air. A combination of Carbotrap (300 mg) and Carbotrap-C (100 mg) sorbents was used as the adsorbent. Target compounds included two rings PAHs such as naphthalene, acenaphthylene, and acenaphthene. Among them, naphthalene was listed as one of the main HAPs together with a number of VOCs in petroleum refining industries in the USA. For comparison purposes, a method based on adsorption sampling and solvent extraction with GC/MS analysis was adopted, which is in principle same as the NIOSH 5515 method. The performance of the adsorption sampling and thermal desorption method was evaluated with respect to repeatabilities, detection limits, linearities, and storage stabilities for target compounds. The analytical repeatabilities of standard samples are all within 20%. Lower detection limits was estimated to be less than 0.1 ppbv. In the results from comparison studies between two methods for real air samples. Although the correlation coefficients were more than 0.9, a systematic difference between the two groups was revealed by the paired t-test (${\alpha}$=0.05). Concentrations of two-rings PAHs determined by adsorption and thermal desorption method consistently higher than those by solvent extraction method. The difference was caused by not only the poor sampling efficiencies of XAD-2 for target PAHs and but also sample losses during the solvent extraction and concentration procedure. This implies that the levels of lower molecular PAHs tend to be underestimated when determined by a conventional PAH method utilizing XAD-2 (and/or PUF) sampling and solvent extraction method. The adsorption sampling and thermal desorption with GC analysis is very simple, rapid, and reliable for lower-molecular weight PAHs. In addition, the method can be used for the measurement of VOCs in the air simultaneously. Therefore, we recommend that the determination of naphthalene, the most volatile PAH, will be better when it is measured by a VOC method instead of a conventional PAH method from a viewpoint of accuracy.
Adsorption capacity for the charcoal were tasted in this study to verify the performance of them for the use of the sampling media in industrial hygiene field. Two set of experiments were conducted. The first experiment was to test performance of the tested charcoal tube that were assembled in the laboratory with the use of the GR grade charcoal. The other tests were investigate the adsorption capacity of the charcoal tested in this study and charcoals embedded in the commercial charcoal tubes. Known air concentration samples for benzene, toluene, and o-xylene were prepared by the dynamic chamber. 1. At low air concentration levels (0.1${\times}$TLV), there was no significant differences between the tested charcoal tubes and the SKC charcoal tubes. This implies that there is no defect with the adsorption capacity of the charcoal. 2. At high concentration with 60 minutes sampling, the breakthrough were found only in the tested charcoal while no breakthrough were shown in the SKC charcoal. 3. From the breakthrough tests for the charcoal, the micropore volume(Wo) were calculated by the curve fitting with the use of Dubinin/Radushkevich(D/R) adsorption isotherm equation. The calculated values were 0.687cc/g for SKC, 0.504cc/g for Sensidyne, and 0.419cc/g for the tested charcoal(Aldrich). 4. Adsorption capacities were obtained from the isotherm curves shown adsorption capacities at several levels of the challenge concentration. All range of the air concentration concerned in industrial hygiene, the SKC charcoal showed approximately two times of adsorption capacity compared to the tested charcoal.
A field comparison study was carried out to quantify differences among various sampling and analytical methods for volatile organic compounds (VOCs) at a site in Vlsan in June 1997. Air sampling containers (SUMMA canisters) were used by the Korea Institute of Science and Technology (KIST) and adsorption tubes (carbotrap) were used by Yeungnam University (YN Univ.) for sampling ambient air. Duplicate samples obtained by KIST were analyzed by KIST with a GC-MS system for aromatics and halogenated hydrocarbons and by Atm AA with a GC -FID system for C2∼C9 hydrocarbons, respectively. The adsorption tube samples were analyzed by YN Univ. with a GC-FID system for aromatics. VOC levels for the duplicate canister sampls analyzed by KIST and Atm AA were in good agreement. Concentrations of aromatics by the adsroption tube method were generally higher than those by the canister sampling method by factor of 1.5 to 2.0. Differences between the two sampling methods were discussed.
This study was designed to investigate effects of relative humidity on the breakthrough of charcoal tubes at a fixed vapor concentration and sampling time during mixed organic vapor sampling. A vapor generator was used to generate three different concentrations of mixed organic vapor and a stainless steel chamber was fabricated and utilized to maintain three different percentages of relative humidity while maintaining a constant temperature. The results were as follows; 1. At high relative humidity, breakthrough of mixed organic vapor occurred quickly at low vapor concentration than at high vapor concentration because of the reduced adsorption volume of charcoal tube due to humidity. 2. Breakthrough by competitive adsorption of vapors onto charcoal tube was observed at first from n-hexane having the lowest boiling point and highest vapor pressure among the three organic vapors investigated, followed by TCE. No breakthrough was observed from toluene under all experimental conditions. 3. For n-hexane, breakthrough was observed after 2 hours of sampling and breakthrough rates were increased as relative humidity increased. For TCE, breakthrough was found after 3 hours of sampling and breakthrough rates by sampling time were increased as vapor concentration increased. 4. The adsorbed amount of mixed organic vapor at breakthrough was shown to have statistically significant correlations with sampling time, relative humidity, and vapor concentration in descending order of correlation. Relative humidity and sampling time for n-hexane and sampling time and concentration for TCE were both statistically significantly correlated. 5. Relative humidity was found to affect the amount of breakthrough of mixed organic vapor and n-hexane. Among three percentages of relative humidity investigated, the amount of breakthrough at 85 % relative humidity was significantly larger than those of at lower percentages of relative humidity. No statistically significant difference was found between 25 % and 55 % relative humidity. 6. The results of multiple regression analysis between breakthrough and relative humidity, vapor concentrations showed that the coefficient of determination of mixed organic vapor was 0.263 and those of n-hexane and TCE were 0.275 and 0.189, respectively. 7. Flow rates of sampling pumps used were found to be affected by relative humidity present. At 25 %, 55 %, and 85 % relative humidity, the relative errors of sampling pump were 1.4 %, 13.4 %, and 18.6 %, respectively. In conclusion, the results of this study showed that high relative humidity could reduce the adsorption volume of charcoal tubes and subsequently increase breakthrough rates. Therefore, to prevent breakthrough when sampling mixed organic vapors, it is suggested that either sampling volume be reduced on the flow rate be lowered so as to minimize breakthrough of the most volatile organic vapor in the mixture. In addition, since the flow rates of a sampling pump can be adversely affected by high relative humidity, it is recommended to use a constant flow mode pump when sampling in the highly humid environment.
This study describes (1) the impact of positive sampling artifacts caused by not only a filter-based sampling, but also a denuder-based sampling in the determination of particle-phase organic carbon (POC), (2) the effect of sample flow rate on positive artifacts, and (3) an optimum flow rate that provides a minimized negative sampling artifact for the denuder-based sampling method. To achieve the goals of this study, four different sampling media combinations were employed: (1) Quartz filter-alone (Q-alone), (2) quartz filter behind quartz-fiber filter (QBQ), (3) quartz filter and quartz filter behind Teflon filter (Q-QBT), and (4) quartz filter behind carbon-based denuder (Denuder-Q). The measurement of ambient POC was carried out in an urban area. In addition, to determine gas-phase OC (GOC) removal efficiency of the denuder, a Teflon filter and a quartz filter were deployed upstream and downstream of the denuder, respectively with varying sample flow rates: 5, 10, 20, and 30 LPM. It was found that Q-alone sampling configuration showed a higher POC than QBQ, Q-QBT, and Denuder-Q by 12%, 28%, and 23%, respectively at a sample flow rate of 20 LPM due to no correction for positive artifact caused by adsorption of GOC onto the filter. A lower quantity of GOC was collected from the backup quartz filter on QBQ than that from Q-QBT. This was because GOC was not in equilibrium with that adsorbed on the front quartz filter of QBQ during the sampling period. It is observed that the loss of particle number and mass across the denuder increases with decreasing sample flow rate. The contribution o f positive arti facts to POC decreased with increasing sample flow rate, showing 29%, 25%, and 22% for 10, 20, and 30 LPM, respectively. The 20 LPM turns out to be the optimum sample flow rate for both filter and denuder-based POC sampling.
Kim, Nack-Joo;Chun, Seung-Kyu;Cha, Daniel K.;Kim, Cheal
Bulletin of the Korean Chemical Society
/
제34권8호
/
pp.2353-2357
/
2013
The objective of this study was to develop a simple, less time-consuming and accurate sampling technique based on solid-phase sorption with activated carbon as the sorbents. The results from solid-phase sorption techniques were compared to that from a conventional solvent impinger-based technique to confirm the efficacy of the proposed method. The laboratory results indicated that the solid-phase sorption method was suitable for the determination of siloxanes as the measured concentrations were similar to that from a solvent impinge method. The data from solid-phase sorption method showed excellent recovery and reproducibility while the sampling was less labor intensive and less time consuming than the solvent impinge method. Following the laboratory tests, the solid-phase sorption technique was successfully applied to sampling biogas from a field site. This study shows that the activated carbon-based solid-phase sorption can be a reliable and less time-consuming option for the sampling and collection of siloxanes under various different landfill conditions.
Toluene, n-hexane, and methyl ethyl ketone(MEK) were exposed to the activated carbon fiber(ACF) and 3M(Model 3500) diffusive samplers under low and high humidity levels. In order to evaluate these two samplers, the sampling capacity, sampling rate, reverse diffusion, and storage stability were obtained. At low humidity level($8{\pm}3%RH$), the adsorption amount of all three organic vapors to the ACF diffusive sampler showed a positive linear relationship up to 8 hours. However, at high humidity level($90{\pm}5%RH$), n-hexane and MEK maintained a positive linear relationship up to 1.5 hrs, but decreased in their adsorption amounts afterwards. On the other hand, the adsorption amount of n-hexane, MEK, and toluene to 3M diffusive sampler showed almost a positive linear relationship up to 8 hours at both humidity levels. At low humidity level, there was almost no reverse diffusion for both 3M and ACF diffusive samplers. However, when the ACF diffusive sampler was used at high humidity level, there was about 52.63% of MEK sample loss and about 92.59% of n-hexane sample loss. The storage stabilities of the ACF and 3M diffusive samplers were both relative stable except for MEK. In the case of MEK, the difference between the analysis of the organic vapor right after the sampling and that of 3 weeks later at room temperature was 45% for the ACF diffusive sampler and 18% for the 3M diffusive sampler. Since the storage stability of the samples stored in a refrigerator was relatively stable, they need to be refrigerated until the analysis is done.
The purpose of this study is to evaluate a method for the measurement of N,N-Dimethylformamide (DMF) and to apply the method to the ambient air samples. For the determination of DMF together with other general VOCs (e.g., benzene, toluene, and xylenes), adsorption sampling and thermal desorption with GC/MS was used in this study. The sampling and analytical approaches tested in this study showed a good repeatability and linearity with lower detection limits of less than 0.35 ppb. Field measurements were carried out at three industrial sites (Daegu-Seongseo, Siwha and Banwall industrial complexes) and one residential site in Daegu city during a period from October 2006 to November 2008. DMF was detected in 71.8% of the total samples from the Seongseo industrial complex, well known for textile industry. In contrast, DMF was detected in only 20.4% and 12.9% of all the samples from the other two sites in Banwall and Siwha industrial complexes, respectively. This implies that sources of DMF should be strongly associated with textile industry. The mean concentration of DMF also appeared to be the highest in Seongseo site (5.95 ppb), followed by a residential site in Daegu (3.28 ppb), Banwall (0.88 ppb) and Siwha (0.55 ppb). In this study, we demonstrated the environmental significance of DMF in urban ambient air. To our knowledge, the DMF measurement introduced in this paper is the first case of an official report in Korea.
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