An infrared evanescent wave sensing system coupled with a hollow fiber membrane for detection of volatile organic compounds in aqueous solutions.

We have developed an on-line sensing method for the detection of volatile organic compounds (VOCs) in contaminated aqueous solutions by combining a microporous hollow fiber membrane with an infrared (IR) sensing system. Polypropylene microporous hollow fibers were used to separate the VOCs from the aqueous solution into the hollow fibers, which were purged countercurrently for detection by the IR sensing systems. An evanescent-wave-type IR sensing system was used to detect the VOCs that were purged from the hollow fibers. The sensing element was coated with polyisobutylene (PIB) to concentrate the VOCs for their detection. To study the performance of this system, we examined a number of factors, such as the purging flow rate, the sample flow rate, and the volatilities of the VOCs. The results indicate that an increase in the purging flow rate reduces the analytical signal significantly, especially for purging flow rates >2 mL/min. The pumping flow rate for the aqueous sample also influenced the analytical signals, but far less sensitively. The volatilities of the examined compounds also affected the analytical signals: the higher the volatility of the compound, the lower the intensity of the analytical signals and the shorter the time required to reach the equilibrium signal. From an examination of the dynamic range of this proposed method, a regression coefficient >0.994 was obtained for concentrations below 250 mg/L, even under non-equilibrium conditions. The response time of the system was studied in an effort to examine the suitability of using this sensing method for automatic detection. The results indicate that new equilibrium conditions were established within 3 min for highly volatile compounds, which suggests that on-line monitoring of the levels of VOCs can be performed in the field.     

Cooled internal reflection element for infrared chemical sensing of volatile to semi-volatile organic compounds in the headspace of aqueous solutions

In this study, the cooling effect was applied to an evanescent wave type infrared (IR) chemical sensing method to effectively trap volatile organic compounds (VOCs), which have been absorbed in the hydrophobic film coated around the internal reflection element (IRE). The detection of VOCs in aqueous solutions was taken in the headspace of the aqueous solution. This method eliminates the long-term instability of hydrophobic film soaked in an aqueous solution and the potential spectral interference caused by the matrix of the aqueous solution. Thermal energy has been applied to the aqueous solution to assist in the evaporation of VOCs out of the aqueous matrix. By applying a cooling system to the IRE, the excess thermal energy can be removed leading to more stable IR signals. After examination of organic compounds with vapour pressure (P_v) ranging from 0.017 to 150 Torr, significant differences were found between IR signals from cooled and un-cooled systems. Because the thermal conductivity of the IRE used in IR detection is typically low; the efficiency in removing the thermal energy is limited. By heating the aqueous solutions to different temperatures, the IR signals showed that the sample temperature was limited to around 80 °C. The IR signal determination results for five different volatility organic compounds indicated that the optimal heating temperature was not necessary to match with the volatilities of organic compounds in cooling system. The linear regression coefficient (R²) of the standard curve for sample concentrations in the range 5-200 μg ml⁻¹ was generally higher than 0.991 and the detection limit was around a few hundred ng ml⁻¹, which was two to three times lower than that of un-cooled system.     

Gondola-shaped tetra-rhenium metallacycles modified evanescent wave infrared chemical sensors for selective determination of volatile organic compounds

Water-stable and cavity-contained rhenium metallacycles were synthesized, and their ability to selectively interact with volatile organic compounds (VOCs) systematically studied using attenuated total reflection infrared (ATR-IR) spectroscopy. Integrating the unique properties of rhenium metallacycles into optical sensing technologies significantly improves selectivity in detecting aromatic compounds. To explore the interaction of rhenium metallacycles with VOCs, the surface of ATR sensing elements was modified with the synthesized rhenium metallacycles and used to detect VOCs. The results indicate that rhenium metallacycles have crown ether-like recognition sites, which can selectively interact with aromatic compounds, especially those bearing polar functional groups. The IR absorption bands of rhenium metallacycles shift significantly upon adsorption of aromatic VOCs, revealing a strong interaction between the tetra-rhenium metallacycles and guest aromatic compounds. Optimizing the thickness of the metallacycles coated on the surface of the sensing element led to rapid response in detection. The dynamic range of response was generally up to 30 mg/L with detection limits ca. 30 μg/L. Further studies of the effect of interferences indicate that recovery can be higher than 95% for most of the compounds tested. The results on the flow-cell device indicated that the performances were similar to a static detection system but the detection of VOCs can be largely simplified.     

On-line flow injection analysis of volatile organic compounds in seawater by membrane introduction mass spectrometry

The combination of flow injection analysis with membrane introduction mass spectrometry for analysis of volatile organic compounds (VOCs) in seawater is examined and is compared to measurements made in water. Membrane introduction mass spectrometry is performed using a benchtop ion trap mass spectrometer, and characterization of various aspects of the flow injection and ion trap combination for the analysis of volatile organic compounds (including anthropogenic halocarbons) in seawater is carried out. The analyte responses are shown to be linear over several orders of magnitude (e.g. for methylene chloride), independent of seawater pH (e.g. for chlorobenzene) and independent of matrix effects for the VOCs studied. A comparison of the performance of a microporous (Teflon) membrane with that of an amorphous silicone membrane is made, and the former is shown to provide lower detection limits which are in the parts-per-trillion range (300 ppt for chlorobenzene, 190 ppt for trans-1,2-dichloroethene). The microporous membrane provides faster response times by a factor of four to five for relatively more polar compounds, such as chlorobenzene. An analysis of a seven-component mixture demonstrates the ability of this on-line combination to allow multicomponent analysis of mixtures of some complexity.     

Determination of volatile organic compounds in contaminated air using semipermeable membrane devices

Semipermeable membrane devices (SPMDs) were evaluated as passive samplers for the determination of 26 volatile organic compounds (VOCs) in contaminated air of occupational environments. A direct methodology based on the use of head-space-gas chromatography-mass spectrometry (HS-GC-MS) was developed for VOCs determinations in SPMDs, without any sample pre-treatment and avoiding the use of solvents. A desorption temperature of 150 °C for 10 min was sufficient for a sensitive VOCs determination providing limits of detection in the range of 15 ng SPMD⁻¹ for 21 of 26 studied compounds. Linear and equilibrium uptake models were established for each VOC from compound isotherms. Highly volatile compounds were slightly absorbed and moderately volatile compounds were strongly absorbed by SPMDs. This study is the first precedent of the use of SPMDs for the simultaneous sampling of a wide number of VOCs. The use of SPMDs is a simple and low cost alternative to ordinary sampling devices such as Radiello^® diffusive samplers or badge-type solid-phase supports.     

Optical waveguide sensor of volatile organic compounds based on PTA thin film

In this study, a sensitive optical waveguide (OWG) sensor for the detection and identification of volatile organic compounds (VOCs) was reported. The sensing membrane is constructed by immobilization of peroxopolytungsten acid (PTA) thin film over a single-mode potassium ion (K⁺) exchanged glass OWG by spin-coating method. A laser beam was coupled into and out of the glass optical waveguide using prism couplers, and dry air functioned as a carrier gas. The sensor was tested for various volatile organic compounds (VOCs), and it showed higher response to the chlorobenzene gas compared to other VOCs. Therefore, we used the OWG sensor to detect chlorobenzene gas as a typical example of VOCs. The sensor exhibits a linear response to chlorobenzene gas in the range of 0.4-1000 ppm with rapid response and good reversibility. The constructed sensor is easy to fabricate and it has some unique qualities which can be characterized as inexpensive, sensitive, and reusable.     

Cyclodextrin Polymer Films Optical Waveguide Sensor for Volatile Organic Gas Detection

A sensitive optical waveguide(OWG) sensor which can be used to detect volatile organic compounds(VOCs) was presented. The sensing device(element) was fabricated by means of the immobilization of polyvinyl pyrrolidone(PVP)-cyclodextrin(CD) composite film over a single-mode potassium ion exchanged glass OWG via spin-coating method. The sensor shows higher response to styrene gas than to other VOCs and displays a linear response to styrene gas in a range of 1-1000 μL/L.     

Simple sample transfer technique by internally expanded desorptive flow for needle trap devices

Needle trap devices (NTDs) are improving in simplicity and usefulness for sampling volatile organic compounds (VOCs) since their first introduction in early 2000s. Three different sample transfer methods have been reported for NTDs to date. All methods use thermal desorption and simultaneously provide desorptive flow to transfer desorbed VOCs into a GC separation column. For NTDs having 'side holes', GC carrier gas enters a 'side hole' and passes through sorbent particles to carry desorbed VOCs, while for NTD not having a 'side hole', clean air as desorptive flow can be provided through a needle head by a air tight syringe to sweep out desorbed VOCs or water vapor has been reported recently to be used as desorptive flow. We report here a new simple sample transfer technique for NTDs, in which no side holes and an external desorptive flow are required. When an NTD enriched by a mixture of benzene, toluene, ethylbenzene, and xylene (BTEX) or n-alkane mixture (C6-C15) is exposed to the hot zone of GC injector, the expanding air above the packed sorbent transfers the desorbed compounds from the sorbent to the GC column. This internal air expansion results in clean and sharp desorption profiles for BTEX and n-alkane mixture with no carryover. The effect of desorption temperature, desorption time, and overhead volumes was studied. Decane having vapor pressure of approximately 1 Torr at 20 degrees C showed approximately 1% carryover at the moderate thermal desorption condition (0.5 min at 250 degrees C).     

室内空气中挥发性有机化合物污染及检测方法

室内空气中挥发性有机污染物的释放严重影响了室内空气质量,本文较详细的叙述了这些有机污染物的来源、种类及处理方法等,并对空气中VOCs的采集和检测方法作以介绍,阐述了不同机制的热解吸仪与气相色谱联用时的优缺点及其应用．     

热脱附-气相色谱-质谱法应用于工业源废气中挥发性有机物的目标和非目标筛查

建立了固相吸附热脱附-气相色谱-质谱(TD-GC-MS)综合筛查工业源废气中挥发性有机物(VOCs)的方法。对两种型号的固相吸附管进行了比较,最终选择使用Tenax SS TD Tubes吸附管。气体样品以恒定流速通过吸附管,富集分析物,经热脱附后,用GC-MS进行检测,目标化合物以内标法定量,非目标化合物的含量以甲苯的响应系数计算。方法检出限为1.06~5.44 ng,以采样体积300 mL计算,目标化合物的检出限为0.004~0.018 mg/m~3。吸附管平均加标回收率为78.4%~89.4%,相对标准偏差为3.9%~14.4%(n=7)。应用该方法对大连市某垃圾焚烧发电厂排放的废气进行VOCs目标及非目标化合物综合筛查,共检出29种VOCs,其中仅5种VOCs为预先设定的目标化合物,另外24种为非目标化合物,5种目标化合物含量仅占所有检出物总量的26.7%。证明了工业源废气VOCs分析中非目标化合物筛查的重要性,该研究思路对完整测定工业源挥发性有机污染物分布具有一定的借鉴意义。     

Determination of volatile organic compounds in recycled polyethylene terephthalate and high-density polyethylene by headspace solid phase microextraction gas chromatography mass spectrometry to evaluate the efficiency of recycling processes

A method for the determination of volatile organic compounds (VOCs) in recycled polyethylene terephthalate and high-density polyethylene using headspace sampling by solid-phase microextraction and gas chromatography coupled to mass spectrometry detection is presented. This method was used to evaluate the efficiency of cleaning processes for VOC removal from recycled PET. In addition, the method was also employed to evaluate the level of VOC contamination in multilayer packaging material containing recycled HDPE material. The optimisation of the extraction procedure for volatile compounds was performed and the best extraction conditions were found using a 75 μm carboxen-polydimethylsiloxane (CAR-PDMS) fibre for 20 min at 60 °C. The validation parameters for the established method were linear range, linearity, sensitivity, precision (repeatability), accuracy (recovery) and detection and quantification limits. The results indicated that the method could easily be used in quality control for the production of recycled PET and HDPE.     

Reduction of concentration polarization in pervaporation using vibrating membrane module

A vibrating membrane module currently marketed for filtration applications was evaluated for the separation of volatile organic compounds (VOCs) from aqueous solutions by pervaporation. Preliminary screening experiments with three VOCs, three silicone membranes, and in the presence and absence of a surfactant were performed to determine if further consideration of the vibrating module for a field demonstration project was warranted. The primary process variables studied were vibrational amplitude and liquid flow rate. The vibrations greatly reduced concentration polarization in the system as inferred from an order of magnitude increase in the overall mass transport coefficient. Mass transfer coefficients for the vibrating module compared favorably with those for traditional spiral wound modules.     

Colorimetric Artificial Nose for Identification of Breath Volatile Organic Compounds of Patients with Lung Cancer

A novel and highly sensitive colorimetric sensor array was developed for the detection and identification of breath volatile organic compounds（VOCs） of patients with lung cancer.Employing dimeric metalloporphyrins,metallosalphen complexes,and chemically responsive dyes as the sensing elements,the developed sensor array of artificial nose shows a unique pattern of colorific changes upon its exposure to eight less-reactive VOCs and their mixture gas at a concentration of 735 nmol/L within 3 min.Potential of quantitative analysis of VOCs samples was proved.A good linear relationship of 490-3675 nmol/L was obtained for benzene vapor with a detection limit of 49 nmol/L（S/N=3）.Data analysis was carried out by Hierarchical cluster analysis（HCA） and principal component analysis（PCA）.Each category of breath VOCs clusters together in the PCA score plot.No errors in classification by HCA were observed in 45 trials.Additionaly,the colorimetric sensor array showed good reproducibility under the cyclic sensing experiments.These results demonstrate that the developed colorimetric artificial nose system is an excellent sensing platform for the identification and quantitative analysis of breath VOCs of patients with lung cancer.     

Environmental applications of membrane introduction mass spectrometry

The purpose of this review is to highlight the versatility of membrane introduction mass spectrometry (MIMS) in environmental applications, summarize the measurements of environmental volatile organic compounds (VOCs) accomplished using MIMS, present developments in the detection of semi-volatile organic compounds (SVOCs) and forecast possible future directions of MIMS in environmental applications.     

Preparation of ZnO Nanowires and Study of Surface‐adsorbate Interaction by Fourier‐Transform Infrared Spectroscopy

To study the surface‐adsorbate properties of ZnO nanowires, a hydrothermal method was modified to grow ZnO nanowires directly on ZnSe, which were then characterized by attenuated total reflection infrared (ATR‐IR) spectroscopy. To prepare ZnO nanowires directly on ATR sensing element of ZnSe, ZnO seed layers were first formed by annealing of ZnO seeds on ZnSe surfaces. The ZnO seed layers then were exposed to growth solution, forming ZnO nanowires directly on the ATR crystals. The interaction properties of the resulting surfaces were studied by an ATR‐IR method. The diameter, length and distribution of the ZnO nanowires can be tuned by adjusting the growth conditions, particularly the growing time and the concentrations of reagents. Two surfaces, namely Zn‐rich and Zn‐O ion‐pair surfaces were studied in detail for their adsorption properties toward compounds bearing different functional groups. By examination of several volatile organic compounds (VOCs), it was found that the Zn‐rich surface is less selective and interacts with compounds bearing the functional groups of amino and hydroxyl. The Zn‐O ion‐pair surface is more selective and a much stronger interaction was observed with non‐aromatic amino compounds. These results indicate that the improving of the selectivity of a ZnO‐based sensing device can be achieved by tuning the surface structure of the ZnO nanomaterials.     

Characterization of a mini membrane inlet mass spectrometer for on-site detection of contaminants in both aqueous and liquid organic samples

A mini membrane inlet mass spectrometer (mini-MIMS) of a total weight of 12 kg was constructed using a miniature Multipole mass spectrometer, a small vacuum system and a flexible flat sheet membrane inlet, where the exposed membrane area can be changed by a factor of 80. The variable membrane area together with the possibility of operating the Multipole at pressures up to 1 x 10(-3) Torr made it possible to test the system with three microporous membranes (cellulose, polyether sulfone and polypropylene) normally not compatible with standard electron ionization MIMS systems and a standard non-porous polydimethylsiloxane membrane. We found that the hydrophilic cellulose and polyether sulfone membranes had selectivity characteristics opposite to those of the standard silicone membrane. They demonstrated preferential detection of hydrophilic compounds in hydrophobic organic solvents, whereas the silicone membrane preferentially detects hydrophobic organic compounds in aqueous solution. Using the cellulose membrane, organic contaminants and water could be detected in organic solvents at 10-100 ppm levels by weight, the relative high detection limits primarily caused by interference from a high chemical background from the solvent. When being used with the standard silicone membrane the mini-MIMS behaved just like most standard MIMS systems with detection limits of volatile organic compounds in water at concentrations just below 1 ppm. The hydrophobic microporous polypropylene membrane was not found to be useful with the mini-MIMS.     

Utilization of a multimembrane inlet and a cyclic sudden sampling introduction mode in membrane inlet mass spectrometry

Sudden sampling introduction into a membrane inlet mass spectrometer (MIMS) considerably improves the selectivity of the membrane inlet and is therefore applicable even for compounds with low permeabilities through a silicone membrane. In this study the basics of cyclic non-steady-state sudden increase sample injection were studied using a three-membrane inlet and a portable sector double-focusing mass spectrometer. The operational parameters of the inlet system providing the most efficient enrichment of volatile organic compounds (VOCs) in air were defined. Simulation of the diffusion process following sudden sample introduction into the three-membrane inlet was also carried out. Experimental testing of the three-membrane inlet system with the cyclic sudden sample injection mode for benzene, toluene, styrene, and xylene in air was performed. The simulation and the experimental results demonstrated that, when this mode is used, the VOCs/nitrogen relative enrichment factor of samples introduced into the mass spectrometer equipped with a three-membrane inlet is increased by a factor of approximately 10(5) compared with a direct introduction method. This effect may be used to decrease detection limits of compounds obtained with mass spectrometry to decrease matrix flow through the inlet at the same detection limits.     

Liquid crystal nose,chiral case: towards increased selectivity and low detection limits

In this paper, we describe a simple prototype of an olfaction system based on chiral liquid crystals (LCs) and suitable for sensing volatile organic compounds (VOCs). The detection of small concentrations of VOCs is based on measuring weak colour fluctuations on the surface of the LC droplet. Detection of larger concentrations is based on measuring colour changes (or shift of the selective reflection band) and isotropisation transition of the whole droplet. Thus, a broad range of VOC concentrations can be detected by this LC nose.     

Sampling and characterisation of volatile organic compound profiles in human saliva using a polydimethylsiloxane coupon placed within the oral cavity

Evaluation of published methods reveals that existing methods for saliva sampling do not address the physical-chemical attributes of volatile organic compounds (VOCs). This study describes and presents evidence for adopting in situ sampling of salivary VOCs directly from the oral cavity using a polydimethylsiloxane (PDMS) based sampler. In vitro studies indicated that the vapour pressure of analytes was a factor in both the recovery of analytes and the precision of the recovery. The highest recoveries were observed for VOCs with the lowest vapour pressures, for example 5-nonanol (vapour pressure (P(v)) = 14 Pa) recoveries were approximately 20 times greater than those observed for octane (P(v) = 1726 Pa). Similarly, relative standard deviations reduced with vapour pressure, with the RSD for 5-nonanol responses observed to be 2.7% when compared to RSD = 26% for octane. Evaluation of VOCs recovered from 6 in vivo samples indicated that VOC concentrations in saliva may follow log-normal distributions; log-normal RSDs falling between 4.4% and 18.2% across the range of volatilities encountered. Increasing sampling time from 1 to 30 minutes indicated that the recovery of VOC into the sampler was affected by interaction between different physical-chemical properties and biogenic flux. A sampling time of 10 min was found to offer an acceptable compromise that enabled a representative sample to be acquired for the widest range of observed VOC behaviours with the sampler. The potential to 'tune' the sampling protocol for targeted analysis based on these factors was also noted. Comparison with passive drool saliva collection revealed up to 10(5) enhancement with reduced variability compared to drooled samples. This approach to in situ saliva sampling appears to have significant analytical utility for studying volatile signatures in humans.     

便携式气相色谱-质谱仪测定空气中挥发性有机污染物的准确性

便携式气相色谱-质谱仪(便携式GC-MS)能同时对多组分复杂有机物进行定性定量分析,在环境监测尤其是事故现场应急监测中发挥越来越重要的作用。本文比较了便携式GC-MS与EPATO-14A方法分析测定环境空气中低浓度挥发性有机物(VOCs)的性能,并探讨了利用定量环(loop环)模式测定高浓度VOCs的准确度。结果表明,采用内标标准曲线定量,HAPSITE便携式GC-MS测定空气中VOCs的检出限与EPATO-14A方法相当,准确度和精密度略低,但均符合环境监测分析的要求。利用loop环可对大部分10-6级的高浓度VOCs样品进行较为准确的测定,在突发性环境污染事故中可以得到基本准确的结果。