Modeling the analytical response of optical fiber sensors for aromatic compounds determination

In recent years, there has been an increasing interest in the application of optical fiber sensors for in situ monitoring of chemical pollutants, including volatile organic compounds, regarding air quality assurance. In order to enhance the usefulness and applicability of this methodology to environmental analysis, a proper study of the analytical signal and an adequate calibration model are required. This contribution is focused on the model for optical fiber sensors calibration, discussing some problems associated with the estimates of the figures of merit of these analytical systems. We also suggest and discuss a calibration model based on a cumulative symmetric double sigmoidal (SDS) function, as a suitable and general alternative to the more limited and classical linear calibration model.     

Sampling and analysis of volatile organic compounds in bovine breath by solid-phase microextraction and gas chromatography-mass spectrometry

A relatively noninvasive method consisting of a face mask sampling device, solid-phase microextraction (SPME) fibers, and a gas chromatography-mass spectrometry (GC-MS) for the identification of volatile organic compounds (VOCs) in bovine breath was developed. Breath of three morbid steers with respiratory tract infections and three healthy steers were sampled seven times in 19 days for 15 min at each sampling. The breath VOCs adsorbed on the divinylbenzene (DVB)-Carboxen-polydimethyl siloxane (PDMS) 50/30 microm SPME fibers were transported to a laboratory GC-MS system for separation and identification with an in-house spectral library of standard chemicals. A total of 21 VOCs were detected, many of them for the first time in cattle breath. Statistical analyses using Chi-square test on the frequency of detection of each VOC in each group was performed. The presence of acetaldehyde (P < or = 0.05) and decanal (P < or = 0.10) were associated more with clinically morbid steers while methyl acetate, heptane, octanal, 2,3-butadione, hexanoic acid, and phenol were associated with healthy steers at P < or = 0.10. The results suggest that noninvasive heath screening using breath analyses could become a useful diagnostic tool for animals and humans.     

Determination of very volatile organic compounds in environmental water by injection of a large amount of headspace gas into a gas chromatograph

An injection method for a large amount of headspace gas which enables determination of trace amounts of very volatile organic compounds (VVOCs), dichlorodifluoromethane, chloromethane, vinyl chloride, bromomethane, chloroethane and trichlorofluoromethane in all kinds of environmental water was developed. A gas phase equilibrated with the water phase in a vial was purged with helium for a short time. The VVOCs were then introduced into a trapping tube packed with Tenax TA, which had been cooled using carbon dioxide. After trapping, the VVOCs were thermally desorbed and put into a GC–MS system for subsequent analysis. This method is applicable to various types of samples.     

Quartz crystal microbalance sensor array for the detection of volatile organic compounds

A sensor array system consisting of five quartz crystal microbalance (QCM) sensors (four for measuring and one for reference) and an artificial neural network (ANN) method is presented for on-line detection of volatile organic compounds. Three ionic liquids, 1-butyl-3-methylimidazolium chloride (C₄mimCl), 1-butyl-3-methylimidazolium hexafluorophosphate (C₄mimPF₆), 1-dedocyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (C₄mimNTf₂), and silicone oil II, which is widely used as gas chromatographic stationary phase, have been selected as sensitive coatings on the quartz surface allowing the sensor array effective to identify chemical vapors, such as toluene, ethanol, acetone and dichloromethane. The success rate for the qualitative recognition reached 100%. Quantitative analysis has also been investigated, within the concentration range of 0.6-6.1 mg/L for toluene, 0.9-7.5 mg/L for ethanol, 2.8-117 mg/L for dichloromethane, and 0.7-38 mg/L for acetone, with a prediction error lower than 8%.     

Development and validation of a solid-phase microextraction method for the analysis of volatile organic compounds in groundwater samples

Summary Solid-phase microextraction is a relatively recent extraction technique for sample preparation. It has been used successfully to analyse environmental pollutants in a variety of matrices such as soils, water and air. In this work, a simple and rapid method for the analysis of volatile organic and polar compounds from polluted groundwater samples by SPME coupled with gas chromatography (GC) is described. Different types of fibres were studied and the extraction process was optimised. The fibre that proved to be the best to analyse this kind of samples was CAR-PDMS. The method was validated by analysis of synthetic samples and comparison with headspace—GC. The optimised method was successfully applied to the analysis of ground-water samples.     

Monitoring the absorption of organic vapors to a solid phase extraction medium applications to detection of trace volatile organic compounds by integration of solid phase absorbents with fiber optic Raman spectroscopy

By combining fiber optic Raman spectroscopy with a C-18 solid phase extraction medium, real time in situ detection of organic vapors is demonstrated. The response of the probe is fully reversible for benzene, trichloroethylene and carbon tetrachloride vapors. Because of the high degree of selectivity afforded by Raman spectroscopy, the composition of mixtures of the vapors can also be determined using the C-18 probe. The detection of ppm levels of benzene in water via headspace analysis using the C-18 probe is demonstrated.     

System for the generation of standard gas mixtures of volatile and semi-volatile organic compounds for calibrations of solid-phase microextraction and other sampling devices

Standard gases are used for quality control and quality assurance, development of analysis methods and novel air sampling devices. The use of solid-phase microextraction (SPME) and other novel technologies for research in the area of air sampling and analysis requires systems/devices for reliable standard gas generation and sampling. In this paper we describe a new gas standard generating system for volatile organic compounds (VOCs) and semi-VOCs that was designed, built, and tested to facilitate fundamental and applications research with SPME. The system provided for the generation of a wide range of VOC/semi-VOC concentrations and mixing various standard gases, estimation of detection limits, testing the effects of sampling time, air temperature and relative humidity, testing the effects of air velocity and ozone on sampling/extractions. The system can be also used for calibrations of analytical instrumentation, quality control and quality assurance checks, and cross-validations of SPME with/and other sampling techniques.     

Improvement of HS-SPME for analysis of volatile organic compounds (VOC) in water samples by simultaneous direct fiber cooling and freezing of analyte solution

The sensitivity and precision of headspace solid-phase micro extraction (HS-SPME) at an analyte solution temperature (T _as) of +35 °C and a fiber temperature (T _fiber) of +5 °C were compared with those for HS-SPME at T _as and T _fiber of −20 °C for analysis of the volatile organic compounds benzene, 1,1,1-trichloroethane, trichloroethylene, toluene, o-xylene, ethylbenzene, m/p-xylene, and tetrachloroethylene in water samples. The effect of simultaneous fiber cooling and analyte solution freezing during extraction was studied. The compounds are of different hydrophobicity, with octanol/water partition coefficients (Kow) ranging from 126 and 2511. During a first set of experiments the polydimethylsiloxane (PDMS) SPME fiber was cooled to +5 °C with simultaneous heating of the aqueous analyte solution to +35 °C. During a second set of experiments, both SPME fiber holder and samples were placed in a deep freezer maintained at −20 °C for a total extraction time of 30 min. After approximately 2 min the analyte solution in the vial began to freeze from the side inwards and from the bottom upwards. After approximately 30 min the solution was completely frozen. Analysis of VOC was performed by coupling HS-SPME to gas chromatography-mass spectrometry (GC-MS). In general, i.e. except for tetrachloroethylene, the sensitivity of HS-SPME increased with increasing compound hydrophobicity at both analyte solution and fiber temperatures. At T _as of +35 °C and T _fiber of +5 °C detection limits of HS-SPME were 0.5 μg L⁻¹ for benzene, 1,1,1-trichloroethane, trichloroethylene, and tetrachloroethylene, 0.125 μg L⁻¹ for toluene, and 0.025 μg L⁻¹ for ethylbenzene, m/p-xylene, and o-xylene. In the experiments with T _as and T _fiber of −20 °C, detection limits were reduced for compounds of low hydrophobicity (Kow<501), for example benzene, toluene, 1,1,1-trichloroethane, and trichloroethylene. In the concentration range 0.5–62.5 μg L⁻¹, the sensitivity of HS-SPME was enhanced by a factor of approximately two for all compounds by performing the extraction at −20 °C. A possible explanation is that freezing of the water sample results in higher concentration of the target compounds in the residual liquid phase and gas phase (freezing-out), combined with enhanced adsorption of the compounds by the cooled fiber. The precision of HS-SPME, expressed as the relative standard deviation and the linearity of the regression lines, is increased for more hydrophobic compounds (Kow>501) by simultaneous direct fiber cooling and freezing of analyte solution. Background contamination during analysis is reduced significantly by avoiding the use of organic solvents.     

Enhancement of the detection sensitivity for volatile organic compounds by using an annular type photoionization detector and a pre-concentration system

Photoionization detector (PID) was developed for a sensitive on-site detection of trace amounts of volatile organic compounds (VOCs) based on an annular type ion collection electrode assembly. An ion collector with an annular geometry could detect more stable ion signals in the PID system when compared to the other types of ion collectors when an UV lamp of 10.6 eV was used as an ionization source. In order to enhance the detection sensitivity, a pre-concentration system, which was developed by adopting a ceramic heater packed with rod shaped molecular sieves, was adopted for a detection of VOCs. The adopted ceramic heaters had a resistance of 10-20 Ohm, and the temperature of the heater was optimized by controlling the heating time of the resistor. The enhancement of the detection sensitivity was found to be 8-10 times with the PID system when compared to the signals measured without a pre-concentrator. The overall detection sensitivity of the developed PID system was estimated as 10 ppb or better.     

A passive sampling-based analytical strategy for the determination of volatile organic compounds in the air of working areas

An analytical methodology based on the use of a polyethylene layflat tube filled with activated carbon and Florisil (ACFL-VERAM) was employed for the passive sampling of volatile organic compounds (VOCs) in the air of working areas of packing industries. VOCs amount in the ACFL-VERAM sampler was directly determined through head-space-gas chromatography-mass spectrometry (HS-GC-MS) allowing a direct determination in only 20 min without the need of any previous treatment. Uptake parameters, like sampling rate (R_S) and sampler-air partition coefficient (K_SA), were determined for every studied VOC from adsorption isotherm data. Additionally, experimental equations have been proposed to predict R_S and K_SA from the octanol-air partition coefficients reported in the literature. The proposed methodology reaches method detection levels from 0.007 to 0.2 mg m⁻³ for the studied VOCs.     

Application of solid-phase microextraction to the analysis of volatile compounds in virgin olive oils

Solid-phase microextraction was used as a technique for headspace sampling of extra virgin olive oil and virgin olive oil samples with different off-flavours. A 100 microm coated polydimethylsiloxane fiber was used to extract volatile aldehydes, the sampling temperature was 45 degrees C and the fiber has been exposed to the headspace for 15 min. Nonanal and 2-decenal were present in all the olive oils with extraction off-flavours but were not in extra virgin olive oil sample.     

Sampling and determination of volatile organic compounds with needle trap devices

In this study, a sorbent was immobilized inside a needle resulting in the development of a needle trap (NT) device. This device was applied to extract organic components from gaseous samples and to introduce an enriched mixture into a conventional gas chromatography (GC) injector. Construction of this simple and integrated sampling/extraction/sample introduction device was optimized by considering different ways to immobilize a sorbent in the needle, packing single and multiple-layer sorbent beds, and applying different desorption strategies into the GC injector. A carrier gas system was modified to minimize the carryover for the needle trap with a sealed tip (NT-1), and a narrow-neckliner was used for the blunt-tip needle trap (NT-2). Breakthrough in the device was investigated by connecting two NT-2 devices in series. The needle trap performed very well as an exhaustive spot sampler, as well as in a time-weighted average (TWA) operation. The linear velocity of the mobile phase has no influence on the sampling rate of the needle trap. Validation results against the standard NIOSH 1501 method using charcoal tubes for indoor air surveys demonstrated good accuracy for the NT approach. The reproducibility of the NT-2 was about 1% for benzene. The detection limits for FID detection and for 25 ml gas sample were 0.23 ng/l, 2.10 ng/l and 1.12 ng/l for benzene, ethylbenzene and o-xylene, respectively.     

Limits of separation of a multi-capillary column with mixtures of volatile organic compounds for a flame ionization detector and a differential mobility detector

The resolving power of a multi-capillary column (MCC) was evaluated using 14 mixtures of volatile organic compounds with known composition and complexity which was incremented stepwise up to 129 constituents. The number of constituents in these mixtures versus the number of components separated and detected with a flame ionization detector showed a proportional rise, with a decreasing slope, to 76 peaks after which a plateau was reached. This was improved 23.7% to 94 constituents, or 73% of all compounds in the mixture, after simplex optimization of carrier gas linear velocity, initial temperature and program rate. When the detection method was differential mobility spectrometry (DMS), additional selectivity was introduced through ion formation and separation. Fifty nine compounds were detected by DMS and 46 were separated by retention time; 13 were co-eluted and 7 of these were resolved by differential ion mobility (90% of all components ionized). A correlation of −0.412 between retention time for gas chromatography (GC) and differential mobility for DMS suggested a significant level of orthogonal character and the method of GC–DMS should not be seen as sequential only.     

Electrical sensing of volatile organic compounds in exhaled breath for disease diagnosis

In recent years, electrical sensors toward breath volatolomics have attracted increasing interest owing to their wide feasibility in noninvasive disease diagnostics. In this article, the working principles of active nanomaterials (e.g. metal oxides, polymers, and nanocarbon) toward volatile organic compounds are presented, with a special focus on the influence of surface chemistry and structural feature of these nanomaterials on the sensing performance. The latest and representative achievements on the direct analysis of three typical exhaled volatile organic compounds, including acetone, ammonia, and hydrogen sulfide, that are recognized as important disease biomarkers, are highlighted, indicating the capability of the electrical sensors in enabling noninvasive diagnosis and real-time monitoring. The opportunities and challenges in this field are provided in the end, with an emphasis on the background interference and data recognition which are key factors in developing prospective electrical sensors toward volatolomics analysis.     

呼气中痕量挥发性有机物的质子转移反应质谱在线检测研究

通过对自主研制的大气成分在线检测质子转移反应质谱的进样管路系统进行改造,建立了可在线检测呼气中痕量挥发性有机物的质子转移反应质谱装置。通过对呼气进样系统的旁路流量控制,实现对进样速度的调控,既可提高进样速度,以满足实时监测呼气中指定成分浓度变化;也可适时关闭旁路,以降低进样速度,从而对呼气成分进行全谱分析,避免采样袋采样和浓缩的复杂程序和潜在干扰。以作者呼出气体作为研究对象,对装置性能进行测试,结果表明:装置最快响应时间可达1s,对呼气中丙酮的探测灵敏度高达每10-9(V/V)浓度的信号强度为14.6counts/s,多次呼气测量重复性好,有望广泛应用于呼气疾病诊断研究。     

Differentiating a diverse range of volatile organic compounds with polyfluorophore sensors built on a DNA scaffold

Oligodeoxyfluorosides (ODFs) are short DNA-like oligomers in which DNA bases are replaced with fluorophores. A preliminary study reported that some sequences of ODFs were able to respond to a few organic small molecules in the vapor phase, giving a change in fluorescence. Here, we follow up on this finding by investigating a larger range of volatile organic analytes, and a considerably larger set of sensors. A library of tetramer ODFs of 2401 different sequences was prepared by using combinatorial methods, and was screened in air for fluorescence responses to a set of ten different volatile organics, including multiple aromatic and aliphatic compounds, acids and bases, varied functional groups, and closely related structures. Nineteen responding sensors were selected and characterized. These sensors were cross-screened against all ten analytes, and responses were measured qualitatively (by changes in color and intensity) and quantitatively (by measuring ΔR, ΔG, and ΔB values averaged over five to six sensor beads; R=red, G=green, B=blue). The results show that sensor responses were diverse, with a single sensor responding differently to as many as eight of the ten analytes; multiple classes of responses were seen, including quenching, lighting-up, and varied shifts in wavelength. Responses were strong, with raw ΔR, ΔG, and ΔB values of as high as >200 on a 256-unit scale and unamplified changes in many cases apparent to the naked eye. Sensors were identified that could distinguish clearly between even very closely related compounds such as acrolein and acrylonitrile. Statistical methods were applied to select a small set of four sensors that, as a pattern response, could distinguish between all ten analytes with high confidence. Sequence analysis of the full set of sensors suggested that sequence/order of the monomer components, and not merely composition, was highly important in the responses.     

Full-range analysis of ambient volatile organic compounds by a new trapping method and gas chromatography/mass spectrometry

This study investigated the feasibility of analyzing a full range of ambient volatile organic compounds (VOCs) from C(3) to C(12) using gas chromatograph mass spectrometry (GC/MS) coupled with thermal desorption. Two columns were used: a PLOT column separated compounds lighter than C(6) and a DB-1 column separated C(6)-C(12) compounds. An innovative heart-cut technique based on the Deans switch was configured to combine the two column outflows at the ends of the columns before entering the MS. To prevent the resolved peaks from re-converging after combining, two techniques were attempted (hold-up vs. back-flush) to achieve the intended "delayed" elution of heavier components. Thus, the resulting chromatogram covering the full range of VOCs is a combination of two separate elutions, with the heavier section following the lighter section. With the hold-up method, band-broadening inevitably occurred for the delayed C(6)-C(7) DB-1 compounds while the light compounds eluted from the PLOT column. This broadening problem resulted in peak tailing that was largely alleviated by adding a re-focusing stage while the DB-1 compounds were back-flushed, and this modified technique is referred to as the back-flush method. With this modification, the separation of the C(6)-C(7) compounds improved dramatically, as revealed by the decrease in peak asymmetry (As) and increase in resolution. Linearity and precision for these peaks also improved, yielding R(2) and RSD values better than 0.9990 and 2.8%, respectively.     

Static headspace analysis of volatile organic compounds in soil and vegetation samples for site characterization

Traditional methodologies for the characterization of volatile organic compounds (VOCs) in subsurface soil are expensive, time-consuming processes that are often conducted on samples collected at random. The determination of VOCs in near-surface soils and vegetation is the foundation for a more efficient sampling strategy to characterize subsurface soil and improve understanding of environmental problems.In the absence of a standard methodology for the determination of VOCs in vegetation and in view of the high detection limits of the method for soils, we developed a methodology using headspace gas chromatography with an electron capture detector for the determination of low levels (parts-per-billion to parts-per-trillion) of VOCs in soils and vegetation. The technique demonstrates good sensitivity, good recoveries of internal standards and surrogate compounds, good performance, and minimal waste. A case study involving application of this technique as a first-step vadose-zone characterization methodology is presented.