Sensitive and selective system of benzene detection based on a cataluminescence sensor

Au/La₂O₃ nanomaterials were prepared through calcining Au‐modified La(OH)₃ precursors. Scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X‐ray diffractometry (XRD) were employed to characterize the as‐prepared samples. Benzene, a common volatile organic compound, was selected as a model to investigate the cataluminescence (CTL)‐sensing properties of the Au/La₂O₃ nanomaterials. Results indicated that the as‐prepared Au/La₂O₃ exhibited outstanding CTL properties such as stable intensity, high signal‐to‐noise values, and short response and recovery times. Under optimized conditions, the benzene assay exhibited a broad linear range of 1–4000 ppm, with a limit of detection of 0.7 ppm, which was below the standard permitted concentrations. Furthermore, the gas sensor system showed outstanding selectivity for benzene compared with seven other types of common volatile organic compounds (VOCs). The proposed gas sensor showed good characteristics with high selectivity, fast response time and long lifetime, which suggested the promising application of the Au/La₂O₃ nanomaterials as a novel highly efficient CTL‐sensing material. Copyright © 2013 John Wiley & Sons, Ltd.     

Detection of volatile organic compounds released by wood furniture based on a cataluminescence test system

Wood furniture is an important source of indoor air pollution. To date, the detection of harmful substances in wood furniture has relied on the control of a single formaldehyde component, therefore the detection and evaluation of pollutants released by wood furniture are necessary. A novel method based on a cataluminescence (CTL) sensor system generated on the surface of nano‐3TiO₂–2BiVO₄ was proposed for the simultaneous detection of pollutants released by wood furniture. Formaldehyde and benzene were selected as a model to investigate the CTL‐sensing properties of the sensor system. Field emission scanning electronic microscopy (FESEM), transmission electron microscopy (TEM) and X‐ray diffraction (XRD) were employed to characterize the as‐prepared samples. The results showed that the as‐prepared test system exhibited outstanding CTL properties such as stable intensity, a high signal‐to‐noise ratio, and short response and recovery times. In addition, the limit of detection for formaldehyde and benzene was below the standard permitted concentrations. Moreover, the sensor system showed outstanding selectivity for formaldehyde and benzene compared with eight other common volatile organic compounds (VOCs). The performance of the sensor system will enable furniture VOC limit emissions standards to be promulgated as soon as possible. Copyright © 2015 John Wiley & Sons, Ltd.     

A portable gas sensor based on cataluminescence

We describe a portable gas sensor based on cataluminescence. Miniaturization of the gas sensor was achieved by using a miniature photomultiplier tube, a miniature gas pump and a simple light seal. The signal to noise ratio (SNR) was considered as the evaluation criteria for the design and testing of the sensor. The main source of noise was from thermal background. Optimal working temperature and flow rate were determined experimentally from the viewpoint of improvement in SNR. A series of parameters related to analytical performance was estimated. The limitation of detection of the sensor was 7 ppm (SNR = 3) for ethanol and 10 ppm (SNR = 3) for hydrogen sulphide. Zirconia and barium carbonate were respectively selected as nano‐sized catalysts for ethanol and hydrogen sulphide. Copyright © 2012 John Wiley & Sons, Ltd.     

Development of highly sensitive sensor system for methane utilizing cataluminescence

A gaseous sensor system was developed for the detection of methane based on its cataluminescence emission. Cataluminescence characteristics and optimal conditions were studied in detail under optimized experimental conditions. Results showed that the methane cataluminescence sensor system could cover a linear detection range from 10 to 5800 ppm (R = 0.9963, n = 7) and the detection limit was about 7 ppm (S/N = 3), which was below the standard permitted concentration. Moreover, a linear discriminant analysis method was used to test the recognizable performance of the methane sensor. It was found that methane, ethane, propane and pentane could be distinguished clearly. Its methane sensing properties, including improved sensitivity, selectivity, stability and recognition demonstrated the TiO₂/SnO₂ materials to be promising candidates for constructing a cataluminescence‐based gas sensor that could be used for detecting explosive gas contaminants. Copyright © 2015 John Wiley & Sons, Ltd.     

Zeolite-based cataluminescence sensor for the selective detection of acetaldehyde.

The reactions of acetaldehyde with O atoms in the cages of large-pore zeolites have been discovered to result in light emission. The luminescence characteristics of acetaldehyde vapours passing through the surface of chosen zeolites were studied using a cataluminescence-based detection system. To demonstrate the feasibility of the method, the detection of acetaldehyde using catalysts was studied systematically and a linear response of 0.06-31.2 microg/mL acetaldehyde vapour was obtained. Methanol, ethanol, isopropanol, methylbenzene, chloroform, dichlormethane and acetonitrile did not interfere with the determination of acetaldehyde. Acetaldehyde vapour could also be distinguished from some homologous series such as formaldehyde, cinnamaldehyde, glutaraldehyde and benzaldehyde on this catalyst, possibly due to the stereoselectivity of the zeolite and its specific reaction mechanism. Moreover, acetaldehyde was quantified without detectable interference from formaldehyde in four artificial samples. Thus, this kind of cataluminescence-based sensor could be potentially extended to the analysis of volatile organic compounds in air, and the simple and portable properties of cataluminescence-based sensors could also make them beneficial in many areas of analytical science.     

An ethyl acetate sensor utilizing cataluminescence on Y2O3 nanoparticles

A cataluminescence (CTL) sensor using Y₂O₃ nanoparticles as the sensing materials was proposed for the determination of ethyl acetate. This ethyl acetate sensor showed high sensitivity and specificity at the optimal temperature of 264°C. Quantitative analysis was performed at a wavelength of 425 nm. The linear ranges of CTL intensity vs ethyl acetate concentrations were 2.0–250 ppm (r = 0.9965) and 250–6500 ppm (r = 0.9997) with a detection limit (3σ) of 0.5 ppm. There was no response or weak response when foreign substances such as formic acid, n‐hexane, toluene, acetic acid, benzene, and formaldehyde passing through the surface of Y₂O₃ nanoparticles. The sensor had a long lifetime more than 80 h with 3600 ppm ethyl acetate. It had been applied successfully to determine ethyl acetate in artificial air samples. Copyright © 2009 John Wiley & Sons, Ltd.     

A 1,2‐propylene oxide sensor utilizing cataluminescence on CeO2 nanoparticles

A simple and sensitive gas sensor was proposed for the determination of 1,2‐propylene oxide (PO) based on its cataluminescence (CTL) by oxidation in the air on the surface of CeO₂ nanoparticles. The luminescence characteristics and optimal conditions were investigated in detail. Under optimized conditions, the linear range of the CTL intensity versus the concentration of PO was 10–150 ppm, with a correlation coefficient (r) of 0.9974 and a limit of detection (S/N = 3) of 0.9 ppm. The relative standard deviation for 40 ppm PO was 1.2% (n = 7). There was no or only weak response to common foreign substances including acetone, formaldehyde, ethyl acetate, acetic acid, chloroform, propanol, carbon tetrachloride, ether and methanol. There was no significant change in the catalytic activity of the sensor for 100 h. The proposed method was simple and sensitive, with a potential of detecting PO in the environment and industry. Copyright © 2014 John Wiley & Sons, Ltd.     

Research on benzene,toluene and dimethylbenzene detection based on a cataluminescence sensor

We present a sensitive and quick way to determine benzene, toluene and dimethylbenzene (BTEX) in air, applying a cataluminescence (CTL) sensor based on a nano‐sized composite material, γ‐Al₂O₃/PtO₂. The factors that affect the sensor's performance were studied, including the sensing material, temperature, rate of air carrier and wavelength. It was shown that when Pt accounted for 0.2% of the sensing material, the rate of the air carrier that carries target gas was 450 mL/min, the determination wavelength was 400 nm and temperature was 236°C, this sensor showed the best CTL intensity to BTEX. In addition, the CTL intensity had a high linear relation with the concentration of BTEX, with a linear range from 0.5 to 100 mL/m³, and a detection limit 0.22 mL/m³. This nano‐sized material had a quick response within 1.5 s, short recovery time within 1 min and a long lifetime, showing good potential for a variety of applications. Copyright © 2013 John Wiley & Sons, Ltd.     

Development of a benzene vapour sensor utilizing chemiluminescence on Y2O3

Chemiluminescence (CL) was observed when benzene vapour passed through the surface of Y₂O₃, TiO₂, Y₂O₃–V₂O₅, TiO₂–Y₂O₃, Y₂O₃–Cr₂O₃, Y₂O₃–Al₂O₃ and TiO₂–Al₂O₃, with air as the carrier gas. The strongest CL intensity was found with Y₂O₃ as the catalyst. A novel benzene sensor based on this kind of CL was developed. Quantitative analysis was performed at the wavelength of 425 nm. Under optimal conditions, CL intensity was directly proportional to the concentration of benzene vapour. The linear range was 4–7018 mg/m³ (r = 0.9981, n = 11), with a detection limit of 1 mg/m³ (the signal:noise ratio was 3). This gas sensor can work continuously for >80 h and has been successfully applied to the real‐time determination of benzene vapour. Copyright © 2008 John Wiley & Sons, Ltd.     

A cataluminescence gas sensor for ammonium sulfide based on Fe3O4–carbon nanotubes composite

In the present work, Fe₃O₄–carbon nanotubes (CNTs) composite was explored as a sensing material candidate for ammonium sulfide. Intense chemiluminescence emission can be observed during the catalytic oxidation of ammonium sulfide on the surface of Fe₃O₄–CNTs composite. Based on this phenomenon, a selective and sensitive gas sensor for the determination of ammonium sulfide was demonstrated. Under the optimized conditions, the linear range of cataluminescence intensity vs concentration of ammonium sulfide gas was 1.4–115 µg mL^?1 (R = 0.998) with a limit of detection (S/N = 3) of 0.05 µg mL^?1. The relative standard deviation (n = 5) for 14.3 µg mL^?1 ammonium sulfide was 1.9%. There was no response to common foreign substances, such as sulfur dioxide, toluene, aether, ethanol, acetone, hydrogen sulfide, carbon bisulfide, benzene and ammonia. The proposed sensor was successfully applied for the determination of ammonium sulfide in artificial air samples. Copyright © 2009 John Wiley & Sons, Ltd.     

Detection of hydrogen sulphide using cataluminescence sensors based on alkaline-earth metal salts

Detection of hydrogen sulphide (H₂S) was conducted based on cataluminescence (CTL) sensors, using alkaline‐earth metal carbonates as catalysts. Optimal working conditions, analytical characteristics and the response properties of the sensor were investigated. CTL intensity examination showed that sensors fabricated with CaCO₃, SrCO₃ or BaCO₃ could be used to detect H₂S gas sensitively. The optimal sensing temperature was about 320 °C. Under the sensing conditions with temperature at ca. 320 °C and gas flow rate in the range 180–200 mL/min, the linear range of CTL intensity vs H₂S concentration was 25–500 ppm, with a detection limit of 2 ppm. The response and recovery times of the sensor were within 5 and 25 min, respectively. Also, the sensor had the property of high selectivity to H₂S with very weak or no obvious response to 14 other gases, such as NO₂, NH₃, hydrocarbons and alcohol. Copyright © 2011 John Wiley & Sons, Ltd.     

Sensitive and selective cataluminescence‐based sensor system for acetone and diethyl ether determination

A three‐dimensional hierarchical CdO nanostructure with a novel bio‐inspired morphology is reported. The field emission scanning electronic microscopy, transmission electron microscopy and X‐ray diffractometer were employed to characterize the as‐prepared samples. In gas‐sensing measurements, acetone and diethyl ether were employed as target gases to investigate cataluminescence (CTL) sensing properties of the CdO nanostructure. The results show that the as‐fabricated CdO nanostructure exhibited outstanding CTL properties such as stable intensity, high signal/noise values, short response and recovery time. The limit of detection of acetone and diethyl ether was ca. 6.5 ppm and 6.7 ppm, respectively, which was below the standard permitted concentrations. Additionally, a principal components analysis method was used to investigate the recognizable ability of the CTL sensor, and it was found that acetone and diethyl ether can be distinguished clearly. The performance of the bio‐inspired CdO nanostructure‐based sensor system suggested the promising application of the CdO nanostructure as a novel highly efficient CTL sensing material. Copyright © 2014 John Wiley & Sons, Ltd.     

A novel fluorescent sensor based on electrosynthesized benzene sulfonic acid‐doped polypyrrole for determination of Pb(II) and Cu(II)

To develop conducting organic polymers (COPs) as luminescent sensors for determination of toxic heavy metals, a new benzene sulfonic acid‐doped polypyrrole (PPy‐BSA) thin film was electrochemically prepared by cyclic voltammetry (CV) on flexible indium tin oxide (ITO) electrode in aqueous solution. PPy‐BSA film was characterized by FTIR spectrometry, X‐ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). The optical properties of PPy‐BSA were investigated by ultraviolet (UV)‐visible absorption and fluorescence spectrometry in dimethylsulfoxide (DMSO) diluted solutions. PPy‐BSA fluorescence spectra were strongly quenched upon increasing copper(II) ion (Cu²⁺) and lead(II) ion (Pb²⁺) concentrations in aqueous medium, and linear Stern–Volmer relationships were obtained, which indicated the existence of a main dynamic fluorescence quenching mechanism. BSA‐PPy sensor showed a high sensitivity for detection of both metallic ions, Cu²⁺ and Pb²⁺, with very low limit of detection values of 3.1 and 18.0 nM, respectively. The proposed quenching‐fluorimetric sensor might be applied to the determination of traces of toxic heavy metallic ions in water samples.     

A chiral,porous, organic cage‐based,enantioselective potentiometric sensor for 2‐aminobutanol

A new enantioselective potentiometric sensor containing R‐type chiral porous organic cage CC9 as the chiral selector was designed for the assay of 2‐aminobutanol. Optimized membrane electrodes displayed a linear dynamic range from 10⁻³ ~ 10⁻¹ mol·L⁻¹ with a detection limit of 2.5 × 10⁻⁴ mol·L⁻¹ and a Nernstian response of 27 ± 0.5mV·decade⁻¹ toward S‐2‐aminobutanol within the pH range 7.0–10.0. The potentiometric enantioselectivity coefficient ( ) of this sensor was −1.333, indicating that the porous organic cage‐based electrode exhibited good discrimination toward S‐2‐aminobutanol over R‐2‐aminobutanol.     

Optical sensory arrays for the detection of urinary bladder cancer‐related volatile organic compounds

Non‐invasive detection of urinary bladder cancer remains a significant challenge. Urinary volatile organic compounds (VOCs) are a promising alternative to cell‐based biomarkers. Herein, we demonstrate a novel diagnosis system based on an optic fluorescence sensor array for detecting urinary bladder cancer VOCs biomarkers. This study describes a fluorescence‐based VOCs sensor array detecting system in detail. The choice of VOCs for the initial part was based on an extensive systematic search of the literature and then followed up using urinary samples from patients with urinary bladder transitional cell carcinoma. Canonical discriminant analysis and partial least squares discriminant analysis (PLS‐DA) were employed and correctly detected 31/48 urinary bladder cancer VOC biomarkers and achieved an overall 77.75% sensitivity and 93.25% specificity by PLS‐DA modelling. All five urine samples from bladder cancer patients, and five healthy controls were successfully identified with the same sensor arrays. Overall, the experiments in this study describe a real‐time platform for non‐invasive bladder cancer diagnosis using fluorescence‐based gas‐sensor arrays. Pure VOCs and urine samples from the patients proved such a system to be promising; however, further research is required using a larger population sample.      

Comparison of two soil gas methods used during a field investigation

Soil gas surveys were employed to help determine the nature and extent of contamination resulting from the past operation of source area ST58, the Old Quartermaster Service Station, at Eielson Air Force Base, Alaska. Two Intrusive methods were used for comparison, active conventional gas extraction and the passive Petrex method. Results were comparable, with gasoline identified as the main subsurface contaminant In both surveys. Close spatial correlation was also achieved among screening instruments and laboratory analyses. Contaminant concentrations corresponded very well with unsealed blueprints showing the locations of the above‐ground storage tanks and associated piping, subsequent test pit soil samples, and excavation results. The contamination probably occurred as a result of surface spills and leaks from discontinuities and/or breaks in the underground piping. A finer grid was employed in the Petrex method survey and produced better‐resolved contours. The use of conventional gas extraction provided rapid results but was labor intensive. The Petrex method survey was less labor Intensive but required a longer turnaround time for analytical results. Costs for the two methods were nearly equal. Both methods appear appropriate for other shallow applications in unconsolidated materials where contamination is known to exist.     

A model of isoprene emission based on energetic requirements for isoprene synthesis and leaf photosynthetic properties for Liquidambar and Quercus

We present a physiological model of isoprene (2-methyl-1,3-butadiene) emission which considers the cost for isoprene synthesis, and the production of reductive equivalents in reactions of photosynthetic electron transport for Liquidambar styraciflua L. and for North American and European deciduous temperate Quercus species. In the model, we differentiate between leaf morphology (leaf dry mass per area, M_A, g m ^{? 2}) altering the content of enzymes of isoprene synthesis pathway per unit leaf area, and biochemical potentials of average leaf cells determining their capacity for isoprene emission. Isoprene emission rate per unit leaf area ( μ mol m ^{? 2} s ^{? 1}) is calculated as the product of M_A, the fraction of total electron flow used for isoprene synthesis ( ? , mol mol ^{? 1}), the rate of photosynthetic electron transport (J) per unit leaf dry mass (J_m, μ mol g ^{? 1} s ^{? 1}), and the reciprocal of the electron cost of isoprene synthesis [mol isoprene (mol electrons ^{? 1})]. The initial estimate of electron cost of isoprene synthesis is calculated according to the 1-deoxy- D -xylulose-5-phosphate pathway recently discovered in the chloroplasts, and is further modified to account for extra electron requirements because of photorespiration. The rate of photosynthetic electron transport is calculated by a process-based leaf photosynthesis model. A satisfactory fit to the light-dependence of isoprene emission is obtained using the light response curve of J, and a single value of ? , that is dependent on the isoprene synthase activity in the leaves. Temperature dependence of isoprene emission is obtained by combining the temperature response curves of photosynthetic electron transport, the shape of which is related to long-term temperature during leaf growth and development, and the specific activity of isoprene synthase, which is considered as essentially constant for all plants. The results of simulations demonstrate that the variety of temperature responses of isoprene emission observed within and among the species in previous studies may be explained by different optimum temperatures of J and/or limited maximum fraction of electrons used for isoprene synthesis. The model provides good fits to diurnal courses of field measurements of isoprene emission, and is also able to describe the changes in isoprene emission under stress conditions, for example, the decline in isoprene emission in water-stressed leaves.     

Biofiltration for the removal and ‘detoxification’ of a complex mixture of volatile organic compounds

A study was performed to determine the effectiveness of using biofiltration for the removal of a complex mixture of volatile organic compounds (VOCs) air-stripped from petroleum hydrocarbons. A biofilter was constructed which contained 264 cm³ of packing material (Celite^? R-635). The unit was inoculated with a mixed culture containing a hydrocarbon-degrading Pseudomonas sp and an Alcaligenes sp. Several of the major compounds in the VOC mixture were monitored individually, along with the total VOCs, using gas chromatography. The average influent concentration of the VOC mixture was 320 ppmv and the average total VOC removal rate was over 56%, with the average removal rate of the monitored individual compounds ranging from 49–90%. After 30 days of operation the average overall removal rate was 69% and the removal of the major compounds averaged 92%. The toxicity and mutagenicity of the air stream was monitored using the Microtox and Ames assays, respectively. These data show marked decreases in toxicity and mutagenicity of the air stream as a result of the biofiltration treatment. The biofiltration system, therefore, was not only effective in removing VOCs from the air stream over an extended time-period, but was also effective in greatly reducing the toxicity and mutagenicity associated with the remaining VOCs. Received 03 July 1997/ Accepted in revised form 25 November 1997     

The Effect of Equilibration Time and Tubing Material on Soil Gas Measurements

The collection of soil vapor samples representative of in-situ conditions presents challenges associated with the unavoidable disturbance of the subsurface and potential losses to the atmosphere. This article evaluates the effects of two variables that influence the concentration of volatile organic compounds in soil vapor samples: equilibration time and tubing material. The time for three types of soil vapor probes (i.e., macro-purge, mini-purge, and post-run tubing probes [PRT]) to equilibrate with subsurface conditions was assessed by installing probes and collecting multiple samples over a 72-hour period. The effect of tubing material was evaluated by collocating soil vapor probes constructed with different tubing material and collecting samples over several months. We recommend that soil vapor probes constructed with a sand filter-pack and bentonite seal (i.e., macro-purge probe) equilibrate for 24 to 48 hours prior to sample collection. Post-run tubing (PRT) probes equilibrated within one to two hours while a new probe design, (i.e., mini-purge probe) equilibrated and could be sampled after only 30 minutes for screening assessments. Nylaflow, Teflon®, polyetheretherketone (PEEK), and stainless-steel tubing had comparable trichloroethene (TCE) concentrations over all sampling time frames. We recommend that copper tubing be avoided and polyethylene only be used for screening assessments.