Optimisation of an integrated optical evanescent wave absorbance sensor for the determination of chlorinated hydrocarbons in water

The suitability of an integrated optical chemical sensor for the determination of highly volatile chlorinated hydrocarbons in aqueous solutions has been proven. The analytes are detected by NIR absorption spectrometry in the evanescent field of an integrated optical strip waveguide generated in a BGG31 (Schott, Germany) glass substrate, which is coated with a hydrophobic polymer superstrate as sensing layer. It has been shown that the sensitivity increases when the refractive index of the superstrate is increased from 1.333 up to 1.46. Different UV-cured polysiloxanes with low cross sensitivity to water have been prepared. Due to the good light transmission properties of the IO-sensors prepared by this method, quantitative measurements have been performed with the model system trichloroethene (TCE) in water. A detection limit of 22 ppm has been found and the sensor response times (t₉₀-value) are between five and fourteen minutes for a coating thickness of around 30 m. The sensor response is totally reversible. The analyte desorbes in air within 2 min. The enrichment of trichloroethene in the polysiloxane coating can be described by film diffusion through the aqueous boundary layer as rate determining step.     

Determination of chlorinated hydrocarbons in water by fiber-optic evanescent wave spectroscopy and partial least-squares regression

An application of the multivariate calibration technique of partial least-squares (PLS) regression to near-infrared spectra of a fiber-optic sensor based on the evanescent wave principle is presented. The sensing element consists of a quartz glass fiber with a silicone cladding which enriches nonpolar water contaminants. Due to the interaction of the extracted molecules with the part of the light which is transmitted in the evanescent wave zone of the cladding, absorbance spectra of the contaminants can be collected. In view of a sensor application for in-situ environmental analysis, aqueous solutions of chlorinated hydrocarbon solvents (CHS), which often can be found as major water contaminants, have been measured. PLS regression was applied to three sets of CHS samples, representing typical features of NIR evanescent wave spectral data. These are, e.g., strong overlapping of the absorption bands of different CHS components, peak distortions due to temperature variations between reference and sample measurement and noisy data at analyte concentrations near to the limit of detection, respectively. For trichloroethene and 1,1-dichloroethene, where the calibration model was built for samples within a small concentration range of 1–9 mg l^–1, satisfactory prediction results could be obtained with a relatively small root-mean-square error of 0.3 mg l^–1 compared to analytical reference measurements. In contrast to this, for a three component system of dichloromethane, trichloromethane and trichloroethene with strongly overlapping absorption bands, where samples over a very broad concentration range from 3–4940 mg l^–1 were included in the PLS model, the prediction accuracy decreased enormously and for some samples strong deviations between real and predicted data occurred. Nevertheless, applying multivariate calibration to this difficult system with similar spectral features and huge differences in the concentration of the species allowed an acceptable spectral distinction and at least a semi-quantitative determination of the CHS species.     

Performance studies of an IR fiber optic sensor for chlorinated hydrocarbons in water

Chlorinated hydrocarbons (CHCs) were monitored using a recently presented infrared fiber-optic physico-chemical sensor consisting of an MIR transparent, polymer coated, silver halide fiber coupled to a commercial FTIR spectrometer. The aim of this study was to test the performance of this new fiber optic sensing device with respect to temperature dependence, simultaneous detection of several CHCs, sensitivity and dynamic response behavior. In addition the diffusion process of the CHCs into the polymer was analyzed in order to better understand and evaluate the obtained results. During the investigation of the temperature dependence of the sensor response to real trend could be observed in the temperature range of 0 to 22°C. The dynamic response of the sensor is in the minute range when experiencing an increase in concentration of the analyte while with a decrease in concentration, the response is relatively slow. The sensor enabled the detection of 10 environmentally relevant CHCs at concentrations of 1 to 50ppm. The simulation of the experimental diffusion data revealed Fick's 1st law diffusion for CHCs into the polymer layers. Finally the sensing device was validated with head space-gas chromatography (HSGC) analyses and showed good agreement with these already established methods. This work shows the great potential of IR fiber optic sensors as early warning systems for a variety of CHCs in water (threshold alarm sensor)Dedicated to Professor Dr. Dieter Klockow on the occasion of his 60th birthday     

Ammonia detection via integrated optical evanescent wave sensors

Detection of ammonia in the gas phase by means of integrated optical components, coated with sensitive films which reversibly change their spectral absorption with ammonia concentration, is demonstrated. The evanescent wave of the guided light continuously probes the absorbance of the sensor membrane at 633 nm. The output intensity is compared with that of a reference channel not influenced by the sensitive film. With Bromocresol Green and Bromophenol Blue in silicone as indicators, ammonia levels of less than 1 ppm are detectable, the dynamic range being from 1 to 200 ppm. The response depends on the relative humidity, and acidic gases including sulphur dioxide, carbon dioxide, and nitric oxides are found to reduce the relative signal change caused by ammonia, whilst in the absence of ammonia they remain inert. Aging of the film is observed within a few months after film preparation.     

Determination of hydrocarbons in water by evanescent wave absorption spectroscopy in the near-infrared region

An home-made EFA (evanescent field absorbance)-sensor has been tested for the determination of hydrocarbons in water. The investigations have been performed both with crude oil emulsions and petrol solutions. Cuvette and evanescent wave spectra of crude oil and petrol in the near-infrared region are presented and discussed. The concentration of aromatic compounds in crude oil can be determined semiquantitatively by the standard addition method. The sorption behaviour of the hydrocarbons in the cladding of the fiberoptic sensor has been investigated and a correlation between the sensor signal and the concentration of the aqueous hydrocarbon emulsion/solution could be shown. The desorption of the enriched molecules after the measurements is also presented. The petrol molecules evaporate in ambient air so that the sensor is easily regenerated. In case of oil measurements the hydrocarbon molecules cannot be removed by rinsing the sensor with clear water or by evaporating them in ambient air. It has to be regenerated by washing it with a high volatile solvent instead.     

Determination of hydrocarbons in water by evanescent wave absorption spectroscopy in the near-infrared region

An home-made EFA (Evanescent Field Absorbance)-sensor has been tested for the determination of hydrocarbons in water. The investigations have been performed both with crude oil emulsions and petrol solutions. Cuvette and evanescent wave spectra of crude oil and petrol in the near-infrared region are presented and discussed. The concentration of aromatic compounds in crude oil can be determined semiquantitatively by the standard addition method. The sorption behaviour of the hydrocarbons in the cladding of the fiberoptic sensor has been investigated and a correlation between the sensor signal and the concentration of the aqueous hydrocarbon emulsion/solution could be shown. The desorption of the enriched molecules after the measurements is also presented. The petrol molecules evaporate in ambient air so that the sensor is easily regenerated. In case of oil measurements the hydrocarbon molecules cannot be removed by rinsing the sensor with clear water or by evaporating them in ambient air. It has to be regenerated by washing it with a high volatile solvent instead.     

A microvolume molecularly imprinted polymer modified fiber-optic evanescent wave sensor for bisphenol A determination

A fiber-optic evanescent wave sensor for bisphenol A (BPA) determination based on a molecularly imprinted polymer (MIP)-modified fiber column was developed. MIP film immobilized with BPA was synthesized on the fiber column, and the sensor was then constructed by inserting the optical fiber prepared into a transparent capillary. A microchannel (about 2.0 μL) formed between the fiber and the capillary acted as a flow cell. BPA can be selectively adsorbed online by the MIP film and excited to produce fluorescence by the evanescent wave produced on the fiber core surface. The conditions for BPA enrichment, elution, and fluorescence detection are discussed in detail. The analytical measurements were made at 276 nm/306 nm (λ _ex/λ _em), and linearity of 3?×?10^?9–5?×?10^?6 g mL^?1 BPA, a limit of detection of 1.7?×?10^?9 g mL^?1 BPA (3σ), and a relative standard deviation of 2.4 % (n?=?5) were obtained. The sensor selectivity and MIP binding measurement were also evaluated. The results indicated that the selectivity and sensitivity of the proposed fiber-optic sensor could be greatly improved by using MIP as a recognition and enrichment element. Further, by modification of the sensing and detection elements on the optical fiber, the proposed sensor showed the advantages of easy fabrication and low cost. The novel sensor configuration provided a platform for monitoring other species by simply changing the light source and sensing elements. The sensor presented has been successfully applied to determine BPA released from plastic products treated at different temperatures.

Theoretical and practical response evaluation of a fiber optic sensor for chlorinated hydrocarbons in water

The response behavior of a polymer-coated mid-infrared fiber optical sensor for chlorinated hydrocarbons in water is evaluated practically and theoretically. The sensor response to the target analytes tri- and tetrachloroethylene obtained in a muddy waste water sample is shown to be unaffected by other trace organic pollutants. A theoretical model is presented which can be used to predict the response of this sensing device. The use of this model allows to simulate the sensor response not only for increasing chlorinated hydrocarbon concentrations, but rather for any change in its concentration in the surrounding medium. In addition, the asymmetric sensor response, depending on the direction of the concentration change and the lag time after a concentration change can be explained by digital simulations and are shown to occur due to diffusion processes in the membrane.     

Nafion-based optical sensor for the determination of selenium in water samples

An optical chemical sensor responsive to selenium (SeO₃²⁻) in water samples was developed. Its matrix was nafion membrane suffused with an organic ligand p-amino-p’-methoxydiphenylamine or variamine blue (VB). The method of analysis was flow injection (FI) where in the membrane was fixed in a flow-through demountable measuring cell and connected to a computer-controlled simple spectrophotometer.

Variamine blue was previously established to determine amounts of selenium in water and other media by means of a spectrophotometer. The method involved reacting selenite with potassium iodide to generate iodine gas, which reacts with variamine blue to form a colored species.

Experimental results showed the optrode to be an effective tool in analyzing the selenium content of water samples particularly for remote or in situ applications. Interference studies proved that the method is free of intervention from tested ions.     

Single-use optical sensor for the determination of iron in water and white wines

A new method, based on the use of a disposable sensor, for the determination of Fe(II) in waters and wines is proposed. The sensor is formed by an inert rectangular strip of polyester (Mylar) and a circular film (6 mm in diameter) adhered on its surface. This film, which contains the required reagents for the fixation of the analyte by means of a complexation reaction, forms the sensing zone of the sensor. When the sensor is introduced in an acidified (pH 2.5) sample solution containing between 4.0 and 300.0 μg/L of Fe(II), a violet-red colour develops in the initially colourless sensing zone. The linear range of the method depends of the equilibration time of the sensor with the sample solution. Thus, when the equilibration time was 5 min, the linear range was 41.0–300.0 μg/L, while for 60 min the range was 4.0– 50.0 μg/L. Detection and quantification limits were 12.0 and 41.0 μg/L, respectively, for an equilibration time of 5 min. The precision of the method, expressed as relative standard deviation of ten samples of 100.0 μg/L of Fe(II), was 4.9%. Interferences produced by other species usually present in waters or wines have been studied. Cu(II) and Co(II) interfered seriously at concentration levels higher than 100.0 and 150.0 μg/L, respectively. The method was applied to the determination of Fe(II) in different types of waters and wines, using atomic absorption spectrometry as a reference method.     

Single-use optical sensor for the determination of iron in water and white wines

A new method, based on the use of a disposable sensor, for the determination of Fe(II) in waters and wines is proposed. The sensor is formed by an inert rectangular strip of polyester (Mylar) and a circular film (6 mm in diameter) adhered on its surface. This film, which contains the required reagents for the fixation of the analyte by means of a complexation reaction, forms the sensing zone of the sensor. When the sensor is introduced in an acidified (pH 2.5) sample solution containing between 4.0 and 300.0 micrograms/L of Fe(II), a violet-red colour develops in the initially colourless sensing zone. The linear range of the method depends on the equilibration time of the sensor with the sample solution. Thus, when the equilibration time was 5 min, the linear range was 41.0-300.0 micrograms/L, while for 60 min the range was 4.0-50.0 micrograms/L. Detection and quantification limits were 12.0 and 41.0 micrograms/L, respectively, for an equilibration time of 5 min. The precision of the method, expressed as relative standard deviation of ten samples of 100.0 micrograms/L of Fe(II), was 4.9%. Interferences produced by other species usually present in waters or wines have been studied. Cu(II) and Co(II) interfered seriously at concentration levels higher than 100.0 and 150.0 micrograms/L, respectively. The method was applied to the determination of Fe(II) in different types of waters and wines, using atomic absorption spectrometry as a reference method.     

Alcohol determination using an acoustic wave sensor

An acoustic wave methodology was developed to quantify alcohols in aqueous solutions. The frequency at minimum impedance of a bare quartz crystal in contact with ethanol solutions was found to be a suitable parameter to quantify ethanol. Ethanol in several Portuguese white wines was analyzed both by the proposed methodology and by the usual areometric method with no statistically significant differences (alpha = 0.05) in precision or accuracy of the results.     

Design of an optical sensor for indirect determination of isoniazid

The characterization of an optical sensor membrane is described for indirect determination of isoniazid. The sensing membrane was consisted of immobilized 3-(2-pyridyl)-5,6-diphenyl-1,2,4-triazine (PDT) on a triacetylcellulose membrane. The procedure is based on the reaction of Fe(III) with isoniazid in the presence of PDT. Fe(III) is reduced by isoniazid to Fe(II) which forms a complex with PDT. The complex shows an absorption maximum at 558nm. By measuring the absorbance of the complex at this wavelength, isoniazid can be determined in the range of 0.62-6.15mugmL(-1). This method was applied to the determination of isoniazid in pharmaceutical formulation and enabled the determination of isoniazid in microgram quantities.     

The quality of our drinking water: aluminium determination with an acoustic wave sensor

A new methodology based on an inexpensive aluminium acoustic wave sensor is presented. Although the aluminium sensor has already been reported, and the composition of the selective membrane is known, the low detection limits required for the analysis of drinking water, demanded the inclusion of a preconcentration stage, as well as an optimization of the sensor. The necessary coating amount was established, as well as the best preconcentration protocol, in terms of oxidation of organic matter and aluminium elution from the Chelex-100. The methodology developed with the acoustic wave sensor allowed aluminium quantitation above 0.07 mg L(-1). Several water samples from Portugal were analysed using the acoustic wave sensor, as well as by UV-vis spectrophotometry. Results obtained with both methodologies were not statistically different (alpha=0.05), both in terms of accuracy and precision. This new methodology proved to be adequate for aluminium quantitation in drinking water and showed to be faster and less reagent consuming than the UV spectrophotometric methodology.     

Reusable split-aptamer-based biosensor for rapid detection of cocaine in serum by using an all-fiber evanescent wave optical biosensing platform

A rapid, facile, and sensitive assay of cocaine in biological fluids is important to prevent illegal abuse of drugs. A two-step structure-switching aptasensor has been developed for cocaine detection based on evanescent wave optical biosensing platform. In the proposed biosensing platform, two tailored aptamer probes were used to construct the molecular structure switching. In the existence of cocaine, two fragments of cocaine aptamer formed a three-way junction quickly, and the fluorophore group of one fragment was effectively quenched by the quencher group of the other one. The tail of the three-way junction hybridized with the cDNA sequences immobilized on the optical fiber biosensor. Fluorescence was excited by evanescent wave, and the fluorescence signal was proportional to cocaine concentration. Cocaine was detected in 450 s (300 s for incubation and 150 s for detection and regeneration) with a limit of detection (LOD) of 165.2 nM. The proposed aptasensor was evaluated in human serum samples, and it exhibited good recovery, precision, and accuracy without complicated sample pretreatments.     

A collecting and analysing system for the determination of chlorinated hydrocarbons in working place atmospheres

Conclusion The method allows to collect and analyse a wide range of chlorinated hydrocarbons in longtime measurements with good results. It works with the gaseous chloromethane (b. p. –23.8°C) as well as with the high-boiling hexachloro-1,3-butadiene (b.p. 215°C) and the reactive 1 -chloro-2,3-epoxy-propane. If the concentration of volatile compounds is very high it may be necessary to shorten the sampling time in order to prevent overloading, but in general sampling during a full shift of 8 h is possible.

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Sammel- und Analysensystem zur Bestimmung von CKW in der Luft am Arbeitsplatz

     

A fiber optic evanescent field absorption sensor for monitoring organic contaminants in water

Summary A fiber optic chemical sensor for determination of organic compounds in aqueous solution has been developed. Based on the evanescent field principle, a quartz glass fiber with a polysiloxane cladding is used as in-situ measuring probe. A compact sensor built from a 6-m coiled fiber has been connected to a commercially available fast scanning dispersive NIR spectrometer. The siloxane cladding fulfils two functions: on the one hand, it acts as protecting layer of the fragile silica fiber core, and on the other hand, it is selective with respect to non-polar organic compounds due to its organophilic properties. Hence, interactions of the evanescent field at the core/cladding interface with organic species penetrating into the cladding can be measured without interferences from broad water OH absorption bands. Aqueous solutions of chlorinated hydrocarbon solvents (CHS) have been used to test the sensor response. NIR evanescent field absorbance spectra of methylene chloride, chloroform and trichloroethylene diffused into the fiber cladding are shown in the 900–2100 nm spectral range. Different amounts of CHCl₃ dissolved in water have been determined in order to evaluate the quantitative sensor response. A linear absorbance/concentration relationship has been found for solutions between 80–6800 mg l^–1. Kinetic experiments performed with CHCl₃ solutions resulted in sensor response times of 5–10 min. The sensor seems to be promising for the remote monitoring of organic contaminants, e.g. CHS, in drainage waters of contaminated areas.     

A novel optical sensor for uranium determination

A metal ion indicator, Alizarin Red S, was tested for its potential use in uranium selective optode membrane. The water-soluble indicator was lipophilized in the form of an ion pair with tetraoctylammonium bromide, and subsequently immobilized on a triacetyl cellulose membrane. The membrane responds to uranium ions, giving a color change from yellow to violet in acetate buffer pH 5. This optode has a linear range of (1.70-18.7) × 10⁻⁵ M of UO₂²⁺ ions with a limit of detection of 5 × 10⁻⁶ M. The response time of optode was within 6 min depending on the concentration of UO₂²⁺ ions. The sensor can readily be regenerated with hydrochloric acid solution (0.01 M). The optode is fully reversible.