Development of an infrared hollow waveguide sampler for the detection of organic compounds in aqueous solutions with limited sample volumes.

In this study, an infrared (IR) hollow waveguide sampler was developed to detect organic compounds in aqueous samples with sample volumes less than 50 microL. This sampler was prepared by coating a thin hydrophobic film inside the IR hollow waveguide. After injecting a certain amount of aqueous solution, organic compounds could be absorbed into the hydrophobic film by partitions. By removing the residual water in the hollow waveguide sampler with a nitrogen purging gas, the absorbed organic compounds could be sensed using IR radiation. To investigate the applicability of this hollow waveguide sampler in the detection of small amounts of aqueous samples, an analytical working function was developed following an examination of the parameters which influence the analytical signals. Such factors as the volume of the aqueous solution, the sample concentration, the length of the hollow waveguide, and the sensitivity of this method were investigated. Excellent agreement between the analytical and theoretical predicted values was observed. Upon examining the linear relationship between the analyte signals and the concentration, the regression coefficients were generally higher than 0.998 in the examined concentration range of 1 to 100 ppm. Under the condition that the sample volume was 300 microL and based on three-times the spectra noise level, the calculated detection limits for this method were found at around 1 ppm for the examined analytes.     

Development of the infrared hollow waveguide sampler for the detection of chlorophenols in aqueous solutions

A method based on the infrared hollow waveguide sampler was developed for sensing chlorophenols in aqueous solutions. This sampler was constructed by coating a suitable hydrophobic film onto the inner surface of an infrared hollow waveguide. By passing the aqueous solution through the hollow waveguide sampler, analytes can be absorbed into the hydrophobic layer. The adsorbed analytes can be sensed later by using Fourier transform infrared spectrometry. Six hydrophobic polymers were investigated for their performance in conjunction with the infrared hollow waveguide sampler for the detection of chlorophenols. Results indicated that poly(acrylonitrile-co-butadiene) was a most suitable hydrophobic material for absorption of chlorophenols in aqueous solutions. To further increase the detection sensitivity, factors such as sampling flow rate, sampling time, and thickness of the hydrophobic film were also investigated. Results indicated that the infrared signals were similar in the examined flow rates (2-30 mL/min), but that a higher flow rate tended to produce a higher analytical signal. Fast detection speed was an advantage of this method for the detection of chlorophenols, and the sampling/detection time can be <10 min. In addition, analytical signals were nearly proportional to the thickness of the hydrophobic film coating the inside of the hollow waveguide. With the optimal conditions found in this work, detection limits based on 3 times the peak-to-peak noise level were around 300 ppb for the chlorophenols examined. A high degree of linearity in the standard curves was also observed for this method in the concentration range of 10-100 ppm. The typical regression coefficients were >0.994 for the chlorophenols examined.     

Development of a solid-phase microextraction/reflection-absorption infrared spectroscopic method for the detection of chlorinated aromatic amines in aqueous solutions.

In this paper, the reflection-absorption infrared (IR) spectroscopic method combined with the principle of solid-phase micro-extraction (SPME) is proposed to detect chlorinated aromatic amines in aqueous solutions. This proposed method provides simplicity in both the optical system and equipment setup. Compared to the SPME/attenuated total reflection-IR method, this method reduces the cost for internal-reflection elements and optical systems. Meanwhile, it has no SPME/transmission IR method problems, which require high polymer film preparation techniques to obtain a standing film that has no physical/chemical property changes when immersed in an aqueous solution. The typical linear coefficients obtained using this method for chloroanilines in aqueous solutions are around 0.995 and the detection can be lower than 100 ppb. The thickness of the hydrophobic film is relatively important in the SPME/ATR-IR method, but the uncertainty caused by the film thickness can be partially eliminated in the proposed method. This is because the IR signals are proportional to the film thickness and can be corrected using hydrophobic film signals. The low detection limits have also indicated that this proposed method can compete with the currently existing IR methods, but allowing much simpler detection.     

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.     

Membrane-introduced infrared spectroscopic chemical sensing method for the detection of volatile organic compounds in aqueous solutions

A novel membrane-introduced infrared (IR) chemical sensing method has been developed for the detection of volatile organic compounds (VOCs) in aqueous solutions. In this method, a porous Teflon membrane was used to eliminate the problems associated with conventional IR spectroscopic sensing methods. The porous Teflon membrane was sealed below an IR spectroscopic sensing element pre-coated with a hydrophobic film and a two-channel flow cell configuration was established. In this configuration, the aqueous sample was allowed to pass through the lower channel and the VOCs that penetrated through the membrane to the upper channel were detected by the IR sensor. In this manner, the performance of the sampling at the headspace was improved while the problems caused by the presence of water were eliminated. Meanwhile, using a purging channel allowed the sensing element to be regenerated rapidly and enabled automation of the detection process. The parameters that influenced the analytical signals were studied, such as the sampling flow rate, the pH and ionic strength of the sample solutions, the effect of the volatilities of the VOCs, and the regeneration efficiency of the sensing element. The results indicated that the analytical signals were insensitive to the sampling flow rate and to the pH and ionic strength of the sample solutions. The results obtained from the detection of seven different volatile compounds indicated that this method is highly suitable for the detection of organic compounds that have vapor pressures >1 Torr and that it is potentially usable for organic compounds that have vapor pressures between 20 mTorr and 1 Torr. The regression analysis of the standard curves indicated that a regression coefficient (R(2)) > 0.99 was obtainable in the concentration range from 1 to 100 microg mL(-1). The detection limits for the tested compounds were around a few hundred ng mL(-1).     

Reflection–absorption infrared sensing device for detection of semivolatile aromatic compounds in soils

In this article, a new IR-sensing device is described for the examination of chlorinated aromatic compounds in soils. To prepare this sensing device, a 20-mL glass vial was modified for use in the analysis of soil samples by conventional Fourier-transform infrared (FT-IR) spectroscopy. In this sampling device, an aluminium plate coated with a hydrophobic film was placed on top of the cap of the sample vial to absorb the analytes that evaporated from the soil matrix. After this absorption process was complete, the cap was placed in an FT-IR spectrometer, and the absorbed analytes were detected in the reflection–absorption (RA) mode. To accelerate the rate of evaporation of the analytes, the soil samples were heated to various temperatures. Meanwhile, other factors, such as the moisture content, sampling time, thickness of the hydrophobic film, and the volatilities and concentrations of the analytes, were also examined to optimize the analytical conditions. The results indicated that the time required to reach equilibrium conditions was short, and evaporation/absorption could be achieved within 10?min. With a water content of 10% (v/w) or less, the intensities of the analytical signals were increased greatly when compared with those of dry samples; when the water content was above 10% (v/w), these intensities decreased, partially as a result of the heating efficiency. After examining the compounds that had different vapour pressures, the analytical results indicated that this method was applicable to the examination of compounds that had vapour pressures below 1.0?Torr. Using the optimal conditions determined in this study, the detection limits for semivolatile aromatic compounds were lower than 100?ng/g, and the regression coefficients of the standard curves for compounds that had a vapour pressure lower than 1.0?Torr were larger than 0.99 in the concentration range of 1–100?µg/g.     

Determination of methylmercury and phenylmercury in water samples by liquid-liquid-liquid microextraction coupled with capillary electrophoresis

A novel method for determination of methylmercury (MeHg) and phenylmercury (PhHg) by liquid-liquid-liquid microextraction (LLLME) coupled with capillary electrophoresis (CE) with ultraviolet (UV) technique was developed. The method based on MeHg and PhHg was complexed with 1-(2-pyridylazo)-2-naphthol (PAN) to form hydrophobic complexes. When the sample solution was stirred, analytes were extracted into the organic layer (200 microL toluene) and back-extracted simultaneously into the 4.0 microL 0.1% (w/v) l-cysteine microdrop. The factors affecting on the LLLME of two mercury species, including sample pH, complex reagent concentration, extraction time, volume of organic solvent, stirring rate and phase volume ratio, were investigated. Under the optimized conditions, the detection limits (S/N=3) of MeHg and PhHg were 0.94 and 0.43 ngmL(-1) (as Hg), respectively. The precisions (RSDs, c=10 ngmL(-1), n=7) were in the range of 3.3-3.4% for migration time, 6.1-7.2% for peak area response, and 6.7-7.5% for peak height response for the two mercury species. The enrichment factors of 324 for MeHg and 210 for PhHg were obtained with 40 min LLLME. The developed method was successfully applied to the determination of trace amounts of MeHg and PhHg in water samples.     

Solid-phase Microextraction of Volatile Polar Compounds in Water

A method was developed for the analysis of volatile polar compounds in a water matrix using open cap vials Solid Phase Micro-Extraction (SPME) and Capillary Gas Chromatography (CGC). Both SPME techniques – direct sampling and headspace – were tested. Optimization of experimental conditions – exposure time, desorption time, with headspace SPME in addition the influence of the temperature and ionic strength of the sample solution on compound sorption, and finally GC response – were investigated. The analytes were extracted by directly immersing the 85 μm polyacrylate fiber in the aqueous sample or in the headspace. The linear range of the preconcentration process and the precision were examined. The amount of polar analytes sorbed on the fiber was determined and was found to be concentration dependent; it amounted to 0.014–0.64% in the concentration range of 0.00425–425 ppm studied in aqueous solution for direct sampling SPME and to 0.011–2.76% for solutions of concentration 0.0425–255 ppm for headspace SPME. The limits of determination were ascertained. Headspace SPME was applied to the analysis of real-life samples.     

液-液-液微萃取/高效液相色谱法测定人血浆中的西地那非和伐地那非

建立了液-液-液微萃取与高效液相色谱联用同时测定血浆中西地那非和伐地那非的方法。考察了萃取溶剂、溶剂体积、接受相液滴大小、搅拌速度和萃取时间等因素对富集因子的影响,得到了萃取溶剂为300 μL 甲苯、接受相为2 μL 0.2 mol/L HCl、搅拌速度为600 r/min和萃取时间为40 min的最佳实验条件。在该条件下,获得了较高的富集因子。两种组分的线性范围均为5 μg/L~1.0 mg/L,加标回收率高于87%,其相对标准偏差小于5%。以信噪比为3计,西地那非的检测限为1 μg/L,伐地那非为0.5 μg/L。该方法能有效地去除复杂基体的干扰,有机溶剂消耗少,萃取效率高,是一种有效的、灵敏的样品前处理方法,适用于血浆中微量西地那非和伐地那非的测定。     

Development of the Headspace SPME/ATR‐IR Method for Detection of Chlorinated Aromatic Compounds in Soils

In this paper, a new method based on attenuated total reflection infrared (ATR‐IR) spectroscopy was developed to detect chlorinated aromatic compounds in soil. To eliminate the problems associated in inspection of soil samples by the ATR‐IR method, chlorinated compounds were evaporated from soil matrices and detected in the headspace. The sensing device was constructed by an internal reflection element (IRE) coated with a hydrophobic film to attract and concentrate chlorinated compounds evaporated to the headspace. Factors that influence the analytical signals were studied such as the moisture content, volatilities of analytes, and effect of heating temperature. Results indicated that the addition of thermal energy to the soil sample resulted in an increase of IR signal. However, the IRE was also warmed up and caused a slight decrease of the IR signals after a long detection time. The studies of the influence of moisture indicated that a small amount of water present in soils could tremendously increase the intensity of detected IR signals. The further increase of moisture contents resulted in a decrease of the analytical signals, and the optimal signal was found when soil samples contained 5% (v/w) water. Results in analyses of compounds with different volatilities indicated that even with vapor pressure lower than 0.017 Torrs, quality IR spectra could still be obtained. Using the optimal conditions found in this work, the results in determination of five compounds in soil samples indicated that the linear regression coefficients (R‐square) were higher than 0.992 with detection limits around a few hundreds of ppb.     

Sensitive determination of bromine and iodine in aqueous and biological samples by electrothermal vaporization inductively coupled plasma mass spectrometry using tetramethylammonium hydroxide as a chemical modifier

A procedure for the simultaneous determination of bromine and iodine by inductively coupled plasma (ICP) mass spectrometry was investigated. In order to prevent the decrease in the ionization efficiencies of bromine and iodine atoms caused by the introduction of water mist, electrothermal vaporization was used for sample introduction into the ICP mass spectrometer. To prevent loss of analytes during the drying process, a small amount of tetramethylammonium hydroxide solution was placed as a chemical modifier into the tungsten boat furnace. After evaporation of the solvent, the analytes instantly vaporized and were then introduced into the ICP ion source to detect the (79)Br(+), (81)Br(+), and (127)I(+) ions. By using this system, detection limits of 0.77 pg and 0.086 pg were achieved for bromine and iodine, respectively. These values correspond to 8.1 pg mL(-1) and 0.91 pg mL(-1) of the aqueous bromide and iodide ion concentrations, respectively, for a sampling volume of 95 microL. The relative standard deviations for eight replicate measurements were 2.2% and 2.8% for 20 pg of bromine and 2 pg of iodine, respectively. Approximately 25 batches were vaporizable per hour. The method was successfully applied to the analysis of various certified reference materials and practical situations as biological and aqueous samples. There is further potential for the simultaneous determination of fluorine and chlorine.     

A high-throughput liquid chromatography/tandem mass spectrometry method for simultaneous quantification of a hydrophobic drug candidate and its hydrophilic metabolite in human urine with a fully automated liquid/liquid extraction

ABT-869 (A-741439) is an investigational new drug candidate under development by Abbott Laboratories. ABT-869 is hydrophobic, but is oxidized in the body to A-849529, a hydrophilic metabolite that includes both carboxyl and amino groups. Poor solubility of ABT-869 in aqueous matrix causes simultaneous analysis of both ABT-869 and its metabolite within the same extraction and injection to be extremely difficult in human urine. In this paper, a high-performance liquid chromatography/tandem mass spectrometry (HPLC/MS/MS) method has been developed and validated for high-speed simultaneous quantitation of the hydrophobic ABT-869 and its hydrophilic metabolite, A-849529, in human urine. The deuterated internal standards, A-741439D(4) and A-849529D(4), were used in this method. The disparate properties of the two analytes were mediated by treating samples with acetonitrile, adjusting pH with an extraction buffer, and optimizing the extraction solvent and mobile phase composition. For a 100 microL urine sample volume, the lower limit of quantitation was approximately 1 ng/mL for both ABT-869 and A-849529. The calibration curve was linear from 1.09 to 595.13 ng/mL for ABT-869, and 1.10 to 600.48 ng/mL for A-849529 (r2 > 0.9975 for both ABT-869 and A-849529). Because the method employs simultaneous quantification, high throughput is achieved despite the presence of both a hydrophobic analyte and its hydrophilic metabolite in human urine.     

The influence of organic sample solvents on the separation efficiency of basic compounds under strong cation exchange mode

This study investigated the influence of organic sample solvents on separation efficiency of basic compounds under strong cation exchange (SCX) mode. The mixtures of acidic aqueous solution and organic solvent such as acetonitrile, ethanol, methanol and dimethyl sulfoxide (DMSO) were tested as sample solvents. For later-eluting analytes, the increase of sample solvent elution strength was responsible for the decrease of separation efficiency. Thus, sample solvents with weak elution strength could provide high separation efficiencies. For earlier-eluting analytes, the retention of organic sample solvents was the main factor affecting separation efficiency. Weakly retained solvents could provide high separation efficiency. In addition, an optimized approach was proposed to reduce the effect of organic sample solvent, in which low ionic solvent was employed as initial mobile phase in the gradient. At last, the analysis of impurities in hydrophobic drug berberine was performed. The results showed that using acidic aqueous methanol as sample solvents could provide high separation efficiency and good resolution (R > 1.5).     

Three-phase system in solvent bar microextraction: An approach for the sample preparation of ionizable organic compounds prior to liquid chromatography

In this article, a simple new solvent microextraction technique is described for the extraction of ionizable organic compounds. This involves performing simultaneous forward- and back-extraction across an organic film immobilized in the pores of a porous polypropylene hollow fiber. Four chlorophenoxyacetic acid herbicides were chosen as model compounds. The target compounds are extracted from the stirred acidic aqueous sample (adjusted to 0.5 M HCl; donor phase) through a thin film of an organic solvent residing in the pores of a polypropylene hollow fiber; they are then finally extracted into another alkaline aqueous phase (1 M NaOH; acceptor phase). Both ends of the fiber are pressure-sealed. The acceptor phase was analyzed by liquid chromatography (LC). This method gave good enrichment (by a factor of 438-553) of the analytes in 40 min extraction time with reasonably good reproducibility. The analytical potential of the method was demonstrated by applying the method to spiked river water sample.     

IR absorption and reflectometric interference spectroscopy (RIfS) combined to a new sensing approach for gas analytes absorbed into thin polymer films

Hydrophobic polymer layers (3 μm) were spin-coated on Si or Ge plates and placed in a flow through gas chamber. FTIR reflection spectra of the layers were recorded showing the characteristic IR absorption bands of the polymer and the interference pattern generated by layered structure of the polymer film. Upon exposure of the polymer layer to gaseous analytes enrichment in the polymer film occurred. This was evidenced by the appearance of analyte specific absorption particular in the mid-IR part of the spectrum, as well as by a shift in the interference pattern across the whole spectrum. Qualitative information concerning the analyte was accessible in the mid-IR part of the spectrum, whereas quantitative assessment was obtained from the interference pattern. Polyetherurethane, polydimethylsiloxane, Makrolon^® and polyisobutylene polymer layers were tested for such IR–RIfS measurements, whereas toluene, o-dichlorobenzene, m-xylene, ethyl acetate and cyclohexane were employed as analytes. There was no influence of water vapour neither on the IR absorptions nor the interference pattern as hydrophobic polymers were used.     

Solid-phase extraction of polycyclic aromatic hydrocarbons in surface water. Negative effect of humic acid

The effect of humic acid on solid-phase extraction of polycyclic aromatic hydrocarbons (PAHs) from surface water was studied. The hydrophobic PAHs show significant association with humic acid, and this was confirmed to be the cause of negative effect when conventional reversed-phase solid-phase extraction (RP-SPE) was employed to extract the analytes from aqueous samples. As an alternative, dynamic ion-exchange (DIE) SPE could simultaneously extract both the fraction of the analytes which was associated with humic acid, and that which was freely dissolved. Using the 16 US Environmental Protection Agency priority PAHs as model compounds, the recoveries of the highly hydrophobic components by DIE-SPE were 10-30% higher than those by RP-SPE for a 1000-ml water sample dissolved with Aldrich humic acid (of 4.1 mg/l dissolved organic carbon content). A similar result was also obtained for 500 ml of natural surface water although the difference in recoveries between the two methods for this sample was smaller than that for the simulated sample. For validation of the method, the artifacts in connection with DIE-SPE in extracting the fraction of analytes which was freely dissolved and that which was associated with humic acid were investigated.     

Coupling of air-assisted liquid–liquid microextraction method with partial least squares for simultaneous spectrophotometric determination of some preservatives

An air-assisted liquid–liquid microextraction method coupled with a multivariate calibration method, namely partial least squares (PLS), was developed for the extraction and simultaneous determination of benzoic acid (BA) and sorbic acid (SA) via a spectrophotometric approach. In this work, a two-step microextraction method was used. In the first step, analytes were extracted from acidic aqueous solution into octanol, as an organic solvent, and in the second step, the analytes were simultaneously back-extracted into an alkaline aqueous solution. The high absorption signal of octanol was the main reason to perform this back-extraction step. The effects of different parameters on the method efficiency were investigated; the parameters included extraction solvent volume, ionic strength of aqueous solution, pH, number of extraction cycles, and aqueous sample volume. Under optimum conditions, calibration graphs were seen to be linear over the range of 0.1–2.0 µg mL^?1 for the both analytes. Other analytical parameters were obtained as follows: Enrichment factors (EFs) were found to be 14.98 and 13.03, and limits of detection were determined to be 0.03 and 0.04 µg mL^?1 for BA and SA, respectively. As the last step, binary mixtures of the analytes were prepared and simultaneously extracted using the proposed method. Finally, PLS modeling was used for multivariate calibration of spectrophotometric data. It was successfully utilized for the analysis of the target analytes in real samples.     

Solid-phase microextraction under controlled agitation conditions for rapid on-site sampling of organic pollutants in water

An electric drill coupled with a solid-phase microextraction (SPME) polydimethylsiloxane (PDMS) fiber or a PDMS thin film was used for rapid sampling of polycyclic aromatic hydrocarbons (PAHs) in aqueous samples. Laboratory experiments demonstrated that the sampling rates of SPME fiber and thin film can be predicted theoretically. Compared with the SPME fiber, the PDMS thin film active sampler exhibited a higher sampling rate and much better sensitivity due to its higher surface-to-volume ratio and its larger extraction phase volume. The amount of the analytes extracted by the thin film was around 100 times higher than those obtained by fiber, for both 5 min rapid sampling and equilibrium extraction. A new thin film active sampler was then developed for rapid on-site water sampling. The sampling kit included a portable electric drill, a copper mesh pocket, a piece of thin film, and a liner. Laboratory experiments indicated that the sampling remained in the linear uptake phase with this sampler to 8 min for the PAHs. Field test illustrated that this novel sampler was excellent for rapid on-site water sampling due to its short sampling period, high sampling efficiency and durability The thin film sampling kit facilitates on-site sampling, sample preparation, storage and transport. This new sampler is more user-friendly and easier to commercialize than previous samplers.     

Solid phase microextraction assisted by droplets-based liquid-liquid microextraction for analysis of volatile aromatic hydrocarbons in water by gas chromatography

A new technique for the analysis of volatile aromatic hydrocarbons by combining liquid-liquid microextraction with solid phase microextraction has been developed. The analytes were extracted from aqueous samples by an immobilized polydimethylsiloxane fiber assisted by the droplets of an appropriate organic solvent. Benzene, toluene, ethylbenzene, and o-xylene were used as target analytes. The main factors potentially affecting the microextraction such as the nature and the volume of organic solvent, polydimethylsiloxane (PDMS) swelling, extraction time, agitation, temperature, and salts were optimized. The method requires a very low consumption of organic solvent. The relative enrichment factor is in the range of 7.1-32.4 for extraction in the presence of dichloromethane at an optimum volume of 18 μL mL(-1) of aqueous sample. This enhancement over regular polydimethylsiloxane fiber is primarily the result of the fiber swelling and of a stable thin layer of organic solvent attached to the surface of the PDMS fiber. The limit of detection ranges from 0.02 to 0.65 ng mL(-1) for the target compounds using a 7-μm bonded polydimethylsiloxane coating and a flame ionization detector. The validity of this method is demonstrated by the analysis of a real waste water sample.