Analysis of organic pollutants in sewage by supercritical fluid extraction

Summary Analytical methods have been developed for the determination of organic pollutants of intermediate polarity in sewage. Water samples are first passed through a solid phase adsorption cartridge. The analytes are then extracted from the absorbent with supercritical CO₂ into a small volume of trapping solvent. Finally, the extracts are analyzed directly by capillary gas chromatography and gas chromatography-mass spectrometer. The various parameters (pressure, temperature, type and concentration of modifiers, trapping solvent, flow rate and volume of supercritical fluid and equilibrium time) influencing the efficiency of extraction were studied. Extraction efficiencies for the test compounds are >70%, and relative standard deviations are <4.6% (n=3). The methods established were applied to the analysis of sewage at the Lanzhou Wastewater Treatment Plant, China. 66 organic pollutants were detected, of which 15 compounds appeared in the list of priority pollutants suggested by the US EPA.     

Influence of a water vapor admixture in the carrier gas on capacity coefficients of polar organic compounds

The influence of a water vapor admixture in helium, nitrogen, and carbon dioxide on capacity coefficients of C₃−C₅ alcohols and pyridine during chromatography process in capillary columns with polar (PEG-20M) and nonpolar (SE-30) stationary phases was studied. The introduction of a water admixture into the carrier gas, increases the capacity coefficient of polar organic compounds on the capillary column with PEG-20M and has almost no effect on this value in the case of SE-30. The change in retention of polar organic compounds on the capillary column with the PEG-20M polar phase occurs due to a change in the properties of the stationary phase when it adsorbs water from the mobile phase. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2258–2261, November, 1998.     

Using different types of capillary chromatographic columns as denudation traps: a comparison of sorption properties

The research presented concerns segments of capillary chromatographic columns of different types (WCOT, SCOT, PLOT) used as traps for collection of samples of volatile organic analytes from a stream of air utilizing the equilibrium denudation technique. During the model experiments (utilizing standard mixtures), values of the partition coefficients (Kfs) were determined for volatile organic compounds frequently occurring as pollutants of atmospheric air (benzene, toluene, ethylbenzene, o-xylene, chlorobenzene). The conducted research demonstrated that the stationary phase film thickness did not affect the partition coefficient value. It was also proved that there is no dependence between the manner of applying the stationary phase in the column and the partition coefficient value.     

A novel open-tubular capillary electrochromatography with magnetic nanoparticle coating as stationary phase

A novel open‐tubular capillary electrochromatography (OT‐CEC) with modified core/shell magnetic nanoparticles coating as stationary phase was introduced using external magnetic force to fix magnetic nanoparticles. The magnetic nanoparticles coating inside the capillary columns could be easily regenerated by removing and re‐applying the external magnetic field. Magnetic field intensity, concentration and flow rate of nanoparticles suspension were investigated to achieve simple and stable preparation. Mixture of five organic acids was used as the marker sample to evaluate the OT‐CEC system, and the relative column efficiency of anthranilic acid reaches 220 000 plates/m. The excellent within‐column and between‐column repeatability has been testified with the RSDs of retention time of less than 1.51 and 5.29%, respectively. The aqueous extract of rhizoma gastrodiae was analyzed by the OT‐CEC system, and 23 peaks were eluted in 30 min. Compared with conventional open‐tubular capillary column, this new system shows faster separation speed and higher column efficiency from the larger surface area of nanoparticles. It has great potential in the method development for the analysis of complex samples, since magnetic coating can effectively prolong the column life by expediently replacing stationary phase to eliminate the pollution or irreversible adsorption.     

Sol‐gel technique for the preparation of β‐cyclodextrin gold nanoparticles as chiral stationary phase in open‐tubular capillary electrochromatography

A novel open‐tubular capillary electrochromatography column coated with β‐cyclodextrin was prepared using the sol‐gel technique. In the sol‐gel approach, owing to the three‐dimensional network of sol‐gel and the strong chemical bond between the stationary phase and the surface of capillary columns, good chromatographic characteristics and unique selectivity in separating enantiomers were shown. The influences of capillary inner diameter, coating time, organic modifier, buffer pH, and buffer concentration on separation were investigated. The sol‐gel‐coated β‐cyclodextrin column has shown improved enantioseparation efficiency of chlorphenamine, brompheniramine, pheniramine, zopiclone in comparison with the sol‐gel matrix capillary column. The migration time relative standard deviation of the separation of the enantiomers was less than 0.89% over five runs and 2.9% from column to column. This work confirmed that gold nanoparticles are promising electrochromatographic support to enhance the phase ratio of open‐tubular capillary electrochromatography column in capillary electrochromatography.     

Temperature‐programmed multicapillary gas chromatograph microcolumn for the analysis of odorous sulfur pollutants

We report the fabrication and performance of a silicon‐on‐glass micro gas chromatography eight‐capillary column based on microelectromechanical systems technology that is 50 cm long, 30 μm wide, and 300 μm deep. According to the theory of a gas chromatography column, an even gas flow among different capillaries play a vital role in the peak broadening. Thus, a flow splitter structure is designed by the finite element method through the comparison of the velocity distributions of the eight‐capillary columns with and without splitter as well as an open tubular column. The simulation results reveal that eight‐capillary column with flow splitters can receive more uniform flow velocity in different capillaries, hence decreases the peak broadening and in turn increases the separation efficiency. The separation experiment results show that the separation efficiency of about 22 000 plates/m is achieved with the chip column temperature programmed for analysis of odorous sulfur pollutants. This figure is nearly two times higher than that of the commercial capillary column coated the similar stationary phase. And the separation time of all the components in the microcolumn is less than 3.8 min, which is faster than the commercial capillary column.     

Preparation and evaluation of open‐tubular capillary column combining a metal–organic framework and a brush‐shaped polymer for liquid chromatography

In this work, an open‐tubular capillary liquid‐phase column was prepared by modifying chain polymer on the inner surface of capillary and chemical bonding of metal organic frameworks, NH₂‐UiO‐66, to the brushes of chain polymer (poly(glycidyl methacrylate)). Besides advantages of facial preparation and good permeability, the chain polymer effectively increases the modification amount of NH₂‐UiO‐66 nanoparticles to increase the phase ratio of open‐tubular capillary column and enhance the interactions with analytes. The results of scanning electron microscope energy‐dispersive X‐ray spectra indicated that NH₂‐UiO‐66 nanoparticles were successfully bonded to the chain polymer. Because of the hydrophobic interaction and hydrogen bonding interaction between the analytes and the ligand of NH₂‐UiO‐66, different analytes were well separated on the NH₂‐UiO‐66‐modified poly(glycidyl methacrylate) capillary (1.12 m × 25 μm id × 365 μm od) with the high absolute column efficiency reaching 121 477 plates, benefiting from an open‐tubular column and low mass transfer resistance provided by polymer brush and metal–organic framework crystal. The relative standard deviations of the retention time for run‐to‐run, day‐to‐day, and column‐to‐column (n = 3) runs are below 4.28%, exhibiting good repeatability. Finally, the column was successfully applied to separation of flavonoids in licorice.     

Simultaneous determination of nanomole amounts of sulphur dioxide and hydrogen sulphide by flow injection analysis with on-line preconcentration by means of capillary denuder tubes

A simple and rapid method for trace determination of SO2 and H2S in gaseous samples by using a flow injection system with on line preconcentration on capillary denuder is described. The gaseous samples are led through a 0.4 M sulphamic acid solution, retaining nitrogen dioxide, ammonia and hydrogen chloride. The sulphur dioxide is collected from the carrier gas stream (250 cm3 min-1) as sulphuric acid in a capillary denuder tube coated with a thin layer of 0.01-0.03 M hydrogen peroxide solution of 0.05 mM sulphuric acid; hydrogen sulphide passes into a second tube coated with 0.075 mM sodium sulphide solution of 0.1 M aqueous sodium hydroxide. The films containing the sulphuric acid and the sodium sulphide, respectively, are eluted with the corresponding circulating absorbent streams and pass through the detectors. Sulphuric acid is detected by conductimetry and sulphide is determined spectrophotometrically at 230 nm. If nanoequivalent amounts of H2S are present in the sample containing a large concentration of SO2 (SO2/H2S concentration ratio > 20), the sulphur dioxide is filtered out of the sample gas stream by solid sodium hydrogen carbonate. A limit of detection of 3.5 micrograms m-3 is obtained.     

Direct trace determination of organic compounds in aqueous solutions by capillary gas chromatography

The possibility of the direct determination of methyl alkyl ketones with four to eight carbon atoms in the alkyl chain and heterocyclic compounds (2-acetylpyridine, 2,3-diethylpyrazine, and 2-acetylthiophene) in aqueous solutions at a level ofn × 10^-3 vol % by gas chromatography with the injection of samples into an open tubular column with carrier gas flow splitting is studied. A significant effect of the calibration plot relating the concentration and the relative area of a gas-chromatographic peak on the results of determination is demonstrated. Factors that make it possible to optimize the calibration process, increase the rapidness of analysis, and decrease the relative error in the determination of organic compounds in water to 3% are discussed. Model mixtures of compounds were analyzed on a open tubular column with the nonpolar OV-101/KF stationary phase, which is stable in work with aqueous solutions for three years     

Influence of the carrier gas on retention factors of gaseous hydrocarbons on polytrimethylsilylpropyne using capillary gas chromatography

The retention factor and height equivalent of a theoretical plate for gaseous hydrocarbons C₁—C₄ were studied on capillary columns with the layer of the new polymeric adsorbent polytrimethylsilylpropyne (PTMSP) as functions of the nature and pressure of the carrier gas. The retention factor k increases in the series helium < nitrogen < carbon dioxide. The k values depend linearly on the average pressure of the carrier gas in a capillary column with the adsorption PTMSP layer.     

Prediction of gas collection efficiency and particle collection artifact for atmospheric semivolatile organic compounds in multicapillary denuders

A modeling approach is presented to predict the sorptive sampling collection efficiency of gaseous semivolatile organic compounds (SOCs) and the artifact caused by collection of particle-associated SOCs in multicapillary diffusion denuders containing polydimethylsiloxane (PDMS) stationary phase. Approaches are presented to estimate the equilibrium PDMS–gas partition coefficient (K_pdms) from a solvation parameter model for any compound, and, for nonpolar compounds, from the octanol–air partition coefficient (K_oa) if measured K_pdms values are not available. These estimated K_pdms values are compared with K_pdms measured by gas chromatography. Breakthrough fraction was measured for SOCs collected from ambient air using high-flow (300 L min⁻¹) and low-flow (13 L min⁻¹) denuders under a range of sampling conditions (−10 to 25 °C; 11–100% relative humidity). Measured breakthrough fraction agreed with predictions based on frontal chromatography theory using K_pdms and equations of Golay, Lövkvist and Jönsson within measurement precision. Analytes included hexachlorobenzene, 144 polychlorinated biphenyl congeners, and polybrominated diphenyl ethers 47 and 99. Atmospheric particle transmission efficiency was measured for the high-flow denuder (0.037–6.3 μm diameter), and low-flow denuder (0.015–3.1 μm diameter). Particle transmission predicted using equations of Gormley and Kennedy, Pich, and a modified filter model, agreed within measurement precision (high-flow denuder) or were slightly greater than (low-flow denuder) measured particle transmission. As an example application of the model, breakthrough volume and particle collection artifact for the two denuder designs were predicted as a function of K_oa for nonpolar SOCs. The modeling approach is a necessary tool for the design and use of denuders for sorptive sampling with PDMS stationary phase.     

Diffusion technique for the generation of gaseous halogen standards

Halogens are known to play an important role in the tropospheric ozone-depletion chemistry and are of special interest because of their influence on the atmospheric oxidation capacity. In this paper, we investigate the application of a capillary diffusion technique for the generation of gaseous halogen standards like Br₂, IBr, ICl and I₂. The influence of capillary dimension (i.e. length and inner diameter), ambient pressure and headspace volume of the diffusion vessel on the test gas output has been evaluated. The experimental output rates are determined from the mass loss of the analyte vessel on a regular schedule and compared with their respective theoretical predictions. We also demonstrate that a 1,3,5-trimethoxybenzene-coated diffusion denuder is capable of collecting gaseous ICl quantitatively, which provides an attractive alternative for the rapid determination of the output of test gas devices. The output rates of ICl measured by the denuder method are in close agreements with the data obtained by the gravimetric method.     

Annular diffusion denuder for simultaneous removal of gaseous organic compounds and air oxidants during sampling of carbonaceous aerosols

A specially designed annular diffusion denuder for simultaneous removal of organic gaseous compounds and atmospheric oxidants in carbonaceous aerosol sampling is presented. Various kinds of denuder coatings were compared with respect to the collection efficiency of both organic gaseous compounds and NO₂ and ozone. The optimum sorbent is a mixture of activated charcoal and sulfite on molecular sieve. To ensure high collection efficiency over long-term field operation, two annular diffusion denuders are combined in series. The first half of the first denuder is filled with Na₂SO₃ on molecular sieve (23 cm long layer) while the second half of the first denuder and the whole second denuder are filled with activated charcoal (the total length of the charcoal section is 67 cm).     

The effect of column characteristics on the minimum analyte concentration and the minimum detectable amount in capillary gas chromatography

The need for faster and more efficient separations of complex mixtures of organic compounds by gas chromatography has led to the development of small inner diameter open tubular columns. Owing to their decreased plate height, extremely narrow peaks are obtained. When differently sized columns with equal plate numbers are compared, injection of a fixed amount of a solute will give the highest detector signals for the smallest bore columns. When P is defined as the ratio of the column inlet and outlet pressures, it can be seen from theory that under normalized chromatographic conditions the minimum detectable amount (Q_º) for a mass flow sensitive detector increases proportionally to the square of the column diameter for P = 1. In the situation of greater interest in the practice of open tubular gas chromatography where P is large, a linear relationship is derived between Q_º and the column diameter. It is a widespread misunderstanding, however, that narrow bore capillary columns should be used for this reason in trace analysis. If a fixed relative contribution of the injection band width to the overall peak variance is allowed, a decreased plate height drastically restricts the maximum sample volume to be injected. It is shown that the minimum analyte concentration in the injected sample (C_º) is inversely proportional to the column inner diameter when a mass flow sensitive detector is used. For actual concentrations less than C_º, sample preconcentration is required. The effect of peak resolution and selectivity of the stationary phase in relation to C_º and Q_º will be discussed as well. The validity of the given theory is experimentally investigated. Minimum analyte concentrations and minimum detectable amounts are compared using columns with different inner diameter.     

Solubility of Organic Solvents. I. Gas Chromatographic Determination of Olive Oil-Gas Partition Coefficients

A gas chromatographic method of measuring the olive oil-gas partition coefficients is described. It is based on the relationship existing between the retention time of each substance and its solubility in olive oil used as a stationary liquid phase. The validity of this method has been tested by varying the length of the column, the percentage of liquid phase and the flow rate of the carrier gas. Using this technique, the partition coefficients of 24 hydrocarbons, 8 aliphatic, 6 aromatic and 10 chlorinated, have been determined (see Table 4).     

High‐throughput gas chromatography for volatile compounds analysis by fast temperature programming and adsorption chromatography

The synergy of combining fast temperature programming capability and adsorption chromatography using fused silica based porous layer open tubular columns to achieve high throughput chromatography for the separation of volatile compounds is presented. A gas chromatograph with built‐in fast temperature programming capability and having a fast cool down rate was used as a platform. When these performance features were combined with the high degree of selectivity and strong retention characteristic of porous layer open tubular column technology, volatile compounds such as light hydrocarbons of up to C₇, primary alcohols, and mercaptans can be well separated and analyzed in a matter of minutes. This analytical approach substantially improves sample throughput by at least a factor of ten times when compared to published methodologies. In addition, the use of porous layer open tubular columns advantageously eliminates the need for costly and time‐consuming cryogenic gas chromatography required for the separation of highly volatile compounds by partition chromatography with wall coated open tubular column technology. Relative standard deviations of retention time for model compounds such as alkanes from methane to hexane were found to be less than 0.3% (n = 10) and less than 0.5% for area counts for the compounds tested at two levels of concentration by manual injection, namely, 10 and 1000 ppm v/v (n = 10). Difficult separations were accomplished in one single analysis in less than 2 min such as the characterization of 17 components in cracked gas containing alkanes, alkenes, dienes, branched hydrocarbons, and cyclic hydrocarbons.     

Halogenated methyl-phenyl ethers (anisoles) in the environment: Determination of vapor pressures, aqueous solubilities, Henry's law constants, and gas/water- (Kgw), n-octanol/water- (Kow) and gas/n-octanol (Kgo) partition coefficients

Halogenated methyl-phenyl ethers (methoxybenzenes, anisoles) are ubiquitous organics in the environment although they are not produced in industrial quantities. Modelling the fate of organic pollutants such as halogenated anisoles requires a knowledge of the fundamental physico-chemical properties of these compounds. The isomer-specific separation and detection of 60 of the 134 possible congeners allowing an environmental fingerprinting are reported in this study. The vapor pressure p0(L) of more than 60 and further physico-chemical properties of 26 available congeners are given. Vapor pressures p0(L), water solubilities S(L)W, and n-octanol/water partition coefficients Kow were determined by capillary HR-GC (High Resolution Gas Chromatography) on a non-polar phase and by RP-HPLC (Reversed Phase High Performance Liquid Chromatography) on a C18 phase with chlorobenzenes as reference standards. From these experimental data the Henry's law constants H, and the gas/water Kgw and gas/n-octanol Kgo partition coefficients were calculated. We found that vapor pressures, water solubilities, and n-octanol/water partition coefficients of the halogenated anisoles are close to those of the chlorobenzenes. A similar environmental fate of both groups can, therefore, be predicted.     

Determination of the solubilising character of 2-methoxyethyl-(dimethyl)ethylammonium tris(pentafluoroethyl)trifluorophosphate based on the Abraham solvation parameter model

Gas–liquid chromatographic retention factors have been measured for 42 different organic probes on a 2-methoxyethyl(dimethyl)ethylammonium tris(pentafluoroethyl)trifluorophosphate, ([MeoeM₂EAm]⁺[FAP]^–), stationary phase capillary column at 323 and 353 K. The measured retention factors were combined with published gas-to-liquid partition coefficient data for solutes dissolved in ([MeoeM₂EAm]⁺[FAP]^–) and with published gas-to-water partition coefficient data to yield 107 gas-to-anhydrous ionic liquid and 105 water-to-anhydrous ionic liquid partition coefficients. Abraham model correlations for describing solute transfer into ([MeoeM₂EAm]⁺[FAP]^–) were derived from the three sets of experimental partition coefficient data. The derived correlations back-calculated the experimental gas-to-([MeoeM₂EAm]⁺[FAP]^–) and water-to-([MeoeM₂EAm]⁺[FAP]^–) partition coefficient data to within 0.13 and 0.15 log units, respectively.     

热解吸调制,顶空—毛细管气相色谱法测定二元液系的活度系数

本文采用热解吸调制器作毛细管气相色谱直接顶空进样测定二元液体混合物苯－甲苯和丙酮－氯仿的活度系数。热解吸调制器是在毛细管柱前端的一段短的加热段。调制器段外部镀以一薄层导电膜。所体样品连续不断地流经调制器和毛细管柱。     

Estimating the PDMS-Coated, SPME-Fibre/Water- and Fibre/Gas-Partition Coefficients of Chlorinated Ethenes by Headspace-SPME

In this work, a simple, fast and reproducible method is presented for the determination of fibre/liquid-phase and fibre/gas-phase partition coefficients of five chlorinated ethenes on a poly-(dimethylsiloxane), PDMS-coated, solid-phase microextraction fibre, by employing a headspace HS-SPME coupled with gas chromatography. The partition coefficients were estimated by a numerical method using a Level-I fugacity method coupled with parameter-estimation software. Dimensionless partition coefficients between SPME fibre and liquid as well as gas phases were obtained at temperatures of 10 °C, 25 °C and 30 °C. The partition coefficients of the fibre and the gas phase, K _fg, increase with decreasing temperature by a factor of ≈2 to 6, and they are directly proportional to the linear slope of the regression line. The same tendency is observed for the partition coefficient of the fibre and liquid phase, K _fw, in a factor ≈1.2 to 2.0. The sorption enthalpy is higher in the gas phase; therefore, the sorption onto the fibre is favoured at lower temperatures. The correlation of the log K _ow versus log K _fw and log K _oa versus log K _fg shows a linear relationship with the number of chlorine atoms in the C = C molecule. Long-term experiments resulted in sorption to Teflon surfaces and possible losses in 43 mL vials, not observed in 250 mL Boston bottles.