Determination of methanol partition coefficient in octanol/water system by a three-phase ratio variation headspace gas chromatographic method.

Determining the methanol partition coefficient (Kow) in octanol/water system is important to assess the risk of its impact to humans and the environment. In this paper, we report a novel method for the determination of the Kow of methanol with headspace gas chromatography (HS-GC), using a three-phase equilibrium-based phase ratio variation approach. Three headspace vials with different phase ratios [(1) 0.2 mL of water plus 3 mL of octanol, (2) 1 mL of water plus 3 mL of octanol and (3) 1 mL of water plus 10 mL of octanol] were used in the experiment. After pre-standing at 25 °C for > 10 h and equilibrating in the headspace oven at a temperature of interest for additional 25 min, the methanol signals of the vapor phase (i.e., the headspace) in these vials were measured by HS-GC, from which the Kow of methanol can be calculated based on the established equations. The results showed that the method has good precision (within 0.06 log unit in standard deviation) and acceptable accuracy (with method error within 0.5 log unit). A correlation between the Kow of methanol and temperature extrapolated the Kow values in a temperature range of interest. The present method represents a simple and in-situ approach for the determination of the Kow of methanol and is also suitable to be applied to other volatile compounds.

Simultaneous Determination of Amphiphobicities of Material Surface by A Dual-Indicator Headspace Gas Chromatography.

This paper reports on a new method for simultaneously determining the amphiphobicities of material surface by a dual-indicator assisted headspace gas chromatography. After adding 40 µL of both methanol-water and toluene-oil droplets on the sample surface for 20 s, the sample was turned vertically (to remove water and oil) and then placed in a headspace vial. The amount of methanol and toluene in the residual water and oil adhered to material surface was quantified using headspace gas chromatography. The results showed that the method has good measurement precision (RSD < 4.58%). It can be an effective tool for simultaneously determining the amphiphobicities of material surface.

Determination of water content in municipal sludge by multiple headspace extraction gas chromatography.

This paper reports a new method for the determination of sludge water content by a multiple headspace extraction gas chromatographic (MHE-GC) method. It is based on measuring the GC signals for the water vapor in a sample vial from the first five headspace extractions, from which the water content in the sludge sample can be extrapolated according to the established calculation equation. The results show that the method has a good repeatability (the relative standard deviation is less than 1%) and accuracy. The maximum relative difference is less than 16% compared to the reference method. The present method is very simple and efficient, and suitable for rapid sample testing in related applications.

Determination of activity of denitrifying enzyme in soil samples by a headspace gas chromatographic technique.

This paper reported a headspace gas chromatography (HS-GC) for the determination of denitrifying enzyme activity in soil samples. It was based on measuring the NO2 signal in a set of closed/air-free vials containing soil samples that incubated at the designated conditions. The results showed that the method has a good measurement precision (RSD < 5.0%) and reasonable accuracy for determining the denitrifying enzyme activity in soil samples. It is simple and efficient, and very suitable to be used in batch sample analysis.

Determination of water distribution in sludge by a multiple headspace extraction analytical technique.

This paper reported a new method for the determination of the water distribution in sludge. It was based on a multiple headspace extraction (MHE) procedure to step-wise remove the water vapor from a closed vial containing a sludge sample, followed by a gas chromatographic measurement (GC). By plotting the GC signal of water vapor vs. the headspace extraction number, three different trend lines from the profile can be observed. From which two transition points can be determined and thus the stages for the free water, capillary water, and adsorption water release can be divided. Based on the sum of GC peak areas ate each stage, the content of these water types in the sludge can be calculated through a method calibration. The results showed that the MHE-GC method has a better measurement repeatability (RSD < 18.6%) and sensitivity (limit of quantitation = 0.028%) than the thermal drying method (used as a reference method). There was also a good agreement between the MHE-GC and the reference method on the free water and capillary water analysis. Moreover, the results on the adsorption water and bound water testing by the present method is more justifiable than the reference method.

In-situ determination of the observed yield coefficient of aerobic activated sludge by headspace gas chromatography.

This paper describes a headspace gas chromatographic (HS-GC) method for the in-situ determination of the observed yield coefficient (Yobs) of aerobic activated sludge from domestic wastewater treatment plants. It is based on the measurement of oxygen and carbon dioxide in samples that have been incubated in headspace vials for relatively short periods of time. The method has good precision (the relative standard deviation < 5.46%) and accuracy (the relative differences < 9.23% when compared with the data from the reference method). The new method is much simpler and more efficient than the reference methods and should greatly facilitate the testing in aerobic activated sludge related applications, such as system design, operation and management.

A simple high-throughput headspace gas chromatographic method for the determination of dissolved oxygen in aqueous samples.

This paper reports on a headspace gas chromatographic method (HS-GC) for the accurate determination of dissolved oxygen (DO) in domestic and industrial wastewater. It was based on GC measurement of oxygen in the headspace gas that is released from the dissolved oxygen in a liquid sample in a closed vial. The results show that the relative standard deviation of the method in quintuplicate testing was < 2.0% and the relative differences of results were less than 4.0% for the real river water samples when compared with the widely used reference method (the electrode method); The linear range of the method is about 0-9.0 mg/L with the limit of detection of 0.30 mg/L. The present method is simple in both sample preparation and method calibration. It is particularly efficient in the batch testing mode. Overall, the method is more reliable than the current reference method when used with samples from a wide range of sources.

Simultaneous Determination of the Degree of Deacetylation and Substitution on Carboxymethyl Chitosan by Headspace Gas Chromatography.

This study reported a new headspace gas chromatography (HS-GC) for simultaneously determining the degree of deacetylation (DD) and the degree of substitution (DS) in carboxymethyl chitosan (CMCS), which were based on HS-GC measuring the amounts of CO2 released from both the bicarbonate decomposition suppressed by -NH2 and the reaction between the bicarbonate and the acidified carboxymethyl and amino groups in CMCS. The results showed that the present method has a good measurement precision (RSD < 2.55%) and accuracy (relative differences <5.90%). Compared with the current titration-based method, the present HS-GC techniques provide a more reliable testing in the quantification of amino and carboxymethyl contents in CMCS. Moreover, since the HS-GC can perform an automated sample reaction equilibration and measurement, it could be much more efficient than the existing methods in the batch sample analysis.

Determination of starch gelatinization temperatures by an automated headspace gas chromatography.

This paper reports on an automated temperature-programmed headspace GC technique for the determination of gelatinization temperature of starch. 1-butanol was used as a tracer and added to the starch-solution for the test. Based on measuring the GC signal of 1-butanol in the headspace with the temperature increasing, two transition points (corresponding to the onset temperature and the ending temperature of starch gelatinization) were observed by plotting the GC signal of 1-butanol vs. the temperature. The results showed that the method has a good measurement precision (the standard deviation < 1 °C) and accuracy (the average relative differences = 3.9%, compared to a standard reference method). The present method is simple and suitable for the gelatinization temperature testing for starch samples.

A Zero-Valent Pd/Fe Loaded and Nanofibrillated Cellulose-Reinforced Carboxymethyl Cellulose Hydrogel for Dechlorination of 2,4,6-Trichlorophenol.

A full-cellulose derived hydrogel, composed of carboxymethyl cellulose (CMC) and nanofibrillated cellulose (NFC), was successfully manufactured and immobilized with Pd/Fe bimetallic nanoparticles for the dechlorination of 2,4,6-trichlorophenol. The NFC-reinforced CMC hydrogels with or without loading of bimetallic nanoparticles were characterized by Fourier transform infrared spectroscopy, Transmission electron microscopy, Scanning electron microscopy-energy dispersive X-ray, and X-ray diffraction analyses. The effect of amounts of NFC on the loading capacity of Pd/Fe, mechanical properties and specific Brunauer-Emmett-Teller surface areas of NFC-reinforced CMC hydrogel was also investigated. The experimental results showed that Pd/Fe bimetallic nanoparticles were dispersed and fixed in the hydrogel matrix with the nanosize spherical shape. The hydrogel would protect the Pd/Fe nanoparticles from oxidation, and thus providing long-term stability in comparison with only NFC-coated Pd/Fe nanoparticles. The hydrogel loaded with Pd/Fe nanoparticles, as a soft material catalytic system, was investigated to dechlorinate 2,4,6-trichlorophenol and was found to be very effective.

Accurate determination of melting Point of industrial grade alkyl ketene dimer wax by a simple and automated headspace gas chromatographic technique.

This study demonstrated a novel method for determining the melting point (MP) of industrial grade alkyl ketene dimer (AKD) wax by an automated headspace gas chromatographic (HS-GC) technique, in which methanol was used as the tracer. It was based on measuring the GC signal of methanol released from an aqueous solution during the temperature increasing. When the temperature of AKD MP reached, the AKD granules floated on the surface aqueous solution was liquidized and completely isolated the methanol transfer from the solution to the headspace. Thus, a transition point, corresponding to the MP of AKD wax, was observed when plotting the GC signal of methanol vs. the temperature. The results showed that the method has a good measurement precision (RSD < 0.68%) and accuracy (the relative differences were < 7.16%, compared to a reference method). The present method is simple, accurate and particularly suitable to be used in the batch sample testing. This new measurement concept can be also adopted to many related applications.

Simple and efficient dual-wavelength spectroscopy for the determination of organic matter in sewage sludge from wastewater treatment.

In this study, a dual-wavelength spectroscopic method for rapid determination of organic matter in sludge was developed. The contents of the organic matter were calculated by determining the consumption of potassium dichromate (K2Cr2O7) based on the production of trivalent chromium ions (Cr3+). Cr3+ could be determined by subtracting the absorption at 800 nm (spectral interference) from the absorption at 650 nm (only contributed by Cr3+). The results showed that the relative standard deviation in the test was less than 5%. The same set of samples was used and when the content of organic matter was more than 150 g kg-1, the relative difference between the spectroscopic method and titration method was within 1%. Furthermore, the method does not require calibration based on the standard samples. In conclusion, the present method is simple, reliable, accurate and suitable for application in mass testing for sludge samples.

A rapid screening method for evaluating the total migratable hydrocarbons in paper products by headspace gas chromatography.

Herein, we report a rapid screening method for evaluating the hydrocarbon contamination in paper samples by headspace gas chromatography (HS-GC). This method was based on conducting the near-complete migratable release of hydrocarbons from a paper matrix to the headspace in 35 min at 98 °C. By programming the GC column temperature, other co-existing volatile organic compounds in the sample can be effectively separated from the migratable hydrocarbons. To simplify the method calibration, the concept of total migratable hydrocarbons was introduced and n-pentadecane was used as the standard hydrocarbon compound in the calibration. The results indicate that the present method offers good precision (the relative standard deviation < 9.8%) and accuracy (recovery between 94.3 and 101%). The present method can be a valuable tool for the quality assessment of total migratable hydrocarbons of paper products, aiming at providing a good guidance for safely using the recycled paper-based materials in various applications.

Determination of total phosphorus in soil and sludge by an effective headspace gas chromatographic method.

This paper reported a novel method for the determination of total phosphorus (TP) content in soil and sludge by a headspace gas chromatography (HS-GC) method. It was based on a reaction between the soluble phosphate in the digestion solution and calcium oxalate solid to form a calcium phosphate precipitate and release oxalate ions, which can react with permanganate to form carbon dioxide, which was then measured by HS-GC. The results showed the complete conversion of phosphate (meanwhile to free oxalate ions in calcium oxalate) in 15 min at 60 °C. The present method has good repeatability (RSD < 2.6%) and good accuracy (RD < 7.3%) compared to the reference method. Therefore, the present HS-GC method can become a more effective method for determining the TP content in soil and sludge samples.

Determination of the softening point of rosin by a simple and automated headspace gas chromatographic technique.

We report a simple and automated headspace gas chromatographic technique for the determination of the softening point of rosin. A lumpy solid of rosin is added into a headspace vial, then an automated stepwise temperature ramping and headspace sampling was performed at each temperature stage and gas chromatography measurement. By plotting the gas chromatography signal for an impurity in rosin versus the temperature, a transition point (corresponding to the rosin softening point) was determined. The results show that the present method has a good precision (<0.76%), and good accuracy (the relative differences compared to the ring and ball method was <4.0%). The present method is simple, accurate, and automated. It is practical and suitable for testing the softening of rosin and derivatives in mills.

Determination of lysine content based on an in situ pretreatment and headspace gas chromatographic measurement technique.

This work reports on a simple method for the determination of lysine content by an in situ sample pretreatment and headspace gas chromatographic measurement (HS-GC) technique, based on carbon dioxide (CO2) formation from the pretreatment reaction (between lysine and ninhydrin solution) in a closed vial. It was observed that complete lysine conversion to CO2 could be achieved within 60 min at 60 °C in a phosphate buffer medium (pH = 4.0), with a minimum molar ratio of ninhydrin/lysine of 16. The results showed that the method had a good precision (RSD < 5.23%) and accuracy (within 6.80%), compared to the results measured by a reference method (ninhydrin spectroscopic method). Due to the feature of in situ sample pretreatment and headspace measurement, the present method becomes very simple and particularly suitable to be used for batch sample analysis in lysine-related research and applications. Graphical abstract The flow path of the reaction and HS-GC measurement for the lysine analysis.

Determination of 3-chloro-1,2-propanediol in polyamideamine epichlorohydrin resin solution by reaction-based headspace gas chromatography.

We report on a headspace gas chromatographic method for determining the content of 3-chloro-1,2-propanediol in polyamideamine epichlorohydrin resin solution. It was based on quantitatively converting 3-chloro-1,2-propanediol to formaldehyde by periodate oxidation in a closed headspace sample vial at a room temperature for 10 min, and then to methanol by borohydride reduction at 90°C for 40 min followed by the headspace gas chromatographic measurement. The results showed that the present method has an excellent measurement precision (relative standard deviation < 2.60%) and accuracy (recoveries from 96.4-102%) in 3-chloro-1,2-propanediol analysis. The limit of quantitation was 0.031 mg/mL. It is simple and suitable for determining the 3-chloro-1,2-propanediol content in polyamideamine epichlorohydrin resin solution.

A high-throughput headspace gas chromatographic technique for the determination of nitrite content in water samples.

This paper reports on a high-throughput headspace gas chromatographic method (HS-GC) for the determination of nitrite content in water sample, based on GC measurement of cyclohexene produced from the reaction between nitrite and cyclamate in a closed vial. The method has a relative standard deviation of <3.5%; The differences between the results of the nitrite measurements obtained by this method and those of a reference method were less than 5.8% and the recoveries of the method were in the range of 94.8-102% (for a spiked nitrite content range from 0.002 to 0.03 mg/L). The limit of detection of the method was 0.46 µg L-1. Due to an overlapping mode in the headspace auto-sampler system, the method can provide an automated and high-throughput nitrite analysis for the surface water samples. In short, the present HS-GC method is simple, accurate, and sensitive, and it is very suitable to be used in the batch sample testing.

Modeling and prediction of methanol air release from bleached chemi-thermo mechanical pulp board.

This paper reports on the modeling, prediction and evaluation approaches of methanol release from bleached chemi-thermo mechanical pulp (BCTMP) board during storage. A pseudo-first order desorption kinetics model of methanol release was established for describing the desorption behavior of methanol from BCTMP, i.e., , in which the desorption constant (K) and rate constant (k des) were well described by van't Hoff and Arrhenius equations. Based on the simulation experiments at various temperatures, the desorption activation energy of methanol and its adsorption enthalpy is calculated and is 53.7 and -86.2 kJ mol-1 K-1, respectively. With the developed model, the risk of methanol release for the storage of BCTMP board can be examined by either the time-dependent kinetics model or a two-step thermodynamic approach using the equilibrium concentration of methanol in indoor air. This paper provides a valuable tool to assess the risk of methanol release for the paper industry and related warehouse departments.

Biological activities and nitrogen and phosphorus removal during the anabaena flos-aquae biofilm growth using different nutrient form.

This work investigated the biological activities and nitrogen and phosphorus removal during the anabaena flos-aquae biofilm growth on the polyvinyl chloride (PVC) carriers, in different nutrient form mediums. The study showed that the production of dehydrogenase activity (DHA) and extracellular polymeric substances (EPS) can reach 40.4 g/(h·m2) and 115 × 10-2 g/m2 in an 11-day period, respectively, indicating that the anabaena flos-aquae biofilm had high biological activities. The results showed that the nitrogen and phosphorus removal reached 94.9 and 96.8%, respectively, in the ammonium form nitrogen group; while 97.7% of phosphorus were removed in the orthophosphate form phosphorous group. A comparison study was conducted and results showed that the present anabaena flos-aquae based biofilm provided a better removal of nitrogen and phosphorus than the other microalgae biofilms.