Simultaneous speciation of iron(II) and iron(III) by ion chromatography with chemiluminescence detection.

This study reports on a method for the speciation of iron in aqueous samples by the simultaneous analysis of divalent and trivalent iron ions with ion chromatography equipped with chemiluminescence detection (IC-CLD). Ferrous and ferric ions are first chelated by pyridine-2,6-dicarboxylic acid (PDCA) to form complexed anions, and separated by a mixed-bed ion-exchange column. The separated complexed ions are then detected with a CLD system containing luminol and hydrogen peroxide in a basic solution. This luminescence system has a linear dynamic range of ca. 3 orders of magnitude, with method detection limits as low as 7 µg L(-1) for Fe(II) and 3 µg L(-1) for Fe(III), measured in the simultaneous detection mode. This system resists interferences from common cations such as Cd, Ca, Cr, Cu, Mg, Ni, Pb, and Zn. Evaluation by analyzing real samples shows that this method is rapid, accurate, sensitive, and selective.

Rapid and efficient purification of chrysophanol in Rheum Palmatum LINN by supercritical fluid extraction coupled with preparative liquid chromatography in tandem.

Chrysophanol has high pharmaceutical values. However, it was difficult to use the traditional extraction method to extract high-concentration chrysophanol. Therefore, the purpose of this study is to purify and separate chrysophanol in traditional herb, Rheum Palmatum LINN, by using supercritical fluid extraction (SFE) and preparative high-performance liquid chromatography (P-HPLC) for rapid and large-scale isolation. The method is efficient for selective extraction of chrysophanol from the herbs, which have complex compositions. The extraction efficiency of chrysophanol with SFE is 25 × higher than that of boiled water extraction under the same extraction time. The optimal conditions for SFE were 210 atm and 85 °C for 30 min; for P-HPLC, a C18 column was used with a gradient elution of methanol and 1% acetic acid at a flow rate of 10 mL/min. According to (1)H NMR and LC-MS analyses, the purity of the isolated chrysophanol was as high as 99%. The recovery for chrysophanol in Rheum after SPE/PHPLC processing was in the range of 88-91.5%. Compared with other extraction and purification methods, the sequential system (SFE/P-HPLC) achieved the highest amount of extracted chrysophanol from Rheum Palmatum LINN (0.38 mg/g) and the shortest run time (3h). Hence, this rapid and environmentally friendly method can separate compounds based on polarity with high efficiencies and, coupled with P-HPLC, it may be applicable in the large-scale production of foods and medicines in the future.

Electrochemical immunoassay of cotinine in serum based on nanoparticle probe and immunochromatographic strip.

A disposable sensor for the determination of cotinine in human serum was developed based on immunochromatographic test strip and quantum dot label. In this assay, cotinine linked with quantum dot competes with cotinine in sample to bind to anti-cotinine antibody in the test strip and the quantum dots serve as signal vehicles for electrochemical readout. Some parameters governing the performance of the sensor were optimized. The sensor shows a wide linear range from 1 ng mL(-1) to 100 ng mL(-1) cotinine with a detection limit of 1.0 ng mL(-1). The sensor was validated with spiked human serum samples and it was found that this method was reliable in measuring cotinine in human serum. The results demonstrate that this sensor is rapid, accurate, and less expensive and has the potential for point of care (POC) detection of cotinine and fast screening of tobacco smoke exposure.

VOC amounts in ambient areas of a high-technology science park in Taiwan: their reciprocal correlations and impact on inhabitants.

INTRODUCTION: This study presents bihourly, seasonal, and yearly concentration changes in volatile organic compounds (VOCs) in the inlet and effluent water of the wastewater treatment plant (WWTP) of a high-technology science park (HTIP) in Taiwan, with the VOC amounts at different sites correlated geologically. MATERIALS AND METHODS: This research adopted a combination of two systems, solid-phase microextraction with a gas chromatography/flame ionization detector and an assembly of purge and trap coupled with gas chromatography/mass spectrometry, to monitor polar and nonpolar VOCs in wastewater. This paper investigated the total VOCs, acetone, isopropyl alcohol (IPA), and dimethylsulfide (DMS) concentrations in real water samples collected in the ambient area of the HTIP. RESULTS AND DISCUSSION: The major contents of VOCs measured in the effluent of the WWTP in the HTIP and the surrounding river region were DMS (14-176 ppb), acetone (5-95 ppb), and IPA (15-316 ppb). In comparison with the total VOCs in the inlet wastewater of the WWTP, no corresponding relationship for total VOC concentration in the wastewater was observed between the inlet water and effluent water of the WWTP. CONCLUSIONS: The peak VOC concentrations appeared in the third season, and the correlation of different VOC amounts reflects the production situation of the factories. In addition, VOC concentrations at different sites indicate that the Ke-Ya River is seemingly an effective channel for transporting wastewater to its final destination. The data are good indications for the management of environmental pollution near the HTIP.

Identification and anti-human glioblastoma activity of tagitinin C from Tithonia diversifolia methanolic extract.

The Tithonia diversifolia methanolic extract (TDM), which showed antiproliferative activity against human glioblastoma U373 cells, with an IC50 value of 59.2±3.7 µg mL(-1), was passed through silica gel chromatography and successively eluted with different percentages of EtOAc/hexane. The 10-60% EtOAc/hexane subfractions, which exhibited a comparatively higher antiproliferative activity, were isolated, and then structural identification was proceeded with 1H nuclear magnetic resonance. The isolated compound was tagitinin C, a kind of sesquiterpenoid. The IC50 value was 6.1±0.1 µg mL(-1) in U373 treated with tagitinin C. In flow cytometric analysis and inhibition of pan-caspase, the results showed that the anti-glioblastoma effect was apoptosis-independent. In PARP, p-p38, ULK1, and LC3-II expression, the anti-glioblastoma induced by tagitinin C was likely via autophagy. In the ULK1 siRNA transfection experiment, autophagy blockade counteracted the suppression induced by tagitinin C. The result suggested that tagitinin C induces U373 cell death dependent upon autophagy under certain conditions.

Catalytic hydrogenation rate of polycyclic aromatic hydrocarbons in supercritical carbon dioxide containing polymer-stabilized palladium nanoparticles.

Catalytic hydrogenation of polycyclic aromatic hydrocarbons (PAHs) with up to four fused benzene rings over high-density-polyethylene-stabilized palladium nanoparticles in supercritical carbon dioxide via in situ UV/Vis spectroscopy is presented. PAHs can be efficiently converted to saturated polycyclic hydrocarbons using this green technique under mild conditions at 20 MPa of CO2 containing 1 MPa of H2 at 40-50°C. Kinetic studies based on in situ UV/Vis spectra of the CO2 phase reveal that the initial hydrogenation of a given PAH and the subsequent hydrogenations of its intermediates are pseudo-first-order. The hydrogenation rate of the latter is always much smaller than that of the former probably due to increasing steric hindrance introduced by the hydrogenated benzene rings of PAHs which impedes the adsorption process and hydrogen access to PAHs on catalyst surfaces.

Process sampling module coupled with purge and trap-GC-FID for in situ auto-monitoring of volatile organic compounds in wastewater.

An automatic sampling device, i.e., process sampling module (PSM), connected with a purge and trap-GC-FID system has been developed for real-time monitoring of VOCs in wastewater. The system was designed to simultaneously monitor 17 compounds, including one polar compound, i.e., acetone, and 16 non-polar compounds. The trapping tube is packed with two adsorbents, Carbopack B and Carbosieve III, to trap target compounds. For the purpose of in situ monitoring, the flush valve of the sampling tube is composed of two two-way valves and a time controller to prevent absorption interference of the residue. The optimal conditions for the analytical system include a 12 min purge time at a temperature of 60 degrees C, and 4 min of desorption time with a desorption temperature of 260 degrees C. Good chromatograms have been obtained with the analytical system even if a cryogenic device and de-misting were not used. The relative standards deviation (RSD) of the system is between 2% and 13.4%, and accuracies between 0.3 and 23.5% have been achieved. The detection limits of the method range from 0.32 to 2.39 ppb. In this system, the four parts, i.e., PSM, P&T, GC, and FID, were simple, reliable and rugged. Also, the interface of these four parts was simple and dependable.

Impact of inclement weather on the characteristics of volatile organic compounds in ambient air at the Hsinchu Science Park in Taiwan.

This study describes continuous monitoring of the volatile organic air pollutants, acetone and toluene, in Hsinchu Science Park (HSP) during an occurrence of inclement weather, i.e., a typhoon. Using a lab-designed sampling system coupled with a continuous automated GC-MS analysis system, a total of 53 polar and nonpolar compounds were identified and quantified. The concentration of polar compounds dropped sharply from 41.4 ppbv before the typhoon to the stage of no detection during the storm, but rose again after the typhoon. The amount of nonpolar compounds remained unaffected during the storm. The polar compounds were more affected by both the rainfall and wind than were the nonpolar compounds. The severity of air pollution strongly correlates with the concentration of acetone released into the atmosphere by a wastewater treatment facility. The system used in this study has been proved reliable while working in inclement weather condition; in addition, the results can probably be applied in the monitoring of the environment during the typhoon season in high-tech research areas.

Extraction of chromium(III) and chromium(VI) species from solid matrices using green solvent supercritical carbon dioxide.

Supercritical fluid extraction (SFE) provides an environmentally green technique to decontaminate chromium species from solid matrices using supercritical fluid carbon dioxide (ScCO2). Methanol and a small amount of water were found to significantly improve the extraction efficiency. The fluorinated chelating agent lithium bis(trifluoroethyl)-dithiocarbamate (LiFDDC) was effective in removing Cr ions in methanol-modified CO2 via in situ chelation/SFE technique. This paper indicates that the extraction efficiencies of Cr(III) and Cr(VI) from solid matrices can be greatly increased to more than 92% in the presence of a small amount of water, using 5% methanol-modified CO2 containing LiFDDC as an extractant. Chromium species in a wood waste sample in the form of chromated copper arsenate (CCA) can be extracted, but the extraction efficiency is not as good as expected, possibly due to the complications of the chemistry of Cr species in different oxidation states and to matrix effects.

Determination and impact of volatile organics emitted during rush hours in the ambient air around gasoline stations.

This study analyzes the volatile organic compounds (VOCs) in the ambient air around gasoline stations during rush hours and assesses their impact on human health. Results from this study clearly indicate that methyl tertiary butyl ether (MTBE), toluene, and isobutane are the major VOCs emitted from gasoline stations. Moreover, the concentrations of MTBE and toluene in the ambient air near gasoline stations are remarkably higher than those sampled on surrounding roads, revealing that these compounds are mainly released from gasoline stations. The concentration of VOCs near the gasoline stations without vapor recovery systems are approximately 7.3 times higher than those around the gasoline stations having the recovery systems. An impact on individual health and air quality because of gasoline station emissions was done using Integrated Risk Information System and Industrial Source Complex Short Term model.

Mass balance of metal species in supercritical fluid extraction using sodium diethyldithiocarbamate and dibutylammonium dibutyldithiocarbamate.

The objective of this work is to track the amount of metal complexes distributed in the extraction cell, collection vial, and tubing used in supercritical fluid extraction (SFE) systems after progressive removal of metal ions in supercritical carbon dioxide (SC-CO2). Sodium diethyldithiocarbamate (NaDDC) and dibutylammonium dibutyldithiocarbamate (DBDC) ligands were used to form complexes with Cd, Cu, Pb, and Zn and CO(2)/5% methanol as a supercritical fluid. The mass balance of metal complexes were obtained before and after extraction, and metals in different locations in the system were flushed out using an organic solvent and nitric acid (HNO3). These results infer that the stability constant (beta) of the metal-ligand complex has a strong correlation with SFE. Because of the composition of the stainless-steel cell, Fe, Cr, and Ni or other trace elements in the cell might interfere with the mass balance of metal complexes in SFE due to an exchange mechanism taking place between the cell and the sample.

Sampling and analysis of volatile organics emitted from wastewater treatment plant and drain system of an industrial science park.

Volatile organic compounds (VOCs) were monitored in the different sections of a wastewater treatment plant (WWTP), the outlet of both the WWTP and rainfall water, and the downstream of the WWTP joining the river in the area or vicinity of an industrial science park located in Hsinchu, Taiwan. Levels of VOCs were determined by collecting air samples over several sampling points and analyzed using gas chromatography. Among VOCs identified in the drainage and effluent system in each season, acetone, isopropanol (IPA) and dimethyl sulfide (DMS) were the major emission species and maximum concentrations were 400.4, 22.8 and 641.2 ppbv, respectively. The ambient air and wastewater sample analysis from neighboring wastewater streams identified pollutants being discharged from unaccounted sources other than the industrial park. According to the 24h semi-continuous monitoring data (27/7/2002-29/7/2002), the total VOC concentration was an average of 93 ppbv (acetone contributed approximately 78%) with a dramatic variation during the day and night. The emission rate of measured VOCs estimated using fixed box model projected an average of 2-4 microg m(-2) h(-1)) during the day and 9-17 microg m(-2) h(-1) during the night. In addition, the isopleth maps show that the acetone and DMS emissions influence adversely the nearby residential area located at less than 100 m downwind from the plant. Eventually, based on this study, an on-line monitoring and alerting system could be built for a long-term performance, and with regular information on the varying pollutants over time construction of a green strategy and creation of a sustainable environment can be achieved.

Distribution of volatile organic compounds over a semiconductor Industrial Park in Taiwan.

This study examined volatile organic compounds (VOC) concentration in ambient air collected during the years 2000--2003 at several different locations of Hsinchu Science-based Industrial Park (HSIP) in Taiwan. A canister automated GC-MS system analyzed the volatile organics in ambient air grasp samples according to T0-15 method. Oxygenated volatiles were the most abundant VOC detected in HSIP followed by aromatics that are commonly used as solvents in the semiconductor industries. The major components measured in the ambient air are 2-propanol (29-135 ppbv), acetone (12-164 ppbv), benzene (0.7-1.7 ppbv), and toluene (13-20 ppbv). At some of the sampling locations, odorous compounds such as carbon disulfide and dimethyl sulfide levels exceed threshold values. The estimated toluene/benzene ratio is very high at most of the sites. However, the total amount of VOC is reduced over the years from 2000 to 2003 due to strict implementation on use and discharge of solvents in industries. There exists no definite seasonal pattern for sporadic occurrence of high levels of some of the volatile organics. Stagnant weather conditions with low wind speeds aid accumulation of toxic species at ground level. The results entail that hi-tech semiconductor industries are still a potential source for harmful organic substances to surrounding microenvironment.

Dry ice-originated supercritical and liquid carbon dioxide extraction of organic pollutants from environmental samples.

Packed in a high-pressure vessel and under calculated conditions, dry ice can be used as a source of carbon dioxide for supercritical CO(2) extraction or liquid CO(2) of organic compounds from environmental samples. Coupled with a fluid modifier such as toluene, dry ice-originated supercritical CO(2) (Sc CO(2)) achieves quantitative extraction of many volatile organic compounds (VOCs) and semivolatile organic compounds (SOCs) including polycyclic aromatic hydrocarbons (PAHs), n-alkanes, and polychlorinated biphenyls (PCBs) from solid matrices. Compared to contemporary manual or automated supercritical fluid extraction (SFE) technologies, this novel technique simplifies SFE to a minimum requirement by eliminating the need of a high-pressure pump and any electrical peripherals associated with it. This technique is highly suitable to analytical areas where sample preservation is essential but difficult in the sampling field, or where sample collection, sample preparation, and analysis are to be done in the field.