Donghao Li

Distribution characteristics of nonylphenolic chemicals in Masan Bay environments, Korea

To understand the distribution characteristics of nonylphenolics and sterols, samples such as in creek water, sea surface water, waste water treatment plant (WWTP) effluent water, sediment and mussel were collected and analyzed. The principal analytes are nonylphenol (NP), nonylphenol monoethoxylate (NP1EO), nonylphenol diethoxylate (NP2EO), coprostanol (5beta) and cholestanol (5alpha). All these target pollutants showed 100% detection frequency in all of the samples analyzed. Total concentration of nonylphenolic compounds ranged from 334 to 3628ngl(-1) (average: 1331ngl(-1)) in creek water, from 15 to 36400ngl(-1) (average: 1013ngl(-1)) in sea surface water, from 131 to 2811ngg(-1) dry weight (average: 581ngg(-1) dry weight) in sediment and from 50.5 to 289ngg(-1) dry weight (average: 139ngg(-1) dry weight) in mussel. For water samples, levels of nonylphenolics determined in summer season were higher than those in spring season. Among them, nonylphenol and NP1EO was dominant in creek water and seawater, respectively. The highest concentration was recorded in sediment near a WWTP effluent outlet. And high levels of nonylphenolics and sterols were found in about 3km area surrounding WWTP effluent outlet. Coefficient of linear regression (R(2)) for NP in mussel and in sediment was 0.90. Similarly good correlation (R(2)=0.98) was obtained between concentration in water and in mussel indicating that a steady state has been reached in this bay. The calculated bio concentration factor (BCF=2990) for NP in Masan Bay agrees well with reported values in the literature.

Microextraction techniques for the determination of volatile and semivolatile organic compounds from plants: A review

Vegetables and fruits are necessary for human health, and traditional Chinese medicine that uses plant materials can cure diseases. Thus, understanding the composition of plant matrix has gained increased attention in recent years. Since plant matrix is very complex, the extraction, separation and quantitation of these chemicals are challenging. In this review we focus on the microextraction techniques used in the determination of volatile and semivolatile organic compounds (such as esters, alcohols, aldehydes, hydrocarbons, ketones, terpenes, sesquiterpene, phenols, acids, plant secondary metabolites and pesticides) from plants (e.g., fruits, vegetables, medicinal plants, tree leaves, etc.). These microextraction techniques include: solid phase microextraction (SPME), stir-bar sorptive extraction (SBSE), single drop microextraction (SDME), hollow fiber liquid phase microextraction (HF-LPME), dispersive liquid liquid microextraction (DLLME), and gas purge microsyringe extraction (GP-MSE). We have taken into consideration papers published from 2008 to the end of January 2013, and provided critical and interpretative review on these techniques, and formulated future trends in microextraction for the determination of volatile and semivolatile compounds from plants.

MALDI-TOF-MS analysis of small molecules using modified mesoporous material SBA-15 as assisted matrix

Mesoporous silica, SBA-15 was successfully functionalized with quinoline moiety, and was applied as a matrix in the MALDI-TOF-MS analysis of small molecules. The modified SBA-15 material [SBA-15-8-(3-(triethoxysilyl)propoxy) quinoline, SBA-15-8QSi] was obtained by using calcined SBA-15 and 8-hydroxy quinoline. The structure of the functionalized mesoporous material was systemically characterized by TEM, the N2 adsorption-desorption isotherm technique and FT-IR spectra. Compared with DHB and SBA-15, SBA-15-8QSi demonstrated several advantages in the analysis of small molecules with MALDI-TOF-MS, such as less background interference ions, high homogeneity, and better reproducibility. Based on these results, the various analytical parameters were optimized. The ideal operating conditions were (1) methanol used as the dissolving solvent; (2) sample first dropping method; (3) a ratio between the analyte and the matrix of 3.5:10. Under these optimization conditions, a low detection limit (8 pmol for L-Arginine-HCl) and high reproducibility (≤29%) were obtained. This technique was successfully applied to the analysis of various types of small molecules, such as saccharides, amino acids, metabolites, and natural honey.

Gas purge microsyringe extraction for quantitative direct gas chromatographic-mass spectrometric analysis of volatile and semivolatile chemicals.

Sample pretreatment before chromatographic analysis is the most time consuming and error prone part of analytical procedures, yet it is a key factor in the final success of the analysis. A quantitative and fast liquid phase microextraction technique termed as gas purge microsyringe extraction (GP-MSE) has been developed for simultaneous direct gas chromatography-mass spectrometry (GC-MS) analysis of volatile and semivolatile chemicals without cleanup process. Use of a gas flowing system, temperature control and a conventional microsyringe greatly increased the surface area of the liquid phase micro solvent, and led to quantitative recoveries of both volatile and semivolatile chemicals within short extraction time of only 2 min. Recoveries of polycyclic aromatic hydrocarbons (PAHs), organochlorine pesticides (OCPs) and alkylphenols (APs) determined were 85-107%, and reproducibility was between 2.8% and 8.5%. In particular, the technique shows high sensitivity for semivolatile chemicals which is difficult to achieve in other sample pretreatment techniques such as headspace-liquid phase microextraction. The variables affecting extraction efficiency such as gas flow rate, extraction time, extracting solvent type, temperature of sample and extracting solvent were investigated. Finally, the technique was evaluated to determine PAHs, APs and OCPs from plant and soil samples. The experimental results demonstrated that the technique is economic, sensitive to both volatile and semivolatile chemicals, is fast, simple to operate, and allows quantitative extraction. On-site monitoring of volatile and semivolatile chemicals is now possible using this technique due to the simplification and speed of sample treatment.

Distribution of persistent organic pollutants in bivalves from the northeast coast of China.

To assess the levels of organochlorine compounds (OCs) in the Chinese coastal environment, monitoring study using bivalves was conducted in 2005. A total of 21 bivalve samples covering the northeastern coast of China were collected and analyzed. Organochlorine compounds were widely distributed in the Chinese coastal environment, with dichlorodiphenyltrichloroethane (DDT) contamination being particularly prevalent. The overall concentrations of PCBs, DDTs, HCHs, chlordane compounds (CHLs), dieldrin, and endosulfans in bivalves were in the ranges of 3.27-25.4, 54.8-2680, 1.42-25.5, n.d. (not detected)-2.28, n.d.-4.02, and n.d.-9.55 ng g(-1) on a dry weight basis, respectively. The concentrations of DDT and HCH compounds are relatively higher than those from the coastal areas of other Asian countries. DDT metabolites were predominant, suggesting that the degradation of DDT is in progress in the Chinese coastal environment. Still, however, DDTs of high concentration exceeding 1000 ng g(-1) were observed at 19% of the stations surveyed. Among HCH compounds, beta-HCH, which is an isomer with strong persistency, was observed predominantly. Compositions of DDT and HCH compounds imply that fresh input of the two compounds into the Chinese coasts is possibly low.

Automatic heating and cooling system in a gas purge microsyringe extraction

The gas purge microsyringe extraction (GP-MSE) technique offers quantitative and simultaneous extraction, and rapid gas chromatographic-mass spectrometric determination of volatile and semivolatile chemicals is possible. To simplify the application, a new automatic temperature control system was developed here. Stable heating and cooling over a wide range of temperatures were achieved using a micro-heater and thermoelectric cooler under varying gas flow conditions. Temperatures could be accurately controlled in the range 20-350°C (heating) and 20 to -4°C (cooling). Temperature effects on the extraction performance of the GP-MSE were experimentally investigated by comparing the recoveries of polycyclic aromatic hydrocarbons (PAHs) under various experimental conditions. A sample treatment was completed within 3 min, which is much less than the time required for chromatographic analysis. The recovery of chemicals determined ranged from 81 to 96%. High reproducibility data (RSD ≤ 5%) were obtained for direct extraction of various analytes in spiked complex plant and biological samples. The data show that the heating and cooling system has potential applications in GP-MSE system for the direct determination of various kinds of volatile and semivolatile chemicals from complex matrices without any, or only minor, sample pretreatment.

Gas flow headspace liquid phase microextraction

There is a trend towards the use of enrichment techniques such as microextraction in the analysis of trace chemicals. Based on the theory of ideal gases, theory of gas chromatography and the original headspace liquid phase microextraction (HS-LPME) technique, a simple gas flow headspace liquid phase microextraction (GF-HS-LPME) technique has been developed, where the extracting gas phase volume is increased using a gas flow. The system is an open system, where an inert gas containing the target compounds flows continuously through a special gas outlet channel (D=1.8mm), and the target compounds are trapped on a solvent microdrop (2.4 microL) hanging on the microsyringe tip, as a result, a high enrichment factor is obtained. The parameters affecting the enrichment factor, such as the gas flow rate, the position of the microdrop, the diameter of the gas outlet channel, the temperatures of the extracting solvent and of the sample, and the extraction time, were systematically optimized for four types of polycyclic aromatic hydrocarbons. The results were compared with results obtained from HS-LPME. Under the optimized conditions (where the extraction time and the volume of the extracting sample vial were fixed at 20min and 10mL, respectively), detection limits (S/N=3) were approximately a factor of 4 lower than those for the original HS-LPME technique. The method was validated by comparison of the GF-HS-LPME and HS-LPME techniques using data for PAHs from environmental sediment samples.

An etched stainless steel wire/ionic liquid-solid phase microextraction technique for the determination of alkylphenols in river water

In this study, a stainless steel wire/ionic liquid-solid phase microextraction technique was developed for the direct extraction of APs from water samples. Some parameters were optimised, such as selection of the substrate and ILs, extraction time, extraction temperature, stirring rate and sample pH, etc. The experimental data demonstrated that the etched stainless steel wire was a suitable substrate for IL-coated SPME. The coating was prepared by directly depositing the ILs onto the surface of the etched stainless steel wire, which exhibited a porous structure and a high surface area. The [C8MIM][PF6] IL exhibited maximum efficiency with an extraction time of 30 min, and the aqueous sample was maintained at 40 °C and adjusted to pH 2 under stirring conditions. The enrichment factor of the IL coating for the four APs ranged from 1382 to 4779, the detection limits (LOD, S/N=3) of the four APs ranged from 0.01 to 0.04 ng mL(-1) and the RSD values for purified water spiked with APs ranged from 4.0 to 11.8% (n=3). The calibration graphs were linear in the concentration range from 0.5 to 200 ng mL(-1) (R(2)>0.9569). The optimised method was successfully applied for the analysis of real water samples, and the method was suitable for the extraction of APs from water samples.

Water-based gas purge microsyringe extraction coupled with liquid chromatography for determination of alkylphenols from sea food Laminaria japonica Aresh

A novel organic solvent-free mode of gas purge microsyringe extraction, termed water-based gas purge microsyringe extraction, was developed. This technique can directly extract target compounds in wet samples without any drying process. Parameters affecting the extraction efficiency were investigated. Under optimal extraction conditions, the recoveries of alkylphenols were between 87.6 and 105.8%, and reproducibility was between 5.2 and 12.1%. The technique was also used to determine six kinds of alkylphenols (APs) from samples of Laminaria japonica Aresh. The OP and NP were detected in all the samples, and concentrations ranged from 26.0 to 54.5ngg(-1) and 45.0-180.4ngg(-1), respectively. The 4-n-butylphenol was detected in only one sample and its concentration was very low. Other APs were not detected in L. japonica Aresh samples. The experimental results demonstrated that the technique is fast, simple, non-polluting, allows for quantitative extraction, and a drying process was not required for wet samples. Since only aqueous solution and a conventional microsyringe were used, this technique proved affordable, efficient, and convenient for the extraction of volatile and semivolatile ionizable compounds.

Nonylphenol in bivalves and sediments in the northeast coast of China

To understand nonylphenol (NP) contamination in the northeast coastal environment in China, NP was determined in 19 sediment and 20 bivalve samples collected during November 2005. NP was identified in all sediment samples in the range of 8.8 to 1.0 x 10(3) ng/g dw (dry weight), with an average of 0.12 x 10(3) ng/g dw. Most of the bivalve samples (oysters and mussels) contained detectable amounts of NP that ranged from ND (not detected) to 7.6 x 10(3) ng/g dw, with an average value of 0.79 x 10(3) ng/g dw. These results indicated that NP is ubiquitous in sediments and bivalves from the northeast coast of China, and are even present in bivalves sold as seafood. Serious contamination with NP was recorded off the coast of Bohai Strait and in semi-enclosed coastal environment such as Jiaozhou Bay and Liaodong Bay. Possible environmental and human health implications were understood in this study.