Tiangang Luan

Carbon nanotube-coated solid-phase microextraction metal fiber based on sol–gel technique

A novel carbon nanotube (CNT)-coated solid-phase microextraction fiber was prepared based on sol-gel technique. Commonly used fragile fused silica fiber was replaced with stainless steel wire, which made the fiber unbreakable. An approach was also proposed for batch producing, and good reproducibilities for fiber to fiber and between fibers were achieved. Experiments showed that the sol-gel-CNT fiber exhibited high thermal stability to resist 350 degrees C and excellent solvent durability in methanol and acetonitrile. Compared to commercial polydimethylsiloxane (PDMS) fiber, the sol-gel-CNT fiber represented significantly improved extraction efficiencies for both polar (phenols) and non-polar (benzene, toluene, ethylbenzene, and o-xylene) compounds. Meanwhile, no replacement effect, low carry-over and wide linear range demonstrated that the newly prepared sol-gel-CNT coating has liquid properties, which allow a relatively easy quantification procedure. Moreover, the characterization of the sol-gel-CNT coating was also evaluated with McReynold probe solutes. The results showed that the coating has better affinity for all the five types of solutes compared to commercial 7microm PDMS fiber, which suggested that the coating has the potential to be developed as GC stationary phase.

Toxicity of bisphenol A and its bioaccumulation and removal by a marine microalga Stephanodiscus hantzschii

The toxicity of bisphenol A (BPA) to Stephanodiscus hantzschii, a diatom isolated from tidal water of Futian Mangrove Nature Reserve, China, and the bioaccumulation and removal capability of the marine microalga to BPA were investigated in the present study. Toxicity experiments showed that the 96-h EC50 of BPA was 8.65+/-0.26 mg/L, and the cell number and chlorophyll a content of S. hantzschii decreased significantly with increases in BPA at concentrations higher than 3.00 mg/L. S. hantzschii had high removal capability at low BPA concentrations as BPA was bioaccumulated and biodegraded by cells. After 16-day treatment, 88%, 99%, 92%, 61%, 48%, 28% and 26% of BPA were removed by the diatom in the media supplemented with 0.01, 0.10, 1.00, 3.00, 5.00, 7.00 and 9.00 mg/L BPA, respectively. The present study demonstrated that S. hantzschii was a tolerant isolate that could be used to remove BPA from contaminated waters.

Removal and biodegradation of polycyclic aromatic hydrocarbons by Selenastrum capricornutum

The removal and degradation of a mixture of polycyclic aromatic hydrocarbons (PAHs), namely phenanthrene (PHE), fluoranthene (FLA), and pyrene (PYR), by a green microalgal species, Selenastrum capricornutum, at different initial cell densities were studied. The PAH removal efficiency increased with the initial cell density, and 96% of PHE, 100% of FLA, and 100% of PYR in the medium were removed by live S. capricornutum at the density of 1 x 10(7) cells/ml in 4 d, whereas less than 50% of PAHs were removed at the lowest cell density (5 x 10(4) cells/ml) in 7 d. The removal mechanisms included initial adsorption onto the cell walls of both live and dead cells, and the adsorbed PAHs were then absorbed and degraded in live cells only. Among different PAHs in a mixture, irrespective of whether they were added to medium at the same or different concentrations, the removal preference by live S. capricornutum was in the descending order of PYR > FLA > PHE, whereas the biodegradation rates followed the descending order of FLA > PYR > PHE. Initial findings regarding PAH metabolites revealed that PHE was converted into four different monohydroxyphenanthrenes and two dihydroxyphenanthrenes, whereas FLA and PYR were converted into three hydroxylated derivatives through the monooxygenase pathway. The presence of dihydroxylated PAHs suggested that the dioxygenase pathway also might have taken place at the same time.

Potential use of mangroves as constructed wetland for municipal sewage treatment in Futian, Shenzhen, China.

A pilot-scale mangrove wetland was constructed in Futian, Shenzhen for municipal sewage treatment. Three identical belts (length: 33m, width: 3m, depth: 0.5m) were filled with stone (bottom), gravel and mangrove sand (surface). Seedlings of two native mangrove species (Kandelia candel, Aegiceras corniculatum) and one exotic species (Sonneratia caseolaris) were transplanted to the belts with one species for each belt. The hydraulic loading was 5m(3)d(-1) and hydraulic retention time 3d. High levels of removal of COD, BOD(5), TN, TP and NH(3)-N were obtained. The treatment efficiency of S. caseolaris and A. corniculatum was higher than that of K. candel. Faster plant growth was obtained for S. caseolaris. The substrate in the S. caseolaris belt also showed higher enzyme activities including dehydrogenase, cellulase, phosphatase, urease and beta-glucosidase. The removal rates of organic matter and nutrients were positively correlated with plant growth. The results indicated that mangroves could be used in a constructed wetland for municipal sewage treatment, providing post-treatment to remove coliforms was also included.

Preparation of graphene-coated solid-phase microextraction fiber and its application on organochlorine pesticides determination

The coating material determines the sensitivity and selectivity of solid-phase microextraction (SPME). Graphene is predicted to have remarkable properties, such as high thermal conductivity, superior mechanical properties, excellent electronic transport properties and good extraction ability. In this work we immobilized the graphene onto a stainless steel wire to obtain a novel SPME coating based on sol-gel technique. The new fiber possessed a homogeneous, porous surface and showed excellent thermal and solvent stability. Under the optimized conditions, its extraction efficiencies for seven organochlorine pesticides (OCPs) were higher than those of two commercial fibers (PDMS, 85μm; PDMS/DVB, 65μm). Using the self-made sol-gel-graphene SPME fiber, the limits of detections for seven OCPs were found to be ranged from 0.19ngL(-1) (o,p-DDT) to 18.3ngL(-1) (heptachlor). The repeatabilities for each single fiber were evaluated and the relative standard deviations (RSDs) ranged from 4.7% to 10.6%. The reproducibilities of fiber-to-fiber were 2.3-13.6%. The developed method was successfully applied to the determination of OCPs in rainwater. Hexachlorobenzene (62.7ng/L), trans-chlordance (79.6ng/L) and p,p-DDT (9.30ng/L) were detected. The relative recoveries ranged from 77.7% to 120%.

Determination of octylphenol and nonylphenol in aqueous sample using simultaneous derivatization and dispersive liquid–liquid microextraction followed by gas chromatography–mass spectrometry

A simple and fast sample preparation method for the determination of nonylphenol (NP) and octylphenol (OP) in aqueous samples by simultaneous derivatization and dispersive liquid-liquid microextraction (DLLME) was investigated using gas chromatography-mass spectrometry (GC/MS). In this method, a combined dispersant/derivatization catalyst (methanol/pyridine mixture) was firstly added to an aqueous sample, following which a derivatization reagent/extraction solvent (methyl chloroformate/chloroform) was rapidly injected to combine in situ derivatization and extraction in a single step. After centrifuging, the sedimented phase containing the analytes was injected into the GC port by autosampler for analysis. Several parameters, such as extraction solvent, dispersant solvent, amount of derivatization reagent, derivatization and extraction time, pH, and ionic strength were optimized to obtain higher sensitivity for the detection of NP and OP. Under the optimized conditions, good linearity was observed in the range of 0.1-1000 μg L⁻¹ and 0.01-100 μg L⁻¹ with the limits of detection (LOD) of 0.03 μg L⁻¹ and 0.002 μg L⁻¹ for NP and OP, respectively. Water samples collected from the Pearl River were analyzed with the proposed method, the concentrations of NP and OP were found to be 2.40 ± 0.16 μg L⁻¹ and 0.037 ± 0.001 μg L⁻¹, respectively. The relative recoveries of the water samples spiked with different concentrations of NP and OP were in the range of 88.3-106.7%. Compared with SPME and SPE, the proposed method can be successfully applied to the rapid and convenient determination of NP and OP in aqueous samples.

Effects of metals on biosorption and biodegradation of mixed polycyclic aromatic hydrocarbons by a freshwater green alga Selenastrum capricornutum.

The effects of metals (cadmium, zinc, copper and nickel in a mixture) on biosorption and biodegradation of five mixed polycyclic aromatic hydrocarbons (PAHs), namely fluorene (FLU), phenanthrene (PHE), fluoranthrene (FLA), pyrene (PYR) and benzo[a]pyrene (BAP), by Selenastrum capricornutum were investigated. Exposure to metals significantly influenced the interactions between cells and PAHs and, such impact was PAH species dependent. For low molecular weight PAHs (FLU and PHE), both metal dosage and exposure time posed a significant, positive effect on their removal, with up to 99% of FLU and 89% of PHE were removed from the medium in seven days, which was mainly due to the cellular degradation induced by metal stress. For high molecular weight PAHs (FLA, PYR and BAP), the presence of metals did not affect the removal efficiency, but the uptake in the ethyl acetate-extractable fraction of the biomass was increased.

Production of metabolites in the biodegradation of phenanthrene, fluoranthene and pyrene by the mixed culture of Mycobacterium sp. and Sphingomonas sp

The effects of the mixed culture of Mycobacterium sp. strain A1-PYR and Sphingomonas sp. strain PheB4 on the degradation characteristics of single polycyclic aromatic hydrocarbon were investigated. In the mixed bacterial culture, phenanthrene, fluoranthene and pyrene were degraded by 100% at Day 3, 71.2% and 50% at Day 7, respectively. Compared to their respective pure cultures, the degradation of phenanthrene and fluoranthene decreased, but that of pyrene increased significantly. Based on GC-MS analysis, eight and six new metabolites were produced from the biodegradation of phenanthrene and fluoranthene, respectively, while only two new metabolites were formed from pyrene. To our knowledge, this is the first report that the mixed bacterial culture could increase the diversity of metabolites from PAH, but the diverse metabolite pattern was not necessarily beneficial to the degradation of the recalcitrant PAH. The enhancement on pyrene degradation was possibly attributed to the rapid growth of strain PheB4.

Simultaneous determination of UV filters and polycyclic musks in aqueous samples by solid-phase microextraction and gas chromatography-mass spectrometry.

A simple, precise and accurate method for the simultaneous determination of four UV filters and five polycyclic musks (PCMs) in aqueous samples was developed by solid-phase microextraction coupled with gas chromatography-mass spectrometry (SPME-GC-MS). The operating conditions affecting the performance of SPME-GC-MS, including fiber thickness, desorption time, pH, salinity, extraction time and temperature have been carefully studied. Under optimum conditions (30 μm PDMS fiber, 7 min desorption time, pH 7, 10% NaCl, 90 min extraction time at 24°C), the correlation coefficients (r(2)) of the calibration curves of target compounds ranged from 0.9993 to 0.9999. The limit of detection (LOD) and limit of quantification (LOQ) ranged from 0.2 to 9.6 ng L⁻¹ and 0.7 to 32.0 ng L⁻¹, respectively. The developed procedure was applied to the determinations of four UV filters and five PCMs in river water samples and internal standard was used for calibration to compensate the matrix effect. Good relative recoveries were obtained for spiked river water at low, medium and high levels. The proposed SPME method was compared with traditional SPE procedure and the results found in river water using both methods were in the same order of magnitude and both are quite agreeable.

Preparation and characterization of porous carbon material-coated solid-phase microextraction metal fibers.

Two kinds of porous carbon materials, including carbon aerogels (CAs), wormhole-like mesoporous carbons (WMCs), were synthesized and used as the coatings of solid-phase microextraction (SPME) fibers. By using stainless steel wire as the supporting core, six types of fibers were prepared with sol-gel method, direct coating method and direct coating plus sol-gel method. Headspace SPME experiments indicated that the extraction efficiencies of the CA fibers are better than those of the WMC fibers, although the surface area of WMCs is much higher than that of CAs. The sol-gel-CA fiber (CA-A) exhibited excellent extraction properties for non-polar compounds (BTEX, benzene, toluene, ethylbenzene, o-xylene), while direct-coated CA fiber (CA-B) presented the best performance in extracting polar compounds (phenols). The two CA fibers showed wide linear ranges, low detection limits (0.008-0.047μgL(-1) for BTEX, 0.15-5.7μgL(-1) for phenols) and good repeatabilities (RSDs less than 4.6% for BTEX, and less than 9.5% for phenols) and satisfying reproducibilities between fibers (RSDs less than 5.2% for BTEX, and less than 9.9% for phenols). These fibers were successfully used for the analysis of water samples from the Pearl River, which demonstrated the applicability of the home-made CA fibers.