Chongyu Lan

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.

Influence of growth medium on cometabolic degradation of polycyclic aromatic hydrocarbons by Sphingomonas sp. strain PheB4

The influence of growth medium on cometabolic degradation of polycyclic aromatic hydrocarbons (PAHs) was investigated when Sphingomonas sp. strain PheB4 isolated from surface mangrove sediments was grown in either phenanthrene-containing mineral salts medium (PMSM) or nutrient broth (NB). The NB-grown culture exhibited a more rapid cometabolic degradation of single and mixed non-growth substrate PAHs compared to the PMSM-grown culture. The concentrations of PAH metabolites were also lower in NB-grown culture than in PMSM-grown culture, suggesting that NB-grown culture removed metabolites at a faster rate, particularly, for metabolites produced from cometabolic degradation of a binary mixture of PAHs. Cometabolic pathways of single PAH (anthracene, fluorene, or fluoranthene) in NB-grown culture showed similarity to that in PMSM-grown culture. However, cometabolic pathways of mixed PAHs were more diverse in NB-grown culture than that in PMSM-grown culture. These results indicated that nutrient rich medium was effective in enhancing cometabolic degradation of mixed PAHs concomitant with a rapid removal of metabolites, which could be useful for the bioremediation of mixed PAHs contaminated sites using Sphingomonas sp. strain PheB4.

Seasonal and spatial variations in microbial community structure and diversity in the acid stream draining across an ongoing surface mining site.

This study examined the microbial community in an acidic stream draining across the Yun-Fu pyrite mine (Guangdong, China), where extremely acidic mine water is a persistent feature due to the intensive surface mining activities. Analysis of terminal restriction fragment length polymorphism (TRFLP) of 16S rRNA gene sequences showed that microbial populations varied spatially and seasonally and correlated with geochemical and physical conditions. After the stream moves from underground to the surface, the microbial community in the acidic water rapidly evolves into a distinct community close to that in the downstream storage pond. Comparisons of TRFLP peaks with sequenced clone libraries indicated that bacteria related to the recently isolated iron-oxidizer Ferrovum myxofaciens dominated the acidophilic community throughout the year except for the samples collected in spring from the storage pond, where Ferroplasma acidiphilum-like archaea represented the most abundant group. Acidithiobacillus ferrooxidans-affiliated organisms increased along the acid stream and remained common over the year, whereas Leptospirillum ferrooxidans-like bacteria were negligible or even not detected in the analyzed samples. The data indicate that changes in environmental conditions are accompanied by significant shifts in community structure of the prokaryotic assemblages at this opencast mining site.

One-step extraction and derivatization liquid-phase microextraction for the determination of chlorophenols by gas chromatography–mass spectrometry

A sample pretreatment method for the determination of 18 chlorophenols (CPs) in aqueous samples by derivatization liquid-phase microextraction (LPME) was investigated using gas chromatography-mass spectrometry. Derivatization reagent was spiked into the extraction solvent to combine derivatization and extraction into one step. High sensitivity of 18 CPs derivatives could be achieved after optimization of several parameters such as extraction solvent, percentage of derivatization reagent, extraction time, pH, and ionic strength. The results from the optimal method showed that calibration ranging from 0.5 to 500microgL(-1) could be achieved with the RSDs between 1.75% and 9.39%, and the limits of detection (LOD) are ranging from 0.01 to 0.12microgL(-1) for the CPs. Moreover, the proposed LPME method was compared with solid-phase microextraction (SPME) coupled with on-fiber derivatization technique. The results suggested that using both methods are quite agreeable. Furthermore, the recoveries of LPME evaluated by spiked environmental samples ranged from 87.9% (3,5-DCP) to 114.7% (2,3,5,6-TeCP), and environmental water samples collected from the Pearl River were analyzed with the optimized LPME method, the concentrations of 18 CPs ranged from 0.0237microgL(-1) (3,5-DCP) to 0.3623microgL(-1) (2,3,6-TCP).

Culturable and molecular phylogenetic diversity of microorganisms in an open-dumped, extremely acidic Pb/Zn mine tailings

A combination of cultivation-based and molecular-based approaches was used to reveal the culturable and molecular diversity of the microbes inhabiting an open-dumped Pb/Zn mine tailings that was undergoing intensive acid generation (pH 1.9). Culturable bacteria found in the extremely acidic mine tailings were Acidithiobacillus ferrooxidans, Leptospirillum ferriphilum, Sulfobacillus thermotolerans and Acidiphilium cryptum, where the number of acidophilic heterotrophs was ten times higher than that of the iron- and sulfur-oxidizing bacteria. Cloning and phylogenetic analysis revealed that, in contrast to the adjacent AMD, the mine tailings possessed a low microbial diversity with archaeal sequence types dominating the 16S rRNA gene library. Of the 141 clones examined, 132 were represented by two sequence types phylogenetically affiliated with the iron-oxidizing archaea Ferroplasma acidiphilum and three belonged to two tentative groups within the Thermoplasma lineage so far represented by only a few environmental sequences. Six clones in the library were represented by the only bacterial sequence type and were closely related to the well-described iron-oxidizer L. ferriphilum. The significant differences in the prokaryotic community structures of the extremely acidic mine tailings and the AMD associated with it highlights the importance of studying the microbial communities that are more directly involved in the iron and sulfur cycles of mine tailings.

Metabolite production in degradation of pyrene alone or in a mixture with another polycyclic aromatic hydrocarbon by Mycobacterium sp

Degradation of pyrene (PYR) alone and in the presence of phenanthrene or fluoranthene by Mycobacterium sp. strain A1-PYR isolated from mangrove sediments was investigated. When PYR was the only polycyclic aromatic hydrocarbon compound and the sole carbon source, only 33% of the added PYR was slowly degraded during 7 d of incubation. Seven metabolites were obtained, including four-ring metabolites (monohydroxypyrene and three different dihydroxypyrenes) and three-ring metabolites (dihydroxyphenanthrene, 4-phenanthrene-carboxylic acid, and 4-phenanthrol), of which more four-ring metabolites accumulated compared with three-ring metabolites. To our knowledge, this is the first report in which PYR was initially attacked by Mycobacterium sp. to form three different dihydroxypyrenes. Pyrene degradation was significantly stimulated when mixed with phenanthrene or fluoranthene. In the presence of fluoranthene, PYR was rapidly degraded (up to 57%), and significant amounts of dihydroxypyrene were formed within 3 d of incubation, followed by a period of minimal PYR degradation from 3 to 7 d with disappearance of four-ring metabolites and accumulation of three-ring metabolites. In contrast, PYR was removed completely, and little evidence of metabolites was detected in the presence of phenanthrene. These results showed that PYR was degraded to a larger extent when mixed with another polycyclic aromatic hydrocarbon concomitant with a higher turnover of PYR metabolites. The induction of complex enzyme systems and increase in biomass possibly affected the transformation of PYR metabolites in the mixture with phenanthrene or fluoranthene.

Determination of Bisphenol A in Landfill Leachate by Solid Phase Microextraction with Headspace Derivatization and Gas Chromatography-Mass Spectrophotometry

Abstract A method of headspace derivatization solid phase microextraction (SPME) coupled with gas chromatography-mass spectrometry (GC-MS) for determination of Bisphenol A (BPA) in landfill leachate has been developed. Using 85-μm polyacrylate (PA) fibers, the influences of several parameters on the SPME and derivatization procedure such as extraction time of the fiber in the aqueous sample, derivatization time and temperature, desorption time and temperature, the pH value as well as the salt content of the sample have been studied. The derivatization was carried out at room temperature without damaging the fiber coating. A linear response of silylated BPA compounds over a concentration range from 0.09 to 200 μg/l, with detection limit at 0.03 μg/l (3 s criteria) were obtained. The proposed method has been applied for the determination of BPA in landfill leachate.