Prevalence of the neurotoxin domoic acid in the aquatic environments of the Bohai and Northern Yellow seas in China.

Domoic acid (DA), a natural marine phytotoxin produced by toxigenic algae, is harmful to fishery organisms and the health of seafood consumers. In this study, we performed a whole-sea area investigation of DA in seawater, suspended particulate matter (SPM), and phytoplankton of the Bohai and Northern Yellow seas to clarify the occurrence, phase partitioning, spatial distribution, potential sources, and environmental influencing factors of DA in the aquatic environment. DA in different environmental media was identified using liquid chromatography-high resolution mass spectrometry and liquid chromatography-tandem mass spectrometry. DA was found to be predominantly in a dissolved phase (99.84 %) in seawater with only 0.16 % in SPM. Dissolved DA (dDA) was widely detected in nearshore and offshore areas of the Bohai Sea, Northern Yellow Sea, and Laizhou Bay with concentrations ranging from < limits of detection (LOD) to 25.21 ng/L (mean: 7.74 ng/L), < LOD to 34.90 ng/L (mean: 16.91 ng/L), and 1.74 ng/L to 38.20 ng/L (mean: 21.28 ng/L), respectively. dDA levels were relatively lower in the northern part than in the southern part of the study area. In particular, the dDA levels in the nearshore areas of Laizhou Bay were significantly higher than in other sea areas. This may be due to seawater temperature and nutrient levels exerting a crucial impact on the distribution of DA-producing marine algae in Laizhou Bay during early spring. Pseudo-nitzschia pungens may be the main source of DA in the study areas. Overall, DA was prevalent in the Bohai and Northern Yellow seas, especially in the nearshore aquaculture zone. Routine monitoring of DA in the mariculture zones of the northern seas and bays of China should be performed to warn shellfish farmers and prevent contamination.

Occurrence and distribution of marine natural organic pollutants: Lipophilic marine algal toxins in the Yellow Sea and the Bohai Sea, China.

For the first time, the composition, concentration and distribution characteristics of typical lipophilic marine algal toxins (LMATs) are investigated in surface seawater, suspended particulate matter (SPM) and sediments from the Yellow Sea and the Bohai Sea, China. Pectenotoxin-2 (PTX2) and okadaic acid (OA) were detected in offshore surface seawater samples (n=67) of the Yellow and Bohai Seas, and PTX2 was found in higher concentrations than OA. The concentrations of PTX2 were between 0.49 and 14.14ng/L. OA, dinophysistoxin-1(DTX1), PTX2 and gymnodimine (GYM) were detected in the nearshore surface seawater samples (n=20) of the Haizhou Bay of the Yellow Sea. OA concentrations were between 11.47 and 55.85ng/L. There was a large degree of variation in the concentrations of DTX1, from

Screening of lipophilic marine toxins in marine aquaculture environment using liquid chromatography-mass spectrometry.

This study aimed to develop an exact mass suspect screening approach to perform finding of multiple lipophilic marine toxins (LMTs) in seawater, suspended particulate matter (SPM), and marine sediment from marine aquaculture area using liquid chromatography-time of flight mass spectrometry (LC-TOF/MS). The method was validated and proven to be reliable for the screening of various LMTs. Then, the method was applied to screen LMTs in marine environmental samples collected from mariculture area of Jiaozhou Bay, China. Okadaic acid (OA), pectenotoxin 2 (PTX2), etc were detected and tentatively identified. Positive detection results were confirmed by liquid chromatography-tandem mass spectrometry (LC-MS/MS), and contents of OA and PTX2 in seawater, SPM and marine sediment were also quantified. The mean concentration of OA ranged from 2.71 to 14.06 ng L-1 in seawater and from 0.78 to 3.34 ng g-1 dry weight in marine sediment. The mean concentration of PTX2 ranged from 0.86 to 7.90 ng L-1 in seawater, from 1.56 to 10.67 ng in SPM obtained from 1 L seawater sample and from 0.95 to 2.23 ng g-1 dry weight in marine sediment. The above results suggested that the proposed method was convenient and reliable for the screening of LMTs in different marine environmental samples. In addition, typical LMTs exist in different marine environmental media of the mariculture area of Jiaozhou Bay, China. Follow-up studies should focus on improving current understanding on the environmental behavior of these LMTs in the marine aquaculture environment.

[Determination of arsenic speciation in Scomberomorus niphonius by capillary electrophoresis-inductively coupled plasma mass spectrometry].

A method for the detection of arsenocholine (AsC), arsenobetaine (AsB), As(III), dimethylarsinic (DMA), monomethylarsonic (MMA) and As (V) by capillary electrophoresis-inductively coupled plasma mass spectrometry (CE-ICP-MS) was established. The results showed that the six species of arsenic were separated within 20 min under the optimized conditions. Good linearities of 6 arsenic species were observed in the range from 2 to 50 µg x L(-1) with the linear correlation greater than 0.996, the detection limits were 0.10-1.08 µg x L(-1) and the RSDs (n = 5) of the peak areas were smaller than 7%. The method was successfully adopted to the determination of the species in Scomberomorus niphonius. The recoveries were between 93% and 98%, and we found the arsenobetaine (AsB) was the main species in the sample. The method was suitable for the analysis of other biological samples with the advantages of good stability, less sample consumption, short analysis time and convenience.

[Determination and distribution patterns analysis of rare earth elements in sediments of Prydz Bay].

A sensitive quantificational method was developed for the analysis of Sc, Y, La, Ce, Pr, Nd, Sm, Eu, etc. in sediments of Prydz Bay by inductively coupled plasma mass spectrometry, and then the REE distribution patterns were analyzed. The samples were digested by microwave using HNO3-H2O2-HF as oxidant. The results showed that the total contents of rare earth elements in eight sites ranged from 117.35 to 348.63 microg x g(-1) and the maximum value was 2.97 times of the minimum value. The REE distribution patterns of different sites in sediments were basically identical and there was an obvious fractionation between LREEs and HREEs. The linear correlation of the method was preferable (r=0.999 7 - 1.000 0). The RSDs (n=3) were no more than 5.0%, and the relative errors were no more than 10%. The detection limits of rare earth elements reached ng x L(-1) level except for Sc. This method was suitable for the analysis of REEs in sediments with the advantages of rapidness, simplicity, high precision and accuracy.

A quartz crystal microbalance sensor based on mussel-inspired molecularly imprinted polymer.

In this work, we describe a simple, inexpensive and fast method for the generation of molecularly imprinted polymer (MIP) film on quartz crystal microbalance (QCM) crystals using mussel-inspired polymer. Commonly known as a neurotransmitter, dopamine is also a small-molecule mimic of the adhesive proteins of mussels. Polymerization of dopamine in the presence of template molecule (1,3,5-pentanetricarboxylic acid, an analogue of domoic acid, in this case) could produce an adherent molecularly imprinted polydopamine film coating on QCM crystals. Advantages, such as high hydrophilicity, high biocompatibility and controllable thickness, make this molecularly imprinted polydopamine film an attractive recognition element for sensors. Selective rebinding of domoic acid on mussel-inspired molecularly imprinted polymer (m-MIP) coated crystal was observed as a frequency shift quantified by piezoelectric microgravimetry with the QCM system. The decreasing frequency shows a good linear relationship with the concentration of domoic acid. The quantitation limit of domoic acid was 5 ppb with the linear range of 0-100 ppb. The QCM sensor has high selectivity and was able to distinguish domoic acid from its analogous p-phthalic acid and o-phthalic acid owing to the molecular imprinting effect. In addition, the practical analytical performance of the sensor was examined by evaluating the detection of domoic acid in mussel extracts with satisfactory results. It is envisaged that m-MIP could be suitable as recognition element for sensors and the proposed m-MIP QCM sensor could be employed to detect analyte of interest in complex matrices.

[Water-soluble anions of atmosphere on Tianwan nuclear power station].

Three major water-soluble anions (Cl-, SO4(2-) and NO3-) in the atmosphere of the Tianwan nuclear power station in Lianyungang were determined by ion chromatography from June 2005 to May 2006. The results showed that the annual average concentration of Cl-, SO4(2-) and NO3- in the atmosphere of Tianwan nuclear power station was (33.12 +/- 53.63) microg x m(-3), (53.34 +/- 30.34) microg x m(-3) and (8.34 +/- 4.47) microg x m(-3), respectively. The concentrations of the three water-soluble anions showed evident trend of seasonal variation. The concentrations of Cl-, SO4(2-) reached the highest level in summer and the lowest level in winter, while the concentration of NO3- in autumn and winter was higher than those in summer and spring. Meteorological parameters such as wind direction, wind speed, temperature and relative humidity were studied and showed definite influence to the anions concentration of the atmosphere. This is the first simultaneous monitoring of corrosive anions in the atmosphere of Chinese coastal nuclear power plant, and it will provide basis for the prevention of marine atmospheric corrosion, which will ensure the safely operating of our nuclear power industry.

Amplified detection of protein cancer biomarkers using DNAzyme functionalized nanoprobes.

The high sensitive immunoassay of protein cancer biomarkers is achieved by using of peroxidase-mimicking DNAzyme heavily functionalized gold nanoparticles as catalytic probe.

Molecularly imprinted polymer as SPE sorbent for selective extraction of melamine in dairy products.

In this paper, a highly selective sample cleanup procedure combining molecular imprinting and solid-phase extraction (MI-SPE) was developed for the isolation of melamine in dairy products. The molecularly imprinted polymer (MIP) was prepared using melamine as the template molecule, methacrylic acid as the functional monomer and ethylene glycol dimethacrylate as the cross-linking monomer. The melamine imprinted polymer was used as selective sorbent for the solid-phase extraction of melamine from dairy products. An off-line MI-SPE method followed by high-performance liquid chromatography with diode-array detection for the detection of melamine was also established. The mean recoveries of melamine from ultra-heat treatment (UHT) milk and milk powders were 92.9-98.0% and 91.6-102.8%, respectively. Good linearity was obtained from 0.5 microM to 10 microM (r>0.999) with a quantitation limit of 0.5 micromol/L (0.06 ppm) which was sufficient to analyse melamine at the maximum level permitted by U.S. Food and Drug Administration (1 ppm) in dairy products. It was demonstrated that the proposed MI-SPE-HPLC method could be applied to direct determination of melamine in dairy products.