An improved method for the simultaneous analysis of phenolic and steroidal estrogens in water and sediment.

This paper describes an improved method for the extraction and analysis of seven endocrine disrupting chemicals with wide-ranging polarities from water and sediments using gas chromatography-tandem mass spectrometry (GC-MS/MS). The analytes were 4-tert-octylphenol, 4-nonylphenol, bisphenol A, estrone, 17beta-estradiol, 17alpha-ethynylestradiol and 16alpha-hydroxyestrone. The optimised GC-MS/MS method produces increased selectivity and sensitivity compared to GC-MS, with limit of detection ranging from 0.01 to 0.49 ng L(-1) in water and from 0.05 to 0.14 ng g(-1) in sediment. Extraction from aqueous samples was performed by solid-phase extraction (SPE) and from sediment samples by microwave-assisted extraction (MAE). The improved method for the clean-up of sediment extracts carried out by SPE enhanced EDC recovery (86-102%) while reducing matrix interference and sample drying time. Derivatisation of final sample extracts was achieved using N,O-bis(trimethylsilyl)trifluoroacetamide and pyridine, and their stability was enhanced by reconstituting the derivatised extracts with hexane. The method was validated by spiking experiments which showed good recovery and reproducibility. The method was applied to samples taken from the Medway estuary in Kent, UK, where non-conservative behaviour of EDCs was demonstrated.

Organochlorine micropollutants in the Jiulong River Estuary and Western Xiamen Sea, China.

Organochlorine contaminants including 12 polychlorinated biphenyl (PCB) congeners and 18 insecticides were determined in water, pore water and sediments of the Jiulong River Estuary and Western Xiamen Sea, China. The results showed that the levels of the total PCBs ranged from non-detectable to 1500 ng l(-1) in water, from 209 to 3870 ng l(-1) in pore water, and from 2.78 to 14.8 ng g(-1) dry weight in sediments. Total organochlorine insecticide concentrations were from below the limit of detection to 2480 ng l(-1) in water, from 267 to 33400 ng l(-1) in pore water, and from 4.22 to 46.3 ng g(-1) dry weight in sediments. Concentrations of PCBs and insecticides in pore water were significantly higher than those in surface water, due to the high affinity of these hydrophobic compounds for sediment phase. The PCB congeners with the highest concentrations were CB153, CB180 and CB194, which together accounted for 68-87% of total PCBs in water, pore water and sediment. Among the hexachlorocyclohexane (HCH) compounds, beta-HCH was found to be a major isomer. Analysis of 1,1,1-trichloro-2,2-bis-chlorophenyl-ethane (DDT) and its metabolites showed that 1,1-dichloro-2[o-chlorophenyl]-2[p-chlorophenyl]-ethylene (DDE) was dominant in the group. In comparison to a 1998 study in the Western Xiamen Sea, levels of organochlorines were enhanced due probably to recent inputs and changes in sediments.

Microbial modulation in the biomass and toxin production of a red-tide causing alga.

The effect of S10, a strain of marine bacteria isolated from sediment in the Western Xiamen Sea, on the growth and paralytic shellfish poison (PSP) production in the alga Alexandrium tamarense (A. tamarense) was studied under controlled experimental conditions. The results of these experiments have shown that the growth of A. tamarense is obviously inhibited by S10 at high concentrations, however no evident effect on its growth was observed at low concentrations. Its PSP production was also inhibited by S10 at different concentrations, especially at low concentrations. The toxicity of this strain of A. tamarense is about (0.95-12.14) x 10(-6) MU/cell, a peak toxicity value of 12.14 x 10(-6) MU/cell appeared on the 14th day, after which levels decreased gradually. The alga grew well in conditions of pH 6-8 and salinities of 20-34 per thousand. The toxicity of the alga varied markedly at different pH and salinity levels. Toxicity decreased as pH increased, while it increased with salinity and reached a peak value at a salinity of 30 per thousand, after which it declined gradually. S10 at a concentration of 1.02 x 10(9) cells/ml inhibited growth and the PSP production of A. tamarense at different pH and salinity levels. S10 had the strongest inhibitory function on the growth of A. tamarense under conditions of pH 7 and a salinity of 34 per thousand. The best inhibitory effect on PSP production by A. tamarense was at pH 7, this inhibitory effect on PSP production did not relate to salinity. Interactions between marine bacteria and A. tamarense were also investigated using the flow cytometer technique (FCM) as well as direct microscope counting. S10 was identified as being a member of the genus Bacillus, the difference in 16S rDNA between S10 and Bacillus halmapalus was only 2%. The mechanism involved in the inhibition of growth and PSP production of A. tamarense by this strain of marine bacteria, and the prospect of using it and other marine bacteria in the bio-control of red-tides was discussed.

Distribution of polycyclic aromatic hydrocarbons in water and surface sediments from Daya Bay, China.

Marine culture is thriving in China and represents a major component of the regional economy in coastal zones, yet the environmental quality of many of those areas has never been studied. This paper attempts to investigate the quality status of Daya Bay, a key aquaculture area in China. The levels of 16 polycyclic aromatic hydrocarbons (PAHs) were determined in water and sediment samples of the bay. The total concentrations of 16 PAHs varied from 4228 to 29325 ng l(-1) in water, and from 115 to 1134 ng g(-1) dry weight in sediments. In comparison to many other marine systems studied, the PAH levels in Daya Bay waters were relatively high, and at six sites they were sufficiently high (> 10 microg l (-1)) to cause acute toxicity. The PAH composition pattern in sediments suggest dominance by medium to high molecular weight compounds, and the ratio of certain related PAHs indicate important pyrolytic and petrogenic sources. Further analysis showed that the distribution coefficient (KD) increased with the particular organic carbon content of sediments, consistent with the PAH partition theory. The organic carbon normalised distribution coefficient (K(oc)) also increased with the compounds' octanol/water partition coefficient (K(ow)), confirming the potential applicability of the linear free energy relationships in the modelling and prediction of PAH behaviour in marine environments.

Contamination by polycyclic aromatic hydrocarbons in the Jiulong River Estuary and Western Xiamen Sea, China.

The distribution of 16 polycyclic aromatic hydrocarbons (PAHs) was determined in water, sediment and pore water of the Jiulong River Estuary and Western Xiamen Sea, China. Total PAH concentrations varied from 6.96 to 26.9 microg/l in water, 59-1177 ng/ g dry weight in surficial sediments, and 158-949 microg/l in pore water. The PAHs were present in higher levels in pore water than in surface water, due possibly to higher concentrations of dissolved organic carbon or colloids with which the hydrophobic pollutants were strongly associated. Such a concentration gradient implies a potential flux of pollutants from sediment pore water to overlying water. The levels of PAHs in water and pore water were significantly higher than those found in 1998, suggesting recent inputs of these compounds into the area and re-working of sediment phase. The composition pattern of PAHs in the three phases was dominated by high molecular weight PAHs, in particular 5-ring PAHs. The salinity profile of dissolved PAHs suggested that they all behaved non-conservatively due to deviation from the theoretical dilution line. No correlation was found between PAH concentrations in sediment and those in pore water, and the correlation between the partition coefficients of PAHs and sediment organic carbon content was not significant, suggesting the complexity of the partition behaviour of PAHs. As a result of high PAH concentrations in water and pore water, it is likely that they may have caused mortality to certain exposed organisms.

Polychlorinated biphenyl congeners and organochlorine insecticides in the water column and sediments of Daya Bay, China.

Samples of sub-surface water, suspended particulate matter (SPM) and surface sediments collected from Daya Bay, China have been analysed for 12 polychlorinated biphenyl (PCB) congeners and 18 organochlorine insecticides, using gas chromatography electron capture detection. Total PCB levels varied from 91.1 to 1355.3 ng l-1 in water and from 0.85 to 27.37 ng g-1 dry weight in sediments. The levels of total organochlorine insecticides were in the range 143.3-5104.8 ng l-1 in water and 2.43-86.25 ng g-1 dry weight in sediment. None of the target compounds were detected in SPM. The levels of total hexachlorocyclohexanes in water varied from 35.5 to 1228.6 ng l-1, whilst in sediments they ranged from 0.32 to 4.16 ng g-1 dry weight. For the sum of dichlorodiphenyltrichloroethanes (DDTs), their levels were in the range 26.8-975.9 ng l-1 in water, and 0.14-20.27 ng g-1 dry weight in sediments. The distribution profiles of these contaminants in water and sediments suggest that there are a number of sources contributing to total contaminant burden in the bay, including soil runoffs, wastewater discharges, sewage outfalls and shipping activites. Ratios of DDT/(DDE + DDD) in the water and sediments indicate recent inputs of such chemicals into the day. The results, therefore, provide important information on the current contamination status of a key aquacultural area in China, and point to the need for urgent actions to stop the use of persistent agrochemicals such as DDT and lindane.