Organotin Speciation Analysis In The Marine Environment And Its Metabolic Degradation

Organotin compounds have been widely used as heat and light stabilizers in the production of polyvinylchloride materials, and as anti-bacterial and anti-fungal agents in pesticides and anti-fouling applications. The toxicity of Organotin compounds, especially those of tributyltin and triphenyltin has resulted in deleterious effects on non-target organisms such as shellfish and fish in coastal environments. The bioaccumulation of these compounds in shellfish and fish can result in serious health damage on human who consumed these contaminated species. Many countries around the world have formulated their respective laws and regulations prohibiting or restricting the use.of organotin compounds. Trace and ultra-trace analytical technique for organotin compounds in today's environment and food safety areas is a kind of cutting-edge technology, as a result of a wide variety of alkyl tin, the existence of differences in physical and chemical properties. There are a large of difficulties in the extraction, separation and determination of organotin compounds in the marine environmental samples. .In the present work, a hyphenated technique of high-performance liquid chromatography (HPLC) coupled with inductively coupled plasma mass spectrometry (ICP-MS) was established for a rapid and simultaneous determination of several important organotin compounds; the sample pre-treatment technology for those organotin in marine environmental samples was developed. The distribution, metabolism and degradation of organotin in marine organisms were characterized primarily, and a rapid detection method for trace elements was established. The five species of organotin was detected rapidly by use of the method developed in the present work. The detection limits of five organotin compounds all are less than 0.3μg/L.The case study forganotin pollution for marine organisms in the Southern Yellow Sea was performed with the method developed in the present work, and a commercial statistical software (SPSS) was applied to analyze the experimental results obtained. It was found that 97.2% of marinounde organisms contained butyltin and phenyltin compounds, and the concentrations ranged from the detection limits of those compounds upto 1487.8ng Sn/g. The average concentration of the total organotin in the shellfish samples was 416.9ng Sn/g, which was much higher than the average concentration of total organotin in the fish samples (211.9ng Sn/g). The fact of organotin with high concentration in marine organisms indicates that the pollution of organotin in this area is serious, which may damage the ecological environment and human life. The main pollution source might be attributed to the application of antifouling paint along the costal. Therefore the critical point is to take the necessary steps of controlling the use of organotin in this area.In order to accurately analyze the seawater and sediment samples, a simple and rapid extraction method for five organotin compounds was established in this study. By adding 2% of tropolone into CH2Cl2, the organotin in seawater samples was extracted with a higher rate. The extraction rate of DPhT, DBT, TBT and TPhT were all more than 80%, while the extraction rate of TMT was only 50%. by using of mobile phase and 0.2% tropolone, the international standards sediment (PACS-2) was analyzed after ultrasonic extraction and high-speed centrifugation, the analytical results illustrate that the experimental data obtained are agree well with the the certified results of the international standard materials. This indicates that the method established could be applied to the analysis of organotin compounds in real marine sediment samples.Meanwhile, a method for direct determination of trace elements in seawater with hyphenated technique of flow injection coupled to inductively coupled plasma mass spectrometry(ICP-MS) was established, which was successfully applied to the case study for the determination of heavy metals in South China Sea. The results showed that the concentrations of Cd, Cr and As in this area are lower than the limits of first-degree seawater of China regulation. The method was characterized with its high efficiency to reduce the interferences from Na, Mg, Ca and Cl in seawater by using the trace sampling technique. The method could also be used to measure trace-class elements including V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Mo, Cd, Pb, Hg and U.A sediment digestion method in closed-vessel without removing HF acid was recommended, which could reduce the sample treatment time from 20 hours to 10 hours. With this digestion method, tin and other heavy metals in the sediment of South Yellow Sea were accurately determined with ICP-MS. The heavy metal pollution history of marine sediments around South Yellow China Sea was surveyed. From which, it was found that the pollution from Cu, Zn, Cr, Ni, Pb, Co and Mn in the sediments had been increased gradually from 2001 to 2007. Also a method of microwave digestion-ICP-MS was established to determine the harmful heavy metals such as tin, arsenic, cadmium, mercury and lead. Seven seafood samples from the Southern Yellow Sea and twenty nine seafood samples from the South China Sea were analyzed. Different degrees heavy metal pollution in seafood could be found. The heavy metal contents in different types and regions were varied, which could provide a useful reference for seafood quality control.The distribution, metabolism and the degradation processes of organotin compounds were studied primarily, and a novel method to characterize organotin compounds.with LC-APCI-TOF-MS was established in this work. The experimental results showed that organotin contents varied in different organs of shellfish samples. Their contents in internal organs were higher than those in muscle. It was recommended that the common cooking methods may not reduce the contents of organotin in sea food.