Organotin Compounds In Seawater Research Articles

Spatio-temporal variation of organotin compounds in seawater and sediments from Cape Town harbour, South Africa using gas chromatography with flame photometric detector (GC-FPD)

The spatio-temporal variation of two organotin compounds (OTCs) of tributyltin and triphenyltin in the seawater and sediment of Cape Town harbour was investigated. The organotin compounds were determined by GC-FPD following prior extraction with 0.02% tropolone. The concentration of OTCs varies for locations in Cape Town harbour. The concentration of OTCs in seawater ranges from 0.067±0.01 to 111.290±32.20×10−3μg/l for TBT while that of TPT ranges between between ND±SD and 23008.0±0.03×10−3μg/l respectively between locations. Relatively higher concentrations were measured for TBT and TPT during summer than in winter and spring seasons (p⩽0.05). Apparently, the observed high or low values recorded for TBT in Cape Town harbour could be the result of an increase or decrease in the traffic of ships and boats. TBT was detected in all the sediment samples analysed except for location 9 (entrance to harbour), the two control sites (which are located far away from the inner harbour where boating activities are taking place), and location 12 (Robinson dry dock 2) where the samples were not at all found. For the control sites, antifouling compounds TBT and TPT were not detected throughout except for TBT that was found in control A during summer. The seasonal variation of OTC abundance in sediment was also investigated. The results indicated that TBT is present throughout the seasons but is predominantly present in this order summer>winter>spring.

Speciation of Organotin Compounds in Seawater by Headspace Solid Phase Microextraction and Gas Chromatography-Tandem Mass After Ethylation

A method for the determination of five organotin compounds( OTs),monobutyltin( MBT),dibutyltin( DBT),tributyltin( TBT),monophenyltin( MPhT) and diphenyltin( DPhT),in seawater was developed using solid phase microextraction( SPME) coupled with gas chromatography and triple quadrupole tandem mass spectrometer( GC-MS/MS) after ethylation with sodium tetraethylbroate( NaBEt4).After the internal standard( Tripropyltin,TPrT) was added,the pH was adjusted to 5.0 by HAc-NaAc buffer,and NaBEt4 was added,the seawater sample was stirred with a magnetic agitator and the headspace solid phase microextraction was performed with a 75 μm polydimethylsiloxane/carboxen( PDMS/CAR) fiber for 20 min.After extraction,the SPME fiber was directly injected into the GC inlet for GC-MS/MS analysis.The method has very low detection limits for the five organotin compounds in the range of 0.10-0.20 ng/L( Sn).The recoveries are in the range of 80.2%-93.6%,and the relative standard deviations are all below 13% for the five organotin compounds at the spike level of 20 ng/L( Sn).The method is simple,fast,sensitive and solventless.No more than 25 minutes were needed for each sample in routine analysis.The proposed method was applied to96 seawater samples collected from mariculture areas along the Bohai Bay and the detection rate was 42.7%.

Utilization of regenerated iron oxide for treatment of organotin compounds in seawater

We examined the removal and degradation efficiencies of regenerated amorphous iron oxide on tributyltin (TBT) and triphenyltin (TPT) in seawater. It was confirmed that following contact with iron oxide at 20 and 60 °C, the half-lives of TBT and TPT were shortened. These half-lives were from one-thousandth to one-tenth for natural environment conditions. Dibutyltin and benzene were identified as the reaction products from TBT and TPT, respectively, indicating that the degradation pathways were mainly dealkylation and dephenylation. These results indicate that the treatment method by natural energy will enable the economical and rapid reduction of organotin compounds (OTCs). For OTCs in seawater will be adsorbed on the iron oxide by the ebb and flow of the tide and solar energy will be heat source for degradation when iron oxide is prepared in coastal locations.

Organotin compounds in seawater and Mytilus galloprovincialis mussels along the Croatian Adriatic Coast

In this work, data on the level of organotin compounds (OTCs) in seawater and mussels collected along the entire Croatian Adriatic Coast are presented. The samples were collected in 2009 and 2010 at 48 locations representing different levels of maritime activities, including marinas, ports and reference sites. Butyltins (BuTs) were found in all analyzed samples, representing >97% of OTCs, and ranged from 0.46 to 27.98ngSnL−1 in seawater and from <6 to 1675ngSng−1 in mussels. The results indicate a recent input of TBT, with the highest concentrations of BuTs found in the marinas. It appears that the Adriatic coast is still polluted with TBT despite the fact that TBT-containing antifouling paints have been banned in Croatia since 2008. It is questionable how much TBT pollution decreased since 2005, when a high incidence of imposex was established in the same area.

副生酸化鉄の有機スズ処理剤としての利用検討

In this study, we examined the removal and decomposition efficiencies of regenerated amorphous iron oxide on tributyltin (TBT) and triphenyltin (TPT). The results indicated that removal capacity could be estimated from Freundlich function, and also that half-life period of TPT by contact with the iron oxide at 20 °C was 3.1 hours, which was from one hundredth to one tenth in comparison with natural environment condition. Furthermore, the romoval rate of TBT and TPT on the treatment of high polluted sea water made from actual polluted sediment were 80% and 97% respectively. These observations indicate that this iron oxide is useful for treatment of organotin compounds in seawater.

Analysis of organotin compounds in seawater using GC/pulsed flame photometric detection.

A method for a highly sensitive determination of tributyltin (TBT) and triphenyltin (TPT) in seawater has been developed using GC/pulsed flame photometric detector (PFPD). After deuterated TBT and TPT, as surrogates compounds, were added in seawater, TBT and TPT were derivatized by Grignard reagent propylation. Then, derivatized TBT and TPT were extracted with hexane. PFPD showed high selective and sensitivity for the detection of propyl TBTand TPT. The minimum detection limits, defined as the signality equal to three-times the baseline noise, were 0.078 ng/ml and 0.087 ng/ml, respectively. The mean recoveries at 10 ng/l for water were 84 and 98% for TBT and TPT, respectively, and the mean relative standard deviations were 8.2 and 7.4%, respectively. PFPD made it possible to determine TBT and TPT at less than the ng l-1 level in sea water.

Monitoring of organotin compounds in seawater using semipermeable membrane devices (SPMDs)--tentative results.

The impact of anthropogenic pollutants on the marine ecosystem is related to the concentrations experienced by the biota in the seawater and the resulting concentration in the organism. Results from monitoring of pollutants in water samples provide snapshots that can be high or low depending on a wide range of variables. To provide more integrated information, semipermeable membrane devices, SPMDs, have been used to monitor different organic pollutants. In this survey, SPMDs were used to monitor organotin compounds in the marine environment. Time-integrated sampling using SPMDs and direct water sampling was carried out at six stations in the inner Oslofjord, Norway. The sample work-up procedure for both water and SPMDs was based on direct derivatisation using NaBEt4 and simultaneous extraction with an organic solvent. Analysis was performed using a gas chromatograph equipped with an atomic emission detector. The results show that SPMDs do accumulate organotin compounds from the water phase. Both tributyl- (TBT) and dibutyltin were detected in all of the analysed membranes while no monobutyltin was found. Levels found in SPMDs range from < 1 to 220 ng Sn SPMD(-1). Water concentrations range from 0.4 to 10 ng Sn L(-1). An investigation of relative levels of TBT showed a similar concentration gradient in the inner Oslofjord using either direct water sampling or passive sampling by SPMDs. As the membranes are able to accumulate the organotins from the water it will be possible to locate lower concentrations than with direct analyses of water samples.

Contamination of French Coastal Waters by Organotin Compounds: 1997 Update

Fifteen years ago, France took regulatory measures to limit the use of organotin compounds in antifouling paints for the protection of boat hulls. France was the first country to take these emergency steps, which were intended to defend the oyster-farming industry. Since then, the regulations have been confirmed on several occasions, most recently in October 1992. What is the situation at the present time? The campaign conducted by IFREMER from July to September 1997 to measure organotin compounds in seawater provided an update. The contamination of French coasts is still a problem, and the measurements obtained showed persistent sources of pollution for many port facilities. Concentrations measured in the coastal area outside port facilities very often exceeded recognized toxic levels. Seventy-five percent of the measurements were above the threshold of 1 ng.l −1, which is known to cause toxic effects for some marine species. There was considerable variability in the results for the 237 measurement points sampled. In general, the eastern English Channel and the French Riviera are the regions concerned most systematically by excessive levels. The tributyltin concentration was 4.6 ng.l −1 on average, but for ten stations, the contamination was above 100 ng.l −1. The improvement noted during the 1980s has ceased. Comparison with the previous assessment performed by IFREMER in 1992 indicates that the situation today has stagnated at levels which are still far too high. Regulations and monitoring remain necessary. The development of non-toxic alternatives to organotin antifouling paints is required.

Determination of Organotin Compounds in Seawater by Capillary Column Gas Chromatography-Atomic

Determination of Organotin Compounds in Seawater by Capillary Column Gas Chromatography-Atomic

Chemical Species of Organotin Compounds in Seawater and Their Seasonal Variations

Tri-n-butyltin and its degradation products were measured in seawater samples between July 1994 and August 1995 at a marina that is located at a sequestered site of an enclosed harbor, Aburatsubo Bay, in Yokosuka, Japan. Dibutyltins, hydroxylated and oxo compounds of tributyltins and dibutyltins, carboxylated derivatives, and monobutyltin were observed in the summer months (from July to September) and only formed, if at all, in small quantities in the other seasons. Their structures were identified by comparison with synthesized authentic standards using GC/MIP/AED and four GC columns. The degradation products in the seawater in the summers between 1992 and 1995 and those in the oysters collected in the same area in the summer of 1992 showed very similar patterns. This result suggests that the degradation of tri-n-butyltin compounds may be attributable to microorganism flourishing in summer. Keywords: Tributyltin; seawater; degradation; chemical species; seasonal variation; organotin compounds

Analytical Methods for the Determination of Organotins in the Marine Environment

Abstract Analytical procedures for the determination of organotin compounds in sea water, sediments and mussels have been adopted in our laboratory, intercomparison/certification exercises with other European laboratories giving satisfactory results. The characteristics of the different methodologies are discussed, the balance between practical and analytical aspects leading to the selection of the following procedures. For water samples two alternative extraction techniques are used: liquid/liquid extraction (0.3% tropolone in methylene chloride) or liquid/solid extraction (C18- or Carbopack B-loaded extraction tubes). Solid-phase extraction ensures good results and is more suitable in the field, avoiding high volumes of organic solvents and transport of fragile glassware. Extraction rubes can be easily stored, and problems with the transfer of whole samples to the laboratory, and storage and conservation problems are prevented. For sediments and mussels, sonication (0.05% tropolone in methanol) can be u...

Tributyltin analysis in seawater by GC FPD after direct aqueous‐phase ethylation using sodium tetrathylborate

AbstractUsing sodium tetraethylborate as an alkylation reagent, one‐step ethylation and extraction of organotin compounds in seawater was performed directly in the aqueous phase to obtain optimal rection conditions. No further purification or concentration of the extract was required before GC FPD analysis. The detection limit for monobutyl‐dibutyl‐and tributyl‐tin was approximately 0.4 ng dm−3, which is adequate for any currently know toxicity effect. The linearity range (0–200 ng dm−3) was solely dependent on the detector response curve. Compared with the Grignard reaction after extraction in an organic solvent, this new ethylation procedure reduces the number of analytical steps, thus saving time and improving reliability.

Organotin speciation in aquatic matrices by CGC/FPD, ECD and MS, and LC/MS

The sensitivity and reproducibility of CGC coupled to selective detectors for the determination of alkyl and aryltin compounds (RxSnYz, where R=C4H9 or C6H5, and Y=CH3 or Cl) (x+z=4) have been evaluated. In this regard, single or dual flame FPD configurations, with or without interference filter (600 nm) have been compared. The electron impact (EI) selected ion monitoring detection (SIM) CGC-MS was also considered for confirmation of the FPD assignments as well as for quantitative purposes. Alternatively, the accuracy and sensitivity of the direct analysis of organotin chlorides (Y=Cl) by cold on-column injection CGC-ECD or by thermospray LC-MS were determined. According to this, an analytical protocol based on acid digestion, extraction with organic solvents modified with tropolone, derivatization with CH3MgCl, cleanup with alumina and CGC-FPD analysis has been successfully applied to the characterization of organotin compounds in seawater, sediments and biota. The relative detection limits of the whole procedure were dependent of the tin species and the environmental compartment considered, ranging from 0.5 to 6.5 ng l−1 for seawater, in the filterless operation mode, and 0.1–2 ng g−1 and 0.7–8 ng g−1 for sediments and biota, respectively, using a 600 nm interference filter. Reproducibility was in the range of 15% RSD. Aryl and hydroxyalkyltin were identified for the first time in the aquatic compartments.

Gas Chromatographie Determination of Di- and Tributyltin Compounds in Seawater Using Simultaneous Hydride-Formation and Extraction

A gas chromatographic method is described for the determination of di- and tributyltin compounds in seawater. Organotin compounds in seawater led to their chlorides with hydrochloric acid. The chlorides were reacted with sodium borohydride to produce hydrides and simultaneously extracted with hexane by stirring extraction. The organic layer was concentrated by a gentle stream of nitrogen and passed through a SEP-PAK silica cartridge for cleaning. The trapped organotin compounds were eluted with hexane, concentrated by a gentle stream of nitrogen and determined by gas chromatography with a flame photometric detector. Separation of the organotin compounds was successfully carried out using a DB-1 wide bore column. The detection limits of di- and tributyltin compounds as their chlorides were 0.10ng (25ng/l for 400ml of the sample) and 0.08ng (20ng/l for the same sample). Compounds yielding dibutyltin dihydride and tributyltin hydride were found in Hakata port seawater at levels of 240 to 480ng/l and 27 to 93ng/l as their chlorides.

海水中の微量有機スズ化合物の分析ならびにその海洋環境における挙動に関する研究 第５報 海水試料中のジブチルスズおよびトリブチルスズ化合物の分析に適する試料容器の検討

The container materials suitable for determination of dibutyltin (DBT) and tributyltin (TBT) compounds in seawater have been studied. Three commercial container materials of glass, polyethylene and polycarbonate bottles were used. One bottle of each material was filled with a stock solution dissolving dibutyltin dichloride (DBTC) and tributyltin chloride (TBTC) in seawater, and the concentrations of DBTC and TBTC were analyzed periodically by gas chromatography with flame photometric detection (GC-FPD). It was found that polyethylene bottle was not suitable for use as seawater container because of adsorption of TBTC on the surface of container, but the glass and polycarbonate bottles were suitable. Studies on the Determination of Trace Amounts of Organotin Compounds in Seawater and the Behavior of their Compounds in Marine Environment. V.

Speciation and determination of tin(IV) and organotin compounds in sea-water by hydride generation—atomic-absorption spectrometry with an electrically heated long absorption cell

A method is described for the determination of nanogram or subnanogram amounts of Sn(IV) and the halides of methyltin, dimethyltin, trimethyltin, n-butyltin, dibutyltin, and tributyltin. These compounds are volatilized from water samples by hydride generation, collected on a chromatographic stationary phase, desorbed in order of increasing boiling point, and detected by atomic-absorption spectrometry with atomization in a long electrothermally heated alumina tube furnace. The absolute detection limits are in the range 0.4–1.5 ng with a reproducibility of 4–15% for inorganic tin and organotin compounds.

Determination of inorganic and organotin compounds in sea water by graphite furnace atomic absorption spectrometry

Inorganic tin and organotin compounds in artificial sea water were determined at sub-p.p.b. levels. These compounds are separated from matrix elements in aqueous solutions by benzene extraction of their iodide forms from a 2 M sulphuric acid-1.5 M sodium iodide solution containing 1%m/V ascorbic acid. The organic phase was partially vaporised to pre-concentrate the analytes and was injected directly into the treated graphite tube; the signal was measured by a Zeeman atomic absorption spectrometer. Using a matrix modifier, inorganic tin could be directly determined at sub-p.p.m. levels in the presence of organotin compounds.