Organotin Compounds In Sediments Research Articles

Green and sensitive method combining ultrasonic solvent extraction, stir bar sorptive extraction and thermal desorption-gas chromatography–tandem mass spectrometry for determination of organotin compounds in sediment

A method integrating ultrasonic solvent extraction (USE) and stir bar sorptive extraction (SBSE) with thermal desorption-gas chromatography–tandem mass spectrometry (TD-GC–MS/MS) was developed and validated for determining critical organotin compounds (OTCs)—tributyltin (TBT) and triphenyltin (TPhT)—in sediment. In preparing a 0.5 g sediment sample, two 1-min cycles of US bath solvent extraction (using equal parts CH3COOH and MeOH), were followed by derivatization with NaBEt4 in the presence of a methanolic-aqueous solution of CH3COONa and SBSE for 1 h, achieving analyte recoveries of 64–94 %. Matrix-matched internal standard calibration and the use of an isotopically labelled recovery standard corrected for analyte losses and matrix effect (ME), ensuring accurate results for triorganotins. However, the method was not suitable for mono- and diorganotins due to low and anomalous recoveries caused by ME. Miniaturizing and optimizing the sample preparation reduced chemicals use and waste, contributing to the method being deemed ’an excellent green analysis’ by the Analytical Eco-Scale assessment. The method achieved a limit of quantification (LOQ) of 0.081 ng g−1 and an expanded uncertainty (U) value of 15 % for TBT, meeting the environmental quality standards (EQS) criteria of the European Union Water Framework Directive. Its applicability was demonstrated through the analysis of actual sediment samples and natural matrix certified reference materials.

Mobility of metal-organic pollutants in the emerging coastal-marine sediment of the Baltic Sea: The case-example of organotin compounds in sediments of the Gulf of Finland

Results of organotin and heavy metals pollution study of bottom sediment within three key areas in the Eastern Gulf of Finland (Baltic Sea) in the vicinity of Gogland and Moschny Islands and Vyborg Bay sampled during two seasons of 2017 and 2018 are presented.The studied bottom sediments contain organotin compounds in amounts (∑OTs from 5.7 to 123 ng/g) exceeding the permissible international standards, which can have a toxic effect and lead to pathological changes of aquatic organisms. The tributyltin was the prevail component of organotin compounds in bottom sediments in 2017, which high content (average 6.3 and 30 ng/g for Moschny and Gogland islands respectively) and low degradation coefficient (BDI: 0.1–0.8) indicate a permanent source of pollution. But the 2018 samples show an increase in BDI up to 1.7–3.3 that reveals the degradation of tributyltin over the annual period. But further monitoring of environmental pollution in the study areas is obviously necessary in view of the potential impact of these components on the irreversible change in the environmental situation for the entire Baltic region.

Rapid and sensitive determination of antifouling organotin compounds in sediments using Gas chromatography with Tandem MS (GC – MSMS / GC – QTOF)

ABSTRACT Organotin compounds are causing deterioration effect on non-targeted aquatic species in the environment, such as shell anomalies in oysters and imposex in gastropods, even at concentrations as low nanograms per litre. Specific analytical methods have been developed for different environmental matrices. Analysis of organotin compounds in sediment because of hydrophobic properties and tend to adsorb onto particulate matter is valuable for assessing the environmental distribution and fate. Therefore, in this study, a rapid, reliable, sensitive and effective method developed for quantification and identification of antifouling organotin butyl- and phenyltin compounds in sediment samples by using Gas chromatography with Tandem MS detector (GC-MSMS and GC-QTOF). The method is based on the single extraction step followed by GC-MSMS and GC-QTOF detection. The sample extraction steps were decreased for low labour laboratory costs and time-consuming. Not only the extraction procedure but instrumental method parameters were carefully optimised in order to increase sensitivity and precision. The QTOF system with the help of mass accuracy and mass resolution showed a good sensitivity and precision to analyse sediment samples. The isotopic disturbance and utilisation isotopic space for confirmation of organotin compounds have been scrutinised in GC-QTOF. GC Triple Quadrupole (GC-MSMS) system also utilised as a secondary confirmation method for organotin compound analysis. Additionally, the sensitivity of both MS detectors under the matrix effect was investigated. The recoveries of extraction were in the range of 82–106%. The acquired results have shown that the concentration range in 10–250 ppb (ng/ml) level was denoted good linearity (r2 = 0.9725–0.9983). Moreover, limits of detection (LOD) for both butyl and phenyl fractions of organotin compounds were ranged between 0.23 and 22.11 pg/ml. Consequently, the developed method successfully was applied to certificated reference material (BCR – 462) and the targeted organotin compounds in a real marine/harbour sediment sample.

Spatiotemporal variation and source apportionment of organotin compounds in sediments in the Yangtze Estuary

BackgroundThe Yangtze Estuary is a vital habitat and breeding ground for many rare species (e.g., Chinese sturgeon, Chinese paddlefish). From the view of marine ecosystem health, organotin compounds (OTCs) should be of great concern in this area based on their broad applications and potential threats. At present study, five OTC species were determined in 28 and 26 surface sediments from the Yangtze Estuary (including the Nearshore area, Estuarine Turbidity Maxima (ETM) zone and Plume zone) in 2015 and 2016, respectively. Meanwhile, four sludge samples were collected from the adjacent Shidongkou Wastewater Treatment Plant to perform a source apportionment.ResultsThe sum of OTCs presented a decreasing trend towards the open sea, averaging 4.8 ± 6.0 ng Sn g−1 dw in the Plume zone. While OTC levels in the Nearshore area (2.9–34.6 ng Sn g−1 dw) were similar with those in the ETM zone (5.6–36.0 ng Sn g−1 dw), and the sites belonging to the Deepwater Navigation Channel showed heavier contamination in the ETM zone than the Nearshore area. There are abundant suspended particles and organic matters in the ETM zone that can effectively capture the hydrophobic compounds. Besides, OTC contamination in shoreside zone was more serious than those in channel center. High OTC loads (average 633 ± 124 ng Sn g−1 dw) were also found in sludge samples from adjacent wastewater treatment plant.ConclusionLand-based sources (e.g. sewage discharge, runoff) are probably one of the predominant pathways of OTCs entering the ocean. Combining with previous observation in 2014, OTC contamination in the same ten sites varied slightly with years. Risk assessment indicated that the concentrations of tributyltin (TBT) are sufficient to pose ecosystem threats especially in the ETM zone. Hence, OTC contamination issues in the Yangtze Estuary still can not be neglected.

Seasonal changes in organotin compounds in sediments from the Bahía Blanca Estuary

Fil: Quintas, Pamela Yanina. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro Cientifico Tecnologico Conicet - Bahia Blanca. Instituto Argentino de Oceanografia. Universidad Nacional del Sur. Instituto Argentino de Oceanografia; Argentina

Organotin persistence in contaminated marine sediments and porewaters: In situ degradation study using species-specific stable isotopic tracers

This paper provides a comprehensive study of the persistence of butyltins and phenyltins in contaminated marine sediments and presents the first data on their degradation potentials in porewaters. The study’s aim was to explain the different degradation efficiencies of organotin compounds (OTC) in contaminated sediments. The transformation processes of OTC in sediments and porewaters were investigated in a field experiment using species-specific, isotopically enriched organotin tracers. Sediment characteristics (organic carbon content and grain size) were determined to elucidate their influence on the degradation processes. The results of this study strongly suggest that a limiting step in OTC degradation in marine sediments is their desorption into porewaters because their degradation in porewaters occurs notably fast with half-lives of 9.2 days for tributyltin (TBT) in oxic porewaters and 2.9±0.1 and 9.1±0.9 days for dibutyltin (DBT) in oxic and anoxic porewaters, respectively. By controlling the desorption process, organic matter influences the TBT degradation efficiency and consequently defines its persistence in contaminated sediments, which thus increases in sediments rich in organic matter.

Speciation and quantification of organotin compounds in sediment and drinking water by isotope dilution liquid chromatography-inductively coupled plasma-mass spectrometry

A rapid, simple isotope dilution method for detecting organotins in sediment samples.

Organotin Compounds in Sediments of Northern Lakes, Egypt

This pioneered study is aimed to determine the levels and distributions of organotin compounds (OTCs) in sediment samples collected from five Egyptian lakes located in the southern-eastern Mediterranean Sea. The paper has given an account of and the reasons for the widespread distribution of Tributyltin (TBT) in northern lakes. The percentage of TBT ranged from 4% - 100% OTC revealing recent inputs of TBT. The highest average of TBT (2.84 μg/g Sn dry wt) was measured in lake Edku. Dibutyltin (DBT) was observed at most sampled sites. Relatively higher abundance of DBT was observed in sediments of EL-Burullus (0.69 μg/g Sn dry wt). One of most significant findings to emerge from this study is the absence of any strong and significant correlation between TBT and DBT in sediments from five northern lakes. The absence of such correlation might give a clear evidence that both compounds did not come from the same source. The observed OTC levels indicate some highly localized areas of contamination which are severe enough to cause harmful effects on marine flora and fauna. Except for El-Burllus, Triphenyltin (TPhT) was not measured in sediments of most stations. TPhT was the predominant species in El-Burullus, which indicate a source of pollution mostly originated from industrial and agricultural waste water discharge, organic wastes, commercial fertilizers, chemical wastes and pesticides. The percentages of OTC to total tin ranged from 1% to 35%. El-Brullus, Edku and El-Bardaweel exhibited the highest percentages. As a result of lack of enforcement on the control of OTC, the study has thrown up many questions need further detailed environmental assessment of OTC.

The Speciation of Organotin Compounds in Sediment and Water Samples from the Port of Gdynia

Organotin compounds (OTC) are toxic towards all living organisms. The application of organitin-based antifouling systems is becoming the main source of OTC in the ocean. Harbor sediments and water contain large deposits of organotin compounds due to application of antifouling systems in the shipping industry. OTC contamination presents a potential risk to the marine environment. Sediment and water samples were collected in 2009 from Gdynia Harbor. For all the analyzed organotin compounds, the mean concentration values were determined: water samples monobutyltin (MBT): 13.2, dibutyltin (DBT): 16.7, tributyltin (TBT): 60.7 (ng cation dm−3), and sediment samples MBT: 261.4, DBT: 751.9, TBT: 2148.2 (ng cation g−1 d.w.). The estimated content of monophenyltin (MPhT), diphenyltin (DPhT), triphenyltin (TPhT), monooctyltin (MOT), dioctyltin (DOT), and tricyclohexyltin (TCHT) were below the detection limit of the applied method. It was found that the content of organic matter, the amount of fine fraction, and the pH all play a significant role in the distribution and sorption process of OTC between the water and the sediment on the bottom. Compared to an earlier study, the concentrations of all OTC are much lower, confirming that the applied legislation has had a positive impact.

Hazardous substances in the aquatic environment of Estonia

The Water Framework Directive (WFD) aims to regulate the management of European surface water bodies. Directive 2008/105/EC, which establishes the environmental quality standards of priority substances and certain other pollutants, the content of which in the surface water should be monitored, has been transposed by the Estonian Ministry of Environment 9 September 2010 Regulation No. 49.Sampled hazardous substances were selected primarily based on their toxicity, as well as their lifetime in environment and ability to accumulate in living organisms (bioaccumulation). The contents of hazardous substances and their groups determined from Estonian surface waters remained below the limits of quantifications of used analysis methods in most cases. However, the content of some heavy metals, mono- and dibasic phenols in the surface water/waste water and sewage sludge/bottom sediments can still reach the delicate levels in the Estonian oil shale region in particular. Among new substances analysed in Estonia historically first time in 2010, amounts of organotin compounds in sediments and some alkylphenols, their ethoxylates and phthalates were found in various sample matrices.

Speciation Analysis of Organotin Compounds in Sediment by Hyphenated Technique of High Performance Liquid Chromatography-Inductively Coupled Plasma Mass Spectrometry

A hyphenated technique of high-performance liquid chromatography coupled with inductively coupled plasma mass spectrometry (HPLC-ICP-MS) was applied to the simultaneous determination of five organotin compounds in the sediment samples. Agilent TC-C18 column was selected; mobile phase of the HPLC was CH3CN:H2O-CH3COOH(65:23:12, V/V), 0.05% TEA, pH 3.0 at flow rate 0.6 mL min−1, and 30% O2/Ar mixed gas was added to the make-up gas, which not only reduced the carbon buildup on the cones but also protected the cones. To reduce solvent loading on the plasma, the double-pass spray-chamber was peltier cooled to −5 °C. The high RF power (1500 W) helped the samples to decompose completely. A mixed standard solution of five mixed organotin compounds from 100 μg L−1 to 1 μg L−1 was used for the method assessment. The results indicate that the correlation coefficient of calibration curves (R2) for each organotin compound was over 0.998. The international standard reference PACS-2 samples were treated by supersonic extraction with mobile phase added 0.2% tropolone. Two organotin compounds including dibutyltin (DBT) and tributyltin (TBT) were detected with this method. The values of dibutyltin (DBT) and tributyltin (TBT) were 0.99 mg kg−1 and 0.83 mg kg−1, respectively. The results showed good accordance with the certified values. The recoveries from the standard addition for five organotins were over 80%.

Organotin compounds in sediments of three coastal environments from the Patagonian shore, Argentina

One of the most toxic compounds that have been introduced into the marine environment is Tributyltin (TBT) used as a biocide in antifouling paints. The aim of this study was to obtain the first information of TBT pollution in sediments of three environments of the Argentinean coastline. Sediments from the Bahia Blanca estuary, San Antonio Bay and Ushuaia Bay were sampled to determine TBT and dibutyltin (DBT) concentration. The butyltin compounds were identified and quantified by gas chromatography and mass spectrometry (GC?MS). The different amount of organotin compounds detected shows dissimilar pollution levels and degradation processes along the Argentinean coasts.

Speciation of organotin compounds in sediments of semi-closed areas along the Mediterranean coast of Alexandria

Organotin compounds were measured in sediments of four different semi-closed areas of the Mediterranean coast of Alexandria: the Eastern Harbour, Western Harbour, El-Max Bay, and Abu-Qir Bay. Due to the commercial trade activity inside the Western Harbour, in addition to the effect of wastes discharged from El Noubaria canal, it shows the highest concentrations of total tin (6.34 μg g−1 dry weight), dibutyl tin (1.63 μg g−1 wet weight), tributyl tin (0.33 μg g−1 wet weight) and diphenyl tin (1.06 μg g−1 wet weight) compared with other locations. The concentrations of TBT species showed the highest contents compared with DBT and DPhT compounds in all sampling areas. This trend might be due to the worldwide use of TBT not only as biocides in antifouling paints but also as preserving agents for wood, fungicides in agricultural activities, and heat and UV stabilizers of PVC, which results in a direct release of TBT into the water body, accumulation in aquatic fauna. There is also precipitation into sediments and a decrease in degradation rate into its derivatives. Variations, types, concentrations, and distribution of different organotin compounds are discussed in the areas under investigation. The study reveals a new record of organotin compounds along the Alexandria coast and makes comparisons with other surrounding areas of interest.

Application of a Gas Chromatography/Mass Spectrometric Method for the Determination of Butyltin Compounds in Sediment

A gas chromatography/mass spectrometric (GC/MS) method has been developed for the determination of trace mono-n-butyltin (MBT), di-n-butyltin (DBT), and tri-n-butyltin (TBT) compounds in sediments. Samples were extracted by 10% acetic acid in methanol containing 0.03% tropolone and were then derivatized for GC/MS analysis. Ethylation by sodium tetraethylborate and phenylation by sodium tetraphenylborate were evaluated as a derivatization reaction of the organotins in sample extract. n-Hexane was added into reaction media in the beginning of the reaction for the continuous extraction of derivatized organotins. Ethylation requires less than 2 hours to get proper derivatization yields for MBT, DBT, and TBT altogether and produces relatively low amounts of side reaction products. Compared to ethylation, phenylation requires much longer time but provides relatively lower yield and produces considerable amounts of side reaction products. Therefore, the ethylation reaction was applied for the analysis of organotin compounds in sediment. An isotope dilution mass spectrometric (IDMS) method based on GC/MS has been applied to the accurate determination of DBT compounds in the sediments. The IDMS results from the analyses of sediment samples showed a reasonable repeatability and a good agreement with the values obtained by IDMS based on liquid chromatography/induced coupled plasma/mass spectrometry.

Concentrations of organotin compounds in sediment and clams collected from coastal areas in Vietnam

Levels of butyltin (BT) and phenyltin (PT) compounds were determined in sediments and clam Meretrix spp. collected from north and central coastal areas in Vietnam. Concentrations of TBT in sediments ranged from 0.89 to 34 ng g −1 dry wt and those in clams ranged from 1.4 to 56 ng g −1 wet wt. The levels of TBT in sediments and clams from Vietnam were within limits reported from other countries. Further, the TBT level in clams was lower than the tolerable average residue level (TARL) estimated based on tolerable daily intake (TDI). Trace amounts of PTs were also found in both sediment and clam samples. In sediments from north and central Vietnam, the concentrations of TBT were highest in the order of Hue (28 ng g −1 dry wt), Cua Luc (15 ng g −1 dry wt), Sam Son (6.3 ng g −1 dry wt), and Tra Co (5.5 ng g −1 dry wt). Among the clams from north and central Vietnam, the levels of TBT in clams from Cua Luc were dramatically high at 47 ng g −1 wet wt. TBT formed the principal butyltin species in sediment at all sites studied. The ratios of TBT in sediment were higher among BT compounds at all study sites. Of total BTs, TBT was the dominant species in clams from almost all sites studied. In spatial distribution, TPT showed a pattern similar to TBT, suggesting the use of TPT as an antifouling paint. The partition coefficient between sediment and calms was calculated. The partition coefficients of TBT and TPT were 2.01 (0.56–5.5) and 9.23 (3.1–20), respectively. These results show that sediment-bound TBT is a source of contamination to clams in addition to dissolved TBT.

A new polymeric adsorbent for screening and pre-concentration of organotin compounds in sediments and seawater samples

A new adsorbent based on the imprinting technique with high retention capacity and pre-concentration factor has been synthesized and tested for retention of inorganic and organotin compounds [tributyltinchloride (TBT), dibutyltindichloride (DBT), monobutylytintrichloride (MBT) and triphenyltinchoride (TPhT)]. The polymerization has been carried out in the presence of TBT, the target organotin compound of this work. These compounds can be quantitatively retained on this adsorbent over a wide pH range and after elution these compounds are determined by graphite furnace atomic absorption spectrometry (GFAAS). Only organotin compounds are eluted from the adsorbent with 0.1 M hydrochloric acid (HCl) in methanol (MeOH) solution whereas inorganic tin is eluted later on with a suitable complexing agent such as citric acid. Linearity is obtained in the concentration range 0.1–4 ng (5–200 μg l −1) for each organotin compound with a correlation coefficient not less than 0.994 and relative standard deviation <5% even for complex samples such as sediments and seawater samples. The detection limit has been found to be 30 ng l −1. Various parameters related to determination, pre-concentration and GFAAS conditions have been optimized. The screening method proposed has been applied to the determination of organotin in natural sediments and seawater samples. The recovery is between 82 and 90% for TBT, DBT and TPhT and 50–55% for MBT in the case of sediment samples, while it is 97–103% for all the organotin compounds in seawater samples. The method has been conveniently validated using a standard sediment reference material.

Organotin compounds in sediments from the Göta älv estuary

Concentrations of organotin compounds in sediments from four sites in the Gota alv estuary, SW Sweden, rangefrom 17 to 366 ng/g dw for tributyltin (TBT) and from1.5 to 71 ng/g dw for triphenyltin (TPT), similar toresults from other harbours and marinas and from an earlier study in the Goteborg Harbour, which is located in the estuary. Also dibutyltin, monobutyltin, diphenyltin and monophenyltin, the degradation products of TBT and TPT, werefound. TBT concentrations are the highest in the inner harbour and in the upper sediment layer of ca. 10 cm, indicating the risk for mobilisation of TBT bound in surface sediments in thefrequently disturbed harbour environment.

Improvement of Extraction Recovery for the Organotin Compounds in Sediment

Improvement of Extraction Recovery for the Organotin Compounds in Sediment

Chemical species of organotin compounds in sediment at a marina.

A bottom sediment collected in a marina was analyzed for organotin species, and >20 organotin compounds including biodegraded ones were confirmed by comparison with the synthesized standards using gas chromatography (GC)/mass spectrometry and a GC/atomic emission detection system. Their structures were also determined in comparison with those in a technical grade of tri-n-butyltin chloride (TBTC). Eleven organotin compounds were found in the technical TBTC. Among them, unexpected organotin compounds, such as di-n-butyl(2-ethylhexyl)tin chloride and di-n-butyloctyltin chloride, were identified, although the levels were low. These compounds were also found in the sediment sample. The relationship between organotin compounds in the technical TBTC and those in marine products was also discussed.

Speciation analysis for organotin compounds in sediments by capillary gas chromatography with flame photometric detection after microwave-assisted acid leaching

A rapid method is described for the speciation of butyl-and phenyltin compounds in sediments. The procedure was based on the quantitative microwave-assisted leaching of the target compounds from a sediment sample with ethanoic acid followed by their derivatization with sodium tetraethylborate in the aqueous phase. The ethyl derivatives of the analyte compounds were subsequently extracted into iso-octane and separated by capillary GC. A modified flame photometer with a graphite burner fitted with a 610 nm bandpass filter was used for detection. A desulfurization procedure used prior to GC was optimized and then incorporated into the analytical scheme in order to remove the sulfur present in sediments which would otherwise interfere with the detection of the organotin compounds. The leaching of the analyte species in a focused microwave field took only 3–4 min and the analysis time was limited by the duration of the gas chromatographic run (15 min). The effects of pH, temperature and time for ethylation of methyl-, butyl-, phenyl-, octyl- and dodecyltin compounds were evaluated. The possibility of accelerating the ethylation, by using a focused microwave field, was examined. The detection limit of the procedure was 10 ng g–1 for 0.5 g of sediment. A typical precision for this determination was 5–10%. The method developed was validated by analysing two CRMs (NRCC PACS-1 and BCR CRM 462). A series of applications in the Arcachon Bay and Greek coastal monitoring programme demonstrated the presence of butyl and phenyltin species.