Spéciation des organoétains dans les eaux et sédiments du bassin Adour-Garonne

De par leurs nombreuses propriétés physico- chimiques, les organoétains sont très utilisés dans l’industrie et en agriculture et entrent dans la composition de nombreux produits domestiques. Ils sont cependant extrêmement toxiques et la Communauté Européenne les a classés parmi les substances prioritaires dans le domaine de l’eau.Un suivi des organoétains a été réalisé sur onze rivières du bassin Adour-Garonne et sur l’estuaire de l’Adour. Ces composés y sont systématiquement présents, les butylétains et les octylétains étant les espèces les plus fréquemment détectées. Les concentrations varient de la limite de détection (0.2-0.5 ng(Sn)/l en moyenne) à 50 ng(Sn)/l dans les eaux, et de 15 à 300 µg(Sn)/kg dans les sédiments dulcicoles. Des pics de contamination ont été observés en fin de printemps et d’été, dans plusieurs rivières. Ils correspondent à la présence des mono- butyl- et -phénylétains principalement, leurs concentrations pouvant atteindre 700 à 900 ng(Sn)/l d’eau. Les rivières les plus contaminées sont la Garonne, le Gave de Pau, l’Adour, la Charente et le Thoré. Dans les matières en suspension de l’estuaire de l’Adour les concentrations atteignent quelques mg(Sn)/kg. L’ensemble des données recueillies a permis de mieux comprendre les origines et le devenir des organoétains dans le cycle hydrologique.Because of their physico-chemical properties, organotin compounds (OTC) are widely used in industry and are present in a significant number of agricultural pesticides and domestic products. They are highly toxic and the European Community has listed them as priority pollutants in the aquatic environment. Organotins have been monitored in the Adour- Garonne basin and the Adour estuary. They are systematically present in the rivers, with butyl- and octyltins being the species most frequently detected. These species, especially octyltins, probably come from the continuous leaching of plastic tubes. The OTC concentrations ranged from just over detection limits (≥ 0.2-0.5 ng (Sn)/L) to 50 ng (Sn)/L in water and from 15 to 300 µg (Sn)/kg in freshwater sediment. Important seasonal variations were also observed. Thus, at the end of spring and summer, very high monophenyltin (MPhT) concentrations of up to 700-900 ng (Sn)/L were found in the dissolved phase. This phenomenon could be partly attributed to specific triphenyltin (TPhT)-based agricultural treatments, MPhT being one of the TPhT degradation products. High monobutyltin (MBT) concentrations of up to 150 ng (Sn)/L were also detected during the same period. This latter compound comes from leaching of plastics and from tri- and di-butyltin (TBT, DBT) degradation. It represents 80 to 100% of the butyl species found in sediments.Considering OTC concentrations, speciation and toxicity, the most contaminated rivers appeared to be the Garonne, Gave de Pau, Adour, Charente and Thoré. Urban activities have significant influence on the levels of OTC contamination for most of the rivers, demonstrating continuous OTC inputs from domestic and industrial treatment plants. This is especially the case for the Charente and Thoré rivers, where some specific industrial activities devoted to leather and wood are present close to the sampling points.A statistical study was performed on the different physico-chemical parameters (temperature, water flow rate, dissolved oxygen concentration) and OTC concentrations. A significant positive correlation between water flow rate and organotin concentrations in the dissolved phase was observed. This correlation was very important when only sampling points far from potential OTC sources were considered, the octyltin concentrations showing the strongest correlation. These observations confirm the presence of a continuous OTC diffusion into aquatic media. A comparison between the present results in Adour-Garonne and OTC monitoring performed in the Rhin- Meuse basin shows that the level of contamination was quite similar in the two basins, especially considering rivers without fluvial traffic. A similar correlation existed between OTC concentrations in the dissolved phase and water flow rate.Special attention was given to the Adour sub-basin because of its particular geographic position and especially the large built-up area in the estuary. Butyltins remain the main OTC compound present, in terms both of frequency and concentration. According to the different sampling points in this sub-basin, mean OTC concentrations in the estuary did not appear to be really influenced by human activities located upstream, the concentrations in this part reaching 50 ng (Sn)/L in the dissolved phase. In contrast, OTC amounts found in the estuary were considerable higher. The built-up area of the estuary had a strong influence on concentrations, which were 6 to 14 times higher in the city centre than those upstream from the city (in an agricultural region). In addition to the influence of local sources, both a strong dilution effect and significant adsorption/ sedimentation phenomena in the downstream region of the estuary could be important. In the suspended matter of the Adour estuary, organotin concentrations were extremely high, reaching concentrations as high as mg (Sn)/kg. Such concentrations have already been reported for nearby regions of the harbour [Bravo et al. (2004)]. However, in the present case, there should be considerable concern considering the possible environmental consequences. The estuarine sediments appeared obviously contaminated by butyltins, but the concentrations were lower than those that could be expected (2000 µg (Sn)/ kg maximum). This observation could be explained by water flow rates as well as the tide, which could export large amounts of suspended matter outside the estuary. MPhT and TPhT were also detected, especially in sediments from the extreme downstream region of the estuary. Their presence could be attributed to the marina. The different solid/ dissolved partition coefficients were also evaluated. These partition coefficients ranged from over 40x104 for sediments up to 200x104 for suspended matter. Finally, the information on the Adour sub-basin showed that the estuary was more strongly contaminated than the upstream region.Generally, all these data have contributed to the first evaluation of OTC contamination in the Adour-Garonne basin, and identified organotin sources. The statistical study, comparisons between the different parts of the aquatic environment, and the observation of solid/ liquid distributions lead to a better understanding of the environmental fate of OTCs. Even if differences exist between the level of contamination in freshwater and estuarine environments, the ubiquitous presence of OTC must remain a subject of concern, especially with regard to the high toxicity of organotins. For example, TBT and TPhT have lethal effects on trout and algal species at aquatic concentrations in the µg (Sn)/L range or even below this concentration [TOOBY et al. (1975), WONG et al. (1982)]. Considering this high toxicity, other studies will have to be performed in order to increase the current database concerning OTC in rivers. It is also important to know the conditions that control OTC uptake by biota, and in order to propose effective environmental management strategies

Optimisation of the storage of natural freshwaters before organotin speciation

cited By 28International audienceThe speciation of organotin compounds is essential due to the species-dependent toxicity, especially in natural waters. Precautions have to be taken during sampling and storage of waters in order to prevent degradations and losses. Experimental design methodology has been used to study the conditions of stability of organotins after water sampling in rivers. The modelling of results allows the determination of optimal conditions of preservation. After acidification at pH=4 with nitric acid, the storage in polyethylene containers at 4°C in the dark is suitable to preserve the most degradable trisubstituted (butyl-and phenyl-) species over 1 month.These conditions of sampling and storage are applied to two different freshwaters. The rate of species decomposition appears to be only dependent on the water nature, whatever the organotin concentrations in the sample. Speciation could be so preserved between 1 and 3 months

Improvement of measurement precision of SPME-GC/MS determination of tributyltin using isotope dilution calibration

A unique approach was developed to improve the precision of quantification of tributyltin (TBT) in sediments by solid phase microextraction (SPME) using isotope dilution GC/MS. The precision of the analytical technique was initially evaluated using standard calibration solutions. In selective ion monitoring (SIM) mode, the relative standard deviation (RSD) obtained for TBT based on peak area response was 18% (n = 11). When an internal standard, tripropyltin (TPrT), was used, the RSD decreased to 12%. A significant improvement in the precision using SPME was noted when a 117Sn-enriched TBT spike was employed; the RSD decreased 4-fold to 3%. Detection limits of 0.2 and 20 ng(Sn) L-1 were achieved with SPME sampling and liquid 12liquid extraction, respectively. Six analyses were performed for determination of TBT in PACS-2 sediment Certified Reference Material using both standard additions and isotope dilution procedures. For the latter, a 117Sn-enriched TBT spike was used. A concentration of 0.88 \ub1 0.03 \u3bcg g-1 (RSD 3.4%) obtained using standard additions was in good agreement with the certified value of 0.98 \ub1 0.13 \u3bcg g-1 as tin. Concentrations found using isotope dilution were 0.895 \ub1 0.015 \u3bcg g-1 (RSD 1.73%) as tin and 0.874 \ub1 0.014 \u3bcg g-1 (RSD 1.66%) as tin using a liquid 12liquid extraction and SPME sampling, respectively. A 2-fold improvement in the precision of TBT concentration measurement using isotope dilution was clearly achieved, demonstrating its superiority in providing more accurate and precise results as compared to the method of standard additions. The isotope dilution technique eliminated the problem of poor reproducibility, which typically plagues SPME.NRC publication: Ye

Impact of tributyltin (TBT) on the bacterial activity in suspended-growth biological wastewater treatment Systems (conventional activated sludge and membrane bioreactor)

International audienceThe economic crisis affecting Europe has brought back the typically taboo term "reindustrialization" into everyday vocabulary. Reindustrialization is the economic, social, environmental and political process of organizing national resources for the purpose of revitalizing industry and is often achieved through the development of new and innovative activities. This is a means to the neo-industrialization of Europe. Industrial development is certainly one means for reindustrialization, especially since it will aide in restructuring the economy. Here, R&D sectors have a vital role in providing innovation and technical expertise and knowledge, which are essential for any ambitious industrial revitalization. Further, reindustrialization aims at developing traditional industries via the integration of new technologies and sustainability. For example, resolution of the petroleum crisis will require an entire reorganization of the economy, whereby less and less carbon energy is employed and replaced by sustainable solutions. In this situation, it is obvious that chemical engineering and biochemical engineering will play an important role. As reported by several economists, the reindustrialization and the development of industries of the future will need to consider three key fields: environmental preservation and remediation, energy efficiency and human health protection, involving adapted education to new industrial challenges. This group of events aims at participating in this large economical project, which concerns all countries in Europe. Through scientific sessions, workshops and symposia, scientists and industrialists will present their steps towards a new sustainable process industry

Occurrence and removal of butyltin compounds in a waste stabilisation pond of a domestic waste water treatment plant of a rural French town

The aim of this study was to investigate the fate and behaviour of butyltin pollutants, including monobutyltin (MBT), dibutylin (DBT), and tributyltin (TBT), in waste stabilisation ponds (WSP). The study was conducted as part of a baseline survey and included five sampling campaigns comprising bottom sludge and the water column from each pond from a typical WSP in France. Butyltins were detected in all raw wastewater and effluents, reflecting their widespread use. Our results revealed high affinity between butyltins and particulate matter and high accumulation of butyltins in the sludge taken from anaerobic ponds. The dissolved butyltins in the influent ranged from 21.5 to 28.1 ng(Sn).L-1 and in the effluent, from 8.8 to 29.3 ng(Sn).L-1. The butyltin concentrations in the sludge ranged from 45.1 to 164 and 3.6-8.1 ng(Sn).g(-1) respectively in the first and last ponds. Our results showed an average treatment efficiency of 71% for MBT, 47% for DBT, 55% for TBT. Laboratory sorption experiments enabled the calculation of a distribution coefficient (Kd = 75,000 L.kg-1) between TBT and particulate matter from the WSPs. The Kd explained the accumulation and persistence of the TBT in the sludge after settling of particulate matter. The continuous supply of contaminated raw wastewater and the sorption-desorption processes in the ponds led to incomplete bio- and photolytic degradation and to the persistence of butyltins in dissolved and particulate matrices throughout the survey period. It is thus recommended to use shallow ponds and to pay particular attention when sludge is used for soil amendment

Gas phase detection of tributyltin chloride arising from aqueous and solid matrices

The vapour phase above water spiked with tributyltin chloride (TBTCl) and PACS-2 sediment certified reference material was sampled with a solid phase microextraction fiber. The collected volatile compounds were analysed by GC-MS using a HBr\u2013methanol-treated capillary column. Two ion sources were used for this study and their performance characteristics compared. These were electron impact (EI) and negative chemical ionisation (NCI), which allowed both detection of trace amounts of analytes (NCI source) and their identification. This approach provides structural information on the sampled species; at this stage no quantitation was attempted. TBTCl can be detected in the vapour phase above saline water or PACS 2 sediment after one night of passive sampling without any stirring or heating of the sample. This work indicates the need to consider evaporation of TBT as the chloride as a mechanism of loss of this analyte from water or sediment. This may take place from natural settings and contributes to the global biogeochemical cycle of tin; hydride or methyl forms of trace metals are not the only compounds capable of volatilising into the atmosphere.NRC publication: Ye

Headspace single-drop microextration for the detection of organotin compounds

The performance of single-drop microextraction (SDME), coupled with gas chromatography/mass spectrometry, was assessed for the determination of tributyltin compounds in water and solid samples. Experimental parameters impacting the performance of SDME, such as microextraction solvent and sampling and stirring time, were investigated. Analytical results obtained by SDME were compared with those generated by conventional solid phase microextraction (SPME) and liquid\u2013liquid extraction (LLE) for the determination of TBT in PACS-2 sediment certified reference material (CRM).NRC publication: Ye

Occurrence and removal of butyltin compounds in a waste stabilisation pond of a domestic waste water treatment plant of a rural French town

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