Speciation of butyltin derivatives in surface sediments of three southern Brazilian harbors

For the first time, organotin compounds were determined in surface sediment samples collected from Sao Francisco do Sul, Itajai-Navegantes and Imbituba Harbors, located in Santa Catarina State, Brazil. Butyltins (BTs) were determined by gas chromatography with a pulsed flame photometric detector (GC-PFPD) after being modified using the Grignard derivatization method. The concentrations of BTs derivatives ranged from n.d. to 1136.6 ng (Sn) g(-1) of dry weight (dw) sediment for tributyltin (TOT), n.d. to 394.4 ng (Sn)g(-1) dw for dibutyltin (DOT) and n.d. to 312.2 ng (Sn)g(-1) dw for monobutyltin (MBT). The highest concentration of total BTs was found at the Itajai-Acu River dockyard, indicating intense inputs of antifouling paints to the environment. The relative difference in the BTs levels is a particular characteristic of sediments from harbors and may be related to the shipyards and the boat traffic which still use TBT-based antifouling paints.

Occurrence and behavior of butyltins in intertidal and shallow subtidal surface sediments of an estuarine beach under different sampling conditions

Contamination by butyltin compounds (BTs) has been reported in estuarine environments worldwide, with serious impacts on the biota of these areas. Considering that BTs can be degraded by varying environmental conditions such as incident light and salinity, the short-term variations in such factors may lead to inaccurate estimates of BTs concentrations in nature. Therefore, the present study aimed to evaluate the possibility that measurements of BTs in estuarine sediments are influenced by different sampling conditions, including period of the day (day or night), tidal zone (intertidal or subtidal), and tides (high or low). The study area is located on the Brazilian southeastern coast, Sao Vicente Estuary, at Pescadores Beach, where BT contamination was previously detected. Three replicate samples of surface sediment were collected randomly in each combination of period of the day, tidal zone, and tide condition, from three subareas along the beach, totaling 72 samples. BTs were analyzed by GC-PFPD using a tin filter and a VF-5 column, by means of a validated method. The concentrations of tributyltin (TBT), dibutyltin (DBT), and monobutyltin (MBT) ranged from undetectable to 161 ng Sn g(-1) (d.w.). In most samples (71%), only MBT was quantifiable, whereas TBTs were measured in only 14, suggesting either an old contamination or rapid degradation processes. DBT was found in 27 samples, but could be quantified in only one. MBT concentrations did not differ significantly with time of day, zones, or tide conditions. DBT and TBT could not be compared under all these environmental conditions, because only a few samples were above the quantification limit. Pooled samples of TBT did not reveal any difference between day and night. These results indicated that, in assessing contamination by butyltin compounds, surface-sediment samples can be collected in any environmental conditions. However, the wide variation of BTs concentrations in the study area, i.e., over a very small geographic scale, illustrates the need for representative hierarchical and composite sampling designs that are compatible with the multiscalar temporal and spatial variability common to most marine systems. The use of such sampling designs will be necessary for future attempts to quantitatively evaluate and monitor the occurrence and impact of these compounds in nature

Tributyltin in Crustacean Tissues: Analytical Performance and Validation of Method

The hermit crab Clibanarius vittatus is a typical organism from intertidal regions being considered as a good bioindicator of tributyltin presence at these environments. Thus this study presents the analytical performance and validation method for TBT quantification in tissues of C. vittatus by gas chromatography with pulsed flame photometric detector (GC-PFPD) after extraction with an apolar solvent (toluene) and Grignard derivatization. The limits of detection of the method (LOD) were 2.0 and 2.8 ng g(-1) for TBT and DBT (dibutyltin), respectively, and its limits of quantification (LOQ) were 6.6 and 8.9 ng g(-1) for TBT and DBT, respectively. The method was applied to samples from Santos Estuary, Sao Paulo State, Brazil. TBT and DBT concentrations ranged from 26.7 to 175.0 ng g(-1) and from 46.2 to 156.0 ng g(-1), respectively. These concentrations are worrisome since toxic effects (such as endocrine disruption) have been reported for other organisms even under lower levels of registred at this study.

Tributyltin in crustacean tissues: analytical performance and validation of method

The hermit crab Clibanarius vittatus is a typical organism from intertidal regions being considered as a good bioindicator of tributyltin presence at these environments. Thus this study presents the analytical performance and validation method for TBT quantification in tissues of C. vittatus by gas chromatography with pulsed flame photometric detector (GC-PFPD) after extraction with an apolar solvent (toluene) and Grignard derivatization. The limits of detection of the method (LOD) were 2.0 and 2.8 ng g-1 for TBT and DBT (dibutyltin), respectively, and its limits of quantification (LOQ) were 6.6 and 8.9 ng g-1 for TBT and DBT, respectively. The method was applied to samples from Santos Estuary, São Paulo State, Brazil. TBT and DBT concentrations ranged from 26.7 to 175.0 ng g-1 and from 46.2 to 156.0 ng g-1, respectively. These concentrations are worrisome since toxic effects (such as endocrine disruption) have been reported for other organisms even under lower levels of registred at this study.

Optimization of in situ derivatization SPME by experimental design for GC-MS multi-residue analysis of pharmaceutical drugs in wastewater

This paper presents the development of a procedure, which enables the analysis of nine pharmaceutical drugs in wastewater using gas chromatography-mass spectrometry (GC-MS) associated with solid-phase microextraction (SPME) for the sample preparation. Experimental design was applied to optimize the in situ derivatization and the SPME extraction conditions. Ethyl chloroformate (ECF) was employed as derivatizing agent and polydimethylsiloxane-divinylbenzene (PDMS-DVB) as the SPME fiber coating. A fractional factorial design was used to evaluate the main factors for the in situ derivatization and SPME extraction. Thereafter, a Doehlert matrix design was applied to find out the best experimental conditions. The method presented a linear range from 0.5 to 10 mu g/L, and the intraday and interday precision were lower than 16%. Applicability of the method was verified from real influent and effluent samples of a wastewater treatment plant, as well as from samples of an industry wastewater and a river.

Contribution of AT-, GC-, and methylated cytidine-rich DNA to chromatin composition in Malpighian tubule cell nuclei of Panstrongylus megistus (Hemiptera, Reduviidae)

The Malpighian tubule cell nuclei of male Panstrongylus megistus, a vector of Chagas disease, contain one chromocenter, which is composed solely of the Y chromosome. Considering that different chromosomes contribute to the composition of chromocenters in different triatomini species, the aim of this study was to determine the contribution of AT-, GC-, and methylated cytidine-rich DNA in the chromocenter as well as in euchromatin of Malpighian tubule cell nuclei of P. megistus in comparison with published data for Triatoma infestans. Staining with 4',6-diamidino-2-phenylindole/actinomycin D and chromomycin A(3)/distamycin, immunodetection of 5-methylcytidine and AgNOR test were used. The results revealed AT-rich/GC-poor DNA in the male chromocenter, but equally distributed AT and GC DNA sequences in male and female euchromatin, like in T. infestans. Accumulation of argyrophilic proteins encircling the chromocenter did not always correlate with that of GC-rich DNA. Methylated DNA identified by immunodetection was found sparsely distributed in the euchromatin of both sexes and at some points around the chromocenter edge, but it could not be considered responsible for chromatin condensation in the chromocenter, like in T. infestans. However, unlike in T. infestans, no correlation between the chromocenter AT-rich DNA and nucleolus organizing region (NOR) DNA was found in P. megistus. (c) 2011 Elsevier GmbH. All rights reserved.