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Fulltext Comparative study of tributyltin adsorption onto mesoporous silica functionalized with calix[4]arene, p-tert-butylcalix[4]arene and p-sulfonatocalix[4]arene

Alahmadi S, Mohamad S, Maah MJ

Molecules, 2014 Apr 10;19(4):4524-47.
PMID: 24727422 DOI: 10.3390/molecules19044524

The adsorption of tributyltin (TBT), onto three mesoporous silica adsorbents functionalized with calix[4]arene, p-tert-butylcalix[4]arene and p-sulfonatocalix[4]arene (MCM-TDI-C4, MCM-TDI-PC4 and MCM-TDI-C4S, respectively) has been compared. Batch adsorption experiments were carried out and the effect of contact time, initial TBT concentration, pH and temperature were studied. The Koble-Corrigan isotherm was the most suitable for data fitting. Based on a Langmuir isotherm model, the maximum adsorption capacities were 12.1212, 16.4204 and 7.5757 mg/g for MCM-TDI-C4, MCM-TDI-PC4 and MCM-TDI-C4S, respectively. The larger uptake and stronger affinity of MCM-TDI-PC4 than MCM-TDI-C4 and MCM-TDI-C4S probably results from van der Waals interactions and the pore size distribution of MCM-TDI-PC4. Gibbs free energies for the three adsorption processes of TBT presented a negative value, reflecting that TBT/surface interactions are thermodynamic favorable and spontaneous. The interaction processes were accompanied by an increase of entropy value for MCM-TDI-C4 and MCM-TDI-C4S (43.7192 and 120.7609 J/mol K, respectively) and a decrease for MCM-TDI-PC4 (-37.4704 J/mol K). It is obviously observed that MCM-TDI-PC4 spontaneously adsorbs TBT driven mainly by enthalpy change, while MCM-TDI-C4 and MCM-TDI-C4S do so driven mainly by entropy changes.

Matched MeSH terms: Trialkyltin Compounds/chemistry*
Contamination profiles of antifouling biocides in selected coastal regions of Malaysia

Harino H, Arai T, Ohji M, Ismail AB, Miyazaki N

Arch Environ Contam Toxicol, 2009 Apr;56(3):468-78.
PMID: 18979060 DOI: 10.1007/s00244-008-9252-0

The concentrations of butyltins (BTs) in sediment from Peninsular Malaysia along the Strait of Malacca and their spatial distribution are discussed. The concentrations of BTs were high in the southern part of Peninsular Malaysia where there is a lot of ship traffic, because trade is prosperous. The concentrations of monobutyltin (MBT), dibutyltin (DBT), and tributyltin (TBT) in sediment from the coastal waters of Peninsular Malaysia were in the range 4.1-242 microg/kg dry weight (dw), 1.1-186 microg/kg dw, and 0.7-228 microg/kg dw, respectively. A higher percentage of TBT was observed in the area where TBT concentrations were high. The concentrations of monophenyltin (MPT), diphenyltin (DPT), and triphenyltin (TPT) were in the range <0.1-121 microg/kg dw, 0.4-27 microg/kg dw, and 0.1-34 microg/kg dw in sediment from Peninsular Malaysia, respectively. MPT was the dominant phenyltin species. MBT, DBT, and TBT in green mussel (Perna viridis) samples were detected in the range 41-102 microg/kg, 3-5 microg/kg, and 8-32 microg/kg, respectively. A tolerable average residue level (TARL) was estimated at 20.4 microg/kg from a tolerable daily intake (TDI) of 0.25 microg TBTO/kg body weight/day. The maximum value of TBT detected in green mussel samples was the value near the TARL. TPTs were not detected in green mussel samples. The concentrations of Diuron and Irgarol 1051 in sediment from Peninsular Malaysia were in the range <0.1-5 microg/kg dw and <0.1-14 microg/kg dw, respectively. High concentrations of these compounds were observed in locations where the concentrations of TBT were high. Sea Nine 211, Dichlofluanid, and Pyrithiones were not detected in sediment. The concentrations of antifouling biocides in Melaka and the Strait of Johor were investigated in detail. BTs were found in similar concentrations among all sampling sites from Melaka, indicating that BT contamination spread off the coast. However, Sea Nine 211, Diuron, and Irgarol 1051 in the sediment from Melaka were high at the mouth of the river. BT concentrations at the Strait of Johor were higher than those in Peninsular Malaysia and Melaka and were high at the narrowest locations with poor flushing of water. The concentrations of antifouling biocides were compared among Malaysia, Thailand, and Vietnam. A higher concentration and wide variations of TBT and TPT in sediment from Malaysia were observed among these countries. The Irgarol 1051 concentrations in sediment from Malaysia were higher than those in Thailand and Vietnam.

Matched MeSH terms: Trialkyltin Compounds/analysis
Tributyltin distribution in the coastal environment of Peninsular Malaysia

Tong SL, Pang FY, Phang SM, Lai HC

Environ Pollut, 1996;91(2):209-16.
PMID: 15091442

The occurrence of tributyltin (TBT) is reported in the coastal waters of a few selected sites in Peninsular Malaysia. Water, bivalves and sediment samples collected were analysed specifically for TBT using sensitive analytical methods which involved a solvent extraction procedure with appropriate clean-up followed by graphite furnace atomic absorption spectrometric measurements. The levels of TBT in the seawater in unexposed areas were found in the range from <3.4 to 20 ng litre(-1) as compared to coastal areas with high boat and ship activities where TBT levels in seawater were generally above 30 ng litre(-1), with the highest level found at 281.8 ng litre(-1). TBT levels in the tissues of random cockle and soft-shell clam samples from local markets were found in the range from <0.5 to 3.7 ng g(-1) wet weight. The levels of TBT found in green mussel samples both from the market (23.5 ng g(-1) wet weight) and those from a mussel farm (14.2 ng g(-1) wet weight) indicate slight accumulation of TBT. In sediments, TBT levels were found ranging from <0.7 ng g(-1) dry weight in unexposed coastal sites to as high as 216.5 ng g(-1) dry weight for a site within a port area.

Matched MeSH terms: Trialkyltin Compounds
Study on a new mechanism of sterilization in imposex affected females of tropical marine neogastropod, Thais sp

Mohamat-Yusuff F, Zulkifli SZ, Otake T, Harino H, Ismail A

J Environ Biol, 2014 Sep;35(5):995-1003.
PMID: 25204078

The morphological expressions and histopathological analysis of the gonads of a tropical marine neogastropod species (Thais sp.) from East Malaysia revealed new evidence of mechanical sterility in the imposex affected females. The gradual development of imposex was classified into five stages (Stage 0 to Stage 4) with three types of sterility conditions; Type A caused prohibition of copulation and capsule formation; Type B prohibits the releasing process of eggs; and gonads in Type C are infertile. Further analysis is needed to confirm, if the gonad malformation in imposex affected snails is generated specifically by tributyltin (TBT) or by other possible factors. The levels of imposex incidence (stages and percentages) were greater in a marina and decreased with increasing distance from the marina. Organotin tissue burden across the sexes showed that dibutyltin (DBT) as well as TBT might be the elements inducing imposex in Thais sp. from Miri in East Malaysia.

Matched MeSH terms: Trialkyltin Compounds/toxicity*
Description and evaluation of imposex in Strombus canarium Linnaeus, 1758 (Gastropoda, Strombidae): a potential bio-indicator of tributyltin pollution

Cob ZC, Arshad A, Bujang JS, Abd Ghaffar M

Environ Monit Assess, 2011 Jul;178(1-4):393-400.
PMID: 20824325 DOI: 10.1007/s10661-010-1698-7

Strombus canarium Linnaeus, 1758 is an important gastropod species within the study area and was traditionally collected for food by the locals. The objective of the present study is to assess the incidence of imposex and its severity in this species. Adult conchs were sampled during their main reproductive period, from October 2005 to January 2006, at Sungai Pulai estuary, Johor Straits, Malaysia. A total of 32.81% of adult females showed imposex characteristics, with varying degrees of severity though. The relative penis size (RPS) index ranged from 1.74 to 33.29 (mean = 13.40 ± 2.27, n = 21), while the relative penis length (RPL) index ranged from 6.28 to 55.19 (mean = 25.83 ± 3.33, n = 21). The use of vas deferens sequence (VDS) index was however cannot be applied as the presence of egg groove obscured any vas deferens development in affected females. Sequence of imposex (male penis) development in female conch, from merely a small stump to an advance male penis homologous was therefore carefully analyzed and described, and an alternative imposex classification scheme was proposed. S. canarium can be a good indicator for monitoring of organotin pollution within the study area. However, more studies are needed in order to further develop and test its validity and application, such as its correlation with levels of pollutant within the tissues and the environment, as well as its application on other Strombus species.

Matched MeSH terms: Trialkyltin Compounds/toxicity*
Klebsiella sp. FIRD 2, a TBT-resistant bacterium isolated from contaminated surface sediment along Strait of Johor Malaysia

Abubakar A, Mustafa MB, Johari WLW, Zulkifli SZ, Ismail A, Mohamat-Yusuff FB

Mar Pollut Bull, 2015 Dec 15;101(1):280-283.
PMID: 26434791 DOI: 10.1016/j.marpolbul.2015.09.041

A possible tributyltin (TBT)-degrading bacterium isolated from contaminated surface sediment was successfully identified as Klebsiella sp. FIRD 2. It was found to be the best isolate capable of resisting TBT at a concentration of 1000 μg L(-1). This was a concentration above the reported contaminated level at the sampling station, 790 μg L(-1). Further studies revealed that the isolate was Gram negative and resisted TBT concentrations of up to 1500 μg L(-1) in a Minimal Salt Broth without the addition of any carbon source within the first 48 h of incubation. It is expected that additional work could be conducted to check the degradation activity of this new isolate and possibly improve the degradation capacity in order to contribute to finding a safe and sustainable remediation solution of TBT contamination.

Matched MeSH terms: Trialkyltin Compounds/analysis*
Asia-Pacific mussel watch: monitoring of butyltin contamination in coastal waters of Asian developing countries

Sudaryanto A, Takahashi S, Monirith I, Ismail A, Muchtar M, Zheng J, et al.

Environ. Toxicol. Chem., 2002 Oct;21(10):2119-30.
PMID: 12371488

Butyltin compounds (BTs) including mono-, di-, and tributyltin and total tin (sigmaSn), were determined in green mussels (Perna viridis) from various Asian developing countries, such as Cambodia, China (Hong Kong and southern China), Malaysia, India, Indonesia, the Philippines, and Vietnam, to elucidate the contamination status, distribution, and possible sources and to assess the risks on aquatic organisms and humans. Butyltin compounds were detected in green mussels collected from all the sampling location investigated, suggesting widespread contamination of BTs along the coastal waters of Asian developing countries. Among butyltin derivatives, tributyltin (TBT) was the predominant compound, indicating its ongoing usage and recent exposures in Asian coastal waters. Higher concentrations of BTs were found in mussels collected at locations with intensive maritime activities, implying that the usage of TBT as a biocide in antifouling paints was a major source of BTs. In addition, relatively high concentrations of BTs were observed in mussels from aquaculture areas in Hong Kong and Malaysia, as it has been reported in Thailand. With the recent improvement in economic status in Asia, it is probable that an increase in TBT usage will occur in aquaculture. Although contamination levels were generally low in mussel samples from most of the Asian developing countries, some of those from polluted areas in Hong Kong, India, Malaysia, the Philippines, and Thailand revealed levels comparable to those in developed nations. Furthermore, the concentrations of TBT in some mussels from polluted areas exceeded the threshold for toxic effects on organisms and estimated tolerable average residue levels as seafoods for human consumption. A significant correlation was observed between the concentrations of sigmaBTs and sigmaSn in mussels, and sigmaBTs were made up mostly 100% of sigmaSn in mussels taken from locations having intensive maritime/human activities. This suggests that anthropogenic BTs represent the major source of tin accumulation in mussels. To our knowledge, this is a first comprehensive report on butyltin pollution monitoring in developing countries in the Asia-Pacific region.

Matched MeSH terms: Trialkyltin Compounds/analysis
Contamination of butyltin compounds in Malaysian marine environments

Sudaryanto A, Takahashi S, Iwata H, Tanabe S, Ismail A

Environ Pollut, 2004 Aug;130(3):347-58.
PMID: 15182968

Concentration of butyltin compounds (BTs), including tributyltin (TBT), dibutyltin (DBT) and monobutyltin (MBT) and total tin (SigmaSn) were determined in green mussel (Perna viridis), 10 species of muscle fish and sediment from coastal waters of Malaysia. BTs were detected in all these samples ranging from 3.6 to 900 ng/g wet wt., 3.6 to 210 ng/g wet wt., and 18 to 1400 ng/g dry wt. for mussels, fish and sediments, respectively. The concentrations of BTs in several locations of this study were comparable with the reported values from some developed countries and highest among Asian developing nations. Considerable concentration of BTs in several locations might have ecotoxicological consequences and may cause concern to human health. The parent compound TBT was found to be highest than those of its degradation compounds, DBT and MBT, suggesting recent input of TBT to the Malaysian marine environment. Significant positive correlation (Spearman rank correlation: r2=0.82, P<0.0001) was found between BTs and SigmaSn, implying considerable anthropogenic input of butyltin compounds to total tin contamination levels. Enormous boating activities may be a major source of BTs in this country, although aquaculture activities may not be ignored.

Matched MeSH terms: Trialkyltin Compounds/analysis
Fulltext Histological study of gonadal tissues of adult Artemia salina (Linnaeus 1758) and immunohistochemistry by Caspase 3 and HSP70 to detect specific apoptosis markers on gonadal tissues after exposure to TBTCl

Abushaala NM, Elfituri AM, Zulkifli SZ

Open Vet J, 2021 02 08;11(1):112-120.
PMID: 33898292 DOI: 10.4314/ovj.v11i1.17

Background: Several types of research have been recently carried out on the biological effects of TBTs, including investigations of genitals in invertebrates in response to exposure to TBTs in marine water.
Aim: The objective of this research was to investigate the acute effects of tributyltin chloride (TBTCl) on gonads in the adult stage of Artemia salina by use normal histology and immunohistochemistry (IHC) (Caspase 3 and HSP70) to see specific apoptosis markers.
Methods: After exposure of A. salina to different concentrations of TBTCl (25, 50, 100, 200, and 300 ng.l-1), 50 adult A. salina (25 male and 25 female) were selected randomly from each concentration to histologically study the gonads. The gonad tissue was sectioned (5 μm) and some slides were stained with hematoxylin and eosin and others were stained with IHC avidin-biotin complex, and were examined under a light microscope.
Results: The results showed significant differences (p < 0.05) in histological lesions between different concentrations of TBTCl. The histological lesions in the testis and ovary section were undifferentiated cells, degenerating yolk globules, and follicle cells enveloping the oocyte which was then compared with control tissue, and these effects were found to be increased in females more than in males with the highest concentration of TBTCl. Immunohistochemistry (IHC) showed that positive immunostaining was observed in the testis and ovary as brownish deposits to Caspase 3 and HSP70 antibody after exposure to TBTCl, while the testis and ovary section in control tissue had no immunoreactivity to Caspase 3 and HSP70 antibody; these effects were profoundly increased with the highest concentration of TBTCl in females more than in males. Finally, the histological lesions and IHC (Caspase 3 and HSP70) revealed that the apoptosis and immune system stress of A. salina gonad tissue damage in females were more sensitive to TBTCl toxicity as compared to white males.
Conclusion: In general, the present study aimed to observe the effects TBTCl on A. salina gonads by using histological sections and IHC (Caspase 3 and HSP70), which were evaluated for the first time and have been proven to possess an important function in apoptosis marker and immune system stress in Artemia. Finally, the specific mechanisms through which TBTCl affects A. salina Caspase 3 and HSP70 expression need further investigation.

Matched MeSH terms: Trialkyltin Compounds/adverse effects*