S. Bangkedphol

Enhancement of tributyltin degradation under natural light by N-doped TiO2 photocatalyst.

Photo-degradation of tributyltin (TBT) has been enhanced by TiO(2) nanoparticles doped with nitrogen (N-doped TiO(2)). The N-doped catalyst was prepared by a sol-gel reaction of titanium (IV) tetraisopropoxide with 25% ammonia solution and calcined at various temperatures from 300 to 600°C. X-ray diffraction results showed that N-doped TiO(2) remained amorphous at 300°C. At 400°C the anatase phase occurred then transformed to the rutile phase at 600°C. The crystallite size calculated from Scherrers equation was in the range of 16-51 nm which depended on the calcination temperature. N-doped TiO(2) calcined at 400°C which contained 0.054% nitrogen, demonstrated the highest photocatalytic degradation of TBT at 28% in 3h under natural light when compared with undoped TiO(2) and commercial photocatalyst, P25-TiO(2) which gave 14.8 and 18% conversion, respectively.

The partition behavior of tributyltin and prediction of environmental fate, persistence and toxicity in aquatic environments

Tributyltin (TBT) is one of the most toxic anthropogenic compounds introduced into the aquatic environment. It has a relatively high affinity for particulate matter, providing a direct and potentially persistence route of entry into benthic sediments. To understand TBT behavior, computational programs are an exceptionally helpful tool for modeling and prediction. EPISuite program was used for evaluation of the prediction data including fate, persistence and toxicity from the partition coefficient values. Without experimental data, the model is useful for prediction but is essentially a default model. A site specific assessment is possible by measuring the partition coefficients and entering the experimental values obtained into the model. This paper describes the results of a study undertaken to determine the partition coefficients and the effect of various parameters on such partition coefficients. The octanol-water partition coefficient (K(ow)) was determined by the OECD shake-flask method, with the logarithm values obtained ranging from 3.9 to 4.9 depending on salinity. The sediment-water partition coefficient (K(d)) was determined by ASTM method of generating Freundlich adsorption isotherms, the obtained values ranged from 88 to 4909 L kg(-1) depending on sediment properties, salinity, pH, and temperature. The experimental partition coefficient K(ow) and K(oc) (calculated from K(d)) were used as input data into the prediction program to provide accurate values for the natural samples in situ. The experimental prediction showed lower toxicity than the default model, but represent actual toxicity and accumulation at the natural site. Moreover, the environmental fate was significantly different when the experimental values and the default values were compared.

Bioremediation of tributyltin contaminated sediment: degradation enhancement and improvement of bioavailability to promote treatment processes

Bioremediation of tributyltin (TBT) contaminated sediment was studied and degradation enhancement and improvement of bioavailability were also investigated. In TBT spiked sediment, the half-life of TBT in the control sample, representing natural attenuation, was 578 d indicating its persistence. In the stimulated sample (pH 7.5, aeration and incubated at 28°C), the half-life was significantly reduced to 11 d. Further stimulation by nutrient addition (succinate, glycerol and l-arginine) or inoculation with Enterobacter cloacae (∼10(7) viable cells g(-1) of sediment) resulted in half-life reduction to 9 and 10d, respectively. In non-spiked sediment, the indigenous microorganisms were able to degrade aged TBT, but the extended period of contamination decreased the degradation efficiency. To improve bioavailability, addition of surfactant, adjustment of salinity and sonication were studied. The highest percentage solubilisation of TBT in water was obtained by adjusting salinity to 20 psu, which increased the solubility of TBT from 13% to 33%. Half-lives after bioavailability was improved were 5, 4 and 4d for stimulation, stimulation w/nutrient addition and stimulation w/inoculation, respectively. However, natural attenuation in the control sample was not enhanced. The results show that providing suitable conditions is important in enhancing TBT biodegradation, and bioavailability improvement additionally increased the rate and degraded amount of TBT. Unfortunately, nutrient addition and inoculation of the degrader did not enhance the degradation appreciably.

Development of a low-cost method of analysis for the qualitative and quantitative analysis of butyltins in environmental samples

Most analytical methods for butyltins are based on high resolution techniques with complicated sample preparation. For this study, a simple application of an analytical method was developed using High Performance Liquid Chromatography (HPLC) with UV detection. The developed method was studied to determine tributyltin (TBT), dibutyltin (DBT) and monobutyltin (MBT) in sediment and water samples. The separation was performed in isocratic mode on an ultra cyanopropyl column with a mobile phase of hexane containing 5% THF and 0.03% acetic acid. This method was confirmed using standard GC/MS techniques and verified by statistical paired t-test method. Under the experimental conditions used, the limit of detection (LOD) of TBT and DBT were 0.70 and 0.50 μg/mL, respectively. The optimised extraction method for butyltins in water and sediment samples involved using hexane containing 0.05–0.5% tropolone and 0.2% sodium chloride in water at pH 1.7. The quantitative extraction of butyltin compounds in a certified reference material (BCR-646) and naturally contaminated samples was achieved with recoveries ranging from 95 to 108% and at %RSD 0.02–1.00%. This HPLC method and optimum extraction conditions were used to determine the contamination level of butyltins in environmental samples collected from the Forth and Clyde canal, Scotland, UK. The values obtained severely exceeded the Environmental Quality Standard (EQS) values. Although high resolution methods are utilised extensively for this type of research, the developed method is cheaper in both terms of equipment and running costs, faster in analysis time and has comparable detection limits to the alternative methods. This is advantageous not just as a confirmatory technique but also to enable further research in this field.

The ecological complexity of the Thai-Laos Mekong River: I. Geology, seasonal variation and human impact assessment on river quality.

The objective of this study is to assess the variation of pollution in the Thai–Laos Mekong associated with seasonal dynamics concomitant with the natural geological features and human activities that impact on the adverse quality of the river. The complex ecology of the 1500 km stretch of the Thai-Laos Mekong River has been studied in this paper to understand the relationship with the geomorphology, with the sub-tropical monsoonal climate and the impact of human activity. Sub-surface geology controls the nature and extent of the drainage basin and of the river channel. The volume flow of the river varies naturally and dynamically in phase with the rainfall; traditional models based on steady state hydraulics are inappropriate. Continuous erosion of the river banks and bed generates a sediment load of impure silt, mica, quartz and clay minerals that inhibits light penetration and limits the primary productivity of the river. The river separates two countries at different stages of development; it flows through or close to eight non-industrial conurbations (Populations 350,000–2,000,000) but is otherwise sparsely populated. The river is used for subsistence agriculture, village transport, fishing including aquaculture and as a source of domestic water. Hydroelectricity is generated from the Laos tributaries. The river is a depository for partially treated urban waste and untreated village waste, hence populations of E.coli bacteria sometimes render the water unsuitable for drinking unless treated with the highest value of 240/100ml found at station 7 during the summer season of 2003. Furthermore the river is polluted by trace metals, notably cadmium and mercury, and by Polycyclic Aromatic Hydrocarbons (PAHs), which are particularly concentrated in the sediments. Previous work has shown that cadmium and mercury exceed the Probable Effect Level (PEL) values of Canadian Environmental Quality Guidelines and that the PAH concentrations were also greater than the Interim Sediment Quality Guidelines (ISQG). Consequently the fish stock, a vital source of protein for the local human population maybe seriously affected. As conflict between the demands of human activities will be exacerbated by the continuing development of the basin; monitoring must be continued and a better model of the rivers ecology is needed to predict the impact of development.

Isolation of tributyltin-degrading bacteria citrobacter braakii and enterobacter cloacae from butyltin-polluted sediment

Tributyltin compound (TBT) released into the aquatic environment is generally degraded by bacteria in water and sediment. The isolation of TBT-degrading bacteria from TBT polluted sediment leads to the indication of specific potential TBT degraders. Two new strains of bacteria designated as B2 and B3 were successfully isolated using glycerol medium containing tributyltin chloride (TBTC) at 130 μM from contaminated sediment collected from Bowling Basin in Glasgow. The observed degradation after 14 days of the microcosm from the sediment and the isolated bacteria were investigated at an initial concentration of 1 μM TBTC. It was found that TBT was degraded by the bacterial strains B2 and B3 at 8.3 and 16.9 %, respectively. The results indicate that B2 and B3 are effective as TBT degraders. EC50 of B2 and B3 in water were 88.73 and 112.53 μM TBTC, which were significantly higher than the concentration of TBT measured at the basin, suggesting a low effect of TBT on the growth and activity of bacteria. After identification using API 20E and 16S sequencing, the bacterial isolate strain B2 is Citrobacter braakii and B3 is Enterobacter cloacae. Therefore, this study has discovered two species of high resistance TBT degrader which have never been previously studied or isolated based upon TBT degradation ability.

The ecological complexity of the Thai-Laos Mekong River : III. Health status of Mekong catfish and cyprinids, evidence of bioaccumulative effects

Histopathology of fish organs was used as biomarkers of toxicity from environmental pollutants. A total of 117 fishes comprising of 52 cyprinids and 65 catfishes were randomly collected from the Mekong River from 5 stations: Chiang Rai, Loei, Nongkhai, Nakhon Phanom and Ubonratchathani. The health of the fish collected in December and April, winter and summer respectively, was evaluated. All fish from the 5 stations developed pathologic lesions with the same characteristics in their livers, kidneys and spleen. In the liver, there was vacuolation of hepatocytes, accumulation of brownish-green granules in the cytoplasm of hepatocytes, necrosis of hepatocytes, granuloma formation and angiogenesis. Kidney lesions consisted of glomerular degeneration, necrosis and focal hyperplasia of renal tubules. In the spleen, there were haemorrhage, melanomacrophage centre infiltration and necrosis of the red pulp and white pulp. The pathologic severity of the catfish was found to be more severe than in the cyprinids and the catfish collected in summer were less healthy than the catfish collected in the winter. These histopathological appearances might arise from the fish feeding on the benthos and thereby accumulating toxic pollutants in their organs. The activities of the serum enzymes, Glutamic Oxalacetic Transaminase (GOT) and Glutamic Pyruvic Transaminase (GPT), were markedly increased, indicating detoxification activity. The highest activity of GOT found in the cyprinids from Chiang Rai 365.30 U/L whereas in the catfish from Nakhon Phanom the activity was 300.73 U/L. The highest GPT activity found in the cyprinids from Nakhon Phanom was 203.23 U/L where as in the catfish from the same station was GPT 389.77 U/L. According to the results from this study, catfish collected from Chiang Rai, Nakhon Phanom and Ubonratchathani showed more severe pathological changes than catfish from the other stations. Fish organs and river water were analysed for Polyaromatic Hydrocarbons (PAHs) and metals. The fish organs showed bioaccumulation of these toxic pollutants. BioConcentration Factors (BCFs) were calculated. Therefore an attempt is made to correlate these findings to the Mekong study in general.

Optimization of microwave-assisted extraction of polycyclic aromatic hydrocarbons from sediments.

The extraction methods for the determination of polycyclic aromatic hydrocarbons (PAHs) from spiked sediment containing benzo[k]fluoranthene, chrysene, acenaphthene, anthracene, carbazole and indeno[1,2,3-c,d]pyrene, using pressurised microwave-assisted extraction (PMAE) and sonication extraction were optimised. Each PAH in the spiked sediment was quantified by using the spectrofluorometric method. The optimised methods were compared on the extraction efficiency of 14 PAHs in a certified sediment reference material, LGC6188. Recoveries of 14 PAHs were performed by HPLC-DAD at 254 nm using the standard addition method. The results showed that the most extraction efficient method was pressurised microwave-assisted extraction with cyclohexane:acetone (3:2) for 15 min at 140% boiling point of acetone. Under this condition for the extracted certified sediment reference material recovery was 96.55%. It can be concluded from the experimental results that pressurised microwave-assisted extraction in a closed system provides a good alternative to sonication extraction for the extraction of PAHs from sediments. Furthermore, the PMAE was also applied to determine PAHs from sediments taken from the main entrance of Kasetsart University on Paholyotin road in Bangkok.

Environmental Monitoring of the Sediment Pollution along the Thai:Laos Mekong

The Mekong is an essential source of water and protein for the denizens of Thai Laos countries. However historic pollution is adversely affecting the water and sediment quality that threatens the short- and long-term supply/use of this major river system. This can have a major impact on the health and population of the marine life and ultimately adversely affect human health and the economy for both countries. As a first stage in the assessment of the scale and extent of the pollution problem, an in-depth program of sampling and analysis has been carried out for both water and sediments for three seasons since 2000. A range of water quality parameters were measured from ten sampling stations. These included the PolyAromatic Hydrocarbons (PAHs) initially measured as chrysene equivalents, then as individual compounds of fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo(a)anthracene, chrysene, benzo(b)fluoranthene, benzo(k)fluoranthene, benzo(a)pyrene, dibenzo(a,h)anthracene, benzo(g,h,i)perylene, and indeno(1,2,3,cd)pyrene. A range of heavy metals were measured including chromium, cadmium, mercury, copper, zinc, lead, and titanium. This paper presents the results of the field study to date and provides a preliminary evaluation of the extent of the pollution and potential for bioaccumulation within the local food chain.

The ecological complexity of the Thai-Laos Mekong River: II. Metals and polyaromatic hydrocarbons (PAHs) monitoring, modelling and environmental fate

The Mekong is an essential source of water and protein for the denizens of Thai Laos countries. It is hypothesized that pollution may be adversely affecting the water and sediment quality, which threatens the short and long-term use of this major river system. This directly impacts on the health and population of the aquatic life and ultimately human health and the economy for both countries is affected. The quality of the river can be assessed from various chemical and physical parameters, such as PAHs and metals content of both the water and the sediment. The introduction of Environmental Quality Standards (EQS) allows comparison of the values obtained with the guidelines. Furthermore the modelling program EPISUITE was used to determine the environmental partitioning of pollutants within the different environmental compartments. Using the data produced for PAHs and metals the experimental model was compared to the default model. This involved experimentally measuring the log Koc for Mekong sediments and from this determining the log Kow. High availability in sediment of pollutants may lead to greater biomagnification in bethnic fish, which may then be hazardous for human consumption even if it is safe for the species that is accumulating pollutants. The potential for this is shown by the calculated accumulation in biota Cbio values exceeding both the Chronic value (ChrV) and Lethal Concentration 50 (LC50) for fish in the Mekong River. When compared to the EQS guidelines the amount of some PAHs, cadmium and lead in sediment were above the lowest effect level but below the severe effect level.