Concentrations Of Butyltin Compounds Research Articles

Degradation kinetics of butyltin compounds during the bioremediation of contaminated harbour sediments

The present study was aimed at the reclamation of harbour sediments contaminated with butyltin compounds (BTCs) by means of biostimulation and/or bioaugmentation experiments carried out in a 5-L slurry bioreactor. In the biostimulation experiment with inorganic nutrients, almost 50% of TBT was degraded in 20 weeks. In the bioaugmentation experiment with a microbial consortium, no significant degradation of TBT was observed. Conversely, bioaugmentation combined with biostimulation led to a decrease of ∼50% in TBT after four weeks. A simple kinetic model fitted to the experimental data of BTC concentration allowed us to estimate that 10 weeks are needed to decrease BTC contamination by 90% using a strategy based on both biostimulation and bioaugmentation, and 29 weeks for a strategy using biostimulation only. Overall, our study indicates that strategies based on biostimulation coupled to bioaugmentation can be effective in significantly reducing the concentration of BTCs over relatively short timescales.

Accumulation of butyltin compounds in finless porpoises (Neophocaena asiaeorientalis) from Korean coast: Tracking the effectiveness of TBT regulation over time

The concentrations of butyltin compounds (BTs) were measured in the livers of finless porpoises (Neophocaena asiaeorientalis) caught off the Korean coast in 2003 and 2010, to assess the effectiveness of legislative action against BTs. The concentrations of BTs ranged from 65.1 to 1432 (average: 370) ng/g wet weight, within the ranges reported by previous studies. The levels of BTs in almost all the samples exceeded the suggested threshold value, implying potential adverse health effects from the BT exposures. Concentrations of BTs were significantly correlated with body length, weight, and age of finless porpoises, but were not correlated with sex. Spatial differences in the concentrations of BTs were not observed between Yellow and South Seas, while there was a significant decrease in BTs between the sampling years of 2003 and 2010. Our result indicates that the effectiveness on TBT ban has reached to marine mammals in the coastal waters of Korea.

<i>Mytilus galloprovincialis</i> as Mussel Watch for Butyltins, Tin, Copper and Zinc Contamination, from Antifouling Paint Particles, in West Algerian Coastal Waters

Butyltin compounds (BTs) including tributyltin (TBT) and its degradation product (DBT) and concentrations of heavy metals (Sn, Cu and Zn) were determined in mussels (Mytilus galloprovincialis) collected from some West Algerian harbours. BTs were detected in all the mussels. Quanti?cation of BTs and heavy metals was carried respectively by Gas Chromatography coupled with Mass Spectrometer (GC-MS) and Atomic Absorption Spectrometry, flame AAS. Concentrations of total butyltin (BTs: DBT + TBT) in mussels ranged from 0.49 to 2438 ng/g wet wt. The concentrations (μg/g wet wt) of heavy metals ranged from 0.40 to 3.55 for Sn, 9.62 to 67.03 for Cu, and 87.13 to 731.51 for Zn. Total of tin in mussels ranged from 0.2 to 1054.78 ng/g. Higher concentrations of butyltin compounds were found in mussels collected from Mers El Kebir shipyard, Arzew, a petroleum harbour (industrial), and Beni Saf fishing harbour. This suggested that maritime activities nearby the harbours play a major role as the source of BTs. Indeed, harbour of Arzew is frequented by voluminous tanker. TBT was the predominant compound in mussels collected from almost all the sampling locations; indicate the fresh input of TBT in harbours.

Organotin compounds in olive flounder Paralichthys Olivaceus and flathead mullet Mugil cephalus from Korean coastal waters

Concentrations of organotin compounds (OTCs) were measured in the muscle and liver of two fish species (Paralichthys Olivaceus and Mugil cephalus) collected in the six developed coastal regions of Korea: Incheon, Gunsan, Yeosu, Masan, Pohang and Jeju. Concentrations of butyltin compounds (ΣBTs) in the muscle and liver of the two fish species were detected in the range of 1.7–28.8 (mean: 8.8) ng/g-wet wt. as Cl and 18.7–5,096.9 (mean: 832.6) ng/g-wet wt. as Cl, respectively. Concentrations of phenyltin compounds (ΣPTs) ranged <0.1–72.5 (mean: 10.89) ng/g-wet wt. as Cl in the muscle and <0.1–316.3 (mean: 28.0) ng/gwet wt. as Cl in the liver. Concentrations of OTCs in the liver were higher than those of OTCs in the muscle. The compositions of ΣBTs in the muscle and liver were different from each other, but those of ΣPTs were similar. Tributytin (TBT) and triphenytin (TPT) levels in the two fish species collected from Korean coastal waters were significantly lower than the tolerable average residue level (TARL) estimated based on the tolerable daily intake (TDI).

Intake and Potential Health Risk of Butyltin Compounds from Seafood Consumption in Korea

Concentrations of butyltin compounds (BTs) were determined in 47 species of seafood commonly consumed in Korea to investigate intakes of BTs from seafood consumption and the potential health risks to the Korean population. The concentrations of BTs (the sum of dibutyltin and tributyltin) in seafood ranged from less than the limit of detection to 96.3 ng/g wet weight, which are levels similar to those reported for other countries. The intake of BTs from seafood consumption by the general population was estimated to be 17.2 ng/kg body weight/day. Fish accounted for 50% of the total intakes of BT, and the next contributor was cephalopods (26%). The estimated intakes for males and females were 18.6 and 15.7 ng/ kg body weight/day, respectively. Among the age groups investigated, children (<2 years and 3-6 years) had higher intakes of BTs compared with adults. The estimated intake of BTs for Korean population groups was 5-8% of the tolerable daily intake of 250 ng/ kg body weight/day set by the European Food Safety Authority. Our results suggest that the Korean population is not expected to exceed the threshold value for adverse health effects.

Tributyltin Solubilization and Degradation from Spiked Kaolin Using Different Reagents

Conditions for tributyltin (TBT) solubilization and degradation were investigated. These conditions were optimized to remove or degrade organotin compounds (OTC) in spiked kaolin. TBT-spiked kaolin and reagents with specific chemical properties were tested in a batch reactor using a solid matrix model. The final concentrations of butyltin compounds in kaolin were determined by gas chromatography coupled with a pulsed flame photometric detector. Best results were obtained under acidic conditions (2 < pH < 5) with up to 87% TBT removal from the spiked kaolin. Acids with reducing properties were more effective (ascorbic and formic acid: 87% and 82% of TBT abatement, respectively). Moreover, final monobutyltin and dibutyltin concentrations were analyzed to determine which species predominate in the solid matrix after batch experiments. OTC speciation shows that degradation of TBT occurs simultaneously with solubilization in the presence of several reagents. These results allow choosing favorable/optimal operating conditions for OTC elimination.

Spatial and seasonal behaviour of organotin compounds in protected subtropical estuarine ecosystems in Okinawa, Japan

The spatial and temporal behaviours of the organotin compounds (OTCs) (butyl- and phenyltin) were investigated in the Manko and Okukubi protected estuarine ecosystems on Okinawa Island, Japan from February to October 2006. Butyltin compounds (BTCs) were frequently detected in all seasons, while phenyltin (PhTs) were found in winter and early spring. In Manko estuary, the total mean concentrations of BTCs and PhTs were 22.78 ± 30.85, (mean ± SD, n = 53) and 0.08 ± 0.27 ng(Sn) L−1, respectively. In Okukubi estuary, BTCs and PhTs were 12.58 ± 23.96 and 0.47 ± 1.67 (n = 55) ng(Sn) L−1, respectively. The Manko sediments can be classified as lightly contaminated, while the Okukubi sediments were uncontaminated with tributyltin (TBT). The mean levels of TBT shown in Manko estuary exceeded the threshold level and represent an ecotoxicological risk to sensitive aquatic life. Generally, the present study reports the occurrence and continuous input of OTCs in the protected estuaries, even 16 years after legal restriction of TBT usage in coastal waters was implemented by the Japanese Environmental Authorities.

Distribution and Fate of Organotin Compounds in Japanese Coastal Waters

In order to elucidate the details of both the distribution and fate of organotin compounds (OTs) in the costal ecosystem, the concentrations of butyltin compounds (BTs) and phenyltin compounds (PTs) were determined in seawater, sediment and blue mussels Mytilus galloprovincialis collected in Maizuru Bay, Japan. The concentrations of tributyltin (TBT) in seawater, sediments and mussels ranged from 3.9 to 27 ng l−1, from 1.2 to 19 ng g−1 dry wt and from 0.77 to 11 ng g−1 wet wt, respectively. Although the levels of TBT in seawater, sediments and mussels from Maizuru Bay were lower than those reported previously at other sites in Japan, the levels can still be toxic to susceptible organisms. Trace amounts of PTs were also found in seawater, sediment and mussel samples, indicating that there is a slight input of triphenyltin (TPT) into the seawater in the bay at present. The highest TBT concentration in seawater among all sites measured in the bay was found near a glass factory, and the lowest concentrations were observed at the center of the bay. The highest concentration of TBT in sediment was detected near a shipyard. In mussels, a high concentration of TBT was detected near a cement plant and timberyard. These results indicate that the major sources of contamination of OTs in the bay are considered to be from those facilities and ships. The proportion of TBT in seawater and mussels showed that, of total BTs, it was the predominant compound at most sites. These results suggested that there is a continuous input of TBT into the seawater and thereafter an accumulation of TBT in mussels due to their low metabolic capacity to degrade TBT. In sediment, the proportion of monobutyltin (MBT) was the highest of BTs at most sites. This could reflect a previous contamination by TBT used before the regulation of its usage in the bay.

Seasonal variation in the composition and concentration of butyltin compounds in marine fish of Taiwan

For the first time, strong evidence is presented to demonstrate that the accumulations of butyltin compounds (BTs) exhibit seasonal variations with respect to their compositions and concentrations in marine fishes. Measurements were made on the benthic ponyfish Leiogenathus splendens and lizardfish Trachinocephalus myops inhabiting the west coast of Taiwan. In the whole body samples of the ponyfish, BT concentrations ranged from 236 to 2501 ng/g wet wt, with those in winter considerably higher than in the other seasons ( p<0.05). In a similar vein, proportions of mono- (MBT), di- (DBT) and tributyltin (TBT) differed significantly ( p<0.001) depending upon the season, with TBT (75 and 50%) dominant in winter and spring and DBT (37 and 57%) and MBT (42 and 24%) dominant in summer and autumn, respectively. In the lizardfish, the concentrations of BTs were one to two orders of magnitude higher in the liver than in the muscle, i.e. 3058–11,473 vs. 36–159 ng/g wet wt, respectively. Concentrations of MBT, DBT and TBT in the muscle ranged, respectively, from 5 to 14, 8 to 35 and 23 to 110 ng/g wet wt, with the major compound being TBT (57–69%) in all seasons. However, in the liver, DBT concentrations, ranging from 992 to 7797 ng/g wet wt, differed seasonally with a descending order of autumn > summer > spring ( p<0.05). Meanwhile, TBT (41%) was predominant in spring, whereas DBT (50 and 68%) was most heavily concentrated in summer and autumn ( p<0.001). Seasonally mediated physiological changes, such as dilution due to growth and metabolic compensation, may play important roles in forming different BT accumulation patterns among seasons and organisms.

Contamination of butyltin compounds in Malaysian marine environments

Concentration of butyltin compounds (BTs), including tributyltin (TBT), dibutyltin (DBT) and monobutyltin (MBT) and total tin (ΣSn) 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 ΣSn, 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.

Electrospray tandem mass spectrometric measurements of organotin compounds

Electrospray mass spectrometry of a series of organotin compounds in solutions of methanol are reported. Low energy collision‒induced dissociation MS/MS analysis of diagnostic precursor ions confirmed the characteristic fingerprint patterns obtained in the conventional electrospray spectra and proved to be a specific and very sensitive method for quantification of the (R3Sn)2O and the series of RnSnX4–ncompounds in environmental matrices. Concentrations of butyltin compounds (TBTX, DBTX2and MBTX3) in sediment reference materials PACS-1 and PACS-2 and butyltin and phenyltin compounds (TBTX, DBTX2, MBTX3, TPTX, DPTX2and DPTX3) in Quasimeme II biota reference material (QSP001BT) were determined. The organotin compounds were extracted from the reference materials with 1-butanol followed by dilution with methanol containing 1 mM ammonium acetate. The extracts were introduced directly into the electrospray source by a continuous flow of MeOH : H2O (60 :40). Quantitation of TBTX, DBTX2, TPTX, DPTX2and DPTX3was achieved by low energy CID tandem mass spectrometry using the Multiple Reaction Monitoring (MRM) analysis with the appropriate MS/MS transitions (positive ion electrospray ionization). Quantitation of MBTX3was achieved using a negative ion electrospray CID tandem mass spectrometry method. For all samples quantitation was achieved by use of the method of standard addition, relative extraction recoveries were determined spiking with internal standards of mono‒, di‒ and triorganotin compounds separately to different samples.

Survey on the presence of butyltin compounds in chinese alcoholic beverages, determined by using headspace solid-phase microextraction coupled with gas chromatography-flame photometric detection.

The use of butyltin compounds in some food packaging leads to the contamination of liquid food and may result in subsequent adverse effects on people's health through the food chain. A survey of butyltin compounds in Chinese alcoholic beverages purchased from retail markets was carried out by using solid-phase microextraction (SPME) followed by gas chromatography coupled with flame photometric detection. Forty-four samples including wine, liquor, and champagne were studied. The levels of monobutyltin and dibutyltin ranged from <0.016 to 5.687 and from <0.0022 to 33.257 microg of Sn/L, respectively. Low levels of tributyltin were detected. The presence of dibutyltin in wine samples was further confirmed by GC-MS. The result indicated that dry wines generally contained more dibutyltin than sweet wines. The concentrations of butyltin compounds in liquor samples were lower than those in wine samples.

Organochlorine and organotin compounds in Caspian seals ( Phoca caspica) collected during an unusual mortality event in the Caspian Sea in 2000

Polychlorinated biphenyls (PCBs), organochlorine pesticides and organotin compounds were determined in the blubber and liver of Caspian seals ( Phoca caspica) found stranded on the coast of the Caspian Sea during an outbreak of canine distemper virus (CDV) in 2000. Among organochlorines analyzed, DDTs were the most dominant contaminants with concentrations ranging from 6.3 to 470 μg/g on a lipid-weight basis. Caspian seals collected in 2000 during the epizootic had higher concentrations of organochlorines than healthy individuals sampled in 1998. However, the blubber layer was generally thinner in the seals collected in 2000 than those in the previous surveys. Although compositions of organochlorine pesticides in seals suggested that the contamination status in the Caspian Sea is improving, the levels found in Caspian seals in 2000 were comparable to those in other marine mammals that have suffered from epizootics. This implies that the present status of contamination found in Caspian seals poses a risk of immunosuppression. Concentrations of butyltin compounds in livers of seals ranged from 0.49 to 17 ng/g on a wet-weight basis and octyltin compounds were below limit of detection in all the samples analyzed, suggesting less contamination by organotin compounds in the Caspian Sea.

Organochlorine pesticides, polychlorinated biphenyls, and butyltin compounds in blubber and livers of stranded California sea lions, elephant seals, and harbor seals from coastal California, USA.

Concentrations of polychlorinated biphenyls (PCBs), DDTs (p,p'-DDE, p,p'-DDD, p,p'-DDT), chlordanes (CHLs; cis-chlordane, cis-nonachlor, trans-nonachlor, and oxychlordane), hexachlorocyclohexane isomers (HCHs), hexachlorobenzene (HCB), tris(4-chlorophenyl)methane (TCPMe), tris(4-chlorophenyl)methanol (TCPMOH), and mono- (MBT), di-(DBT), and tri-butyltin (TBT) were determined in blubber and livers of 15 California sea lions (Zalophus californianus), 6 northern elephant seals (Mirounga augustirostris), and 10 harbor seals (Phoca vitulina) found stranded along the coasts of California, USA, during 1991-1997. Among the organochlorines analyzed, DDTs were predominant, followed in decreasing order by PCBs, CHLs, TCPMe, TCPMOH, HCHs, and HCB. The greatest concentrations of organochlorines were found in California sea lions. The highest DDT and PCB concentrations found in the blubber of California sea lions were 2,900 and 1,300 microg/g, lipid weight, respectively. Concentrations of TCPMe and TCPMOH in California sea lions were correlated significantly with DDT concentrations. Concentration ratios of various organochlorines in harbor seal livers were different from those in California sea lions and elephant seals, which suggested that the sources of exposure of harbor seals to organochlorines were different from those in the other two species. Concentrations of butyltin compounds in livers of pinniped species ranged from 2 to 99 ng/g, wet weight, which were less than those observed in cetaceans and in California sea otters.

Accumulation of butyltin compounds and total tin in marine mammals

Concentrations of butyltin compounds (BTs), including tributyltin (TBT) and its metabolites, di-(DBT) and monobutyltin (MBT), and total tin (ΣSn=organic+inorganic tin) were determined in various tissues and organs of marine mammals collected from Japanese coastal waters. Some marine mammal species from Hong Kong, India, Philippines, Black Sea and North Pacific Ocean were analyzed for comparison. Among the organs and tissues analyzed, concentrations of ΣBTs (TBT+DBT+MBT) and ΣSn were the highest in the liver. Concentrations of ΣBTs and ΣSn in most coastal species were higher than those in offshore species, indicating a greater input of tin compounds in coastal waters. Lower hepatic concentrations of ΣBTs and ratio of ΣBTs to ΣSn observed in pinnipeds may be attributed to higher metabolic capacity to degrade BTs and to their excretion through hair shedding. Age trends in accumulation of both ΣBTs and ΣSn showed increasing concentrations in immature growth stage and stable levels in mature animals.A significant correlation was observed between the hepatic concentrations of ΣBTs and ΣSn in marine mammals. These findings suggest a significant input and/or bioaccumulation of anthropogenic tin. A significant correlation was found between concentrations of ΣBTs (as well as ΣSn) in hair and liver of pinnipeds, suggesting that hair can be used as an indicator for monitoring butyltin contamination in the body of pinnipeds under non-killing condition.

TBT in marine sediments and blue mussels ( Mytilus edulis) from central-west Greenland

Concentrations of butyltin compounds were investigated in the bivalve Mytilus edulis (five sites) and marine sediments (three sites) near the largest town, Nuuk, in Greenland. In seven of the eight samples the extremely toxic compound tributyltin (TBT) was detected. The concentrations of tributyltin and degradation products in the bivalves were close to 1 μg kg −1 wet weight (ww), calculated as Sn, which is lower than those found in Iceland and the Faeroe Islands. In sediments the concentration of TBT ranged from below the limit of detection of 1 μg kg −1 to 171 μg kg −1 dry weight (dw), calculated as Sn, which is comparable to levels found in Europe.

Speciation of butyltin compounds in marine sediments and sea-shells by HG/GC/QFAAS

After optimisation of sample pretreatment and determination procedures, butyltin compounds were determined in selected marine sediments and biota using the hydride generation/gas chromatography/quartz furnace atomic absorption spectrometry method. Butyltins were detected in all surface sediment samples of Arcachon Bay, though at widely different concentrations (from a few ng g-1 in remote areas to 158 ng g-1 in marinas). The relative abundances of mono-, di- and tri-butyltin vary with the distance to point pollution sources and the depth of burial (i.e. the storage time). Half-life times of the three butyltin compounds were estimated in a marina sediment as close to 1.1, 1.9 and 2.1 years, respectively. Quite significant concentrations of butyltin compounds were measured in some commercial sea-shell samples.

Occurrence of Butyltin Compounds in Human Blood

Residues of butyltin compounds, including mono- (MBT), di- (DBT) and tributyltins (TBT), were measured in human blood collected from central Michigan, U.S.A. MBT, DBT, and TBT were detected in 53, 81, and 70% of the 32 blood samples examined. Concentrations of butyltins were in the order of MBT > DBT ≥ TBT, with total butyltin concentrations ranging from less than the limit of detection to 101 ng/mL. Exposure of humans to butyltin compounds used as stabilizers or as biocides in household articles has been regarded as a source in addition to the ingestion of contaminated foodstuffs. There was no significant difference in concentrations of butyltin compounds between sexes. Concentrations of butyltin compounds did not exhibit pronounced age-dependency, which is different from those observed for persistent pollutants such as polychlorinated biphenyls (PCBs). In general, concentrations of butyltins measured in blood were less than that affected human natural killer lymphocytes (a primary immune defense against...

Occurrence of butyltin compounds in beluga whales (Delphinapterus leucas)

Fifty-two beluga whale samples (Six liver samples, and 46 blubber samples including ones from different depths of the fat layer) from the St Lawrence River, Canada, were analyzed for butyltin compounds (mono-, di-, and tri-butyltin) with a view to investigating the occurrence and contamination of butyltin in these animals. A special procedure was also developed for the determination of butyltin compounds in blubber samples with high lipid content (up to 95%). Total-butyltin concentrations in liver samples were found to be much higher than those in the blubber samples. The concentrations of butyltin compounds in blubber samples were observed to be related to their lipid content. Concentration levels of butyltin species in beluga whale were compared with those in other marine vertebrates in other parts of the world. The presence of butyltin compounds in liver and blubber samples suggests the accumulation of these toxicants by beluga whale. © 1998 John Wiley & Sons, Ltd.

Vertical Distribution of Butyltin Residues in Sediments of British Columbia Harbours

Vertical distributions of tributyltin (TBT) and its degradation products di- and monobutyltin have been measured in five sediment cores collected in harbours and marinas of southern British Columbia, Canada. Despite restrictions on the use of organotin-based marine antifouling paints imposed in Canada in 1989, concentrations of butyltin compounds in coastal marine sediments remain high. The highest concentration of TBT, 520 ng g−1 TBT-Sn, was recorded in a core collected from a small marina near Sidney, Vancouver Island. Similar levels of TBT were also recorded in a core collected in inner Vancouver Harbour, indicating that commercial shipping continues to be a significant source of butyltin contaminants to British Columbia's marine environment. Vertical profiles of butyltins differed according to location. The marina core showed the maximum in TBT concentration at 8 cm depth, indicating clearly that the retail ban on organotin-based paints to craft less than 25 m in length has successfully reduced the flux of TBT to surface sediments. However, no such trend was visible in harbour cores, with the highest concentrations of TBT in superficial sediments. The presence of TBT throughout the sediment cores implies that it must be considered a persistent contaminant. Applying a simple regression model to one core, for which an approximate chronology is known, suggests a half-life for the first order degradation of TBT of about 8.7 years. This is a slower rate of degradation than any previously reported, and may be due to inhibition of microbial action in cold waters.