Organotin concentrations in three intertidal neogastropods from the coastal waters of Taiwan

This study was aimed to determine organotin concentrations in the muricids Thais clavigera, Thais tuberosa and Morula granulata on an island wide scale and to find an adequate bioindicator species for long-term monitoring purpose. Samples were collected from the coast of Taiwan and vicinity islands with organotin analysis by graphite furnace atomic absorption spectrophotometry. Because triphenyltin (TPT) could not be discriminated from tributyltin (TBT) by the extraction method, organotins were measured as TBT + TPT and total hexane extractable organotins. Severity of imposex in the muricid population samples expressed as relative penis size (RPS) indices were calculated and compared to determine a suitable bioindicator species. In T. clavigera, T. tuberosa and M. granulata, TBT + TPT were 17-157, 1-44 and 117-1343 ng Sn g(-1) dry wt, respectively. And total organotins varied in the range of 181 to 1125, 23 to 44 and 229 to 1402 ng Sn g(-1) dry wt, respectively. A positive correlation was found between TBT + TPT and total organotins in M. granulata (TBT + TPT = Total organotins x 1.01-110.79; R2=0.97; p<0.001). At the site of Dapaisha, total organotins in M. granulata was 10 times higher than in T. tuberosa (i.e. 242 versus 23 ng Sn g(-1) dry wt). No signs of imposex were found in T. tuberosa (a single site in two subsequent years) and in M. granulata (seven collection sites). The degree of imposex (RPS) of T. clavigera varied from 0.2 to 38.1%. The RPS indices from fishing harbors were not higher than from rocky shores and oyster culture sites. No correlation was found between RPS indices and concentrations of TBT + TPT or total organotins. M. granulata seemed to be insensitive to organotin pollution although organotins were also detected. Our results indicate that organotin pollution is wide spread in coastal waters of Taiwan and pollutants at least include butyltins and phenyltins. As a bioindicator species, T. clavigera is more appropriate than T. tuberosa and M. granulata to monitor organotin contamination.     

Sulphur and seasalt deposition as reflected by throughfall and runoff chemistry in forested catchments

At forested catchments at Lake G?rdsj?n on the Swedish west coast the deposition and runoff chemistry has been followed during the period 1979-1990 by throughfall and runoff measurements as well as by measurements of atmospheric concentrations. The 10-year means in throughfall and runoff are very similar for sulphur and the main seasalt ions sodium and chloride; for sulphur 26.1 and 27.6 kg ha(-1) yr(-1), for sodium 49 and 52 kg ha(-1) yr(-1) and for chloride 96 kg ha(-1) yr(-1) and 93 kg ha(-1) yr(-1), respectively. The actual flows are 100-200% higher than the wet deposition as collected in open bulk precipitation collectors indicating a very large input by dry deposition. One important question is to what extent the throughfall and runoff values can be used as measures of total deposition. We present results from studies at different experimental catchments illustrating the possibilities of using throughfall and runoff data as measures of atmospheric deposition of sulphur and seasalt.     

Organotin contamination in the Atlantic Ocean off the Iberian Peninsula in relation to shipping

Imposex in female snails, a bioindicator of TBT contamination, and the presence of organotins in snails' tissue and sediments were studied at nine sites off the western Iberian Peninsula. The study was part of a European project (acronym HIC-TBT) co-financed by the EU-LIFE programme, intending to investigate and communicate the impact of organotins from ships in marine ecosystems. Snails and sediments were sampled during two cruises in May/June 1999 and in January 2000 in areas of high, intermediate and low-shipping density. Imposex was found in female snails from several sampling sites, some of which had an imposex incidence of 100%. Differences in sensitivity were found between species; hence comparison of imposex levels between locations where different species were collected was not straightforward. Total organotin concentrations in sediments (sum of butyl and phenyltin compounds) ranged from 21 to 185 ng Sn g(-1) with higher values for most sites sampled in the vicinity of shipping lanes. Organotin concentration in snails' tissue ranged from <5 to 196 ng Sn g(-1), which are similar to those found in snails from other offshore areas contaminated by TBT. Overall, these results give further support to the recent ban on the use of organotin based antifouling paints to all ship size.     

A study on organotin levels in Canadian drinking water distributed through PVC pipes

A study on organotin compounds in Canadian drinking water was carried out in winter-spring 1996 (28 sites) and autumn 1996 (21 sites). Approximately 29% and 40% of distribution waters supplied through PVC pipes installed recently (typically less than 6 months) contained organotin compounds in the winter-spring and autumn surveys respectively. Monomethyl-, dimethyl-, monobutyl- and dibutyltin levels ranged up to 291 ng Sn/L, 49.1 ng Sn/L, 28.5 ng Sn/L and 52.3 ng Sn/L, respectively. An additional study in summer 1996, of locations where the highest organotin levels were detected in the winter-spring survey, indicated that organotin levels had decreased in most distribution water samples. Samples of PVC pipe/tubing contained organotin compounds consistent with the organotin patterns found in the distribution water samples.     

Kinetic degradation processes of butyl- and phenyltins in soils

The degradation of organotin compounds (OTC) in agricultural and forest soils is studied in sandy soil samples. Individual experiments involving the three butyl- and the three phenyltins were carried out during 90 d in controlled conditions (darkness, 28 degrees C, aerobic conditions, 13% moisture) and with spiking concentration representative of environmental levels (20-50 micrg(Sn) kg(-1)). After the validation of first-order degradation kinetic model, mechanisms involved throughout the study were considered. Degradation pathways are proposed for butyl- and phenyltins and discussed according to literature data. The degradation of mono- (MBT, MPhT), di-organotins (DBT, DPhT) and TBT is clearly identified as a single successive loss of an organic group whereas TPhT is directly degraded to MPhT. The half-life times were dependent on their substitution degree, ranging from 24 (TPhT) to 220 (MBT) d. The less substituted the OTC is, the more persistent it is. In the range 4.3-5.7, pH does not seem to influence OTC degradation under the present operating conditions. Finally this study shows the significant persistence in soil samples in our experimental conditions for most of studied organotins and highlights the potential impact on soil quality.     

Assessment of tin and butyltin species in estuarine superficial sediments from Gipuzkoa,Spain

Ten superficial sediments from river estuaries of Gipuzkoa (North Spain) were collected and analyzed for nine metals (including tin, Sn) and butyltin compounds (monobutyltin, MBT; dibutyltin, DBT; tributyltin, TBT). Total metal concentration in the fine fraction (<63 micrometer) of the sediment was determined in aqua regia--hydrofluoric acid extracts by atomic absorption spectrometry. The butyltin species (BTs) were firstly extracted from the sediments with hydrochloric acid-methanol mixture. After derivatization with sodium tetraethyl borate, the organotin compounds were extracted by solid phase microextraction (SPME) in headspace mode. A fiber coated with 100 micrometer poly(dimethylsiloxane) was used for SPME. The organotin species were analyzed by gas chromatography-flame ionization detection. Analysis of the certified reference sediment (PACS-2) shown the suitability of the procedures for determination of metal contents and DBT-TBT species in contaminated sediments. Factorial analysis was used to examine the main sources of metals. Three factors represented more than 89% of the total variance of the metal system, and the Sn was related with Cu-Zn-Pb suggesting the same pollution source. The BTs concentrations in the area were high (TBT ranged from 0.05 to 5.48 mg Sn kg(-1)). The percentage of total butyltin species ( summation operator BTs) respect to the total Sn amount was higher than 4% in all the sediments, showing in the Bidasoa river estuary a remarkable value higher than 20%. Hence, the studied estuarine sediments reflect a pollution that is related with historical industrial and fishing activities of the area.     

Quantification of organotin compounds and determination of imposex in populations of dogwhelks (Nucella lapillus) from Norway

Unintentional effects of the antifouling agent tributyltin (TBT) have been discovered in marine gastropods as the induction of male sex characters in females, known as imposex. The occurrence of imposex in dogwhelks (Nucella lapillus) was investigated in 41 populations sampled in 1993-1995 along the Norwegian coast. A method for quantification of organotin species using gas chromatography and atomic emission detection (GC-AED) was developed. Some degree of imposex occurred in almost all populations of dogwhelks studied, except in four from Northern Norway. The concentration of organotin compounds in the gastropods from the unaffected populations was below the detection limit (7 ng Sn/g d.w.). The concentration of TBT in dogwhelks from affected populations was in the range 48-1096 ng Sn/g d.w. A positive relation between the concentration of TBT in dogwhelks and the degree of imposex was found.     

Survey of organotin compounds in rivers and coastal environments in Portugal 1999-2000

In the period from April 1999 to May 2000, organotin pollution, namely butyl and phenyltins, was investigated in coastal and continental waters (46 stations), estuarine sediments (15 stations) and mussels (Mytilus galloprovincialis) (13 stations) throughout Portugal. Sampling points were chosen in areas of specific industrial, agricultural and harbor activities. Butyltins (BTs) were the only tin species identified of which tributyltin (TBT) was found in the whole area. Concentrations of TBT in river water ranged from 3 to 30 ng L(-1) (as Sn), marine sediment ranged from 4 to 12 microg kg(-1) (as Sn), whereas concentrations in mussel tissue ranged from 2.5 to 490 microg kg(-1) (as Sn). Given that some water samples appeared to be contaminated by higher monobutyltin (MBT) and dibutyltin (DBT) concentrations, the role of biological degradation and direct inputs from agricultural and industrial applications areas are discussed. The study compares depleted butyltin pollution in sediments and mussels of the Portuguese coastline associated with antifouling paints with previously reported levels. Inputs in river waters are more related to (i) PVC leaching and (ii) industrial sources, in some cases discharged by municipal wastewaters.     

森林降水化学的变化特征和机理

研究并比较了湖南酸雨区韶山小集水区林内降水的化学特征，结果表明，与大气降水相比，穿冠水和地表穿透水中的富集的离子浓度除了NO3^-和Na^ 外均明显增加，到达地表的降水离子增加倍数最高达34．3倍；离子总量最高倍数为8．1倍，乔木树冠层的离子富集作用大于灌木层。韶山的大气降水、穿冠水和地表穿透水的年均pH分别为4．61、5．54和5．85。持续大量的降水对森林上空的污染物有较高的清除效果。     

Dissolved inorganic nitrogen budget for a forested catchment at Beddgelert, North Wales

An input-output budget for dissolved inorganic-N in a small forested catchment in North Wales is presented. From 1982 to 1990, bulk precipitation inputs averaged 10.3 kg ha(-1) year(-1), whereas throughfall inputs in 1983-1984 were 20.3 kg ha(-1) year(-1). Streamwater outputs were consistently larger than bulk precipitation inputs, averaging 14.6 kg ha(-1) year(-1). Inorganic-N in the forest stream was predominantly nitrate and concentrations were substantially higher than in a nearby moorland stream. Both streams showed seasonal trends in nitrate concentration, with highest concentrations occurring in summer in the forest stream but in winter in the moorland stream. Nitrate concentration in the forest stream increased with increasing soil temperature up to approximately 7 degrees C and decreased at higher temperatures. Nitrification is thought to be responsible for nitrate production at temperatures both below and above 7 degrees C, but root uptake becomes significant only at the higher temperatures. In the forest, dry deposition and cloudwater inputs of inorganic-N are responsible for increased nitrogen fluxes in throughfall compared with wet deposition. Mineralization and nitrification in excess of plant needs causes the organic soil horizons to act as a net source of dissolved inorganic-N. Nitrogen transformations in the soil lead to soil acidification at a rate of 1.0 keq ha(-1) year(-1).     

Three decades of tributyltin in the coastal environment with emphasis on Arcachon Bay, France

This account briefly reviews the fate, bioconcentration and effects of tributyltin (TBT) three decades after its introduction into the coastal environment. Data on TBT-related events that occurred in Arcachon Bay (gastropod imposex, oyster recruitment failure, oyster shell malformations, concentrations in water and sediments) are revised and reinterpreted. Historically, TBT concentrations in the waters of the open bay seldom exceeded 1 ng Sn l(-1) in the 1960s, likely surpassed the range of 100 ng Sn l(-1) from 1977 to 1981 (years when no oyster spat were collected and the local shellfish industry collapsed), and decreased to about 1 ng Sn l(-1) in the late 1980s and early 1990s following legislation in January 1982 banning TBT use. TBT pollution is discussed in relation to the green tides that have developed in Arcachon Bay since 1982.     

Rain and throughfall chemistry in a Norway spruce forest in the Western Prealps

From January 1987 to December 1989 precipitation was collected in an open field in a forested area of the Western Prealps. The site faces the intensely industrialized area of the Po Valley. In a Norway spruce plantation, next to the open field sampler, throughfall was collected from January 1987 to August 1989 for a period of 32 months. In the common sampling period median pH values of the open field precipitation and throughfall were 4.28 and 4.19 respectively. Open field precipitation has yearly deposition rates of acidity, Ca, S, and N of 0.81, 9.82, 24.83 and 32.81 kg/ha(-1) respectively. The throughfall showed significant increases in the deposition rates for Ca, Mg, K, N and S, due to abundant dry deposition and, probably, to nutrient leaching contributed by the canopies of the spruce. On the basis of available data, an initial approach to atmosphere-canopy interaction was made.     

Determination of herbicides in stemflow and throughfall of beeches (Fagus sylvatica L.) and in rainfall

The pesticide contamination of water samples collected in and nearby a beech forest in northern Germany was evaluated. For this purpose, a method for the collection of water samples from stemflow and throughfall of beeches (Fagus sylvatica L.) and rainfall was developed in response to the demands for the analysis of organic contaminants in water samples. Furthermore a sensitive and selective multiresidue method was developed to determine 18 pesticides, frequently used in Germany, in aqueous samples. The samples collected were taken from the stemflow, the crown throughfall and the rainfall between May and November 2001. Analysis based on reversed-phase liquid chromatography with a pneumatically assisted electrospray mass spectrometer followed a solid phase extraction using C-18 extraction cartridges. Isoproturon, metolachlor, prosulfocarb and terbuthylazine were found during and shortly after their application period. In rainfall metolachlor, terbuthylazine and prosulfocarb were detectable in concentrations between 5 and 65 ng l(-1) and isoproturon in concentrations between 20 and 360 ng l(-1) respectively. In most of the samples, concentrations of those four pesticides were higher and detectable for a longer time in stemflow than in rainfall. Crown throughfall samples were collected from the end of August to November. Absolute deposition of isoproturon to forest soil were up to 70 times higher in comparison to rainwater samples.     

Pilot study on the contamination of drinking water by organotin compounds from PVC materials

Raw and treated water samples and tap water samples from four to six houses located on distribution lines where PVC pipe/tubing had been recently installed were collected in five Canadian municipalities for the analysis of organotin compounds. After derivatisation with sodium tetraethylborate the ethylated organotin compounds were extracted with hexane and analysed by gas chromatography-microwave induced plasma atomic emission spectrometry using a wavelength (326.234 nm) specific for tin. Organotin compounds, mainly methyltin and dimethyltin at concentrations ranging respectively from 0.5 to 257 ng Sn/L and from 0.5 to 6.5 ng Sn/L, were detected in samples from ten of the twenty-two houses. No organotin compounds were detected in raw water or treated water leaving the treatment plant, indicating that the organotin compounds were leaching into the water from some component of the distribution system.     

Effect of submergence-emergence sequence and organic matter or aluminosilicate amendment on metal uptake by woody wetland plant species from contaminated sediments

Site-specific hydrological conditions affect the availability of trace metals for vegetation. In a greenhouse experiment, the effect of submersion on the metal uptake by the wetland plant species Salix cinerea and Populus nigra grown on a contaminated dredged sediment-derived soil and on an uncontaminated soil was evaluated. An upland hydrological regime for the polluted sediment caused elevated Cd concentrations in leaves and cuttings for both species. Emergence and soil oxidation after initial submersion of a polluted sediment resulted in comparable foliar Cd and Zn concentrations for S. cinerea as for the constant upland treatment. The foliar Cd and Zn concentrations were clearly higher than for submerged soils after initial upland conditions. These results point at the importance of submergence-emergence sequence for plant metal availability. The addition of foliar-based organic matter or aluminosilicates to the polluted sediment-derived soil in upland conditions did not decrease Cd and Zn uptake by S. cinerea.     

Concentrations of two organic contaminants in precipitation, soils and plants in the Essex region of Southern Ontario

Recent research has indicated that the atmosphere is an important pathway by which pollutants enter terrestrial and aquatic ecosystems. We report here concentrations of PCBs and octachlorostyrene (OCS) in precipitation, soils and plants in Essex County, Ontario. The average PCB concentration in urban precipitation (23 ng litre(-1)) was lower than that previously reported for urban areas in the Great Lakes basin. Differences between sites and with varying wind directions were not significant. OCS concentrations in precipitation averaged 1.6 ng litre(-1). Concentrations of PCBs in soils were 2-3 orders of magnitude greater than in precipitation. Concentrations of these pollutants in city soils and plant roots were consistently higher than those from suburban and rural sites. Ratios of urban to suburban concentrations in soils and precipitation were approximately 5:1 for PCBs. However, concentrations of OCS were similar in urban and suburban samples of precipitation, soils and plant tissues. These comparisons suggest an urban source for PCBs, but not OCS. Concentrations of all contaminants in plant leaves, unlike those in precipitation, roots and soils, were relatively similar in urban and suburban areas. That similarity suggests that direct foliar uptake is not an important pathway for pollutant uptake in plants.     

TBT and TPhT persistence in a sludged soil

The persistence of tributyltin (TBT) and triphenyltin (TPhT) in soils was studied, taking into consideration the quantity of sewage sludge, TBT and TPhT concentrations in soil as well as the soil pH. The organotin compounds (OTC) were introduced into the soil via a spiked urban sludge, simulating agricultural practise. OTC speciation was achieved after acidic extraction of soil samples followed by gas chromatography–pulsed flame photometric analysis (GC–PFPD). Leaching tests conducted on a spiked sludge showed that more than 98% of TBT are sorbed on the sludge. TBT persistence in soil appeared to depend on its initial concentration in sludge. Thus, it was more important when concentration is over 1000 μg(Sn) kg⁻¹ of sludge. More than 50% of the initial TBT added into the soil were still present after 2 months, whatever the experimental conditions. The main degradation product appeared to be dibutyltin. About 90% of TPhT were initially sorbed on sludge, whatever the spiking concentration in sludge was. However, TPhT seemed to be quantitatively exchangeable at the solid/liquid interface, according to the leaching tests. It was also significantly degraded in sludged soil as only about 20% of TPhT remain present after 2 months, the monophenyltin being the main degradation product. pH had a significant positive effect on TBT and particularly TPhT persistence, according to the initial amounts introduced into the soil. Thus, at pH over 7 and triorganotin concentration over 100 μg(Sn) kg⁻¹, less than 10% of TBT but about 60% of TPhT were degraded. When the sludge was moderately contaminated by triorganotins (typically 50 μg(Sn) kg⁻¹ in our conditions) the pH had no effect on TBT and TPhT persistence.     

Atmospheric deposition inputs and effects on lichen chemistry and indicator species in the Columbia River Gorge, USA

Topographic and meteorological conditions make the Columbia River Gorge (CRG) an 'exhaust pipe' for air pollutants generated by the Portland-Vancouver metropolis and Columbia Basin. We sampled fog, bulk precipitation, throughfall, airborne particulates, lichen thalli, and nitrophytic lichen distribution. Throughfall N and S deposition were high, 11.5-25.4 and 3.4-6.7 kg ha(-1) over 4.5 months at all 9 and 4/9 sites, respectively. Deposition and lichen thallus N were highest at eastern- and western-most sites, implicating both agricultural and urban sources. Fog and precipitation pH were frequently as low as 3.7-5.0. Peak NO(x), NH(3), and SO(2) concentrations in the eastern CRG were low, suggesting enhanced N and S inputs were largely from particulate deposition. Lichens indicating nitrogen-enriched environments were abundant and lichen N and S concentrations were 2x higher in the CRG than surrounding national forests. The atmospheric deposition levels detected likely threaten Gorge ecosystems and cultural resources.     

Distribution and speciation of mercury in the peat bog of Xiaoxing'an Mountain,northeastern China

Most reports on mercury (Hg) in boreal ecosystems are from the Nordic countries and North America. Comparatively little information is available on Hg in wetlands in China. We present here a study on Hg in the Tangwang River forested catchment of the Xiaoxing'an Mountain in the northeast of China. The average total Hg (THg) in peat profile ranged from 65.8 to 186.6 ng g(-1) dry wt with the highest at the depth of 5-10 cm. THg in the peat surface was higher than the background in Heilongjiang province, the Florida Everglades, and Birkeness in Sweden. MethylHg (MeHg) concentration ranged from 0.16 to 1.86 ng g(-1) dry wt, with the highest amount at 10-15 cm depth. MeHg content was 0.2-1.2% of THg. THg and MeHg all decreased with the depth. THg in upland layer of soil (0-20 cm) was comparable to the peat surface, but in deeper layers THg concentration in peat was much higher than that in the forested mineral soil. THg in the peat bog increased, but MeHg decreased after it was drained. THg content in plant was different; THg contents in moss (119 ng g(-1) dry wt, n=12) were much higher than in the herbage, the arbor, and the shrubs. The peat bog has mainly been contaminated by Hg deposition from the atmosphere.     

Use of (15)N-labelled nitrogen deposition to quantify the source of nitrogen in runoff at a coniferous-forested catchment at Gårdsjön, Sweden

To determine the source of dissolved inorganic nitrogen (N) in runoff, approx. 35kg N enriched with the stable isotope (15)N (2110 per thousand delta(15)N) was added to a mature coniferous forested catchment for one whole year. The total N input was approx. 50kg ha(-1) year(-1). The enrichment study was part of a long-term whole-catchment ammonium nitrate addition experiment at G?rdsj?n, Sweden. The (15)N concentrations in precipitation, throughfall, runoff and upper forest floor were measured prior to, during, and 3-9years following the (15)N addition. During the year of the (15)N addition the delta(15)N level in runoff largely reflected the level in incoming N, indicating that the leached NO(3)(-) came predominantly from precipitation. Only 1.1% of the incoming N was lost during the year of the tracer addition. The cumulative loss of tracer N over a 10-year period was only 3.9% as DIN and 1.1% as DON.