Deposition of Mn from automotive combustion of methylcyclopentadienyl manganese tricarbonyl beside the major highways in the greater Toronto area, Canada

Methylcyclopentadienyl manganese tricarbonyl (MMT) has been used in Canada since 1976 as an antiknock agent in gasoline, completely replacing Pb in 1990. An early study of much higher Mn concentrations in gasoline showed that the combustion of MMT leads to the formation of inorganic manganese oxides, especially Mn3O4. Recent emission testing by Lawrence Livermore National Laboratory for Ethyl Corp. has shown that Mn is primarily emitted as a phosphate or sulfate along with minor amounts of oxides. The main objective of this research was to analyze the deposition of Mn from MMT to the terrestrial environment beside the major highways in the greater Toronto area (GTA), Canada. The results were compared with Pb and other trace elements such as Al, Ca, Fe, Mg, Cu, Zn, Na, and the Cl ion (water extractable) to study the behavior of Mn in soil. The study area was located near major Toronto highways 401 (urban) and 400 (rural), at 43 degrees 67' N and 79 degrees 37' W (latitude and longitude) (278,560 and 47,835 cars/day), respectively. Surface soil samples (0-5 cm depth) were collected at distances up to 40 m from the roadside. Parameters evaluated included total and available Mn and other trace elements, particle size, pH, organic content, and cation exchange capacity. Based on high traffic density along 401, higher Mn deposition was expected. No significant differences were found between the 401 and 400 Barrie (E(+1)) sites, attributable to the natural background levels of Mn or its contribution by other sources such as Mn-enriched road dust or naturally occurring crustal Mn. However, the 400 King City (E(+2)) site had significantly lower Mn levels than did the other three sites, 401 and 400 Barrie. This may be explained by the types of soil along the 401 and 400 sites. The King City site along 400 was found to be higher in sand content than were the 401 sites. A higher sand content could result in higher leaching of Mn to the bottom layer of the soil. Although MMT has been used continuously for approximately 25 years in Canada, its contribution to the terrestrial environment has been very low and has not significantly increased Mn levels along the highways, as demonstrated by this study.     

Deposition of Mn from Automotive Combustion of Methylcyclopentadienyl Manganese Tricarbonyl beside the Major Highways in the Greater Toronto Area,Canada

ABSTRACT

Methylcyclopentadienyl manganese tricarbonyl (MMT) has been used in Canada since 1976 as an antiknock agent in gasoline, completely replacing Pb in 1990. An early study of much higher Mn concentrations in gasoline showed that the combustion of MMT leads to the formation of inorganic manganese oxides, especially Mn₃O₄. Recent emission testing by Lawrence Livermore National Laboratory for Ethyl Corp. has shown that Mn is primarily emitted as a phosphate or sulfate along with minor amounts of oxides. The main objective of this research was to analyze the deposition of Mn from MMT to the terrestrial environment beside the major highways in the greater Toronto area (GTA), Canada. The results were compared with Pb and other trace elements such as Al, Ca, Fe, Mg, Cu, Zn, Na, and the Cl^- ion (water extractable) to study the behavior of Mn in soil. The study area was located near major Toronto highways 401 (urban) and 400 (rural), at 43° 67′ N and 79° 37′ W (latitude and longitude) (278,560 and 47,835 cars/day), respectively. Surface soil samples (0–5 cm depth) were collected at distances up to 40 m from the roadside. Parameters evaluated included total and available Mn and other trace elements, particle size, pH, organic content, and cation exchange capacity.     

Antifoulant (butyltin and copper) concentrations in sediments from the Great Barrier Reef World Heritage Area,Australia

Antifoulant concentrations were determined in marine sediments collected from commercial harbours, marinas, mooring locations on mid-shelf continental islands, and outer reef sites in four regions within the Great Barrier Reef World Heritage Area in 1999. Highest copper concentrations were present in sediments collected from commercial harbour sampling sites (28-233 microg Cu g(-1) dry wt.). In contrast, copper concentrations in sediments collected from boat mooring sites on mid-shelf continental islands and outer reef sites were at background concentrations (i.e. <20 pg Cu g(-1) dry wt.). Butyltin was only detectable in four of the 42 sediments sampled for analysis, and was only present in sediments collected from commercial harbours (18-1275 ng Sn g(-1) dry wt.) and from marinas (4-5 ng Sn g(-1) dry wt.). The detection of tributyltin at marina sites implies that this antifoulant may continue to be used illegally on the hulls of smaller recreational vessels. Sediment samples were also collected opportunistically from the site of a 22,000 t cargo ship grounding in May 1999 at Heath Reef, in the far northern Great Barrier Reef. Butyltin concentrations were grossly elevated (660-340,000 ng Sn g(-1) dry wt.) at the grounding site. The impact of residual antifoulants at large ship grounding sites should be recognised as a significant, long-term environmental problem unless antfoulant clean-up strategies are undertaken.     

Manganese uptake and accumulation by the hyperaccumulator plant Phytolacca acinosa Roxb. (Phytolaccaceae)

The perennial herb Phytolacca acinosa Roxb. (Phytolaccaceae), which occurs in Southern China, has been found to be a new manganese hyperaccumulator by means of field surveys on Mn-rich soils and by glasshouse experiments. This species not only has remarkable tolerance to Mn but also has extraordinary uptake and accumulation capacity for this element. The maximum Mn concentration in the leaf dry matter was 19,300 microg/g on Xiangtan Mn tailings wastelands, with a mean of 14,480 microg/g. Under nutrient solution culture conditions, P. acinosa could grow normally with Mn supplied at a concentration of 8000 micromol/l, although with less biomass than in control samples supplied with Mn at 5 micromol/l. Manganese concentration in the shoots increased with increasing external Mn levels, but the total mass of Mn accumulated in the shoots first increased and then decreased. At an Mn concentration of 5000 micromol/l in the culture solution, the Mn accumulation in the shoot dry matter was highest (258 mg/plant). However, the Mn concentration in the leaves reached its highest value (36,380 microg/g) at an Mn supply level of 12,000 micromol/l. These results confirm that P. acinosa is an Mn hyperaccumulator which grows rapidly, has substantial biomass, wide distribution and a broad ecological amplitude. This species provides a new plant resource for exploring the mechanism of Mn hyperaccumulation, and has potential for use in the phytoremediation of Mn-contaminated soils.     

Fluoride Emissions and Forest Growth

Abstract

The October 1995 court decision allowing Ethyl Corporation to offer methylcyclopentadienyl manganese tricarbonyl (MMT) for sale to refiners for introduction into unleaded gasoline as an octane enhancer is likely to result in increased fine (PM_2.5) manganese (Mn) concentrations in ambient air. Concern exists regarding possible health effects. In this paper, recent fine Mn concentrations in three monitoring networks and one U.S. Environmental Protection Agency (EPA) study of personal exposure are analyzed. One network consists mainly of rural sites in national parks in the United States, a second consists mainly of urban sites in California, and the third consists mainly of urban sites in Canada where MMT has been used for a number of years. During the late 1980s and early 1990s, mean ambient concentrations ranged from 1 ng/m³ in the mostly rural network to 3 ng/m³ in the mostly urban California network to 12 ng/m³ in the MMT-impacted Canadian network. Several lines of evidence suggested that some of the fine Mn observed in the United States during the 1986-1992 period was contributed by automobiles using leaded gasoline, for which MMT was a registered fuel additive. However, the near-disappearance of leaded gasoline has resulted in a very small portion of fine Mn being attributed to automobiles in the years since 1992.A source apportionment analysis suggested that crustal contributions to ambient fine Mn are on the order of 1-2 ng/m³ in both the United States and Canada.     

Advances in the Analysis of Air Contaminants Comments

Abstract

Methylcyclopentadienyl manganese tricarbonyl (MMT) is an organometallic compound used as an octane improver in unleaded gasoline. The combustion of MMT leads to the formation of manganese (Mn) oxides, mainly Mn₃O₄. The objective of this study is to assess the variations over time and space of respirable (Mn_R) and total (Mn_T) Mn in the urban atmosphere and to evaluate human exposure by inhalation. Two sampling sites were selected on the island of Montreal based on their local traffic density (municipal botanical garden, C^-= 10,000–15,000 vehicles d^-1; Montreal Waterworks, C⁺= 100,000–130,000 vehicles d^-1). Air samplings were made during the day at stations located 10 m from the road using portable pumps, some of which were equipped with a cyclone. Mn_R and Mn_T and other metals were measured on Teflon filters by neutron activation. Mn exposure doses by inhalation were calculated using Monte–Carlo simulations. Mn_R and Mn_T average concentrations were significantly higher at site C⁺ (Mn_R = 0.024 µg m^-3; Mn_T = 0.050 µg m^-3) than at site C^- (Mn_R= 0.015 µg m^-3; Mn_T= 0.027 µg m^-3). Temporal profiles at sites C⁺ and site C^-were similar, with a coefficient of correlation of 0.24 for Mn_R and 0.26 for Mn_T. Trend analyses (ARIMA) also showed that the period of the week (work days vs. off days) was significantly related to Mn_R and Mn_T variations at both sites. The average exposure dose by inhalation to Mn_R and Mn_T ranged from 0.001 to 0.030 µg kg^-1 day^-1 and 0.001 to 0.05 µg kg^-1 day^-1. Mn_R and Mn_T concentrations reflected a positive relationship with traffic density. However, it remains difficult to attribute these results directly to the combustion of MMT in unleaded gasoline. On average, the Mn_R and Mn_T inhalation doses were 2 to 15 times lower than the reference dose (RfC) proposed by the U.S. Environmental Protection Agency (EPA) for the general population.     

Elemental uptake by edible herbs and lettuce (Latuca sativa)

The total concentration of toxic elements (aluminum, cadmium, chromium and lead) and selected macro and micro elements (iron, manganese, copper and zinc) are reported in six leafy edible vegetation species, namely lettuce, spinach, cabbage, chards and green and red types of Amaranth herbs. Although spinach and chards had greater than 125 mv of iron, both the amaranthus herbs recorded > than 320 microg g(-1) dry weight. In both the spinach and chard species, the Mn and Zn levels were appreciable recording > 225 microg g(-1) and 150 microg g(-1) dry weight, respectively. Aluminum concentrations were (in microg g(-1) dry weight) lettuce (10), cabbage (11), spinach (167), chards (65), amaranthus green (293) and amaranthus red (233). All the micro and macro elements and the toxic elements (Ni, Cr, Cd and Pb) elements analyzed, were below the recommended maximum permitted levels (RMI) in vegetables. Further the elemental uptake and distribution of the nine elements, at three growth stages of the lettuce plant grown on soil bed under controlled conditions are detailed. In the soil, except for iron (16%), greater than 33% of the other cations were in exchangeable form. Generally in the lettuce plant, roots retained much of the iron (> 224 microg g(-1)) and aluminum (> 360 microg g(-1)), while leaves had less than 200 microg g(-1) of iron and 165 microg g(-1) of Al. Although the concentrations of elements marginally decreased with growth, the lettuce leaves had significant amounts of Mn (30 microg g(-1)), Zn (50 microg g(-1)) and Cu (3.6 microg g(-1)). Some presence of lead in leaves (2.0 microg g(-1)) was noticed, but all the toxic and other elements analyzed were well below the RMI values for the vegetables.     

Comment on “Methylcyclopentadienyl Manganese Tricarbonyl as an Antiknock: Composition and Fate of Manganese Exhaust Products”

In an article published in the August 1975, Journal of the Air Pollution Control Association entitled “Methylcyclopentadienyl Manganese Tricarbonyl as an Antiknock: Composition and Pate of Manganese Exhaust Products,” the authors conclude that, “… use of MMT in gasoline will result in no public health hazards, because of the low toxicity of manganese and because of the very low concentration of MMT that would be used in gasoline …. If all gasoline contained 0.1 g Mn/gal, the amount of airborne Mn its exhaust would contribute to urban areas would contribute to urban areas would be only 0.02-0.2 μg/m³, with a median value of 0.05 μg/m³.”     

Exposure of Chironomus riparius larvae to uranium: effects on survival, development time, growth, and mouthpart deformities

Among non-biologically essential metals, data concerning uranium effects on freshwater benthic macroinvertebrates are scarce. The effects of uranium on survival, development time, growth and mouthpart deformities of midge Chironomus riparius were investigated. A 10-day static laboratory bioassay was performed exposing first instar larvae to artificial sediment spiked with four concentrations of uranium (2.97; 6.07; 11.44; 23.84 microg U g(-1) dry wt). As uranium was released from the sediment to the overlying water during this bioassay, both the sediment and the water column act as contamination pathways in giving rise to the observed effects. Significant negative effects on survival, development time, and growth were detected at 6.07, 6.07 and 2.97 microg U g(-1) dry wt, respectively. An LC20 of 2.49 microg U g(-1) dry wt (95% CI=1.48-4.27), and an LC50 of 5.30 microg U g(-1) dry wt (95% CI=3.94-7.25) were estimated. With respect to effects of uranium on larvae mouthpart deformities, we found that the lower the concentrations, the higher the deformity rates. These results highlight the potential impact of uranium at population level in environmentally realistic concentrations.     

Manganese and other trace elements in urban snow near an expressway

The Mn contamination arising from the combustion of MMT (methylcyclopentadienyl manganese tricarbonyl) in unleaded gasoline was assessed using snow collected at different distances 15, 25, 125 and 150 m from an expressway (Montreal, Canada) in February 1993. The snow samples were analyzed by atomic absorption and by neutron activation for total Mn, Mg, Cu, V, Al, Zn, Fe, Na, and Ca concentrations in the soluble (<0.4 microm) and particulate fractions. ANOVA with ranked values was performed to compare element concentrations and soluble/particulate ratios among receptor sites and depths. Principal component analysis was used to describe the spatiotemporal variations of the deposition rates and the influence of meteorological factors. The average concentration of all trace elements, except Mg, Cu, and V, decreased significantly (p<0.05) from receptor sites near the road (15-25 m) to those farther away (125-150 m). The deposition rates of all metals and ions, except Cu, were highly positively correlated (tau = 0.5-0.9) with each other and inversely correlated with snowfalls. Wind frequency showed no correlation with deposition rate. The spatial trend was similar for all these elements making it difficult to distinguish Mn arising from the combustion of MMT from that due to other sources, such as road dust. Only the soluble/particulate ratio calculated for Mn seemed higher than that for the other metals, which might be explained by the particle size of Mn from MMT (0.2-0.4 microm). The present study only indicates a direct contamination of the snow by road activities and substantial deposition of trace elements near the roadway; no clear link can be established between motor vehicle emissions and the concentration of Mn in snow.     

Contamination by arsenic and other trace elements in tube-well water and its risk assessment to humans in Hanoi, Vietnam

Concentrations of As and other trace elements and their association were examined in groundwater (n = 25) and human hair (n = 59) collected at Gia Lam District and Thanh Tri District, suburban areas of Hanoi, Vietnam, in September 2001. Concentrations of As in the groundwater ranged from <0.10 to 330 microg/l, with about 40% of these exceeding WHO drinking water guideline of 10 microg/l. Also, 76% and 12% of groundwater samples had higher concentrations of Mn and Ba than WHO drinking water guidelines, respectively. Arsenic concentrations in hair of residents in Gia Lam and Thanh Tri Districts (range 0.088-2.77 microg/g dry wt.) were lower than those in other As-contaminated areas of the world, but were higher than those of people in non-contaminated areas. Concentrations of As and Mn in hair of some individuals from the Gia Lam and Thanh Tri Districts exceeded the level associated with their toxicity and, therefore, a potential health risk of As and Mn is a concern for the people consuming the contaminated water in this area. Cumulative As exposure was estimated to be lower than the threshold levels at the present, which might explain the absence of manifestations of chronic As poisoning and arsenicosis in the residents of Gia Lam and Thanh Tri Districts. To our knowledge, this study revealed for the first time that the residents are exposed not only to As but also Mn and Ba from groundwater in the Red River Delta, Vietnam.     

Content and bioconcentration factors of mercury by Parasol Mushroom Macrolepiota procera

The carpophores of Parasol Mushroom and underlying soil substrate collected from several unpolluted and spatially distant sites across Poland were examined to know content and bioconcentration potential of mercury by this species. The total mercury content of the caps of Parasol Mushroom for the particular sites ranged from 1.1 +/- 1.0 to 8.4 +/- 7.4 microg/g dry matter (total range from 0.05 to 22 microg/g dm), while in the stalks were from 0.53 +/- 0.27 to 6.8 +/- 7.1 microg/g dm (total range from 0.078 to 20 microg/g dm). A top soil layer (0-10 cm) showed baseline mercury concentration from 0.022 +/- 0.011 to 0.36 +/- 0.16 microg/g dm (total range from 0.010 to 0.54 microg/g dm). Parasol Mushroom is an effective mercury accumulator in the carpophores and bioconcentration factor (BCF) values of this element in the caps and depending on the sampling site ranged from 16 +/- 6 to 220 +/- 110 (total range from 0.52 to 470), while for the stalks were from 7.6 +/- 2.6 to 130 +/- 96 (total range from 0.52 to 340). It seems reasonable to state that tolerance (maximum allowable concentration) of the total mercury in a single cap of Parasol Mushroom at unpolluted areas should not exceed 25 microg/g dm. A value greater then 25 mu g/g dm will imply an elevated content due to site pollution problems. Nevertheless, knowledge on highly toxic methylmercury content and its fraction in the total mercury content of Parasol Mushroom is lacking.     

Changes in trace metal concentrations in lake water and biota during experimental acidification of Little Rock Lake, Wisconsin, USA

Little Rock Lake, a small (18 ha), low-alkalinity (25 microeq litre(-1), pH 6.1) seepage lake in northern Wisconsin, was divided into two basins by a flexible, inert barrier and, beginning in spring 1985, the north basin was acidified in three 2-year steps to pH 5.6, 5.1 and 4.7. The annual average pH of the reference basin remained near 6.1. As part of a comprehensive programme to determine the chemical and biological responses to acidification, minor metals (Al, Fe, Mn) and trace metals (Cd, Cu, Pb, Zn) in lake water (0.4 microm pore filtered samples), periphyton, zooplankton, and yellow perch (Perca flavescens) were measured. At pH 5.6, dissolved Mn and Fe increased in the acidified basin. At pH 5.1 and 4.7, dissolved Al, Fe, Mn, Cd and Zn were elevated in the acidified basin. At pH 4.7, dissolved Pb in the acidified basin became elevated over reference basin levels. Dissolved Cu remained similar in both basins down to pH 4.7. Cd burdens in periphyton collected on artificial substrates were lower in the treatment basin at pH 5.1 (1.8 microg g(-1) dry wt.) than in the reference basin at pH 6.1 (7.5 microg g(-1) dry wt.), but Al and Fe burdens in periphyton were similar in both basins. Likewise, Cd levels in muscle tissue of perch from the treatment basin at pH 4.7 were lower (26 ng g(-1) dry wt.) than in the reference basin at pH 6.1 (36 ng g(-1) dry wt.); Al and Fe burdens were similar in perch muscle tissue from both basins. Levels of Cd and Fe in zooplankton from the acidified basin at pH 4.7 were approximately equal to 2x higher than in animals from the reference basin. In both basins of the lake, Al and Cd levels in lake biota decreased with increasing trophic level, demonstrating that food chain biomagnification does not occur for these metals.     

Specific accumulation of mercury and selenium in seabirds

Total mercury (T-Hg), methyl mercury (MeHg) and selenium (Se) concentrations were determined to elucidate the relationship between Hg and Se levels in the liver of 10 seabird species. Highest concentrations of T-Hg (mean 267 microg/g dry wt), MeHg (mean 25.5 microg/g dry wt) and Se (mean 113 microg/g dry wt) were in the liver of black-footed albatross (Diomedea nigripes). An equivalent molar ratio of 1:1 between T-Hg and Se was found in the liver of individuals which contain over 100 microg Hg/g. However, such a relationship was unclear in other individuals which had relatively low Hg levels. This suggests that Se plays a role in Hg detoxification for those individuals with high Hg. In seabird tissues, Hg and Se levels should be a most important factor determining the relationship between Hg and Se, and fluctuation of Hg burden through molting and the species-specific demethylation capacity would also influence their relationships.     

Influence of form and quantity of selenium on the development and survival of an insect herbivore

Even plants classified as 'nonaccumulators' can sequester concentrations of sodium selenate, sodium selenite, selenocystine and selenomethionine that can strongly influence insect development and survival. These forms of selenium (Se), tested in diet-incorporation bioassays, proved toxic to larvae of a generalist insect herbivore at relatively low levels. Sodium selenite was the most toxic form tested against Spodoptera exigua (Hübner), with an LC(50) of 9.14 microg g(-1) wet wt (21.11 microg g(-1) dry wt). Selenocystine was intermediate with an LC(50) of 15.2 microg g(-1) wet wt. The least toxic forms, sodium selenate and selenomethionine, had LC(50)s below 50 microg g(-1) dry wt, the upper level for tissues of plants classified as nonaccumulators. Ingestion of some forms of Se also affected growth and development. Increasing concentrations of sodium selenate and sodium selenite decreased pupal weight and added significantly to the time needed for development to the pupal and adult stages. The time required to complete the larval stage increased by over 25% and the time from egg to adult emergence was extended by 22% to nearly 30%. Selenocystine and selenomethionine did not significantly increase developmental times, even at concentrations that killed 90% or more of the test populations. Analyses of relative growth rate, relative growth index, and an analysis of covariance technique for measuring growth indicated that the form of Se affected growth rates, growth inhibition responses of the larvae, and toxicological effects. Thus, quantity and the form of Se accumulating in plants grown on Se-contaminated sites are likely to influence the population dynamics of insect herbivores. The implications of these results for the ecology of contaminated sites are discussed.     

Multivariate analysis of elements content of Larch Bolete (Suillus grevillei) mushroom

Larch Bolete (Suillus grevillei) mushrooms collected at spatially distant sites in Poland showed on relative abundance of K, P, Mg, Rb, Al, Ca, Fe (at mg/g dw), Ag, Ba, Cd, Cu, Mn, Na and Zn (at microg/g dw) and less of Co, Cr, Ni, Pb and Sr (<1 microg/g dw). Amongst these elements Rb and K were highly bioconcentrated by Larch Bolete (BCF around 1000 and 300 for the caps), and weaker were Cu, Mg, Na, P and Zn (BCF between 4.1+/-2.5 and 62+/-21). Ag and Cd were bioconcentrated mainly in caps with BCF value of 25+/-16 and 13+/-10. Al, Ba, Ca, Co, Cr, Fe, Mn, Ni, Pb and Sr were excluded (BCF<1) by this species. Intake of meal prepared of 300 g of fresh fruiting bodies of Larch Bolete picked-up at the Western Beskid or Pogórze Wielickie sites in the south of Poland will result in exceeding of oral reference dose set for cadmium. In the case of silver, copper or zinc content a meal of 300 g of fresh or 30 g dried Larch Bolete will not result in exceeding reference doses for these elements. Extent of dose that customer would be exposed after eating of three 300 g fresh the Larch Bolete meals during a week will led to intake of lead and zinc within margin of 0.9-5.1% and 9-16% of PTWI for these elements, respectively. In the case of cadmium and specimens from the Western Beskid or Pogórze Wielickie sites in the south of Poland intake will slightly (around 10%) exceed PTWI value, and for other sites will not exceed (between 2% and 26% of PTWI).     

Mercury levels in Great Lakes herring gull (Larus argentatus) eggs, 1972-1992

Since 1971, the herring gull (Larus argentatus) has been used as a sentinel species for monitoring the levels of persistent contaminants in the Great Lakes ecosystem. In this study, 21 herring gull colonies in the Great Lakes and connecting channels were sampled during 1972-1976, 1981-1983, 1985 and 1992. For each year, 10 eggs (usually) were collected from each colony site and analyzed for total mercury (microg/g, wet wt). Results indicated that eggs from Lake Ontario displayed the highest lake-wide mercury levels (0.28-0.73 microg/g), followed by Lake Superior (0.21-0.50 microg/g). Lake Erie typically displayed the lowest mercury levels (0.18-0.24 microg/g). Overall, mercury levels ranged from 0.12 microg/g in 1985 to 0.88 microg/g in 1982 for Channel Shelter Island (Lake Huron) and Pigeon Island (Lake Ontario), respectively. Generally, all colony sites showed peak egg mercury levels in 1982. A significant decline in egg mercury levels was observed in five colony sites for the period 1972-1992 and in three different colony sites for the period 1981-1992. Mercury levels in the eggs of herring gulls for the period of this study were below levels associated with acute toxic effects in this species but were within a range, for certain years, which potentially reduces hatchability in other avian species.     

Concentrations of organotin compounds in sediment and clams collected from coastal areas in Vietnam

Levels of butyltin (BT) and phenyltin (PT) compounds were determined in sediments and clam Meretrix spp. collected from north and central coastal areas in Vietnam. Concentrations of TBT in sediments ranged from 0.89 to 34 ng g(-1) dry wt and those in clams ranged from 1.4 to 56 ng g(-1) wet wt. The levels of TBT in sediments and clams from Vietnam were within limits reported from other countries. Further, the TBT level in clams was lower than the tolerable average residue level (TARL) estimated based on tolerable daily intake (TDI). Trace amounts of PTs were also found in both sediment and clam samples. In sediments from north and central Vietnam, the concentrations of TBT were highest in the order of Hue (28 ng g(-1) dry wt), Cua Luc (15 ng g(-1) dry wt), Sam Son (6.3 ng g(-1) dry wt), and Tra Co (5.5 ng g(-1) dry wt). Among the clams from north and central Vietnam, the levels of TBT in clams from Cua Luc were dramatically high at 47 ng g(-1) wet wt. TBT formed the principal butyltin species in sediment at all sites studied. The ratios of TBT in sediment were higher among BT compounds at all study sites. Of total BTs, TBT was the dominant species in clams from almost all sites studied. In spatial distribution, TPT showed a pattern similar to TBT, suggesting the use of TPT as an antifouling paint. The partition coefficient between sediment and calms was calculated. The partition coefficients of TBT and TPT were 2.01 (0.56-5.5) and 9.23 (3.1-20), respectively. These results show that sediment-bound TBT is a source of contamination to clams in addition to dissolved TBT.     

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.     

Concentrations of lead in aquatic macrophytes from Shoal Lake, Manitoba, Canada

The ability of aquatic macrophytes to accumulate lead was examined in the context of sample site, sample date, depth, organ and species. Considerable variations in lead concentrations were found between the 11 species of macrophytes studied. The mean lead concentration for all species sampled was 16 microg/g (dry weight) ranging from 0-78 microg/g. Analysis of variance indicated that there were significant differences in the mean lead content of macrophytes collected from different sample sites. Similarly, significantly higher values were observed for plants collected from the upper 2m of water. Seasonal trends in lead accumulation were not observed for Shoal Lake macrophytes.