The fate of tributyltin in the aquatic enviroment A look at the data
Elizabeth A. Clark Robert M. Stemtt John N. Lester Imperial College of Science and Techno[ogy London SW72BU The environmental impact of organotins as a group of compounds has been the subject of a large amount of research in the past 10 years (1-10. Much of this work has focused on the fate of tributyltin (TBT) compounds in the aquatic environment. lkibutyltins, including bis(tributy1tin) oxide (TBTO), tributyltin fluoride, tributyltin chloride, tributyltin hydroxide, tributyltin MphtheMte, and tris(tributy1stannyl) phosphate are the principal organotin compounds used as industrial biocides (8, 11). TBTs are used in antifouling paints on ships, boats, and docks and as slimicides in cooling towers (12). They act as fungicides, bactericides, insecticides, and preservatives for wood (1322), textiles, paper, leather, and electrical equipment (23). Of the 10% of polyvinyl chloride (FV ' C) stabilized by organotins, TBTO is used to a small extent to impart light stability (18). TBTO also has been used to control the snail host of the parasite Schistosoma, which causes the disease bilharziasis (24-28). The use of TBT as a biocide in antifouling paints, however, has caused most concern because these paints release the highly toxic tributyltins directly into the aquatic environment. The biological activity of organotin compounds against fungi, bacteria, and algae was recognized in the early 1950s by Van de Kerk and Luijten at the Institute for Organic Chemistry (TNO) in Holland (11).libutyltin as TBTO was 600 Envimn. Sci. Technol..VOl. 22, NO. 6, 1988
first used in antifouling paints in Europe between 1959 and 1961. By 1985, an estimated 20-30% of vessels worldwide utilized tributyltin-containing antifouling paint systems (29). These improved antifoulant systems had an important impact on the international maritime economy, as the costs related to biofouliig were estimated in 1975 at
greater than $1 billion per year (30). The use of TBTO as a biocide was predicted to be the major growth area for organotin compounds (31). Problems were m n recognized, however, and regulations to control the use of these compounds were introduced (8, 3236). With these measures and the development of new antifouling paints,
W13936W8810922-0600$01.5010 0 1988 American Chemical Society
such as the copolymer paints hat release a lesser, more controlled mount of biocide to the environment, the total input of tributyltin into the aquatic environment will probably be reduced in the filture (37). Little information is available on the actual production and use of organotins as a class of Compounds, and even less is known about the tributyltins themselves. Several studies of the various uses of tributyltin and the associated levels of input into the aquatic environ-
ment have been made (1, 8, 31, 3843). The uses of TBTs are so diverse, however, that determination of the actual sources of water pollution by these compounds may be difficult. The maximum levels of tributyltin have generally been detected in areas of high boating activity (44-49,which indicates that antifouling paints on boats, ships, and docks may be the major source of these compounds in the aquatic environment. In situ measurements of tributyltin antifouling paint 1eachate.s have shown that tributyltin is the principal compound released, with very little contributions of dibutyltin or monobutyltin. In some paints, however, significant concentrations of dibutyltin have been shown to leach into water (50. Certain evidence also indicates that different forms of the tributyltin, such as the hydroxide, the chloride, and various carboxylates, are r e l d into water from different types of paint (40,51). When dispersed in water, the structures of the tributyltin compounds are not known, but an equilibrium mixture of speciation products such as the hydrated cation, chloride, carbonate, and hydroxide (52) l i l y exists. The tributyltin has been shown to be in the form of hydrated cations (53-56) and chlorides (57). The equilibrium distribution of these different species is influenced by dissolved chloride ions, dissolved carbon dioxide, and pH, and is easily displaced by variations in the environmental concentration range of these substances (57).
tributyltin leachates from antifouling paints were the most likely cause of the severe problems in culturing oysters on the Atlantic coast of F r a y in 1980, although they determined only the total tin concentration at that time. Since then, attempts have been made to survey the levels of tributyltin compounds and their degradation products in the aquatic environment. Until recently, these surveys have been limited by the absence of analytical techniques capable of detecting the tributyltins and their degradation products at the low (ng/L), yet toxic, environmental levels. Further information on the latest methods for analyzing tributyltin and its breakdown products in environmental samples is available (8, 59-61). These methods, some of which are presented in Table 1, generally involve a combination of four major procedures: First, the desired comoounds are extracted into an organic &Vent; volatile derivatives of the compounds are then produced, sermated into discrete fractions. and finaly quantified by direct measurement of the tin. Environmental surveys have focused on the nine locations listed in Table 2. These surveys measured levels of butyltins in the three main companments of the aquatic system: the surface microlayer, the water column, and the surface layers of the bottom sediments. In the water column the highest level yet measured was 1890 ng/L (as Sn) of tributyltin in Ontario Marina Waters (66). More frequently, maxima in the range of 100-200 ng/L have been found (50, 70, 71). In the surface microlayer a much higher concentration of tributyltin relative to the water column concentration has been found with maxima of 1872 and 1171 relative to water column levels of 464 and 290 ngl L (Sn), respectively (49, 65, 71). The maximum levels of tributyltin measured in sediment have been generally 500-1000 pglkg (Sn) (12, 50, 61, 71, 72) and even as high as 10780 pg/kg
(sn) (66).
With acute effects observed for aquatic organisms at concentrations of as low as 1 pglL of tributyltin oxide (9, the more polluted sites would be expected to be highly toxic, especially at the surface microlayer. Other studies, however, have shown sublethal effects (e.g., in oysters and dogwhelks at concentrations of 10 and 20 ng/L TBT, respectively [n, 74). Thus tributyltin has been shown to be damaging at levels far below those yet recorded for any other marine pollutant (73).The ability of some species of fish, crabs, bivalve molluscs, and microorganisms to bioconcentrate the tributyltins to levels Distribution in aquatic environments 3 orders of magnitude greater than the Alzieu et al. (58) proposed that the exposure concentration also has been Environ. Sci. Technol., Vol. 22, No. 6, 1988 604
shown in many studies, some of which are included in the review by Hall and Pinkney (9). The bioconcentration of these compounds to toxic levels and ingestion of such contaminated organisms for food or of particles with a high loading of tributyltins increases the risk above that initially expected from ambient levels. Margins of safety such as the safe water target concentration of 20 ng/L applied in the United Kingdom in 1986 (33) would therefore he too high to safeguard aquatic communities. Dibutyl- and monobutyltins, tetrabutyltin, and mixed methylbutyltins have been detected in the aquatic environment (12, 47, 48, 60,61. 65, 66, 71, 72, 75-77). The covariance of the concentrations of dibutyl- and tributyltins detected by Seligman et al. (50) and the demonstmtion of dibutyl- and monobutyltins as degradation products of tributyltin imply that these lower butyltins were derived from the environmental breakdown of tributyltin. Several studies have been made with respect to the partitioning of tributyltin between the dissolved and particulate phases of the water column. Laboratory studies and field measurements have shown that most of the tributyltin in the water column (70-9095)was BSsociated with the dissolved phase, and only a small portion of the w o n in the particulate phase was bound to microorganisms (78, 79). Other work has shown that most of the tributyltin was associated with the suspended material (80-82).From the simulated estuarine condition experiments by Randall and Weber (B),significant amounts of tributyltin would be present both in the dissolved phase and on particulate matter; therefore, tributyltin would be expected to be ubiquitous in the aquatic environment.
Persistencein water and sediments Because tributyltin bas been shown to exist at toxic levels in the aquatic environment, the persistence of tributyltin and its effect on abiotic and biotic degradation processes in aquatic systems must be evaluated. Abiotic degradation processes have been put forward as probably the third most important pathway for the removal of tributyltin from the water column (84). The Sn-C bond could be broken by four different abiotic processes: W irradiation, chemical cleavage, gamma irradiation, and thermal cleavage (85). Because gamma irradiation rarely occurs and the Sn-C bond is stable up to 200 "C, gamma irradiation and thermal cleavage have a negligible effect on the environmentalbreakdown of tributyltin. Energetically, only the near-UV spec602 Environ. Sci. Technol., Vol. 22, No. 6,1988
TAN
Sites of tributyltin surveys Site Great Bay. N.H.
San Diego Bay, Calil., and throughout the United States Chesapeake Bay, Md. and Va. Ontario and throughout Canada Oyster culture areas of the Atlantic Coast. France Swiss lakes Southwest coast of England Southeast coast oi England Mediterranean ports
ReIerenEe Weber et al. (63) Seli man et 81. (5%)
Olson and Brinckrnan (48) Hu genet a1 (64) H a j e t al. 1651 , , Maguire et al. (66) lzieu (67)
trum (3M350 nm) is likely to cause direct photolysis of tributyltin. Because of the low transmittance of W light, this breakdown process is expected to OCCUI only in the upper few centimeters of the water column (86). Numerous investigations have confirmed the photolytic degradation of tributyltin (8791) and other organotin compounds (92-99). Photolysis in the environment, however, has been shown to be slow (half-life > 89 days). Because it is possible in only a limited portion of the aquatic environment, photolysis probably is not a significant breakdown process of TBT (86). When undergoing chemical degradation, organotin compounds can be attacked by both nucleophilic and electrophilic reagents. The Sn-C bond is also susceptible to homolytic fission (I@. Therefore many different compounds are capable of causing such degradation of organotins. Most of the information available on the chemical degradation of tributyl and other organ& has, however, been obtained from chemical studies in which the starting compounds were at high concentration and in nonaqueous solvents. This type of degradation was found to have a halflife ranging from 1 min to 115 days. It is, therefm, ditficult to apply the behavior of these compounds under these conditions to the environmental situation of very low original concentrations in d i e or freshwater media (101). Where environmental stndies of the chemical degradation of tributyltin have been carried out, this compound has k e n shown to be both stable (64, 75) and unstable (86,102.1(u) to this mode of breakdown. With respect to biotic removal of tributyltin, a variety of evidence suggests that biodegradation occurs and is the
major breakdown pathway of this compound in aquatic and sedimentary environments. Where microbial activity was inhibited by poisons or by high concentrations of tributyltin, tributyltin did not break down under conditions suitable for chemical and photolytic degradation (51, 104). Surveys of tributyltin distribution, however, have found that TBT breakdown products are widespread. In addition, several laboratory studies have shown biodegradation of tributyltin (18, 66, 104111). The majority of studies on the biodegradation of tributyltin have been made using microorganisms. These studies have investigated TBT breakdown in soils and in the water and sediments of marine, estuarine, and fresbwater systems. Degradation of tributyltin in soil has been shown by Blair (112), Sheldon (113), and Bamg and Vonk (114). In aqnatic environments the breakdown generally has been found to be much more rapid in water than in sediments; half-lives for the disappearance of tributyltin are of the order of 20 days for water and more than 16 weeks for sediments (see Table 3). This disparity may be caused by the inbibition of microbd activity at the higher tributyltin concentrations found in the sediment layers. Such inhibition is also supported by the trend of faster degradation that has been found in water with lower tributyltin concentrations (seeTable 3). The absence of oxygen in the sediments has not been shown to he a possible cause of the slower degradation rate (12, 117). Nor does Table 3 show a distinct difference between the speed of degradation rates in seawater or freshwater. However, an increase has been found in the rate of degradation of tribntyltin under incandescent light and at higher temperatures (48). Only a small proportion of the species of microbes studied, however, has been shown to degrade tributyltin (103, 118). Several studies have attempted to identify the mechanism of biodegradation of tributyltin and to determine whether tributyltin is successively dealkylated from tri- to di- to monobutyltin, finally forming an inorganic tin, or the tributyltin is mainly converted directly to monobutyltin. Henshaw et al. (108), B a g (103), and Stang and Seligman (75) demonstrated that monobutyltin is the only significant product of the degradation of tributyltin. AU other degradation studies, however, have shown that dibutyltin is the major breakdown pmduct of tributyltin and monobutyltin found at lower concentrations (47, 50, 109, 114). In addition', the detection of predominantly monobntyltin (75,103,108) may have been a
sedimentary Seawater sedii
view of the degradation of organotin compounds in the environment and their determination in water”: lnternational Tin Research Institute: Uxbridge, U.K., 1982. (23) Piver, W. T. Environ. Health Pmpect. lWJ,4,61-79. (24) De Villiers, 1. P. S. Afi. Ind. Ckem. 1965, 19, 166-70. (25) Cardarelli, N. E In Molluscicides in Schistosomiaris ControbProceedings of m Internation01 Symposium; Cheng, T. C., Ed.; Academic: New York, 1974; pp. 177240 (26jShim. c. I.; Evans, A. c. cm. A* J. Med. (Suppl.) 1977,23, 6-11. (27) Allen, A. 1.; Quiuer, B. M.; Radick, C. M. In Controlled Release of Biwctive Materials: Cardarelli, N. E ; Evans, W.; Baker, R. W., Eds.; Academic: New York, 1980. p 399413. (28) C&& relli, N. E; Evans, W. In Controlled Release of Eiwctive Materials; Cardarelli, N. p.; Evans, W.; Baker, R. W.. Ed%; Academic: New York, 1980; pp. 357-
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result of measurements made when the dibutyltin was converted to monobutyltin in a stepwise degradation sequence. In Orsler and Holland’s study of the fungal degradation of tributyltin, thinlayer chromatography of the products indicated that derivatives intermediate between tributyltin and dibutyltin and between dibutyltin and monobutyltin were formed (109). Such intermediates also were suggested in the study by Hensbaw et al. (108). Unidentified peaks in the atomic absorption spectra of tributyltin degradation products have been found by Olson and BMckman (48). These could have been additional tributyltin degradation products, methylated mono- and dibutyltin species, or non-tin-containing molecules. Further studies are therefore needed to elucidate the breakdown mechanism. Another possible breakdown product, tetrabutyltin, has been detectedalthough infrequently-in the surface microlayer, in dry-dock samples, and by degradation experiments (48. sa). Mixed butylmethyltins also have been detected infrequently (47). The presence. of te.trabuty1tin and mixed methylbutyltin has, however, been found at very low concentrations. Mass balance measurements of degradation experiments also have shown that di- and monobutyltin made up most of the loss of the original tributyltin and were therefore major degradation products (48).
Thus tributyltin has been shown to be present at toxic levels in aquatic and sedimentary environments in many areas studied. Degradation experiments and the detection of breakdown products in surveys suggest that biotic and abiotic procases will result in the eventual removal of this compound from aquatic systems. With the recent development of more sensitive analytical techniques, the distribution and biotic and abiotic breakdown of tributyltin is being more fully investigated, and the behavior of this compound in aquatic and sedimentary environments will be establiied.
Acknnwledgments This article has been reviewed for suitability as an ES&Tfeaturearticle by R. James McGuire, Canada Centre for Inland Waten, Burlington, Ontario, Canada L7R 4A6; and by Peter T. Kissinger, Purdue University, West Lafayeue, Ind.47907.
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Elizabeth A. Clark i s (i rc.vmrch student i n rhe public heulrh sccrion of the c i v i l engineering program of Imperial College of Science and k h n o l o g y , London.
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604 Environ. Sci. Technal.. Vol. 22, No. 6, 1988
Robert M. Sterrin (I) is u smior envimrrmenial scienrisr with Consulranis in Environmenral Sciences, London. H e obtained his Ph.D. from Imperial College, where he was subsequenrly a research assistanr and Iecfurer in public healrh engineering.
Jahn N. Lester (r) is a reader i n public healrh engineering and environmenral microbiology in the Civil Engineering Deparrmenr of Imperial College of Science and Technology, London. H e has been at Imperial College since 1971 and is now overseeing research related ro micropollufanrs and wafer mamgemenr, including industrial and domestic wastewafer rrearmenr. biadegradarion, immobilization, and sludge rrealmenf and disposal.
