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Butyltins in Dolphin, Shark, and Tuna                                                             21


          Table 1.  Concentrations  of butyltin compounds (ng/g wet wt) in adult   degradation  activity  a  concentration  gradient  of  DBT  >>
          male bottlenose  dolphins  from Italian coast of the Mediterranean  Sea   TBT  -> MBT  has  to  be  expected.  The  concentration  ratios  of
                                                              TBT, DBT and MBT in the blubber is typical for an organ with
          Carcass
                                                              almost  no  or  less  capacity  for  alkyltin  dealkylation. Further-
          decomposition   Tissue   Fat (%)   MBT   DBT   TBT  BTs a
                                                              more,  MBT  is  relatively more  polar  (hydrophilic) than  DBT
           Moderate    Blubber   18    55     16   41   110
                                                              and,  therefore,  eliminated rapidly from  the liver.
                       Liver    7      150   800   250   1200
                                                                The most commonly documented effect of butyltins in mam-
           Moderate    Blubber   8     25      9   14   48
                                                              mals was  immune  suppression  (Snoeij et  al.  1989).  The  resis-
           Fresh       Blubber   27    65     42   210   320
                                                              tance  against  Aeromonas  hydrophilia  was  decreased  in  fish
                       Liver   17     200    1600  400   2200
                                                              exposed  to  butyltins  (de  Vries  et  al.  1991).  It  is  not  known
                                                              whether  the  concentrations  of  BTs  found  in  these  diseased
           ~BTs =  MBT+DBT+TBT,  i.e.,  total  butyltins  (BTs)  is  the  sum  of
           mono-(MBT),  di-(DBT),  and tributyltin  (TBT)     dolphins had any effect on the immune  system, suggesting the
                                                              need  for further  studies.
           noides)  tissues collected from  Japanese coastal waters  for BTs
           showed the highest concentrations in liver with lower concentra-
                                                              BIuefin  Tuna
           tions  in kidney, muscle, blubber and brain  (Iwata et  al.  1995).
           Accumulation of butyltin compounds in dolphin livers is differ-
                                                              Concentrations of BTs in tuna ranged from 67 to 540 ng/g wet
           ent  from  organochlorines,  which  preferentially accumulate  in
                                                              wt  (mean:  210  ng/g)  in  liver and  16-230  ng/g  wet  wt  (mean:
           lipid  rich  blubber  (Tanabe  et  al.  1981).  On  the  other  hand,
                                                              62  ng/g)  in  muscle  (Table  2).  Similar to  dolphins,  liver  had
           butyltin  accumulation  in  the  liver  of  dolphins  is  similar  to
                                                              higher concentrations than muscle in tuna fish. Butyltin concen-
           several trace metals, which prominently concentrate in the liver
                                                              trations in tuna liver were about 8-fold lower than in dolphins.
           or kidney (Honda et al.  1982).  Preferential enrichment of butyl-
                                                              It has  been  shown  that  the butyltin concentration  in  fish liver
           tin compounds in the liver may be associated with the presence
                                                              was  an  order of magnitude  higher  than  in  muscle  (Kannan  et
           of increased amounts of metal binding proteins such as glutathi-
                                                              al.  1995b).  Butyltin  concentrations  in  tuna  were  lower  than
           one,  which  conjugates  with  several  electrophilic  compounds
                                                              those reported in mussels collected from La Spezia and Taranto
           and  plays  a  role  in  the  detoxification  of  potential  alkytating
                                                              harbors  along  the  Italian  coasts  (Caricchia  et  aL  1991)  and
           agents  and  certain  xenobiotics.  The  accumulation  of  butyltin
                                                              comparable  to  those  reported  from  Barcelona  harbor,  Spain
           compounds in the liver of vertebrates and the midgut or hepato-
                                                              (Tolosa et al.  1992).  Similarly, BT concentrations in tuna were
           pancreas of invertebrates has been  shown  (Davies  et  al.  1986;
                                                              comparable to  those reported in  several fish from  the  Gulf of
           Gibbs  et  al.  1990;  Stroben  et  aI.  1992;  Kannan  et  al.  1995a,
                                                              Gdafisk, Baltic Sea  (Kannan  and  Falandysz  1995).
           1995b).  Although  the  number  of samples is  small, the  results
                                                                Analysis  of  mono-,  di-,  and  tributyltin compounds  in  tuna
           indicate  considerable accumulation  of butyltin  compounds  in
                                                              showed  the  presence  of highest concentrations  of DBT  in  the
           higher trophic  vertebrate marine  organisms.
                                                              liver, while TBT  and MBT  were  the prominent  species in  the
            The  concentrations  of BTs  in the blubber of bottlenose dol-
                                                              muscle  (Figure  2).  The  concentrations  of  DBT  in  tuna  liver
           phins  are  comparable  to  those  reported  for  marine  mammals
                                                              were lower than those in dolphin livers. Lower concentrations
           collected from  the North  Pacific, except for a  finless porpoise
                                                              of  MBT  in  liver  than  in  muscle  suggests  metabolism  by  the
           (N. phocaenoides)  collected along the Japanese coast of the Seto
                                                              liver followed by transfer of metabolites to  other  tissues.
           Inland Sea, which was two to three times higher in concentration
                                                                The toxicity of butyltin to fish depends on the developmental
           (Iwata et  al.  1995).  The  residue BT  concentrations  in dolphin
                                                              stage.  It has  been  shown  that yolk sac fry  stage was  the most
           tissues  were  higher  than  those  observed  in  bivalve  mollusks
                                                              sensitive to the toxic effects of TBT  (de Vries et al.  1991).  The
           collected from Mediterranean coastal waters (Alzieu et al.  1991;
                                                              resistance to bacterial challenge by fish was decreased even at
           Caricchia et aI.  1991; Tolosa et al.  1992; Cocchieri et al.  1993),
                                                              TBT water concentrations around 10 ng/L (de Vries et al,  1991).
           but  lower than  in  carnivorous  gastropods  from  the  same  area
                                                              Investigations relating body concentrations and toxic action of
           (Axiak et  al.  1995).
                                                              butyltins  are  necessary  to  assess the  toxic  implications of the
            TBT  was  the  predominant  compound  in  the  fresh  blubber,
                                                              butyltin concentrations  found  in  fish.
           while  DBT  predominated  in  the  liver  (Figure  2).  The  higher
           lipophilicity of TBT compared with DBT and MBT may explain
           its  predominance  in  the  blubber.  However,  in  the  blubber  of
                                                              Blue  Shark
           the  two  dolphins,  which  were  moderately decomposed  at  the
           time  of  sampling,  MBT  levels  were  comparable  to  the  TBT
           concentrations (Table  1). Transformation of TBT  to MBT  dur-   Concentrations of BTs  in shark ranged  1-9 ng/g wet wt (mean
           ing  the  decomposition  of  carcasses  might  have  elevated  the   3.4  ng/g)  in  the  subcutaneous  fat,  20-36  ng/g  wet  wt  (mean:
           proportion  of MBT  in  these  samples.  Dibutyltin was  the  pre-   30 ng/g) in the liver and 75-220  ng/g  (mean:  140  ng/g) in the
           dominant  compound  in  the  liver  (71%),  while  MBT  was  in
                                                              kidney  (Table  3),  suggesting  higher  accumulation  in  kidney
           minor  amounts  (9%).  Metabolism  of  TBT  by  hepatic  micro-
                                                              than  in  liver. Renal  BT  concentrations  were  3-7  times higher
           somal  monooxygenase  enzymes  (Lee  1985)  may  lead  to  the
                                                              than  hepatic  concentrations.  Higher  concentrations  in  kidney.
          production of MBT and DBT. Although, the complete metabo-
                                                              may be associated with the modified physiological function of
           lism  of  TBT  is  expected  to  lead  to  higher  concentrations  of
                                                              this organ in sharks. It is also probable that the kidney of sharks
          MBT  than  DBT,  the rate  of debutylation of DBT  to  MBT  by
                                                              might contain elevated levels of glutathione, which plays a role
          the  microsomal  monoxygenase  system  is  considered  slower
                                                              in conjugating with metals/metalloids. Higher concentration of
          than  of TBT  to  DBT.  Consequently,  in  organs  with  high TBT   butyltins  in  kidney  than  in  liver  was  similar  to  the  pattern
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