United States
                Environmental Protection
                Agency
                 Office of Research and
                 Development
                 Washington, DC 20460
    EPA/600/AP-92/001a
    August 1992
    Workshop Review Draft
&EPA
Chapter 1.
Disposition and
Pharmacokinetics
    Review
    Draft
    (Do Not
    Cite or
    Quote)
600AP92001a
                                      Notice

                This document is a preliminary draft. It has not been formally released by EPA and should not
                at this stage be construed to represent Agency policy. It is being circulated for comment on
                its technical accuracy and policy implications.

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DRAFT                                                            EPA/600/AP-92/001a
DO NOT QUOTE OR CITE                                                   August 1992
                                                                Workshop Review Draft
            Chapter 1.  Disposition and Pharmacokinetics
                                Health Assessment for
                       2,3,7,8-Tetrachlorodibenzo-p-dioxin (TCDD)
                               and Related Compounds
                                      NOTICE

THIS DOCUMENT IS A PRELIMINARY DRAFT.  It has not been formally released by the U.S.
Environmental Protection Agency and should not at this stage be construed to represent Agency
policy.  It is being circulated for comment on its technical accuracy and policy implications.
                       Office of Health and Environmental Assessment
                           Office of Research and Development
                          U.S. Environmental Protection Agency
                                   Washington, D.C.
                                                               Printed on Recycled Paper

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                                       DISCLAIMER


       This document is a draft for review purposes only and does not constitute Agency policy.

Mention of trade names or commercial products does not constitute endorsement or recommendation
for use.
          Please note that this chapter is a preliminary draft and as such represents work
          in progress.  The chapter is intended to be the basis for review and discussion at
          a peer-review workshop. It will be revised subsequent to the workshop as
          suggestions and contributions from the scientific community are incorporated.
                                                                                     08/10/92

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                                      CONTENTS



Tables  	v

Figures	  vi

List of Abbreviations	vii

Authors and Contributors	xii


1. DISPOSITION AND PHARMACOKINETICS	  1-1

   1.1.  ABSORPTION/BIOAVAILABILITY FOLLOWING EXPOSURE	  1-1

        1.1.1.  Oral	  1-1
        1.1.2.  Dermal Absorption	  1-8
        1.1.3,  Transpulmonary Absorption	  1-13
        1.1.4.  Parenteral Absorption	  1-13

   1.2.  DISTRIBUTION	  1-14

        1.2.1,  Distribution in Blood and Lymph	  1-14
        1.2.2,  Tissue Distribution	  1-16
        1.2.3,  Time-Dependent Tissue Distribution	  1-22
        1.2.4.  Dose-Dependent Tissue Distribution	  1-34
        1.2.5,  Potential Mechanisms for the Dose-Dependent
              Tissue Distribution	  1-39

   1.3.  METABOLISM AND EXCRETION	  1-42

        1.3.1,  Structure of Metabolites	  1-43
        1.3.2.  Toxicity of Metabolites	"	  1-51
        1.3.3,  Autoinduction of Metabolism	  1-53
        1.3.4,  Excretion in Animals	  1-57
        1.3.5.  Excretion in Humans	  1-61

   1.4.  PHYSIOLOGICALLY BASED PHARMACOKINETIC MODELS	  1-65

   1.5.  PHARMACOKINETICS IN SPECIAL POPULATIONS	  1-74

        1.5.1,  Pregnancy and Lactation (Prenatal and
              Postnatal Exposure of Offspring)	  1-74
        1.5.2.  Aging	  1-81


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1.6.  REFERENCES
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                                           LIST OF TABLES
1.1       Gastrointestinal Absorption of 2,3,7,8-TCDD and Related
         Compounds Following a Single Oral Exposure by Gavage	  1-2

1.2       Percentage of 2,3,7,8-TCDD in the Liver of Rats 24 Hours
         After Oral Administration of 0.5 mL of Various Formulations
         Containing TCDD	  1-7

1.3       Dermal Absorption of 2,3,7,8-TCDD and Related Compounds in
         the Rat	  1-9

1.4       Tissue Distribution of [14C]-2-3,7,8-TCDD in Female Wistar
         Rats	  1-18

1.5       Elimination of 2,3,7,8-TCDD and  Related Compounds from Major Tissue Depots	  1-25

1.6       Elimination Constants and Half-Lives of Various 2,3,7,8-Substituted CDDs and CDFs in
         Hepatic and Adipose Tissue of Marmoset Monkeys  	  1-31

1.7       2,3,7,8-TCDD Concentrations in Liver and  Adipose Tissue
         Following Different Doses and Calculated Concentration
         Ratios (Liver/Adipose Tissue)	  1-36

1.8       Metabolism and Excretion of 2,3,7,8-TCDD and Related
         Compounds  	  1-44

1.9       Half-Life Estimates  for 2,3,7,8-TCDD and Related  Compound
         in Humans	  1-62

1.10     Pharmacokinetic Parameters for 2,3,7,8-TCDD Used in
         PB-Pk Models  	  1-66

1.11     Pharmacokinetic Parameters for 2,3,7,8-TCDF Used in the
         PB-Pk Model Described by King et al. (1983)	  1-72
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                                  LIST OF FIGURES
1-1     Time Course of the Concentration of 14C-TCDD in Rat Liver and Adipose
       Tissue After a Single Subcutaneous Injection of 300 ng TCDD/kg bw to
       Female Rats (M±SD)	  1_24

1-2     Dose Dependency of the Percentage of the Administered Dose of 14C-TCDD/g
       of Tissue Recovered in Liver and Adipose Tissue  After Single Subcutaneous
       Doses                                                                        _
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                              LIST OF ABBREVIATIONS








ACTH             Adrenocorticotrophic hormone




Ah                Aryl hydrocarbon




AHH              Aryl hydrocarbon hydroxylase




ALT              L-alanine aminotransferase




AST              L-asparate aminotransferase




BDD              Brominated dibenzo-p-dioxin




BDF              Brominated dibenzofuran




BCF              Bioconcentration factor




BGG              Bovine gamma globulin




bw                Body weight




cAMP             Cyclic 3,5-adenosine monophosphate




CDD              Chlorinated dibenzo-p-dioxin




cDNA             Complementary DNA




CDF              Chlorinated dibenzofuran




CNS              Central nervous system




CTL              CytOtoxic T lymphocyte




DCDD            2,7-Dichlorodibenzo-p-dioxin




DHT              5oc-Dihydrotestosterone




DMBA            Dimethylbenzanthracene




DMSO            Dimethyl sulfoxide




DNA              Deoxyribonucleic acid
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DRE




DTG




DTK
ECOD




EGF




EGFR




ER




EROD




EOF




FSH




GC-ECD




GC/MS




GOT




GnRH




GST




HVH




HAH




HCDD




HDL




HxCB




HpCDD




HpCDF
Dioxin-responsive enhancers




Delayed type hypersensitivity




Delayed-type hypersensitivity




Dose effective for 50% of recipients




7-Ethoxycoumarin-O-deethylase




Epidermal growth factor




Epidermal growth factor receptor




Estrogen receptor




7-Ethoxyresurofin 0-deethylase




Enzyme altered foci




Follicle-stimulating hormone




Gas chromatograph-electron capture detection




Gas chromatograph/mass spectrometer




Gamma glutamyl transpeptidase




Gonadotropin-releasing hormone




Glutathione-S-transferase




Graft versus host




Halogenated aromatic hydrocarbons




Hexachlorodibenzo-p-dioxin




High density lipoprotein




Hexachlorobiphenyl




Heptachlorinated  dibenzo-p-dioxin




Heptachlorinated  dibenzofuran
                                            vin
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                            LIST OF ABBREVIATIONS (cont.)
HPLC




HRGC/HRMS




HxCDD




HxCDF
High performance liquid chromatography




High resolution gas chromatography/high resolution mass spectrometry




Hexachlorinated dibenzo-p-dioxin




Hexachlorinated dibenzofuran
I-TEF
LH




LDL




LPL




LOAEL




LOEL




MCDF




MFO




mRNA




MNNG




NADP




NADPH




NK




NOAEL




NOEL
International TCDD-toxic-equivalency




Dose lethal to 50% of recipients (and all other subscripter dose levels)




Luteinizing hormone




Low density liproprotein




Lipoprotein lipase activity




Lowest-observable-adverse-effect level




Lowest-observed-effect level




6-Methyl- 1 ,3,8-trichlorodibenzofuran




Mixed function oxidase




Messenger RNA




/V-methyl-./V-nitrosoguanidme




Nicotinamide adenine dinucleotide phosphate




Nicotinamide adenine dinucleotide phosphate (reduced form)



Natural killer




No-observable-adverse-effect level




No-observed-effect level
                                            IX
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                             LIST OF ABBREVIATIONS (cont.)
OCDD




OCDF




PAH




PB-Pk




PCB




OVX




PEL




PCQ




PeCDD




PeCDF




PEPCK




PGT




PHA




PWM




ppm




PPQ



ppt




RNA




SAR




SCOT




SGPT
Octachlorodibenzo-p-dioxin




Octachlorodibenzofuran




Polyaromatic hydrocarbon




Physiologically based pharmacokinetic




Polychlorinated biphenyl




Ovariectomized




Peripheral blood lymphocytes




Quaterphenyl




Pentachlorinated dibenzo-p-dioxin




Pentachlorinated dibenzo-p-dioxin




Phosphopenol pyruvate carboxykinase




Placental glutathione transferase




Phytohemagglutinin




Pokeweed mitogen




Parts per million








Parts per trillion




Ribonucleic acid




Structure-activity relationships




Serum glutamic oxaloacetic transaminase




Serum glutamic pyruvic transaminase
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                           LIST OF ABBREVIATIONS (cont.)
SRBC





t*



TCAOB




TCB




TCDD




TEF




TGF




tPA




TNF




TNP-LPS




TSH




TTR




UDPGT




URO-D




VLDL




v/v




w/w
Sheep erythrocytes (red blood cells)




Half-time




Tetrachloroazoxybenzene




Tetrachlorobiphenyl




Tetrachlorodibenzo-p-dioxin




Toxic equivalency factors




Thyroid growth factor




Tissue plasminogen activator




Tumor necrosis factor




lipopolysaccharide




Thyroid stimulating hormone




Transthyretrin




UDP-glucuronosyltransferases




Uroporphyrinogen decarboxylase




Very low density lipoprotein




Volume per volume




Weight by weight
                                            XI
                                                               08/10/92

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                             AUTHORS AND CONTRIBUTORS


       The Office of Health and Environmental Assessment (OHEA) within the Office of Research
 and Development was responsible for the preparation of this chapter.  The chapter was prepared
 through Syracuse Research Corporation under EPA Contract No. 68-CO-0043, Task 20, with Carol
 Haynes, Environmental Criteria and Assessment Office in Cincinnati, OH, serving as Project Officer.
       During the preparation of this chapter, EPA staff scientists provided reviews of the drafts as
 well as coordinating  internal and external reviews.

 AUTHORS
 James Olson
 Department of Pharmacology and Therapeutics
 State University of New York - Buffalo
 Buffalo, NY
EPA CHAPTER MANAGER
Jerry Blancato
Office of Research and Development
Environmental Monitory Systems Laboratory
Las Vegas, NV
                                           Xli                                     08/10/92

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                     1.  DISPOSITION AND PHARMACOKINETICS








     The disposition and pharmacokinetics of 2,3,7,8-TCDD and related compounds



have been investigated  in several species and under various exposure conditions.



There are several reviews on this subject that  focus on 2,3,7,8-TCDD and related



halogenated aromatic hydrocarbons (Neal et al., 1982;  Gasiewicz et al., 1983a;



Olson et al.,  1983;  Birnbaum, 1985).  During the last 6 years, considerably more



data have  been published  on  this class of  compounds that  includes  2,3,7,8-



substituted CDDs, BDDs, CDFs, BDFs and the coplaner PCBs  and PBBs.  This chapter



reviews  the  disposition and pharmacokinetics  of  these agents  and identifies



congener and species specific factors that may have an impact on the dose-related



biological responses of these compounds.



1.1.   ABSORPTION/BIOAVAILABILITY FOLLOWING EXPOSURE



     The  gastrointestinal,  dermal  and  transpulmonary  absorption  of  these



compounds are discussed herein because they represent potential routes for human



exposure to  this class of persistent environmental contaminants.   Parenteral



absorption is  reviewed since this  route  of  exposure has been used to generate



disposition and pharmacokinetic data on these compounds.



1.1.1.   Oral



     1.1.1.1.   GASTROINTESTINAL ABSORPTION IN ANIMALS — A major source  of human



exposure to 2,3,7,8-TCDD and related compounds  is thought to be through the diet.




Experimentally,  these  compounds are commonly  administered  in the diet  or by



gavage in an oil vehicle.  Gastrointestinal absorption is usually estimated as



the difference between the administered dose (100%) and the % of the dose that



was not absorbed.  The unabsorbed fraction is estimated as the  recovery of parent



compound in feces within 24-48 hours  of a single oral exposure by gavage.  Table



1-1  summarizes gastrointestinal absorption data  on 2,3,7,8-TCDD  and  related



compounds.



     In  Sprague-Dawley rats given  a  single oral dose of 1.0 pg  [ 14C]-2,3,7,8-




TCDD/kg  bw in  acetone:corn oil  (1:25,  v/v), the fraction absorbed ranged from




66-93% with a mean of 84% (Rose et al.,  1976).  With repeated oral dosing of rats



at 0.1 or 1.0 pg/kg/day  (5 days/week for 7 weeks), gastrointestinal absorption







                                      1-1                              08/11/92

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-------
TABLE 1-1 (cont.)
Chemical
Species (Sex)
Dose
((tmol/kg)
(Kg/kg)
Vehicle

% Administered
Dose Absorbed
[Mean (Range)]
Reference
PCBs
3,3'4,4'-T4CB
C57BL mouse (F)
34.5
10,000
corn oil
77
Uehler et al.,
1989
       Absorption is generally estimated as the difference  between  the  administered dose (100%) and the X of the dose that  was  not  absorbed.   The

        unabsorbed fraction is estimated as the recovery of parent compound in feces within 48 hours of exposure.


        NR = Not reported
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of  2,3,7,8-TCDD  was  observed to be approximately that observed for the  single
oral  exposure  (Rose  et al.,  1976).   Oral exposure of Sprague-Dawley rats to  a
larger  dose of  2,3,7,8-TCDD  in acetone: corn  oil  (50 pg/kg)  resulted in an
average absorption of  70% of the administered dose  (Piper et al.,  1973).
      One  study in the guinea pig reported that  -50%  of  a single oral dose of
2,3,7,8-TCDD  in  acetonercorn  oil was  absorbed  (Nolan  et  al.,   1979).   The
gastrointestinal absorption of 2,3,7,8-TCDD was also  examined in the hamster, the
species most  resistant to the acute toxicity of this compound (Olson et al.,
1980a).  Hamsters were given a single, sublethal, oral dose of [1,6-3H]-2,3,7,8-
TCDD  in olive  oil (650 pig/kg), and an average of  75% of the dose was absorbed.
When 2,3,7,8-TCDD was administered to rats in the diet at 7 or 20 ppb (0.5  or 1.4
A*9/kg/day)  for 42 days, 50-60% of  the  consumed  dose was absorbed (Fries and
Marrow, 1975). These findings indicate that oral exposure to  2,3,7,8-TCDD in the
diet or in an oil vehicle results  in the  absorption  of >50% of the  administered
dose.
     The intestinal absorption of 3H-2,3,7,8-TCDD has  also been investigated in
thoracic duct-cannulated rats (Lakshmanan et  al.,  1986).   The investigators
concluded  that 2,3,7,8-TCDD  was  absorbed into  chylomicrons  and  transported
through the lymphatic system prior to entering the systemic  circulation.
     The absorption of 2,3,7,8-TBDD in male Fischer 344 rats was studied after
oral exposure by gavage at  5  ^g/kg in Emulphor:ethanol:water (1:1:3) (Diliberto
et al., 1990).  The percent of the dose absorbed for this study was defined as
100 — (% total oral  dose in  feces on day 1 and 2  —  %  total intravenous dose in
feces on day 1 and 2) using the intravenous pharmacokinetic data of Kedderis et
al. (1991).
     The relative absorbed dose or bioavailability  of 2,3,7,8-TBDD after oral
exposure was estimated at 78,  82, 60 and  47% at dose levels of 0.001, 0.01, 0.1
and 0.5 pmol/kg, respectively. These results suggest nonlinear absorption  at the
higher doses, with maximal oral absorption at an exposure of <0.01 ^imol/kg (5
/^g/kg).
     The absorption of  2,3,7,8-TCDF has been investigated after oral exposure by
gavage.  Approximately  90%  of the  administered dose  (0.1 and  1.0  ^imol/kg)  of

                                     1-4                              08/11/92

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2,3,7,8-TCDF in Emulphor:ethanol  (1:1) was absorbed in male  Fischer 344 rats



(Birnbaum et al.,  1980).  [Emulphor EL-620 is a polyoxyethylated vegetable oil



preparation (GAF Corp., New York, NY)].  Similarly, >90% of the administered dose



(0.2 pmol/kg,  6  pg/kg and  1-15 pg/kg)  of 2,3,7,8-TCDF in Emulphor: ethanol:water



(1:1:8) was absorbed in male Hartley guinea pigs (Decad et al., 1981a; loannou



et al., 1983).   Thus, 2,3,7,8-TCDF appears to be almost completely absorbed from



the  gastrointestinal tract.   This  may  be  related to  the  greater relative



solubility of 2,3,7,8-TCDF compared to that of 2,3,7,8-TCDD or 2,3,7,8-TBDD.



     The oral bioavailability of 2,3,4,7,8-PeCDF and 3,3',4,4'-TCB in corn oil



were similar to  that of 2,3,7,8-TCDD (Brewster and Birnbaum,  1987; Wehler et al.,



1989;  Clarke  et  al.,   1984).    Furthermore,  2,3,4,7,8-PeCDF absorption  was



independent of  the  dose  (0.1, 0.5 or  1.0 pmol/kg).   Incomplete  and variable



absorption of  1,2,3,7,8-PeCDD  was reported in rats,  with 19-71%  of the dose



absorbed within the  first 2 days after oral exposure (Wacker et al., 1986).



     Early studies on the pharmacokinetic  behavior  of  OCDD by Williams et al.



(1972) and Norback et al.  (1975)  demonstrated that OCDD was poorly absorbed after



oral exposure.  More recently, Birnbaum and Couture (1988)  also found that the



gastrointestinal absorption of OCDD in rats was very limited, ranging  from 2-15%



of the administered dose.  Lower doses (50 pg/kg) in a o-dichlorobenzene:corn oil



(1:1) vehicle  were found to give the best oral bioavailability for this extremely



insoluble compound.




     1.1.1.2.    GASTROINTESTINAL ABSORPTION IN HUMANS  —  Poiger and Schlatter



(1986) investigated  the absorption of 2,3,7,8-TCDD  in  a 42-year-old man after



ingestion of 105 ng 3H-2,3,7,8-TCDD  (1.14 ng/kg bw) in 6 mL corn oil and found




that  >87% of  the oral  dose was  absorbed  from  the  gastrointestinal  tract.



Following  absorption, the half-life  for  elimination was estimated to be 2120



days.



     The above data indicate that gastrointestinal absorption of 2,3,7,8-TCDD and



related compounds is variable, incomplete and  congener specific.  More soluble



congeners,  such as  2,3,7,8-TCDF,  are  almost  completely  absorbed,  while  the



extremely insoluble OCDD is  very poorly absorbed.   In some cases, absorption has



been found to be  dose dependent,  with  increased  absorption occurring at lower








                                     1-5                             08/11/92

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 doses (2,3,7,8-TBDD, OCDD).  The limited data base also suggests that there are



 no major interspecies  differences in the gastrointestinal absorption of  these



 compounds.




      1.1.1.3.    BIOAVAILABILITY  FOLLOWING ORAL  EXPOSURE — Oral  exposure  of



 humans to 2,3,7,8-TCDD and related compounds usually occurs as a complex mixture



 of these contaminants in food,  soil,  dust, water or other mixtures that would be



 expected to  alter  absorption.




      The  influence  of  dose  and  vehicle  or  adsorbent  on  gastrointestinal



 absorption has been investigated in  rats by Poiger and Schlatter (1980),  using



 hepatic  concentrations 24 hours  after dosing  as  an indicator  of the amount



 absorbed  (Table  1-2).  Administration of 2,3,7,8-TCDD in an  aqueous  suspension



 of soil resulted in a decrease  in the hepatic levels of  2,3,7,8-TCDD as compared



 with hepatic levels resulting from administration of 2,3,7,8-TCDD in  50% ethanol.



 The extent of the  decrease was directly proportional to the  length of time the



 2,3,7,8-TCDD had been in contact with the soil.   When 2,3,7,8-TCDD was mixed  in



 an aqueous  suspension of  activated  carbon,  absorption  was  almost  totally



 eliminated (<0.07% of the dose in hepatic tissues).




      Philippi et al.   (1981) and Hutter and  Philippi  (1982)  have  shown that



 radiolabeled 2,3,7,8-TCDD  becomes progressively more  resistant with  time  to



 extraction from soil.   Similarly, the feeding of fly ash, which contains CDDs,



 to rats in the diet for 19 days resulted in considerably lower hepatic levels  of



 CDDs  than did the  feeding  of an extract of the  fly  ash  at comparable dietary



 concentrations of CDDs (van den Berg et al.,  1983).  The CDDs were tentatively



 identified as 2,3,7,8-TCDD, 1,2,3,7,8-PeCDD, 1,2,3,6,7,8-HxCDD and 1,2,3,7,8,9-



 HxCDD and the difference  in  hepatic levels noted between  fly  ash-treated and



 extract-treated rats was greater  for the more  highly chlorinated isomers than  it



 was for 2,3,7,8-TCDD.   These  results  indicate the importance of the formulation



 or vehicle containing the toxin(s) on the relative bioavailability  of 2,3,7,8-



 TCDD, PeCDD and HxCDDs after oral exposure.




     Since 2,3,7,8-TCDD in the environment is likely to be  absorbed to  soil,



McConnell et al.  (1984) and  Lucier et al. (1986) compared the oral  bioavail-



 ability of 2,3,7,8-TCDD  from environmentally contaminated  soil to  that  from









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TABLE 1-2
Percentage of 2,3,7,8-TCDD in the Liver of Rats 24 Hours
After Oral Administration of 0.5 mL of Various
Formulations Containing TCDD*
Formulation
50% ethanol
Aqueous suspension of soil
(37%, w/w) that had been in
contact with TCDD for:
10-15 hours
8 days
Aqueous suspension of activated
carbon (25%, w/w)
TCDD Dose
(ng)
14.7
12.7, 22.9
21.2, 22.7
14.7
No. of
Animals
7
17
10
6
Percentage of
Dose in the Liver
36.7±1.2
24.1±4.8
16.0+2.2
<0.07
*Source:  Poiger and Schlatter, 1980



 w/w = Weight by weight
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2,3,7,8-TCDD administered in corn  oil  in rats and guinea pigs and rats, respec-



tively.  As indicated by biological effects and the amount of 2,3,7,8-TCDD in the



liver, the  intestinal absorption  from Times Beach  and Minker Stout, Missouri,



soil  was  -50%  less than  from  corn  oil.   Shu  et  al.   (1988) reported an oral



bioavailability of -43%  in the rat dosed with three environmentally contaminated



soil  samples from Times Beach, Missouri.  This figure did not  change signifi-



cantly over a  500-fold dose  range  of 2-1450  ng  2,3,7,8-TCDD/kg bw  for soil



contaminated with -2, 30 or 600 ppb of 2,3,7,8-TCDD.  In studies of other soil



types, Umbreit  et al.  (1986a,b) estimated an oral bioavailability in the rat of



0.5%  for soil at a New  Jersey  manufacturing site and  21% for a Newark salvage



yard.  These results  indicate that bioavailability of  2,3,7,8-TCDD from soil



varies between sites and that 2,3,7,8-TCDD content alone may not be indicative



of potential human hazard from contaminated environmental materials.  Although



these data indicate that substantial  absorption may occur from contaminated soil,



soil type and duration of  contact, as suggested from the data that demonstrated



decreased extraction efficiency with increasing contact  time between soil and



2,3,7,8-TCDD (Philippi et al., 1981; Huetter and  Philippi, 1982),  may substan-



tially affect the absorption of 2,3,7,8-TCDD from soils obtained from different



contaminated sites.




1.1.2.   Dermal Absorption.   Brewster et al. (1989) examined the dermal absorp-




tion  of  2,3,7,8-TCDD  and  three CDFs in male Fischer  344 rats  (10  weeks old;



200-250 g).  The fur was  clipped  from the intrascapular  region of  the back of



each animal. A single compound was  then applied over  a 1.8 cm^ area of skin in




60 pL of acetone and covered with a perforated  stainless steel  cap.  Table 1-3



summarizes  data  on the  absorption of each compound at 3 days  after  a single



dermal exposure.  At  an  exposure of  0.1 pmol/kg, the absorption of 2,3,7,8-TCDF



(49% of administered  dose) was  greater than that of 2,3,4,7,8-PeCDF, 1,2,3,7,8-



PeCDF and 2,3,7,8-TCDD.  For each  compound, the relative absorption (percentage



of administered dose)  decreased with increasing dose while the absolute absorp-



tion  (jug/kg) increased  nonlinearly  with  dose.   Results  also suggest  that the



majority of the compound remaining at the  skin exposure site was associated with



the stratum corneum and did not penetrate through to the dermis.   In a subsequent








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TABLE 1-3
Dermal Absorption of 2,3,7,8-TCDD and Related Compounds in the Rata
Chemical
2,3,7,8-TCDD
2,3,7,8-TCDF
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
Dose
(jumol/kg)
0.00015
0.001
0.01
0.1
0.5
1.0
0.1
0.5
1.0
0.1
0.5
1.0
0.1
0.5
1.0
(pg/kg)
0.05
0.32
3.2
32
160
321
31
153
306
34
170
340
34
170
340
% Administered Dose
Skin Siteb
61.73±4.37
59.71±1.90
72.60±0.41
82.21+2.85
80.92±2.74
82.68±3.69
51.18±11.95
82.14±11.22
88.70±5.17
74.7213.58
91.67±2.46
84.23+5.44
65.77+4.80
75.50±1.81
81.84±1.67
Absorbed
38.27±4.37
40.29±1.89
27.40±0.41
17.78+2.85
19.08±2.74
17.30±3.67
48.84±11.95
17.86+11.22
11.32+5.17
25.2713.58
8.3312.46
15.7615.44
34.1914.78
24.5011.80
18.1611.67
aSource:   Brewster et al.,  1989

'Values are the meaniSD of three to four animals  and  represent  the
 amount of administered dose of radiolabeled  congener remaining at
 the application site 3 days after dermal exposure.
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study, Banks and Birnbaum (1991a) examined the rate of absorption of 2,3,7,8-TCDD


over 120 hours  after the dermal application of  200 pmol (1 nmol/kg)  to male


Fischer 344 rats.   The absorption kinetics appeared to be first-order, with an


absorption rate constant of 0.005 hour .  Using a similar exposure protocol, the


dermal absorption  of 2,3,7,8-TCDF was found to follow a first-order process with


a rate constant of  0.009 hour"1 (Banks and Birnbaum,  1991b).   Together, these


results on  dermal absorption indicate that  at lower doses  (<0.1  /jmol/kg),  a


greater percent of  this  administered dose of  2,3,7,8-TCDD and three CDFs was


absorbed.  Nonetheless, the rate of absorption of 2,3,7,8-TCDD is still very slow


(rate constant of  0.005 hour"1) even following  a low dose dermal application of


200 pmol  (1 nmol/kg).   Results  from Table 1-3 also  suggest that  the dermal


absorption of  2,3,7,8-TCDF, 2,3,4,7,8-PeCDF and 1,2,3,7,8-PeCDF occurs at a very


slow rate.   Using  a  similar exposure protocol,  the  dermal absorption of 2,3,7,8-


TBDD was only 30-40% of that observed for 2,3,7,8-TCDD (Jackson et al., 1991).


     Rahman et  al.  (1992)  and  Gallo et  al.  (1992)  compared  the  in vitro


permeation  of  2,3,7,8-TCDD  through hairless  mouse and human  skin.   In both


species, the amount of 2,3,7,8-TCDD permeated increased with the dose, but the


percent of the dose permeated  decreased with increasing dose.  The permeability


coefficient of 2,3,7,8-TCDD  in human skin was about one order of magnitude lower


than that  in  mouse  skin.   The hairless mouse skin does not  appear to  be  a


suitable model for the permeation of 2,3,7,8-TCDD through human skin since the


viable tissues were the  major barrier to 2,3,7,8-TCDD permeation  in hairless


mouse skin, while the stratum corneum layer provided the greater resistance in


human skin.  A significant increase in 2,3,7,8-TCDD permeation through human skin


was observed when the skin was damaged by tape-stripping.   Gallo et al. (1992)


suggested that washing and/or tape-stripping of the exposed area might remove


most of the 2,3,7,8-TCDD and reduce  the  potential for systemic  exposure and


toxicity since most of the 2,3,7,8-TCDD remained within the horny layer of human


skin even at 24 hours following exposure.


     Weber et al.  (1991)  also  investigated the  penetration of 2,3,7,8-TCDD into

                                                    fy
human cadaver skin  at concentrations  of 65-6.5 ng/cm  .  This study also found


that the stratum corneum acted as a protective barrier, as  its removal increased



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                          DRAFT—DO  NOT QUOTE OR CITE



the amount of 2,3,7,8-TCDD absorbed into layers of the skin.  With intact skin


and acetone  as  the  vehicle,  the rate of penetration  of  2,3,7,8-TCDD into the

                                    f\
dermis ranged  from  6-170 pg/hour/cm , while penetration into the  dermis and

                                         o
epidermis ranged  from  100-800 pg/hour/cm .   With mineral oil  as  the vehicle,


there was about a  5- to 10-fold reduction in the rate of penetration of 2,3,7,8-


TCDD into the intact skin.


     1.1.2.1.   BIOAVAILABILITY FOLLOWING DERMAL EXPOSURE — Dermal exposure of


human to 2,3,7,8-TCDD and related  compounds  usually occurs as a complex mixture


of these contaminants in  soil, oils or other mixtures which would be expected to


alter  absorption.   Poiger  and  Schlatter  (1980)  presented  evidence  that the


presence of soil or  lipophilic agents dramatically reduces dermal absorption of


2,3,7,8-TCDD compared to  absorption  of pure  compound dissolved in solvents.  In


a control experiment, 26 ng of 2,3,7,8-TCDD in 50 pL methanol was administered


to the skin  of  rats,  and 24 hours later the liver contained  14.8±2.6%  of the


dose.   By  comparing this  value  to the hepatic levels obtained  after  oral


administration in 50% ethanol (in the same  study), the  amount absorbed from a


dermal application  can be estimated  at  -40%  of  the  amount absorbed  from an


equivalent oral dose.  This comparison assumes that  hepatic  levels are valid


estimates of the amount  absorbed from  both oral and dermal routes  and  that


absorption from methanol  is equivalent to  absorption from 50%  ethanol.  The dose-


dependent distribution of 2,3,7,8-TCDD in the liver  is another factor that may


limit quantitative conclusions regarding  bioavailability  which are based solely


on hepatic levels following exposure to 2,3,7,8-TCDD.   As compared with dermal


application in methanol,  dermal  application  of  2,3,7,8-TCDD  to rats in vaseline


or polyethylene glycol reduced the percentage of  the dose in hepatic tissue to


1.4 and 9.3%, respectively, but had no observable  effect on the dose of 2,3,7,8-


TCDD required  to induce  skin lesions (-1  pg/ear)  in the  rabbit  ear  assay.


Application of 2,3,7,8-TCDD in a soil/water paste decreased hepatic 2,3,7,8-TCDD


to -2%  of the administered dose and increased the amount required to produce skin


lesions to 2-3 pg in rats  and rabbits, respectively. Application in an activated


carbon/water paste essentially eliminated absorption,  as  measured by percent of


dose in the liver, and  increased the amount  of 2,3,7,8-TCDD required to produce




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                         DRAFT—DO NOT QUOTE OR CITE






skin lesions to -160 pg.  These results suggest that the dermal absorption and



acnegenic  potency  of   2,3,7,8-TCDD  depend  on the formulation  (vehicle  or



adsorbent) containing the toxin.




     Shu et al.  (1988) investigated the dermal absorption of soil-bound 2,3,7,8-



TCDD in rats.  Relative dermal  bioavailability was  estimated  by comparing the



level of 2,3,7,8-TCDD in the liver of rats given  soil-bound 2,3,7,8-TCDD dermally



to that of  rats  given  oral doses  of 2,3,7,8-TCDD dissolved in  corn  oil.   The



level of 2,3,7,8-TCDD in livers of rats dosed orally with 2,3,7,8-TCDD in corn



oil, following correction for unabsorbed 2,3,7,8-TCDD,  is assumed to represent



100% bioavailability.  The dermal  penetration of 2,3,7,8-TCDD  after 4 hours of



contact with skin was -60%  of that after 24 hours of  contact.  After 24 hours of



contact with the  skin, the degree of dermal uptake from contaminated soil was -1%



of the administered dose.   The authors observed that the degree of uptake does



not appear to be influenced significantly by the concentration of 2,3,7,8-TCDD



in soil, the presence of crankcase oil as  co-contaminants or by environmentally-



versus laboratory-contaminated soil.




     A major limitation of the  above  studies is the uncertainty regarding the



extrapolation of dermal absorption data on these compounds from the rat to the



human.  The in vitro dermal uptake  of 2,3,7,8-TCDD has been  investigated in



hairless mouse and  human skin  (Gallo  et  al.,  1992;  Rahman et  al.,  1992).   In



vitro dermal uptake  of 2,3,7,8-TCDD from laboratory-contaminated soil found that



aging of soils (up to 4 weeks)  and the presence of additives (2,4,5-trichloro-



phenol and motor oil)  in the soil did  not have  any significant effect of dermal



uptake  (Gallo et  al.,  1992).   Since most of the  2,3,7,8-TCDD  remained in the



stratum corneum layer of human skin,  the permeation of 2,3,7,8-TCDD was signifi-



cantly  lower in human  than  in hairless mouse skin.   Although there  are no



published quantitative in vivo data on the dermal absorption of 2,3,7,8-TCDD and




related compounds in the human,  there are very limited data on the rhesus monkey.



Brewster et  al.  (1988)  found that 1,2,3,7,8-PeCDF was poorly  absorbed in the




monkey after dermal  application with <1% of the  administered dose being absorbed



in 6 hours.   This provides further evidence for the very slow rate of dermal



absorption of 2,3,7,8-TCDD and related compounds.









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1.1.3.   Transpulmonary Absorption.  The use of incineration as a means of solid



and hazardous waste management  results in the emission of contaminated particles



that  may contain  TCDD and  related compounds  into the  environment.   Thus,



significant exposure to TCDD and  related compounds may result from inhalation of



contaminated  fly ash,  dust and soil.  In an  attempt to  address the bioavail-



ability  and potential  health  implications  of inhaling  contaminated particles,



Nessel et al.  (1990) examined the  potential for transpulmonary absorption of TCDD



after intratracheal instillation  of the compound administered to female Sprague-



Dawley rats either  in a corn oil vehicle or  as  a laboratory-prepared contaminant



of gallium  oxide particles.   Several  biomarkers of systemic  absorption were



measured, including the dose-dependent effects of TCDD  on hepatic microsomal



cytochrome P-450 content,  AHH  activity and liver histopathology.   Significant



dose-related  effects were observed at  an  exposure  of  >0.55 fjg TCDD/kg.   The



authors  found that  induction was slightly higher when animals received TCDD in



corn oil than when  animals received TCDD-contaminated particles  and was compar-



able to  induction  after oral exposure.  The  results  from Nessel et al.  (1990)



indicate that systemic  effects occur after pulmonary exposure to TCDD, suggesting



that transpulmonary absorption of TCDD does occur.




     The transpulmonary absorption of 2,3,7,8-TCDD was assessed  in male Fischer



344 rats following  intratracheal instillation of a 1 nmol/kg dose in Emulphor:




ethanol:water  (Diliberto  et  al., 1992).  Transpulmonary  absorption  was -92%,



suggesting that there was  almost  complete absorption  of 2,3,7,8-TCDD by inhala-



tion  under  these  conditions.    Similar results  were  also  observed for  the



transpulmonary  absorption of  2,3,7,8-TBDD  under similar  exposure  conditions



(Diliberto  et  al.,  1991).   These  results  suggest that the  transpulmonary



absorption  of  2,3,7,8-TCDD  and  2,3,7,8-TBDD was  similar  to that  observed



following oral exposure.




1.1.4.   Parenteral Absorption.  In  an  effort  to obtain  more reproducible and



complete absorption of  2,3,7,8-TCDD  and related  compounds for pharmacokinetic




studies, Abraham et al.  (1989) investigated the absorption  of 2,3,7,8-TCDD after



parenteral application  in rats,  using  various vehicles.   These investigators



observed optimal results with the subcutaneous injection of 2,3,7,8-TCDD using



a mixture of toluene:DMSO  (1:2) as vehicle.  At 3 and 5 days after treatment, the




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                         DRAFT—DO NOT QUOTE OR CITE






percentages of administered dose remaining at the injection site under the skin



of the back were -10 and 2%,  respectively.  The vehicle did not cause adverse



effects at  an applied volume of  0.2  mL/kg bw.   The absorption of  a defined




mixture of  CDDs and  CDFs  in the rat  was also  examined  after  subcutaneous



injection using toluene:DMSO (1:2) as  a vehicle.  Of the 97 congeners analyzed,




70 were >95% absorbed 7 days after exposure, 21 were 90-95% absorbed and 1,2,3,9-



TCDD, 1,2,3,6,7,9-/ 1,2,3,6,8,9-HxCDD, 1,2,3,4,6,7,9-HpCDD,  OCDD,  1,2,4,6,8,9-



HxCDF and 1,2,3,7,8,9-HxCDF were 84-89% absorbed.   Greater than 90% absorption



of CDDs and CDFs was also observed under these conditions in the marmoset monkey,



with the exception of 1,2,3,4,7,8,9-HpCDF, OCDF and OCDD, which had -50-80% of



the  administered dose  absorbed  (Neubert  et al., 1990;  Abraham  et  al.,  1989).



Although the  absorption of  CDDs and CDFs after subcutaneous administration in



toluene:DMSO  (1:2)  is  somewhat  slow,  in rats  and  monkeys,  absorption of most




congeners was >90% within 7  days.    Even for  highly  chlorinated  insoluble



congeners, such as OCDD and OCDF, subcutaneous absorption was >84% in the rat and



>50% in the monkey.



     Less complete  and  slower absorption of CDDs  and  CDFs  was  observed after



subcutaneous  injection of  these  compounds  using  an  oil-containing vehicle



(Brunner et al., 1989;  Abraham et  al., 1989).   Using a corn oil:acetone vehicle



(24:1, v/v), Lakshmanan et  al. (1986)  observed  that only 7% of the administered



dose of 2,3,7,8-TCDD was absorbed 24 hours after subcutaneous  injection and that



only 35%  was  absorbed  after intraperitoneal injection.  Also,  Brunner  et al.



(1989) reported that intraperitoneal administration of  CDDs and CDFs revealed a



delayed absorption  from the  abdominal cavity  which varied  for  the  different



congeners.  Therefore, concentrations measured in abdominal adipose tissue after



intraperitoneal administration may not represent average values of adipose tissue



in the whole body, particularly at early time points following exposure.



1.2.   DISTRIBUTION



1.2.1.   Distribution in Blood and Lymph.  Once  a compound  is  absorbed,  its



distribution is regulated initially by its binding to components in blood and its



ability to diffuse through blood vessels and tissue membranes.  Lakshmanan et al.



(1986) investigated the absorption and distribution of  2,3,7,8-TCDD in thoracic



duct-cannulated rats.   Their results suggest  that following gastrointestinal




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                          DRAFT—DO NOT  QUOTE OR CITE






absorption, 2,3,7,8-TCDD  is  absorbed primarily by the  lymphatic  route and is



transported predominantly by chylomicrons.  Ninety percent of the 2,3,7,8-TCDD



in lymph was associated with the chylomicron fraction.  The plasma disappearance



of 2,3,7,8-TCDD-labeled chylomicrons followed first-order decay kinetics, with



67%  of  the  compound  leaving the  blood  compartment  very  rapidly  (t 1^=0.81




minutes), whereas the  remainder  of the 2,3,7,8-TCDD had  a ti^  of 30 minutes.




2,3,7,8-TCDD was then found to distribute primarily to the adipose tissue and the



liver.



     In vitro  studies have investigated the distribution of 2,3,7,8-TCDD in human



whole blood.  Henderson and Patterson (1988) found -80% of the compound associ-



ated with the  lipoprotein  fraction, 15% associated with protein (primarily human



serum  albumin)  and  5% associated  with  cellular components.  Theoretical and



limited experimental data also suggest that 2,3,7,8-TCDD and related compounds



may be associated with plasma prealbumin (McKinney et al., 1985; Pedersen et al.,



1986).  The distribution of [%]-2,3,7,8-TCDD among lipoprotein fractions from




three fasting, normolipemic donors indicated a greater percentage  associated with



LDL (55.3±9.03% SD)  than with VLDL  (17.4±9.07% SD)  or HDL (27.3±10.08% SD).  The



distribution of 2,3,7,8-TCDD among the lipoprotein fractions was  similar to that



reported earlier by Marinovich et  al.  (1983).  When the binding of 2,3,7,8-TCDD



was calculated per mole of lipoprotein,  it  was suggested that the maximal binding



capacity was exerted by VLDL, followed by LDL and HDL  (Marinovich et al., 1983).



The results also suggest that variations in the amounts of each lipoprotein class



may alter the  distribution of 2,3,7,8-TCDD  among lipoproteins in a given subject.



Significant species differences also exist; in the  case of the  rat,  which has



markedly lower  plasma lipids  compared  to  humans,  2,3,7,8-TCDD was distributed



almost equally among the lipoprotein fractions (Marinovich et al., 1983).



     In addition, there is indirect evidence that suggests that the binding of



2,3,7,8-TCDD to lipoproteins may alter the pharmacokinetics and toxic potency of



the  compound.   Marinovich et al.  (1983) found  that  experimentally induced



hyperlipidemia  in rats delayed the  development  of  overt toxicity (lethality).



However,  the  disposition  of   2,3,7,8-TCDD was  not  investigated under  these



conditions.  These investigators suggest that the release of lipoprotein-bound






                                     1-15                             08/11/92

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                         DRAFT—DO NOT QUOTE OR CITE






2,3,7,8-TCDD is related to the metabolic turnover of lipoproteins.  In hyperlipi-



demic rats, the turnover of VLDL and LDL  is delayed  significantly compared to



normolipidemic animals, and this may contribute to the plasma lipoprotein binding



modifying the toxicity of 2,3,7,8-TCDD in hyperlipidemic rats.



     The  uptake  of  lipoprotein-associated  2,3,7,8-TCDD  by  cultured  human



fibroblasts  found the  time-  and  temperature-dependent  cellular uptake  was



greatest from LDL, intermediate from HDL and least from serum (Shireman and Wei,



1986).  Decreased  cellular uptake of LDL and 2,3,7,8-TCDD was observed in mutant



fibroblasts, which lack the normal cell membrane receptor for LDL.  This provides




some evidence  that specific  binding of LDL and  the  LDL receptor  pathway may



account for some of the rapid early uptake of  2,3,7,8-TCDD with LDL entry. The



results suggest that the entry of 2,3,7,8-TCDD into cells may not be solely by



simple  diffusion.   However,  nonspecific  binding of the  LDL and  transfer of



2,3,7,8-TCDD from LDL to the cell membranes are probably also important, since



significant  time- and temperature-dependent  uptake  of  2,3,7,8-TCDD and  LDL



occurred in the mutant fibroblasts.



     Thus, upon absorption, 2,3,7,8-TCDD and probably related compounds are bound



to chylomicrons,  lipoproteins  and other serum proteins  that  assist in distri-



buting  these  uncharged,  lipophilic  compounds  throughout the  vascular system.



These compounds then partition  from blood components into cellular membranes and



tissues, probably  largely by passive diffusion.  In addition, cellular uptake may



be  facilitated partly through the cell  membrane LDL  receptor,  the  hepatic



receptor for albumin (Weisiger et al.,  1981)  and/or other systems.



1.2.2.   Tissue Distribution.  Once absorbed into blood, 2 , 3, 7,8-TCDD and related



compounds readily  distribute to all organs.  Tissue distribution within the first



hour after exposure parallels blood levels and reflects physiological parameters



such as blood flow to a given  tissue and relative tissue size.   For example, high



initial concentrations of 2,3,7,8-TCDD,  1,2,3,7,8-PeCDF  and 3,3',4,4'-TCB were



observed in highly perfused tissue such as the  adrenal glands during the 24-hour



period  after  a single exposure (Birnbaum et  al., 1980;  Olson et  al.,  1980;



Pohjanvirta et al., 1990; Brewster and Birnbaum, 1988;  Durham and Brouwer, 1990).



A high percentage  of the dose of 2,3,7,8-TCDF and  1,2,3,7,8-PeCDF was also found



in muscle  within  the  first  hour after intravenous exposure,  due  to the large




                                     1-16                             08/11/92

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                          DRAFT—DO NOT QUOTE OR CITE






volume of  this tissue  (Birnbaum et al.,  1980;  Birnbaum, 1985;  Brewster and



Birnbaum, 1988).  Nevertheless, within several hours the liver, adipose tissue



and skin become the primary sites of disposition, when expressed as percent of



administered dose per g tissue  and as percent of dose per organ.  Liver, adipose



tissue, skin and thyroid were the only tissue to show an increase in the concen-



tration of 2,3,7,8-TCDD during  the initial 4 days after  a single intraperitoneal



exposure of rats (Pohjanvirta et al., 1990).  In this study,  a similar general



pattern of disposition was observed in  Han/Wistar and Long-Evans rats which are



respectively most resistant and susceptible to the acute toxicity of 2,3,7,8-TCDD



(Pohjanvirta et al., 1990).



     Table 1-4  illustrates the tissue  distribution of  2,3,7,8-TCDD  in female



Wistar rats 7 days after a single subcutaneous exposure  (Abraham et al., 1988).



This general pattern of distribution is similar  to that  observed in mice, rats,



rhesus monkeys, hamsters  and  guinea  pigs,  where  liver  and adipose  tissue



consistently have the highest concentrations of 2,3,7,8-TCDD (Piper et al., 1973;



Fries and Marrow, 1975;  Rose et al.,  1976;  Allen et al.,  1975;  Van Miller et al.,



1976; Kociba et al.,  1978a,b; Gasiewicz et al., 1983; Manara et  al., 1982; Olson



et al., 1980; Gasiewicz  and Neal, 1979;  Birnbaum, 1986;  Pohjanvirta et al., 1990;



Abraham et al., 1988).  A  similar pattern of disposition also was observed for



2,3,7,8-TCDF in the guinea pig, rat,  C57BL/6J and DBA/2J mouse  and rhesus monkey,



with 2,3,7,8-TCDF concentrations highest in liver and adipose tissue (Decad et



al., 1981b; Birnbaum et al., 1980, 1981).  In summary, there do  not appear to be



major species or strain differences in the tissue distribution of 2,3,7,8-TCDD



and 2,3,7,8-TCDF, with the liver and adipose tissue being the primary disposition



sites.




     The tissue distribution of the coplanar PCBs and  PBBs also  appears to be



similar to that of 2,3,7,8-TCDD and 2,3,7,8-TCDF.  Limited studies in rats and



mice found that 3,3',4,4'-TCB, 3,3•,4,4'-TBB and 3,3'4,4'5, 5'-HxBB distributed



preferentially to adipose  tissue and liver (Clarke et al., 1983, 1984; Millis et



al., 1985; Wehler et al.,  1989; Clevenger et al., 1989).




     While the  liver and  adipose tissue contain the highest  concentrations of



2,3,7,8-TCDD and 2,3,7,8-TCDF, there are some congener-specific differences in



the  relative  tissue  distribution  of   related  compounds.   2,3,7,8-TBDD  and




                                     1-17                             08/11/92

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TABLE 1-4
Tissue Distribution of [14C]-2-3,7,8-TCDD in
Female Wistar Ratsa'b
Tissue
Liver
Adipose tissue
Adrenal glands
Ovaries
Thymus
Skin
Lung
Kidney
Pancreas
Spleen
Serum
Bone (with marrow)
Muscle
Brain
Range of 2,3,7,8-TCDD Concentrations
(ng/g)
29.23-30.99
3.72-4.14
0.89-1.08
0.76-0.96
0.60-1.05
0.64-0.68
0.32-0.33
0.27-0.29
0.21-0.31
0.18-0.23
0.16-0.18
0.16-0.16
0.08-0.12
0.07-0.09
aSource:   Abraham et al., 1988

''Distribution    was   assessed    7   days
single subcutaneous exposure  (3 jug/kg bw)
after
                            1-18
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1,2,3,7,8-PeCDD disposition in the rat was very similar to that of 2,3,7,8-TCDD



(Kedderis et al.,  1991; Wacker et al., 1986). The hepatic concentration of OCDD



and 2,3,4,7,8-PeCDF in the rat, however, was approximately 10- to 20-fold greater



than that in adipose tissue, which generally contains the second highest levels



of these compounds  (Birnbaum and Couture, 1988; Norback et al.,  1975; Williams




et al.,  1972; Brewster and Birnbaum,  1987).  The tissue distribution of a defined



mixture of  CDDs and CDFs (28.8  nq CDDs+CDFs/kg bw  containing 120 ng 2,3,7,8-



TCDD/kg bw) was measured in marmoset  monkeys 7 days  after a single subcutaneous



exposure (Abraham et al., 1990).  For most of the 2,3,7,8-substituted congeners,



the highest  concentrations were detected in hepatic  and  adipose  tissue,  with



correspondingly lower values detected in kidney,  brain, lung, heart, thymus or



testes.  The hepatic and adipose tissue concentrations were similar for 2,3,7,8-



TCDD, 1,2,3,7,8-PeCDD, 2,3,7,8-TCDF and 1,2,3,7,8-/ 1,2,3,4,8-PeCDF.  Nonethe-



less, the hepatic  concentrations were approximately 10-fold or more greater than



those of adipose tissue for 1,2,3,4,7,8-HxCDD,  1,2,3,6,7,8-HxCDD,  1,2,3,7,8,9-



HxCDD,  1,2,3,4,6,7,8-HpCDD,  OCDD,  2,3,4,7,8-PeCDF, 1,2,3,4,7,8-/1,2,3,4,7,9-



HxCDF, 1,2,3,6,7,8-HxCDF, 1,2,3,7,8,9-HxCDF, 2,3,4,6,7,8-HxCDF,  1,2,3,4,6,7,8-



HpCDF,  1,2,3,4,7,8,9-HpCDF and  OCDF.  The  lungs  and  thymus contained higher



concentrations of all of the above congeners  than were detected in kidney, brain,



heart and testes.   Unexpectedly, the concentrations of the above HxCDDs, HpCDDs,



OCDD and HxCDFs were similar in the  adipose tissue, lungs  and thymus.   In the




case of HpCDFs and OCDF, the concentrations were greater in the lungs than the



adipose tissue. The enhanced disposition of highly chlorinated congeners to the



lungs and thymus is of interest and deserves  further investigation.  For example,



it is possible that the high  concentration  in the  lungs could  be related to the



insolubility of these compounds.



     Whole-body autoradiography  of mice and rats after intravenous administration




of  [  C]-2,3,7,8-TCDD showed a  selective localization of radioactivity in the




liver and nasal olfactory mucosa (Appelgren et al., 1983;  Gillner et al., 1987).



The selective  localization of  2,3,7,8-TCDD in the  nasal  olfactory mucosa was



apparently overlooked by other distribution  studies  that only  examined selected



organs.  Gillner et al.  (1987) found no 2,3,7,8-TCDD-derived radioactivity in the








                                     1-19                             08/11/92

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olfactory mucosa after solvent extraction of sections, suggesting that 2,3,7,8-



TCDD was not covalently bound in this tissue.  In addition,  Gillner et al. (1987)




reported induction  of mRNA coding  for cytochrome P-4501A2 in  the absence of




P-4501A1 induction in olfactory mucosa of rats.  The selective distribution of



2,3,7,8-TCDD  in the  liver and  olfactory mucosa  correlates  with the  tissue



specific induction of cytochrome P-4501A2, which represents a potential seques-



tration  (binding) protein  (see  Section 1.2.5).   Increases in  the incidence of



squamous cell  carcinoma  of nasal turbinates  and carcinoma of  the liver were



observed in rats after a  2-year exposure to 2,3,7,8-TCDD in rat chow (Kociba et



al., 1978); however, this  effect was not observed in  nasal tissues of mice or



rats intubated with  2,3,7,8-TCDD.  Gillner et  al. (1987) suggested that 2,3,7,8-



TCDD may not be an  initiator  in this tissue  and indicated that future studies



should investigate the possibility  that  2,3,7,8-TCDD may  act  as a  promoter or



cocarcinogen in nasal tissue.




     Evidence has also been reported that suggests that 2,3,7,8-TCDD uptake and



retention by the liver is dependent on the cell type within  the liver.  Hakansson



et al.  (1989) found that at 4 days after exposure of rats  to 2,3,7,8-TCDD, 60%



of the dose distributed to hepatocytes and 12% was retained by stellate cells.



Half-lives  for  2,3,7,8-TCDD  in  hepatocytes  and  stellate  cells were  also



calculated to be 13 and 50 days, respectively, suggesting  that 2,3,7,8-TCDD is



more persistent  in  nonparenchymal  cells.    Further  studies  are needed  to



understand the  pharmacokinetic  and pharmacodynamic significance of  the cell-



specific distribution of 2,3,7,8-TCDD and related compounds.



     1.2.2.1.   TISSUE DISTRIBUTION IN HUMANS — Fachetti et al.  (1980) reported



tissue concentrations of 2,3,7,8-TCDD at levels of 1-2 ng/g  in adipose tissue and



pancreas, 0.1-0.2 ng/g in the liver and <0.1 ng/g in thyroid, brain,  lung, kidney



and blood in a woman who  died  7  months  after potential exposure to 2,3,7,8-TCDD



from the Seveso accident.  This pattern of 2,3,7,8-TCDD distribution,  however,



may not be  representative for humans  since the woman at the time  of  death had an



adenocarcinoma (which was not  considered related to the accident) involving the



pancreas, liver and lung.
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     Ryan et al.  (1985a) examined the distribution  of 2,3,7,8-TCDD in two humans



at autopsy.   They determined on a weight basis that 2,3,7,8-TCDD distributed in



descending order to fat (-6 ppt)  and liver (-2 ppt),  with levels in muscle and



kidney below detection; however,  2,3,7,8-TCDD levels compared on  a  per lipid



basis were  similar between  tissues.   These  data should be  interpreted with



caution,  since  only two subjects were  examined  and  one of the  subjects was



suffering from fatty liver syndrome; therefore, the data cannot be generalized




to the entire population.



     Poiger  and  Schlatter   (1986) estimated  that  -90%  of  the body  burden of



2,3,7,8-TCDD was sequestered in the fat after a volunteer ingested ^H-2,3,7,8-




TCDD in corn oil at a dose of 1.14 ng/kg.  During this 135-day study, elevated



radioactivity was  detected in the  blood only during the  first 2  days after




treatment.  The  data would be consistent  with the high lipid bioconcentration



potential of 2,3,7,8-TCDD  in humans, as calculated by Geyer et al. (1986) from



daily intake assumptions,  levels in human adipose tissue  and pharmacokinetic



models.  Geyer  et al.  (1986)  estimated a BCF of between 104 and 206 for 2,3,7,8-



TCDD in human adipose tissue.



     In human adipose tissue, levels of 2,3,7,8-TCDD averaging 5-10 ppt have been



reported  for background populations in St. Louis,  MO, by Graham et al.  (1986),



in Atlanta,  GA,  and Utah by Patterson et  al.  (1986), and in Canada by Ryan et al.



(1985b).  Sielken  (1987) evaluated these data and concluded that the levels of



2,3,7,8-TCDD  in  human  adipose  are log-normally distributed  and  positively




correlated with age.  Among the observed U.S.  background  levels of 2,3,7,8-TCDD



in human  adipose tissue, more than 10% were >12 ppt.



     Patterson et al.  (1987) developed a HRGC/HRMS analysis  for 2,3,7,8-TCDD in



human serum. The arithmetic mean of the individual human serum samples was 47.9



ppq on a whole-weight basis and 7.6 ppt on a lipid-weight basis.  Paired human



serum and adipose tissue levels of 2,3,7,8-TCDD have been compared by Patterson



et  al.  (1988)   and Kahn et al.   (1988).   Both  laboratories reported  a high



correlation between adipose tissue and serum 2,3,7,8-TCDD levels when the  samples



were adjusted for  total lipid content.   This correlation indicates that serum
                                     1-21                             08/11/92

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 2,3,7,8-TCDD  is  a  valid estimate of the 2,3,7,8-TCDD  concentration in adipose



 tissue.




     In  a  study  of potentially heavily exposed  Vietnam  veterans,  MMMR  (1988)



 reviewed an Air  Force study of Ranch Hand veterans who  were either herbicide



 loaders or herbicide specialists in Vietnam.  The mean  serum 2,3,7,8-TCDD  levels



 of  147 Ranch  Hand  personnel was 49 ppt in 1987,  based on total lipid-weight,



 while the mean serum level of the 49 controls  was  5 ppt. In addition,  79%  of the



 Ranch Hand personnel and 2% of the controls had 2,3,7,8-TCDD levels >10 ppt.  The



 distribution of 2,3,7,8-TCDD levels in this phase of the Air Force health study



 indicates that only a small number of Ranch Hand personnel had unusually heavy



 2,3,7,8-TCDD exposure.  This report also estimated the  half-life of 2,3,7,8-TCDD



 in  humans to  be  -7  years on the basis of  2,3,7,8-TCDD levels in serum samples



 taken in 1982 and 1987 from 36  of the  Ranch Hand personnel who had 2,3,7,8-TCDD



 levels >10 ppt in 1987.   Similar results were obtained  by  Kahn et al.  (1988) who



 compared 2,3,7,8-TCDD levels in blood and adipose tissue of Agent Orange-exposed



 Vietnam veterans and matched  controls  (Kahn  et  al.,  1988).   This  study also



 examined moderately exposed Vietnam veterans who handled herbicides regularly



 while in Vietnam.   Although this  study can distinguish moderately exposed men



 from others, the data do not address the question of identifying persons whose



 exposures are relatively low and who constitute the bulk of the population, both



 military and  civilian,  who may  have  been  exposed to  greater than  background



 levels of 2,3,7,8-TCDD.




 1.2.3.   Time-Dependent Tissue  Distribution.  2,3,7,8-TCDD and related compounds



 exhibit congener  specific disposition, which depends  on tissue, species and time



 after a given  exposure.  In general, these compounds are cleared rapidly from the



 blood and distributed to liver, muscle, skin, adipose  tissue and other tissues



 within the first  hour(s) after  exposure.  This is followed by redistribution to



 the liver and adipose tissue, which exhibit increasing tissue concentrations over



 several days after  exposure.  Elimination from tissues  then occurs at rates that



 are congener-, tissue- and species-specific.  Thus, the ratio of the concentra-



 tion of 2,3,7,8-TCDD and related  compounds in  different  tissues (i.e.,  liver/



 adipose)  may not remain constant over an extended period after  a single exposure.



Abraham et al. (1988) examined the concentrations of 2,3,7,8-TCDD in liver and




                                     1-22                              08/11/92

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                         DRAFT—DO NOT QUOTE OR CITE






adipose tissue  of  female  Wistar rats  over a  91-day period  after a  single



subcutaneous exposure  at  a dose of  300 ng/kg bw  (Figure  1-1).   The  maximum



concentration of 2,3,7,8-TCDD in the liver and adipose tissue was reached at 3



and 7 days after exposure, respectively.  The liver/adipose tissue concentration



ratio does not remain constant over time since the concentration of 2,3,7,8-TCDD



decreases more rapidly  in the liver than  in the adipose tissue. For example, the



liver/adipose tissue concentration ratio  (for 2,3,7,8-TCDD)  was 10.3 at 1 day



after exposure and  0.5 at  91 days after exposure  (Figure  1-1).   Results from



other disposition studies also indicate that the ratio of the concentration of



2,3,7,8-TCDD and related compounds in liver,  adipose  tissue and other tissues



does  not  remain  constant  over  an  extended  period  after  a single exposure



(Pohjanvirta et al., 1990;  Birnbaum,  1986;  Birnbaum et al.,  1980; Decad et al.,



1981a; Birnbaum and Couture,  1988; Olson  et al.,  1980; Kedderis et al., 1991;



Brewster and Birnbaum,  1987,  1988;  Neubert et  al.,  1990).  This relationship is



important in attempting to correlate dose-response data with tissue concentra-



tions of 2,3,7,8-TCDD  and related compounds.



      In an attempt to maintain constant  2,3,7,8-TCDD levels  in tissues to study



long-term  effects,  Krowke  et al.  (1989)   investigated  several loading-dose/



maintenance-dose exposure regimens.  They found that similar liver/adipose tissue



concentrations ranging from 5-8 could be maintained in  rats over a 22-week period



using a loading dose of 25 /jg/kg followed by weekly maintenance doses of  5 ^g/kg.



      A  large body  of  data on the  tissue  concentrations  of 2,3,7,8-TCDD and



related  compounds over  time after  exposure can  be   evaluated  by estimating



congener-specific half-life  values  for  a  given  tissue and species.  Table 1-5



summarizes pharmacokinetic elimination parameters  for 2,3,7,8-TCDD and related



compounds from major tissue depots.   Data from Abraham et al. (1988)  (see Figure



1-1)  were  used to  estimate  the half-life  for  2,3,7,8-TCDD in  the liver and



adipose tissue of rats  (Table 1-5).  The decrease in the 2,3,7,8-TCDD  concentra-



tion in adipose tissue is a linear function in  the  semi-logarithmic  plot in



Figure 1-1 (log concentration versus time), which indicates  apparent first-order



elimination  kinetics with  a  half-life  of  24.5 days (Table 1-5).  Liver tissue



exhibits a biphasic (two-component)  exponential decay pattern with a half-life



of  11.5 days for the first component (days  10-49)  and a half-life of 16.9 days




                                     1-23                             08/11/92

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                            PRAFT—DO NOT QUOTE OR CITE
                                                 A  liter hssuf
                                                 A  odipost I issue
                       0 10
                      0.01
                         0  7  14  21  28 35  42  49 56  63  70 77  84  91
                                                  «t»s tiler IrettiKitl
                                     FIGURE 1-1
     Time Course of the Concentration of 14C-TCDD in Rat Liver and Adipose Tissue
After a Single Subcutaneous Injection of 300 ng TCDD/kg bw to Female Rats  (M±SD).

Source:   Abraham et  al.,  1988
                                        1-24
08/11/92

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TABLE 1-5
• Elimination of 2,3,7,8-TCDD and Related Compounds from Major Tissue Depots
Chemical
CDDs
2,3,7,8-TCDD
2,3,7,8-TCDD
2,3,7,8-TCDD
2,3,7,8-TCDD
2,3,7,8-TCDD
2,3,7,8-TCDD
2,3,7,8-TCDD
2,3,7,8-TCDD
2,3,7,8-TCDD
Species (Sex)
Dose
T i ssue
Half-Life
(days)
Remarks
Reference

Wistar rat (F)
Wistar rat (M)
Sprague-Dawley rat (H)
Sprague-Dawley rat (F)
C57BL/6J mice (M)
Ahb/Ahr
C57BL/6J mice 
-------
ro
o
00
TABLE 1-5 (cont.)
Chemical
OCDD
Species (Sex)
Fischer 344 rat (M)
BDDs
2,3,7,8-TBDD
CDFs
2,3,7,8-TCDF
2,3,7,8-TCDF
2,3,7,8-TCDF
Fischer 344 rat (M)

Fischer 344 rat (M)
C57BL/6J mice (M)
DBA/2J mice (M)
Dose
50 /ig/kg, i.v.
T i ssue
liver
adipose
skin
Half-Life
(days)
84
38
3
69

0.5 fig/kg, i.v.
(0.001 junol/kg)
liver
adipose
skin
muscle
blood
4.5
16.5
57.8
2.5
57.8
1.6
26.7
18.2

30.6 /ig/kg, i.v.
(0.1 /unol/kg)
30.6 jig/kg, i.v.
(0.1 /unol/kg)
30.6 /ig/kg, i.v.
(0.1 /unol/kg)
liver
adipose
skin
muscle
blood
liver
adipose
skin
muscle
liver
adipose
muscle
0.10
1.25
3.75
0.45
11.09
0.02
0.72
0.02
1.14
1.9
1.6
0.15
4.0
0.015
1.1
1.8
7.0
0.02
4.0
Remarks
Pool size (% of total dose):
72.7
7.1
9.0, 1st component
0.3, 2nd component
Reference
Birnbaum and
Couture, 1988

1st component
2nd component
1st component
2nd component
1st component
2nd component

Pool size (X of total dose)
29.09 1st component
31.39 2nd component
17.85
6.84 1st component
1.22 2nd component
24.85 1st component
6.73 2nd component
1.31 1st component
0.89 2nd component
1st component
2nd component
1st component
2nd component
1st component
2nd component
Kedderis et
al., 1991

Birnbaum et
al., 1980
Decad et a I.,
1981b
Brewster and
Birnbaum,
1988
                                                                                                                                                                                                            8
                                                                                                                                                                                                            •8
                                                                                                                                                                                                            o
                                                                                                                                                                                                            H
VO

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TABLE 1-5 (cont.)
Chemi ca I
1,2,3,7.8-PeCDF











1,2,3,7,8-PeCDF

2,3,4,7,8-PeCDF










2,3,4,7,8-PeCDF
1,2,3,6,7,8-HxCDF

Species (Sex)
Fischer 344 rat (M)











Sprague-Dawley rat (F)

Fischer 344 rat (M)










Sprague-Dawley rat (F)
Sprague-Dawley rat (F)
PCBs
S.S'A.A'-TCB



Sprague-Dawley rat (F)



Dose
34 jig/ kg, i ,v.
(0.1 pmol/kg)










4.0 /ig/kg, p.o.

34 /tg/kg, i.v.
(0.1 junol/kg)









5.6 jig/kg, p.o.
6.0 fig/kg, p.o.
T i ssue

liver

adipose
skin

muscle

adrenal

blood

liver


liver
adipose
skin

muscle


blood


liver
liver
Half-Life
(days)

1.36
25.72
12.91
1.32
14.53
0.03
6.96
0.14
2.36
0.07
12.42
3.3


193
69
0.62
1.23
0.04
0.51
9.84
0.04
1.32
55
108
73
Remarks
Pool size (X of total dose):
42.59 1st component
1.27 2nd component
10.19
7.14 1st component
1.49 2nd component
34.81 1st component
7.42 2nd component
0.26 1st component
0.02 2nd component
5.33 1st component
1.29 2nd component
69.8% of total dose

Pool size (X of total dose):
67.71
10.53
3.54 1st component
1.37 2nd component
29.40 1st component
2.01 2nd component
0.78 3rd component
3.18 1st component
0.37 2nd component
0.008 3rd component
78.3% of total dose
63.4% of total dose

5 mg/kg/day, p.o.,
for 21 days,



liver

adipose

0.8

2.5

21 -Day exposure produced steady
state with 300 ng/g in liver and 8
jig/9 in adipose tissue.
Elimination was assessed over a 22-
day post-exposure period.

Reference
Brewster and
Birnbaum,
1988









Van den Berg
et al., 1989
Brewster and
Birnbaum,
1987








Van den Berg
et al., 1989
Van den Berg
et al., 1989

CLarke et
al., 1984



                                                                                                                                                                                                        D
                                                                                                                                                                                                        O
                                                                                                                                                                                                        •8
                                                                                                                                                                                                        o
                                                                                                                                                                                                        H
                                                                                                                                                                                                        M


                                                                                                                                                                                                        8

                                                                                                                                                                                                        O
                                                                                                                                                                                                        H
                                                                                                                                                                                                        H
                                                                                                                                                                                                        M
VO
10

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Chemical
3,3'4,«'-TCB
TABLE 1-5 (cont.)
Species (Sex)
ICR mice (M)
Dose
8 mg/kg, p.o., every
other day for 10
doses
T i ssue
liver
adipose
serum
Half-Life
(days)
2.15
2.60
1.07
Remarks
Steady state tissue concentrations:
1.5 itg/g
19.2 itg/g
0.04 /19/mL

Reference
Clevenger et
al., 1989
        i.v.  =  Intravenous; s.c. = subcutaneous; i.p. = intraperitoneal; p.o.  * per os
                                                                                                                                                                    D

                                                                                                                                                                    S
                                                                                                                                                                    H


                                                                                                                                                                    8
10
oo
•8
O
00
                                                                                                                                                                    3
                                                                                                                                                                    o
vo
N)

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for the second component (days 49-91)  (see Figure 1-1 and Table 1-5).  Results



of Abraham et  al.  (1988) and Lakshmanan et al.  (1986)  indicate that in the rats,



2,3,7,8-TCDD is more persistent in the adipose tissue than in the liver.  This



is in contrast to the mouse, where liver and adipose tissue have similar half-



lives (Birnbaum,  1986).  2,3,7,8-TCDD is exceptionally persistent  in the adipose



tissue of  the rhesus monkey,  with a half-life  approximately 10-  to  40-fold



greater than that observed in the rat and mouse  (Bowman et al.,  1989).  Thus, the



relative persistence  of 2,3,7,8-TCDD is  tissue  specific and  exhibits marked



interspecies variability.



     Most  of  the pharmacokinetic  data  on the relative persistence of other



congeners  in  Table  1-5  has  been reported in rat  studies,  which  limits inter-



species comparisons.   Results  in  the rat  suggest  that the  distribution and



elimination of 2,3,7,8-TBDD  from tissue are similar to that of 2,3,7,8-TCDD.  The



most persistent congeners are OCDD, 2,3,4,7,8-PeCDF and 1,2,3,6,7,8-HxCDF, which



distribute almost entirely to the liver.   OCDD  and 2,3,4,7,8-PeCDF also exhibit



similar elimination kinetics, with a relative half-life in the liver more than



2-fold greater than that in adipose tissue.  The least persistent congeners are



2,3,7,8-TCDF, 1,2,3,7,8-PeCDF and 3,3'4,4'-TCB.  These congeners exhibit similar



elimination kinetics  in  the rat with  half-lives  in  the adipose tissue greater



than those in  liver.  The relative tissue distribution of these congeners varies,



however, with 2,3,7,8-TCDF  and 1,2,3,7,8-PeCDF distributing  primarily to the



liver, while  3,3',4,4'-TCB distributes predominantly to the adipose tissue.



     The experimental tissue distribution  and elimination data in  Table  1-5 were



obtained  after exposure to  a single congener,  while real world  exposure to



2,3,7,8-TCDD  and related compounds occurs as  a  complex mixture  of congeners.



Recently, Neubert et al.  (1990) examined the persistence of various CDDs  and CDFs



in  hepatic and adipose tissue  of  male  and female marmoset  monkeys.   Animals



received a single subcutaneous exposure to a defined CDD/CDF mixture  (total dose



of  27.8 /jg/kg bw), which contained 0.12 jjg 2,3,7,8-TCDD/kg bw.  Using the I-TE



factors (NATO, 1988;  U.S. EPA,  1989), the total administered dose corresponded



to  0.464 ng I-TE/kg bw.  The  concentrations of specific congeners in liver and




adipose  tissue were  measured at  1,  6,   16  or 28  weeks after  exposure, and



elimination constants and half-lives were estimated assuming first-order kinetics




                                     1-29                             08/11/92

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                          DRAFT—DO NOT QUOTE OR CITE






 (Table 1-6).  Data  in Table 1-6  were determined from pregnant and nonpregnant



 female and male marmosets (total  of 12 animals)  since no obvious differences in



 tissue concentrations were observed among these groups.  All 2,3,7,8-substituted



 CDDs and CDFs were consistently more persistent in the adipose tissue than in the



 liver of marmoset monkeys.   In general,  the persistence  in adipose tissue was



 from  -1.3- to  2.0-fold greater  than that  in liver, with  the  exception  of



 l,2,3,4,7,8-/l,2,3,4,7,9-HxCDF, HpCDFs and OCDF, which were even more persistent



 in adipose tissue.   For the  latter congeners and OCDD, there was marked variance



 in half-life values, which may be due to delayed and incomplete absorption of the



 exceptionally persistent congeners and the relatively short (28 weeks) period of



 investigation.  A significant species difference exists for OCDD and 2,3,4,7,8-



 PeCDF, which, in contrast to the marmoset monkey, was found to  be more persistent



 in the liver of the rat, with half-lives more than 2-fold greater than that in



 adipose tissue  (Birnbaum and Couture,  1988;  Brewster  and Birnbaum, 1987) (see



 Table 1-5).  Further comparison of tissue elimination data in the rat (Table 1-5)



 and  monkey   (Table 1-6)  indicates  that  2,3,7,8-TCDD,   OCDD,  2,3,7,8-TCDF,



 1,2,3,6,7,8-HxCDF and 2,3,4,7,8-PeCDF (adipose tissue only) are more persistent



 in the marmoset monkey than  in the rat.  The exception to this relationship is



 2,3,4,7,8-PeCDF, which is more  persistent  in rat  liver, compared to the monkey.



     The exposure of marmoset  monkeys to a complex  mixture of CDDs  and CDFs



 included exposure to both 2,3,7,8- and non-2,3,7,8-substituted  congeners (Neubert



et al.,  1990).  One week after exposure to this complex mixture, the non-2,3,7,8-



 substituted CDDs and CDFs were present in liver and adipose tissue in relatively



minor quantities when compared with 2,3,7,8-substituted congeners; however, non-



2,3, 7, 8-substituted compounds represented a considerable percent of the exposure



mixture. In this study, none of the non-2,3,7,8-substituted TCDDs, PeCDDs, TCDFs



or PeCDFs could be  detected  in  the liver.  Some of the hexa and hepta congeners



were detected in adipose tissue and liver, but after 1 week, the total amount in



the liver was  >5% of the administered  dose only in the case of 1,2,4,6,8,9-HxCDF.



Similar results  were obtained in  rats after  exposure to a  defined,  complex



mixture of CDDs and  CDFs (Abraham et  al., 1989).  Additional short-term studies



in rats  provide evidence that the  low  tissue concentration  of  non-2,3,7,8-



substituted congeners, measured 1 week after  exposure, were the result of rapid




                                     1-30                             08/11/92

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DRAFT—DO NOT QUOTE OR CITE



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            1-31
08/11/92

-------

Congener
1,2,3,4,7,8.9-HpCDF

OCDF
TABLE 1-6 (cont.)
Hepatic Tissue
Ke 1
(weeks )
0.0088±0.0127
0.004010.0096
Half-Life
(weeks)
79
174
95% Conf . Interval
(weeks)
20-»d
30-»d
Adipose Tissue
K« 1
(weeks'1)
0.0011±0.0112
-0.0042±0.0148
Half-Life
(weeks)
660
«d
95% Conf. Interval
(weeks)
30-»d
28-d
       9Source:  Neubert et al., 1990
 I
ui
NJ
 Animals were treated subcutaneously with a single dose of a defined COO\CDF mixture,  and  the tissues were analyzed at different  times following

 treatment.  Half-lives were calculated from tissue concentrations of the 2,3,7,8-substituted congeners in hepatic and adipose  tissue.  Values
 are given as elimination rate constant K  including estimated SD and half-life including 95% confidence intervals.


Calculated from the time period:  >6 weeks after injection.


 Calculated half-life is apparently infinite.   Data for OCDD and OCDF are unreliable due to delayed absorption.


8Not detected in hepatic tissue 6 weeks after treatment; limits of detection used for calculation
       f,
        Due to interference
O
O

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1
3
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CO
        NA - Not applicable
                                                                                                                                                                O
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                         DRAFT—DO NOT QUOTE OR CITE






elimination, since these congeners were detected at higher levels in the liver



13-14 hours after exposure  (Abraham et al., 1989).   These results in monkeys and



rats are compatible with data from analysis of human tissue samples and milk in



which the  non-2,3,7,8-substituted congeners have  also not  been shown  to  be



present in  significant concentrations, when compared with the 2,3,7,8-substituted



congeners  (Schecter et al., 1985,  1986; Ryan, 1986; Rappe et al., 1986; Beck et



al., 1987,  1988; Thoma et al., 1989).



     A potential problem of  tissue distribution  and  elimination studies after



exposure to a complex mixture of CDDs and CDFs is the possible  interaction of the



mixture during the  uptake  and elimination of  specific congeners from tissues.



A similar hepatic distribution (-25% of dose) and liver/adipose tissue concentra-



tions ratio (~2)  for 2,3,7,8-TCDD were observed in rats 7 days after exposure to



2,3,7,8-TCDD  (100  ng/kg bw)  when the compound was  administered alone  or  in



combination  with a large  amount  of  other CDDs/CDFs  (total 23,222  ng/kg bw)



(Abraham et al., 1988,  1989).   This  suggests  that under  these experimental



conditions,  the  tissue distribution  of 2,3,7,8-TCDD was not  altered when the



exposure included a complex  mixture of CDDs/CDFs.  Van den Berg et al.  (1989)



studied  the hepatic  disposition  and  elimination of  CDFs  when administered



individually (see Table 1-5) and as mixtures.   Co-administration of 1,2,3,7,8-



and 2,3,4,7,8-PeCDF resulted in 46% of the dose of  1,2,3,7,8-PeCDF distributing



to the liver, while 70% was distributed to the  liver after administration  of the



single compound  (see Table 1-5).  Nevertheless, this combined exposure did not



alter the rate of elimination of 1,2,3,7,8-PeCDF from the liver.  Co-administra-



tion of 2,3,4,7,8-PeCDF and  1,2,3,6,7,8-HxCDF did not alter the hepatic uptake



of either  congener  or the  hepatic elimination of 2,3,4,7,8-PeCDF but increased



the hepatic half-life of 1,2,3,6,7,8-HxCDF to 156 days  from the single compound



exposure half-life  of  73 days (see Table  1-5).   However,  these values must be



considered rough estimates  since the experimental period of 42 days was too short



to  accurately  calculate half-lives.   Although  there  are few investigations of



potential  interactions of mixtures of CDDs and CDFs on the uptake and elimination



of  individual  congeners, the limited  available  data  suggests that exposure to



complex mixtures (see Table 1-6) may alter the tissue disposition of individual








                                     1-33                             08/11/92

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                          DRAFT—DO NOT  QUOTE OR  CITE






congeners.  There is clearly a need for more understanding of possible pharmaco-



kinetic interactions of complex mixtures of these and other compounds.



1.2.4.   Dose-Dependent Tissue Distribution.  Recent evidence suggests that the



tissue distribution of  2,3,7,8-TCDD and related compounds  is  dose dependent.



Abraham et al.  (1988) investigated the distribution of  2,3,7,8-TCDD  in liver and



adipose tissue of rats 7 days after a single subcutaneous exposure to 2,3,7,8-



TCDD at doses of  1-3000 ng/kg bw.  Greater than  97%  of  the administered 2,3,7,8-



TCDD was absorbed at all doses, with the exception of the 3000 ng/kg group where



84%  of the  dose was  absorbed.    Figure  1-2  illustrates the dose-dependent



disposition of 2,3,7,8-TCDD in liver and adipose  tissue (% dose/g)  7 days after



exposure.  A sharp increase in 2,3,7,8-TCDD concentration in liver was observed



at exposure levels  >10 ng/kg bw.   Disposition in the liver increased from -11%



of the administered dose at an exposure  level  of 1-10 ng/kg bw to -37% of the



dose at an exposure level  of 300  ng/kg bw.  The increase in distribution to the



liver was accompanied by a dose-related decrease in the  concentration of 2,3,7,8-



TCDD in the adipose  tissue.  As a  result,  the liver/adipose tissue concentration



ratio for 2,3,7,8-TCDD at 7 days after exposure  increased with increasing doses,



starting at an exposure level of 30 ng/kg bw  (Table  1-7).  Thus,  the tissue-



specific disposition of 2,3,7,8-TCDD is regulated by a complex relationship,



which includes species, time after a given exposure and dose (see Figures 1-1 and



1-2; Tables 1-5 and 1-6).




     Other  studies  on  the tissue disposition  of 2,3,7,8-TCDD   and  related



compounds report  similar dose-dependent behavior with disproportionally greater



concentrations in the liver at high doses compared with low doses. Poiger et al.



(1989) observed  a  dose-related  increase in  distribution to  the  liver  (%  of



dose/liver) and/or an increase in the liver/adipose tissue concentration ratio




for 2,3,7,8-TCDD, 2,3,4,7,8-PeCDF,  1,2,3,7,8-PeCDF  and 1,2,3,6, 7,8-HxCDF in the



rat.  Kedderis et al.  (1991a)  also observed a dose-related increase in hepatic




disposition (1.27 versus 10.05 % of dose/liver)  and an increase in the liver/



adipose tissue concentration ratio (0.16  versus 2.59) for 2,3,7,8-TBDD at 56 days



after exposure at doses of 0.001 and 0.1  /jmol/kg bw, respectively.   In a related



study, pretreatment of  mice with 2,3,7,8-TCDD (5  or 15 /jg/kg)  produced a dose-



related, enhanced hepatic accumulation of a subsequent  oral dose of 2,3,7,8-TCDD




                                     1-34                             08/11/92

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                          DRAFT—DO NOT QUOTE OR CITE
                                  FIGURE 1-2

     Dose Dependency of the Percentage of the Administered Dose of  14C-TCDD/g of
Tissue Recovered in  Liver and Adipose Tissue After  Single  Subcutaneous Doses
(values from  animals treated with 3000 ng  TCDD/kg bw were corrected  for 84%
absorption).  Concentrations were measured 7 days after the injection.

Source:  Abraham et al., 1988
                                     1-35
OB/11/92

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                             DRAFT—DO  NOT  QUOTE OR CITE
TABLE 1-7
2,3,7,8-TCDD Concentrations in Liver and Adipose Tissue Following Different Doses and Calculated
Concentration Ratios (Liver/Adipose Tissue)8'
Dose
(ng/kg)
1
3
10
30
100
300
1000
3000
Number
6
6
12
6
6
6
6
5
TCDD Concentration
Liver
(ng/g)
0.0031*0.0009
0.0102±0.0020
0.0406±0.0121
0.162±0.032
0.699*0.130
3.38±0.22
10.7*2.2
27.9±2.4
TCDD Concentration
Adipose Tissue
(ng/g)
ND
0.0139±0.0015
0.0494*0.0084
0.139*0.021
0.335*0.065
0.819*0.075
2.02*0.17
3.66*0.31
Concentration Ratio:
Liver/Adipose Tissue
NA
0.74*0.15
0.82*0.20
1.16*0.07
2.10*0.27
4.14*0.31
5.27*0.96
7.65*0.64
Source:  Abraham et al., 1988



Concentrations were measured 7 days after injection



ND =  Not detectable; NA = not applicable
                                            1-36
08/11/92

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                          DRAFT—DO  NOT QUOTE OR CITE






(Curtis et al.,  1990).   Similarly, a dose-related increase in hepatic uptake of



[12^I]-2-iodo-3,7,8-trichlorodibenzo-p-dioxin was observed after pretreatment of




mice with 2,3,7,8-TCDD  (Poland et al.,  1989; Leung et al., 1990).  Shen and Olson



(1987)  also  observed an  increase  in the uptake  of 2,3,7,8-TCDD  by  isolated



hepatocytes from 2,3,7,8-TCDD pretreated mice.



     Chronic  studies also  support  dose-dependent  alterations in  the  tissue



distribution of these compounds.  Kociba et al.  (1978a,b) found  that  female rats



maintained on a daily dietary 2,3,7,8-TCDD intake of 100 ng for 2 years had an



average 2,3,7,8-TCDD content of  8100  ppt in fat and 24,000 ppt  in the liver.



Rats given 10 ng/kg/day had an average of 1700 ppt 2,3,7,8-TCDD in the fat and



5100 ppt  in the liver.   For both  of these exposures the liver/ adipose tissue



concentration ratio  of 2,3,7,8-TCDD was  -3.   At the  lowest  dose  level  of 1



ng/kg/day, both  fat  and  liver contained  an average of  540 ppt  2,3,7,8-TCDD.



Kociba et al.  (1976) presented evidence that steady state had been  reached by <13




weeks of  feeding of 2,3,7,8-TCDD.



     Other studies  do  not  support  the dose-dependent  tissue  distribution of



2,3,7,8-TCDD and related compounds described above.  Rose et al. (1976) reported




a lack of a dose-dependent accumulation of ^C-TCDD in male and  female rat liver




and adipose tissue following 7, 21  and 49 days of exposure at 0.01, 0.1 or 1.0



pg/kg/day, Monday through Friday.   The rates  of  accumulation  of TCDD-derived



radioactivity were similar in fat, liver and whole body;  however, the concentra-




tion in the liver was -5-fold greater than that in fat.  Recently, Clark et al.



(1991)  and Tritscher et  al.  (1992)  also reported a lack of  a dose-dependent



hepatic disposition  of  TCDD in  female Sprague-Dawley rats exposed biweekly to



TCDD for  30 weeks at doses equivalent to 3.5, 10.7, 35.7 and 125 ng/kg/day.  A



linear relationship between administered dose and the concentration in the liver



was observed over the dose range used  in this chronic exposure  study.  Brewster



and Birnbaum  (1987) also observed similar concentrations  (% dose/g) of 2,3,4,7,8-



PeCDF in  liver, adipose tissue and  other tissues at 3 days after oral exposure




at doses  of 0.1, 0.5 or 1.0 pmol/kg bw.  These results conflict with the above



studies which support the dose-dependent tissue distribution of  these compounds.
                                     1-37                             08/11/92

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                          DRAFT—DO NOT QUOTE OR CITE






While it is not possible at this time to explain these differences, most of the



available data support a dose-dependent relationship.



     The dose-dependent tissue distribution of 2,3,7,8-TCDD and related compounds



is a critical factor that must  be  considered  in estimating the concentration of



these compounds  in human tissues  after chronic low-level exposure.   This is



particularly important since the  general  human population is  exposed to much



smaller daily doses  (possibly  0.3 pg 2,3,7,8-TCDD/kg/day) than  those used in



experimental disposition studies.   Due  at  least partly to the long half-life of



2,3,7,8-TCDD in humans, however, this exposure results  in concentrations of 3-18



pg/g in human adipose tissue (Leung et al., 1990).  Similar levels of 2,3,7,8-



TCDD in adipose  tissue  (14 pg/g) were observed in rats  7 days after subcutaneous



exposure to  3  ng/kg bw  (see Table  1-7) (Abraham et al.,  1988).   Under these



experimental conditions,  the liver/adipose tissue 2,3,7,8-TCDD concentration was



0.74.   Nonetheless,  steady  state was definitely  not   reached under  these



conditions, and, with increasing time after exposure,  this ratio may decrease,



based on the observation  that 2,3,7,8-TCDD  was more persistent in adipose tissue



than in liver in rats  exposed  to  300 ng/kg bw  (see Figure 1-1 and Table 1-5)



(Abraham et al.,  1988).  Human data on the liver/adipose  tissue concentration



ratio of 2,3,7,8-TCDD  and  related compounds are limited but suggest  that the



ratio may vary by at least  an order  of magnitude between individuals.  Leung et



al. (1990)  observed a geometric mean adipose tissue 2,3,7,8-TCDD concentration



of 7.78 ppt in 26 individuals and a concentration in  liver at about one-tenth of



that in adipose tissue  on a whole  weight basis.  When measured on a total lipid



basis,  the  concentrations of 2,3,7,8-TCDD in both tissues were approximately the



same.  More  variability  between  individuals was  observed in the CDD  and CDF



concentrations in liver and  adipose tissue  from 25 subjects from the Munich area



(Thoma et al., 1989).  For example, the  liver/adipose tissue concentration ratio



for 2,3,7,8-TCDD  was >1.0  for  5  of the 25 individuals (Thoma et  al.,  1989).



While the majority of individuals  had liver/adipose tissue concentration ratios



<1.0 for CDDs and CDFs, ratios  >1.0 were observed for  HpCDD (5  of 25), OCDD (2



of 25), PeCDF (2  of 25), HxCDF (1 of 25),  HpCDF  (7  of  25)  and  OCDF (3 of 25).



Considerable variability in CDD  and CDF  concentrations  in liver  and adipose



tissues was also observed between  individual marmoset  monkeys (Neubert et al.,




                                     1-38                              08/11/92

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                          DRAFT—DO NOT QUOTE OR CITE





1990),  suggesting that  individual  variability  may  also  contribute to  the



difficulty in assigning a constant liver/adipose tissue ratio for CDDs and CDFs



in humans and nonhuman primates.



1.2.5.   Potential Mechanisms for the Dose-Dependent Tissue Distribution.  The



observation that exposure to higher doses  of 2,3,7,8-TCDD and related compounds



results in a disproportionally greater hepatic  concentration of these compounds



may be explained by a hepatic binding  species that is induced by 2,3,7,8-TCDD and



other agonists for the Ah receptor. The studies of Voorman and Aust  (1987, 1989)



and  Poland et  al.  (1989a,b)  provide evidence that  this binding  species is



cytochrome P-4501A2.



     Poland et al. (1989) reported that TCDD and other Ah agonists  (2, 3,7,8-TCDF,



B-naphthoflavone, 3,3',4,4',5,5'-hexabromobiphenyl) act through the Ah receptor



to  increase a  liver binding species that  increases the hepatic  uptake of



[12^I]-2-iodo-3,7,8-trichlorodibenzo-p-dioxin (a radiolabeled isosteric analogue




of TCDD) in vivo and binding  of this  radioligand to liver  homogenate  in  vitro.



Twenty-four hours after the administration of a non-AHH-inducing dose (1x10"



mol/kg) of  [125I]-2-iodo-3,7,8-trichlorodibenzo-p-dioxin  to C576BL/6J mice, the




hepatic concentration of radioactivity was 1-2% of the administered dose, whereas



in mice pretreated  48  hours earlier  with  an AHH  inducing dose of TCDD  (1x10"'



mol/kg), the hepatic accumulation of  radiolabel was 25-30% of that administered.



A similar, though  less  dramatic  effect, was  observed  in  vitro,  with  liver


                                                                  19S
homogenate from TCDD-treated mice binding about four times more [*  I]-2-iodo-



3,7,8-trichlorodibenzo-p-dioxin than  homogenate from control mice.  The adminis-



tration of  TCDD to C57BL/6J mice produced a dose-related  stimulation of in vivo



hepatic  uptake  of  [125I]-2-iodo-3,7,8-trichlorodibenzo-p-dioxin,   increased



binding of radioligand to  liver homogenate and induction  of hepatic activity,



with an ED5Q ranging from 1.5 to 4.0xlO"9 mol/kg.   In congenic C57BL/6J (Ahd/Ahd)




mice, which express the lower affinity Ah  receptor, the £050 values for all three




 responses were shifted to  doses that were about  10-fold  higher.   The observed



 effects on hepatic disposition were tissue specific, with no remarkable disposi-



 tional changes  being observed in kidney, lung, spleen,  small intestine or muscle.





                                      1-39                             08/11/92

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                          DRAFT—DO NOT QUOTE  OR CITE





This is significant in that TCDD and other agonists for the Ah receptor induce



cytochrome P-4501A1 in liver and other tissues, whereas cytochrome P-4501A2 is



apparently inducible only  in  liver and nasal  olfactory mucosa (Tuteja et al.,



1985; Gillner et al. 1987).  Furthermore, the changes in hepatic disposition were



not species specific; similar  responses were observed in guinea pigs, rats, mice



and hamsters  (Poland et al., 1989).



     The  following evidence  reported  by  Poland et  al.  (1989)  supports  the



hypothesis  that  the  TCDD-inducible  hepatic  binding  protein   is  cytochrome



P-4501A2:  the TCDD-induced hepatic binding species was found predominantly in



the microsomal  fraction  and was inactivated  by heating at  60°C,  trypsin and



mercurials; the TCDD-induced hepatic binding species was specific for the liver,



with a  large  pool size  (Bmax  of 22±5 nmol/g  liver);  and  the major microsomal



binding species covalently labeled  with the photo-affinity ligand [^I]-2-iodo-



3-azido-7,8-dibromodibenzo-p-dioxin migrates with that immunochemically stained



with polyclonal antiserum that binds to cytochrome P-4501A2.



     One observation of Poland et al. (1989) does not support  the hypothesis that



the TCDD-inducible hepatic protein  is cytochrome P-4501A2.  These investigators



found that dietary administration of isosafrole did not stimulate hepatic uptake

    1 ye
of [1'"l]-2-iodo-3,7,8-trichlorodibenzo-p-dioxin or the in  vitro binding of this



ligand to liver homogenate.  Isosafrole is not an agonist for the Ah receptor,



but it selectively induces cytochrome P-4501A2 (Ryan et al., 1980).  Poland et



al. (1989) suggest that this may be attributable to the high affinity binding of



an isosafrole metabolite  to the protein,  which might inhibit the  binding of


 19S
[1'"I]-iodo-3,7,8-trichlorodibenzo-p-dioxin to cytochrome P-4501A2 at or near the



active site of the enzyme.   This  does not explain why  TCDD, which also has high



affinity  for  cytochrome  P-4501A2,  cannot displace  some  of the  isosafrole



metabolite from the protein, which should produce enhanced hepatic disposition



of TCDD.



     Voorman and Aust (1987, 1989) support further the hypothesis that cytochrome



P-4501A2  is the  TCDD-inducible hepatic binding  species.  These investigators



found that 3,3'4,4'5, B'-HxBB, an agonist for the Ah receptor,  was associated only



with cytochrome P-4501A2 through the immunoprecipitation of cytochromes P-4501A1




                                     1-40                             08/11/92

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                          DRAFT—DO  NOT  QUOTE  OR CITE





and 1A2, which were induced in 3,3'4,4'5,5'-HxBB treated rats.  In addition, they



found  that  3,3'4,4'5,5'-HxBB  inhibited estradiol  2-hydroxylase  activity  of



purified cytochrome P-4501A2.  A similar association of PAHs with immunoprecipi-



tated cytochrome P-4501A2 was observed for other agonists for the Ah receptor,



including 2,3,7,8-TCDD,  3,3' ,4,4'-TCB, 3,3 ' ,4,4 ' , 5-PeCB and 3,3 ' ,4,4', 5,5 '-HxCB.



The  association of 2,3,7,8-TCDD  with cytochrome  P-4501A2  occurred  within 2



minutes,  with  maximum  inhibition  of estradiol  2-hydroxylase occurring  at a



concentration comparable to the concentration of the enzyme  (50 nm).  Cytochrome



P-4501A2 was inhibited (complexed) by 2,3,7,8-TCDD with nearly  1:1 stoichiometry



and the Kj for 2,3,7,8-TCDD  was calculated to be 8 nM.  Therefore, 2,3,7,8-TCDD




can be considered a higher binding inhibitor of cytochrome P-4501A2.



     The TCDD-induced binding species was found  to have an apparent equilibrium


                           19S
dissociation constant, KJ-J, [ 1-"I]-2-iodo-3,7,8-trichlorodibenzo-p-dioxin of 56±16




nM and a  pool size, Bmax, of  22±5 nmol/g of  liver in C57BL/6J mice (Poland et




al., 1989).   The  induced microsomal binding  species has  an affinity about  10




times less than the Ah receptor but a pool size that  is -2x10^ greater.  Thus,




agonists for the Ah receptor may significantly affect  their disposition through



a  dose-related  enhancement of  hepatic uptake  which should correlate  with



induction of cytochrome P-4501A2.



     The disposition and pharmacokinetics of 2,2' ,4,4',5,5'-HxCB and -HxBB have



been investigated  in  several species  (Tuey  and Matthews,  1980;  Lutz et  al.,



1984).   These lipophilic compounds are similar to 2,3,7,8-TCDD in that they are



slowly metabolized  and that  metabolism is required  for urinary  and biliary



elimination.   2,2',4,4',5,5'-HxCB and  -HxBB  distribute  primarily  to adipose



tissue with  partition coefficients (tissue/blood ratio) ranging from 300-500 in



the mouse, rat, monkey, dog and human.   The  liver  is  not a major site for the



disposition of  2,2',4,4',5,5'-HxCB  and  -HxBB,  in contrast  to 2,3,7,8-TCDD and



related compounds. Partition coefficients in the liver range from 10-30 in these



species.  2,2' ,4,4' ,5,5'-HxCB and -HxBB do not induce hepatic cytochrome P-4501A1



or 1A2  and do not exhibit dioxin-like activity.  The lack of induction of hepatic



cytochrome P-4501A2 may explain the lack of  a dose-dependent hepatic disposition



of these compounds.




                                     1-41                             08/11/92

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     Kedderis et al.  (1991b)  assessed the dose-response relationship for the



induction of hepatic cytochrome P-4501A1 and P-4501A2 in male Fischer 344 rats



exposed to  2,3,7,8-TBDD  at doses as  low  as  0.1  nmol/kg.  They  reported that




induction of P-4501A2 by 2,3,7,8-TBDD appeared to be a more sensitive response



than P-4501A1 induction over the dose-range studied.   In addition, comparison of



hepatic P-4501A2 levels and liver:adipose tissue concentration ratios suggested



that induction of P-4501A2  alone would not directly account  for the preferential



hepatic accumulation of 2,3,7,8-TBDD, and additional factors must be involved.



One  explanation may be  that at  low 2,3,7,8-TBDD  concentrations,  endogenous



substrates bind to CYP1A2, not allowing  2,3,7,8-TBDD  to  be sequestered by the



protein (Birnbaum,  1992).   At higher 2,3,7,8-TBDD  concentrations,  new protein is



formed and  2,3,7,8-TBDD  can compete  for  binding to CYP1A2, resulting in the



increased  hepatic  deposition  observed  at  higher  exposures of 2,3,7,8-TBDD




(Kedderis et al., 1991a).



     Other factors may also regulate  the  intracellular distribution of 2,3,7,8-



TCDD  and  related  compounds.   The  possible role of hepatic  lipoproteins  as



intracellular carriers in the transport  of 2,3,7,8-TCDD has been  assessed by in



vitro and in vivo studies (Soues et al., 1989a,b).   2,3,7,8-TCDD and 2,3,7,8-TCDF



were bound to lipoproteins in mouse and  rat liver, which subsequently underwent



rapid and pronounced degradative processing, possibly catalyzed  by lipoprotein



lipase, to heavier entities.  The in vitro incubation  of 2,3,7,8-TCDD-lipoprotein



complex with separated Ah receptor demonstrated that a passive  transfer occurred.



The  authors  suggest a  carrier-role for lipoproteins  in  the  intracellular



transport of 2,3,7,8-TCDD  and related compounds.



1.3.   METABOLISM AND EXCRETION



     Although early in vivo and in vitro  investigations were unable to detect the



metabolism  of 2,3,78-TCDD  (Vinopal and Casida, 1973; Van Miller  et al.,  1976),



there is evidence that a wide range of mammalian and  aquatic species are capable



of biotransforming 2,3,7,8-TCDD to polar metabolites (Ramsey et  al.,  1979,  1982;



Poiger and  Schlatter,  1979; Olson et  al., 1980; Olson, 1986; Gasiewicz et al.,



1983; Poiger et al.,  1982; Sijm  et  al.,  1990;  Kleeman et al.,  1986a,b,  1988).



Although metabolites of 2,3,7,8-TCDD have not been directly identified in humans,








                                      1-42                              08/11/92

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                          DRAFT—DO NOT  QUOTE OR  CITE






recent data  regarding feces samples  from humans in  a  self-dosing experiment



suggests that humans can metabolize 2,3,7,8-TCDD (Wendling et al., 1990).



     Table 1-8 summarizes data on the metabolism and excretion of 2,3,7,8-TCDD



and  related  compounds after  exposure  to  a  single radiolabeled  congener.



Investigations of 2,3,7,8-TCDD  in rats, mice, guinea pigs and hamsters found that



>90% of the radiolabeled material excreted in urine and bile represented polar



metabolites.  Similar results were also  observed  for other congeners (see Table



1-8), with the exception of OCDD; however, although studies were often limited



to the rat.  OCDD is apparently not metabolized by the rat or metabolized to a



very minimal extent  (Birnbaum and Couture, 1988).  For all of the congeners in



Table 1-8, essentially all of the  CDD, BDD, CDF or PCB-derived radioactivity in



liver, adipose tissue and other tissues  represented parent compound, suggesting



that the metabolites of these compounds were readily excreted.  Thus, with the



exception  of  OCDD,   the  metabolism of  2,3,7,8-TCDD  and related  compounds is



required for urinary and biliary elimination and therefore plays a  major role in



regulating  the rate  of  excretion  of  these  compounds.   In  addition,  direct



intestinal  excretion of  parent  compound  is  another  route for  excretion of



2,3,7,8-TCDD and related compoundst that is not regulated by metabolism.



1.3.1.   Structure  of  Metabolites.  Several metabolites  of 2,3,7,8-TCDD have



recently  been  identified,   Sawahata  et al.  (1982) investigated  the  in vitro




metabolism of 2,3,7,8-TCDD in isolated rat hepatocytes.  The major product was



deconjugated with B-glucurpnidase, derivatized with diazomethane and separated



into two compounds by HPLC.  These metabolites were subsequently identified as



l-hydroxy-2,3,7,8-TCDD and 8-hydroxy-2,3,7-trichlorodibenzo-p-dioxin.  Poiger et



al.  (1982b)  identified six metabolites  in the bile of  dogs that  were given a



lethal dose of [%]-2,3,7,8-TCDD.  The major metabolite was 1,3,7,8-tetrachloro-




2-hydroxydibenzo-p-dioxin; however, 3,7,8-trichloro-3-hydroxydibenzo-p-dioxin and



l,2-dichloro-4,5-hydroxybenzene  were identified  as  minor  metabolites.   The



structures of the three remaining metabolites were not determined; however, two



appeared to be trichlorohydroxydibenzo-p-dioxins and the third was apparently a



chlorinated 2-hydroxydiphenyl ether.  Poiger and Buser  (1984) reported differ-



ences in the relative amounts of various 2,3,7,8-TCDD metabolites in dog and rat








                                     1-43                             OB/11/92

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TABLE 1-8
Metabolism and Excretion of 2,3,7,8-TCDD and Related Compounds8
Chemical
Spec i es
Dose
CDDs
2,3,7,8-TCDD
2,3,7,8-TCDD
2,3,7,8-TCDD
2,3,7,8, -TCDD
2,3,7,8-TCDD
2,3,7,8-TCDD
2,3,7,8-TCDD
2,3,7,8-TCDD
2,3,7,8-TCDD
2,3,7,8-TCDD
2,3,7,8-TCOD
Sprague-Dawley
rat (M)
Sprague-Dawley
rat 
Sprague-Dawley
rat (F)
Sprague-Dawley
rat (M, F)
Sprague-Dawley
rat (M, F)
Han/Wistar rat
(M)
Long-Evans rat
(M)
Sprague-Dawley
(M)
C57BL/6J mice
(M)
DBA/2 J mice
(M)
B6D2F1J mice

50 fig/kg, P.O.
7 or 72 ppb
in diet for
42 days
7 or 72 ppb
in diet for
42 days
1.0 jig/kg,
p.o
0.1 and 1.0
/ig/kg/day,
5 days/week
for 7 weeks
5 /ig/kg, i.p.
5 M9/kg, i.p.
500 /ig/kg, i.p.
10 /tg/kg, i.p.
10 /ig/kg, i.p.
10 /ig/kg, i.p.
Chemical Nature of
Excretion Products
(% Metabolites)
Urine

NA
NA
NA
NA
NA
>90
>90
100
100
100
100
Bile

NA
NA
NA
NA
NA
NA
NA
100
100
100
100
Feces
Ratio of % of
Dose Excreted
(Feces/Urine)

NA
NA
NA
NA
NA
"70-90
"20-90
NA
85
82
86
4.0
NA
NA
9.9
8.5
14.1
12.0
NA
2.7
1.2
2.5
Half-Life6
(days)

17.4±5.6C
12
15
31±6d
23.7
21.9
20.8
NA
11.0t1.2d
24.4±1.0d
12.6±0.8d
Comment

NC
NC
NC
NC
NC
NC
NC
NC
NC
NC
NC
Reference

Piper et al.,
1973
Fries and
Morrow, 1975
Fries and
Morrow, 1975
Rose et al.,
1976
Rose et a I.,
1976
Pohjanvirta
et al., 1990
Pohjanvirta
et al., 1990
Neal et al.,
1982
Gasiewicz et
al., 1983
Gasiewicz et
al., 1983
Gasiewicz et
al., 1983
                                                                                                                                                                                                                       O
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TABLE 1-8 (cont.)
Chemical
2,3,7,8-TCDO
2,3,7,8-TCDD
2,3,7,8-TCDD
2,3,7,8-TCDO
2-Iodo-3,7,8-TCDD
2-Iodo-3,7,8-TCDD
2,3,7,8-TCDO
2,3,7,8-TCDO
2,3,7,8-TCDD
2,3,7,8-TCDD
Species
C57BL/6J mice
AhD/Aha (M)
C57BL/6J mice
Aha/Aha (M)
DBA/2J Ahb/Ahd
(F)
DBA/2J Ahd/Ahd
(F)
C57BL/6J mice
(F)
C57BL/6J mice

-------
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TABLE 1-8 (cont.)
Chemical
2,3,7,8-TCOD
2,3,7,8-TCDD
2,3,7,8-TCDD
2,3,7,8-TCOD
1,2,3,7,8-PeCOD
OCDD
OCDO
BDDs
2,3,7,8-TBDD
Species
Golden Syrian
hamster (M)
human (M)
rainbow trout
yellow perch
Sprague-Dawley
rat (M, F)
Fischer 344 rat

Fischer 344 rat
(M)

Fischer 344 rat
(M)
Dose
[3H] 650
/ig/kg, p.o.
1.14 ng/kg,
p.o.
494 ppt in diet
for 13 weeks
494 ppt in diet
for 13 weeks
8.42-10.06
Jig/kg, p.o.
50 pg/kg, iv
50 /ig/kg/day,
p.o., for 10
days
Chemical Nature of
Excretion Products
(X Metabolites)
Urine
NA
NA
NA
NA
NA
<33
NA
Bile
NA
NA
"75
'90
100
0
NA
Feces
NA
"50
NA
NA
NA
0
NA

0.001 junol/kg,
iv
NA
100
80-90
Ratio of X of
Dose Excreted
(Feces/Urine)
NA
>3.1
NA
NA
12
>65
NA
Half-Life6
(days)
14.96±2.53
2120e
105
126
29.5±2.7
'70
"173

11.1
0.7
2.9
17.8

Comment
NC
NC
elimination followed
for 13 weeks following
exposure
elimination followed
for 13 weeks following
exposure
NC
whole body t^
estimated from body
burden in liver, skin
and adipose tissue over
56-day period
whole body t^
estimated from body
burden in liver, skin
and adipose tissue over
112-day period

Pool size (X of dose):
11.63 1st component
2.78 2nd component
1 .45 3rd component

Reference
Olson et at.,
1980; Neal et
al., 1982
Poiger and
Sch latter,
1986;
Wend 1 ing et
al., 1990
K Iceman et
al., 1986
Kleeman et
al., 1986
Wacker et
al., 1986
Birnbaum and
Couture, 1988
Birnbaum and
Couture, 1988

Kedderis et
al., 1991
                                                                                                                                                                                                                        D
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            1-47
08/11/92

-------

Chemical
2,3,4,7,8-PeCDF
CBs
3,3'4,4'-TCB
3,3'4,4'-TCB
TABLE 1-8 (cont.)
Species
rhesus monkey
(M)

CD rat (M, F)
rhesus monkey
(F)
Dose
0.1 pmol/kg, iv
Chemical Nature of
Excretion Products
(X Metabolites)
Urine
NA
Bile
NA
Feces
63-70
Ratio of % of
Dose Excreted
(Feces/Urine)
"34

0.6 mg/kg, iv
0.6 mg/kg, iv
>90
97
NA
NA
>90
97
42
7.2
Half-Life13
(days)
38-49

"1.3-1.5
"8-10

Comment
t^/2 represents minimum
value; all animals lost
body weight and
exhibited other signs
of toxicity
Reference
Brewster et
al., 1988

NC
NC
Abdel-Hamid
et al., 1981
Abdel-Hamid
et al., 1981
aAll studies measure the excretion of radiolabeled parent compound and metabolites following exposure to a single congener labeled with H, C or
1 •

'•'Half-life for excretion estimates assume first-order elimination kinetics

c(mean±SE)

d(mean±SD)

§
s
M
O
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O
M
M
      en=1

       i.p. = Intraperitoneal;  i.v. =  intravenous; NA = not available; NC = no  comment;  p.o.  = per os
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                          DRAFT—DO  NOT QUOTE  OR  CITE






bile. Trichlorodihydroxydibenzo-p-dioxin and tetrachlorodihydroxydiphenyl ether



appear to be major metabolites in rat bile.   Furthermore, conjugates, presumably



glucuronides,  were formed in the rat but not in the dog.  The investigators also




observed a generally higher  metabolism rate of 2,3,7,8-TCDD in the dog.  This is



in good  agreement  with  the unique  ability of the dog to  readily metabolize



persistent PCBs such as 2,4,5,2'415'-HxCB (Sipes et al., 1982).



     Biliary metabolites of  2,3,7,8-TCDF have been investigated by Poiger et al.



(1984); however, unequivocal structure assignment of the metabolites could not



be made using  GC/MS.  With the use  of synthetic standards and GC/MS, Burka et al.



(1990)  identified  4-hydroxy-2,3,7,8-TCDF  and  3-hydroxy-2,7,8-TCDF as  major



biliary metabolites of 2,3,7,8-TCDF in rats.  Small amounts of 3-hydroxy-2,4,7,8-



TCDF and 2,2 '-dihydroxy-4,41, 5,5 '-TCB were also detected.  This suggests that the



preferred  site  of metabolism of  2,3,7,8-TCDF is  near  the  furan oxygen with



oxygenation at C4 predominating over C3.  The authors speculate that epoxidation



of the  C4-C4a bond  or  the C3-C4 bond  could  lead  to formation  of  the above



metabolites.   The  results  of Burka  et  al.  (1990)  and  Sawahata  et al.  (1982)



suggest that oxygenation of  the unsubstituted carbon nearest the bridging oxygen



in both 2,3,7,8-TCDF and 2,3,7,8-TCDD is  the major route of metabolism of these



compounds  in  the rat.   Furthermore, data on  the  rate of  elimination of these



compounds summarized in Tables 1-5 and 1-8 indicate that  this reaction occurs at



a faster rate for the furan, since the rate of urinary and biliary elimination



and resulting persistence of these compounds depends on metabolism.



     Data  summarized in Tables 1-5  and  1-8  indicate that  1,2,3,7,8-PeCDF is



metabolized  and  eliminated at  a  greater  rate  than  2,3,4,7,8-PeCDF.    The



preference for oxygenation  at C4 in 2,3,7,8-TCDF offers an explanation for the



observation that 2,3,4,7,8-PeCDF is metabolized at  a  much  slower  rate than



1,2,3,7,8-PeCDF, because one of the preferred sites for metabolism is blocked in



the 2,3,4,7,8-substituted compound.  The rate of metabolism of these compounds



and their  resulting  relative persistence in rodents correlate with analysis of




human  tissues from  the  Yusho cohort where the  relative  concentrations were



2,3,4,7,8-PeCDF > 1,2,3,7,8-PeCDF > 2,3,7,8-TCDF  (Masuda et al.,  1985).




     Pluess et al.  (1987) investigated the structure of  1,2,3,7,8-PeCDF metabo-



lites in rat bile.  A dihydroxy-tetra-CDF was identified as the major metabolite.




                                     1-49                             08/11/92

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                          DRAFT—DO NOT  QUOTE OR  CITE






The  authors propose  that this compound  could be  formed either  via further



oxidation of the hydroxy-tetra-CDF or possibly  via hydrolytic dechlorination of



a hydroxy-penta-CDF.  Minor  metabolites include  a  dihydroxy-tri-CDF, hydroxy-



tetra-CDF and hydroxy-penta-CPF.




     Pluess et al. (1987) also investigated the metabolites of 2,3,4,7,8-PeCDF



in rat bile.  A total of  10 metabolites  were detected with a dihydroxy-penta-CB



and  a hydroxy-penta-CDF  representing  the  major metabolites.   The biphenyl



metabolite  indicates that cleavage  of  the ether  bridge of  the furan  is an



important pathway for metabolism of this congener.  Other less abundant metabo-



lites  of  2,3,4,7,8-PeCDF  include  a  hydroxy-tetra-CDF,  dihydroxy-tri-CDF,



dihydroxy-tetra-CDF  and  a thio-tetra-CDF.   Sulfur-containing  metabolites were



also identified as minor metabolites of 2,3,7,8-TCDF and 1,2,3,7,8-PeCDF in rats



(Kuroki et al., 1990). These sulfur-containing metabolites probably arise from



CDF-glutathione conjugates.



     In another study, a dihydroxy-PeCDF was identified as the only detectable



biliary metabolite of 1,2,3,6,7,8-HxCDF, while  no metabolites of 1,2,3,4,6,7,8-



HpCDF were  detected  in the  bile of rats that  were  treated  with this congener



(Poiger et al., 1989).



     Several in vivo and  in  vitro studies  have investigated the metabolism of



3,3',4,4'-TCB.  Rat  feces were found to contain 5-hydroxy-3,3',4,4'-TCB and 4-



hydroxy-3,3'4',5-TCB  as  major  metabolites   (Yoshimura  et  al.,   1987)  and



2,5-dihydroxy-3,3',4,4'-TCB,    4,4'-dihydroxy-3,3'5,5'-TCB,    5,6-dihydroxy-



3,3',4,4'-TCB, 4-hydroxy-3,3',4-TCB  and 4-hydroxy-4',5'-epoxy-3,3'4',5-TCB as



minor metabolites (Koga et al., 1989).



     Mouse feces were found to contain 5-hydroxy- and 6-hydroxy-3,3' ,4,4'-TCB and



4-hydroxy-3,3 ' ,4'5-TCB while urine contained 2-hydroxy-3,3 ' ,4,4'-TCB in addition



to these metabolites  (Wehler  et al., 1989).  3,3'4,4'-TCB was the major compound



present in mouse liver, while a minor  portion was due to 4-hydroxy-3,3'4,4'-TCB



(Wehler et al., 1989). Darnerud et  al.  (1986)  found 2-hydroxy-3,3'4,4'-TCB and



a  methylsulphonyl-TCB as major  metabolites  in the  mouse fetus.    Sulphur-



containing metabolites of noncoplanar PCBs have also been reported to accumulate



in the bronchial mucosa and uterine luminal fluid of mice  (Bergman et al., 1979;



Brandt et al., 1982)  and in human lung,  liver and adipose tissue (Haraguchi et




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al., 1986,  1989).  PCB methyl sulphones are stable lipophilic metabolites formed



by  the  mercapturic  acid  pathway.   The  toxicological  significance of  these




metabolites remains generally unknown.



1.3.2.   Toxicity of Metabolites.   The  above  discussion indicates that  the



metabolism of  2,3,7,8-TCDD  and  related compounds is required  for urinary and



biliary elimination  and thus plays  a  major  role  in  regulating the  rate of



excretion  of  these  compounds.    At present,  metabolism  is  also  generally




considered a detoxification process.



     Data  on the metabolism  of  2,3,7,8-TCDD  suggests that reactive  epoxide



intermediates may be formed.  Poland  and Glover  (1979) have investigated the in



vivo  binding of  [l,2-3H]-2,3,7,8-TCDD  derived  radioactivity  to  rat  hepatic




macromolecules, and  found  maximum  levels equivalent  to  60 pmol  of 2,3,7,8-



TCDD/mol of nucleotide in RNA, and 6 pmol of 2,3,7,8-TCDD/mol of nucleotide in




DNA.  This corresponds to one  2,3,7,8-TCDD-DNA adduct/35 cells.  These investi-



gators  suggest that it  is  unlikely  that  2,3,7,8-TCDD-induced  oncogenesis is



through a  mechanism  gf  covalent binding to DNA  and somatic mutation.  Further



studies of 2,3,7,8-TCDD  and  related compounds are needed to confirm these results



and assess the relationship  between covalent binding and the short and long-term



toxicity of these compounds.



     Weber et  al. (1982) investigated the toxicity of 2,3,7,8-TCDD metabolites



by administering extracts of bile from 2,3,7,8-TCDD-treated dogs  to male guinea




pigs in single oral doses equivalent to 0.6,  6.0  and 60 pg/kg of parent compound.



Other groups of guinea  pigs  were given  bile  extract form untreated  dogs or



2,3,7,8-TCDD itself.  A comparison of the  mortality data at 5 weeks after dosing



indicated  that the acute toxicity  of 2,3,7,8-TCDD to guinea pigs was at least 100



times higher than wa» the acute toxicity  of its metabolites.



     Mason and Safe (1986)  synthesized  2-hydroxy-3,7,8-TCDD  and  2-hydroxy-



1,3,7,8-TCDD,  which  are metabolites  of  2,3,7,8-TCDD, and  assessed the toxicity



of  these compounds in male  Wistar rats.   The compounds produced  no significant



effect on  body weight gain,  thymus,  liver or spleen weights  after exposure  to  a



dose  of  <5000 ^g/kg bw.   2-Hydroxy-3,7,8-TCDD induced hepatic microsomal  AHH,



EROD  and  4-chlorobiphenylhydroxylase  activity at  an exposure of  1000 and







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 5000  pg/kg  bw, while  2-hydroxy-l,3,7,8-TCDD was inactive as an inducer.  Thus,



 while 2-hydroxy-3,7,8-TCDD has dioxin-like activity as an inducer of the hepatic



 monooxygenase system, the potency of the metabolite is more than three orders of



 magnitude less than that of 2,3,7,8-TCDD.  Furthermore, results are  consistent



 with  the expected rapid conjugation and excretion of these 2,3,7,8-TCDD metabo-



 lites (Weber et al.,  1982).




      Metabolism of coplanar PCBs  and  PBBs also appears to be a detoxification



 process.  5-Hydroxy-3,3•,4,4'-TCB and 4-hydroxy-3,3•,4',5-TCB did not produce



 liver hypertrophy, induction of hepatic AHH or DT-diaphorase activities or thymus



 atrophy (Yoshimura et  al., 1987).  Thus, monohydroxy metabolites of 3,3',4,4'-TCB



 are much less toxic than the parent compound.  Further evidence for metabolism



 as a detoxification process comes  from comparison of the metabolism  and toxicity



 of  two  coplanar PBBs.   Millis et  al.  (1985) found  that 3,3•,4,4',5,5'-HxBB



 exhibited  greater toxic potency in  rats  than   3,3',4,4'-TBB,   even  though



 3,3',4,4'-TBB had about a 10-fold greater affinity for the Ah receptor. Although



 receptor binding affinities imply that  3,3'4,4'-TBB  should be more toxic than



 3,3',4,4'5,5'-HxBB, it was less toxic  than the HxBB  because 3,3',4,4'-TBB was



metabolized at a  much greater rate than  3,3•,4,4',5,5'-HxBB.   In  addition to



 supporting metabolism as a detoxification  process, the  results of Millis et al.



 (1985) also  suggest  that receptor binding  and in  vitro AHH  induction  do not



 accurately  reflect toxicity  for  PAHs, which are more  readily  metabolized,



presumably because continued occupation of  the receptor is required for toxicity.



      Structure-activity studies of 2,3,7,8-TCDD and related compounds support the



widely accepted principle that this parent compound is  the active species.  The



relative lack of activity of  readily  excreted monohydroxylated metabolites of



2,3,7,8-TCDD and  3,3'4,4'-TCB  suggests  that  metabolism  is  a  detoxification



process necessary for  the biliary and urinary excretion of these compounds.  This



concept has  also been  generally  applied  to 2,3,7,8-TCDD  related compounds,



although data are lacking on the structure and  toxicity of metabolites of other



CDDs,  BDDs,  CDFs, BDFs, PCBs and PBBs.




      It  is  possible  that  low levels  of  unextractable  and/or  unidentified



metabolites may contribute to one or more of the toxic responses of 2,3,7,8-TCDD









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 and related compounds.   Further  studies  on  the  nature  of  the  biotransformation



 products  of these compounds  will help to address  this  uncertainty.



. 1.3.3.    Autoinduction of Metabolism. Accurate rate constants  for metabolism are



 important in developing pharmacokinetic models that describe the disposition of



 2,3,7,8-TCDD and  related compounds.  Metabolism  plays a major role in regulating



 the excretion  and relative persistence of these compounds,  since metabolism is



 required  for  urinary  and biliary excretion.   Although  the  relative rate  of



 metabolism of 2,3,7,8-TCDD and related compounds can be  estimated from tissue and



 excretion half-life data (see Tables  1-5  and 1-8),  other factors such as relative



 body composition, hepatic and extrahepatic binding proteins and direct intestinal



 elimination of the parent compound can also regulate the  excretion  of 2,3,7,8-



 TCDD and  related  compounds.  Therefore, in vivo disposition data (see Tables 1-5



 and 1-8)  provide  only a limited approximation of the relative rate of metabolism



 of a specific  congener  in a  given species.   In  vivo disposition data were also



 obtained  at exposures that were associated with induction of cytochromes P-4501A1



 and 1A2 and other potentially adverse responses that could alter metabolism and



 disposition.  Therefore, it may not be appropriate to directly extrapolate these



 data to  predict  the pharmacokinetics at low  levels  of exposure.   Low  dose



 extrapolations can be assisted by assessments of the potential for autoinduction



 of metabolism which may occur at exposures which are associated with  enzyme



 induction.  Characterization of  the  dose dependent disposition  of 2,3,7,8-TCDD



 and related compounds is particularly important  in the  extrapolation of  high



 exposure  animal data to  low  exposure human  data.



      The  excretion of metabolites of 2,3,7,8-TCDD and related compounds into bile



 represents a direct means for estimating the rate of metabolism,  since biliary



 elimination depends on metabolism and is the major route for excretion of these



 compounds.  The  rate  of metabolism  of  CDFs was  estimated from the  relative



 abundance  of  metabolites in  rat bile  (Poiger et al.,  1989).   The rate  of



 biotransformation  of   2,3,7,8-TCDF,   1,2,3,7,8-PeCDF,   2,3,4,7,8-PeCDF   and



 1,2,3,6,7,8-HxCDF were characterized as fairly high, moderate, low and very low,



 respectively.  Kedderis et al. (1991b) observed  10% of the dose of [3H]-2,3,7,8-




 TBDD excreted  in bile  5  hours after  intravenous administration  of 1 nmol/kg to







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male Fischer 344 rats.  All  biliary radioactivity was attributable to metabo-



lites.  This rate of elimination is similar to the fecal excretion (-8% of the



dose) 24 hours after intravenous administration of 1 nmol/kg [3H]-2,3,7,8-TBDD




(Kedderis et al., 1991a) and reflects the effect of intravenous bolus versus oral



administration on distribution and elimination.  The large % dose excreted within



the  first  few days  may also be  due to  a rapidly excreted impurity  in  the



radiolabeled 2,3,7,8-TBDD  (Kedderis  et al., 1992a).   To assess  the ability of



2,3,7,8-TCDD and 2,3,7,8-TBDD to induce their own metabolism (biliary elimina-



tion), rats were pretreated with 100 nmol/kg, per os,  of each  compound 3 days



prior to intravenous injection of 1 nmol/kg of  the respective  [3H]  congeners.




Biliary excretion of the radiolabeled dose was quantitatively and qualitatively



unaffected by pretreatment, despite  a 2-fold increase  in hepatic levels of [3H]




in the pretreated animals and significant induction of cytochrome P-4501A1 and



1A2 (Kedderis et al.,  1991b).  Therefore, under these conditions, autoinduction



of 2,3,7,8-TCDD and 2,3,7,8-TBDD metabolism did not occur in the rat in vivo at



doses that elicited enhanced hepatic uptake.  Similarly, Curtis et al. (1990)



observed no change, or even an apparent decrease,  in gastrointestinal contents



and fecal elimination  of  TCDD  equivalents in pretreated  versus  naive mice 24



hours after  oral administration of  [14C]-2,3,7,8-TCDD,  despite significantly




enhanced levels of 2,3,7,8-TCDD in the  livers of pretreated mice.



     While the above studies  suggest that autoinduction of 2,3,7,8-TCDD metabo-



lism does not occur, other results indicate that metabolism may be induced under



certain conditions.  Poiger and Buser  (1984) observed a small yet significant



increase in biliary excretion over  a 72-hour period,  with pretreated rats (10



jug/kg, intraperitoneal) excreting 9.7±1.9%  of the radiolabeled dose of 2,3,7,8-



TCDD (200-300 pg/kg, per os) compared to 7.0±0.9% excreted by naive animals.  In



addition to being  small changes, these results  were obtained using  a dose of



2,3,7,8-TCDD in  excess of the LD50  in the  rat.   Poiger  and Schlatter (1985)




examined the influence of pretreatment with phenobarbital and 2,3,7,8-TCDD on the



biliary excretion of [3H]-2,3,7,8-TCDD metabolites in a dog given a single oral




dose of  the  [3H] congener (31  or 33.8 ng/kg).  Without pretreatment, 24.5% of the







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absorbed dose was excreted in the  bile within 110 hours.  Phenobarbital did not



alter this rate, whereas pretreatment with 2,3,7,8-TCDD (10 /jg/kg)  9 days earlier



resulted in a doubling of  the amount of  metabolites excreted in bile (47.4%).



Although this observation is limited to one dog and requires further investiga-



tion,  the  results  suggest  that  significant  autoinduction of  2,3,7,8-TCDD



metabolism and biliary excretion may occur in the dog.  Nonetheless, the small



increase in metabolism and biliary excretion of 2,3,7,8-TCDD in the rat observed



by Poiger and Buser (1984) and the negative results of Redderis et al. (1991b)



and Curtis et al. (1990) suggest that autoinduction of 2,3,7,8-TCDD metabolism



and biliary excretion in the rat may not occur, or occurs to an extent that is




not biologically relevant.



     Limited data suggest that autoinduction of metabolism and biliary excretion



does occur  for  CDFs  in  contrast to CDDs and BDDs.   Pretreatment of rats with



2,3,7,8-TCDF (1.0 /jmol/kg, 3 days earlier) significantly increased the biliary




excretion of a  subsequent dose  of [ 14C]-2,3,7,8-TCDF (McKinley et al., 1991).




The naive rats excreted 5.69±2.35% of the dose over the initial 8 hours, while




the pretreated rats excreted 13.18±3.15%  of  the [14C]-2,3,7,8-TCDF.  Similarly,




pretreatment of  rats  with 2,3,4,7,8-PeCDF  (500 /jg/kg,  per os, 3 days earlier)



resulted in a 2-fold  increase in the biliary elimination of a subsequent dose of




[14C]-2,3,4,7,8-PeCDF (Brewster  and Birnbaum, 1987).  These results suggest that




pretreatment with  2,3,7,8-TCDF  and  2,3,4,7,8-PeCDF  induces  the metabolism of



these congeners.



     3,3',4,4'-TCB and 3,3',4,4'-TBB appear to be metabolized by a 3-methylchol-



anthrene-inducible form of hepatic cytochrome P-450  (1A1 and/or 1A2), which is



also induced by  3,3',4,4'-TCB (Shimada and  Sawabe,  1983; Mills et al., 1985).



This suggests that these compounds can induce their own rate of metabolism and



subsequent excretion.



     Isolated hepatocytes in  suspension culture have been demonstrated to provide



a useful  in vitro system  for studying the  hepatic metabolism of 2,3,7,8-TCDD



under the same conditions in  species that  have a wide range of sensitivity to the



compound  (Olson et al.,  1981).  The in vitro rate of metabolism of 2,3,7,8-TCDD



in guinea pig,  rat,  C57BL/6J mouse, DBA/2J mouse  and hamster hepatocytes was






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estimated to  be  0.2,  1.2,  1.1,  0.9 and 1.2 pmol/mg protein/hour, respectively



(Wroblewski and Olson, 1985, 1988; Shen and Olson, 1987).  These results indicate



that 2,3,7,8-TCDD is metabolized by the guinea pig  liver  at a  rate -5-fold less



than that observed for the rat, mouse and hamster.  The  limited ability of the



guinea  pig  to metabolize  2,3,7,8-TCDD can  explain  the limited  excretion of



2,3,7,8-TCDD metabolites in feces, which represents the major route for 2,3,7,8-



TCDD excretion (Olson, 1986).  In addition, the limited metabolism in the guinea



pig may partly explain the relatively long excretion half-life for 2,3,7,8-TCDD



in the guinea pig and  may contribute to the remarkable sensitivity of the guinea



pig to the acute toxicity of this agent (Olson, 1986).



     Isolated hepatocytes in suspension culture  have  been  used as an in vitro



system for studying the autoinduction of metabolism of  2,3,7,8-TCDD  and related



compounds.    Wroblewski  and  Olson  (1988)   investigated  the metabolism  of




[  C]-2,3,7,8-TCDD (2.2 /^M) in hepatocytes isolated from untreated 2,3,7,8-TCDD-,




3-MC-, isosafrole-  and phenobarbital-pretreated rats  and  hamsters.   In both



species,  2,3,7,8-TCDD and 3-MC pretreatments elevated the rate of 2,3,7,8-TCDD



metabolism by  5- to  6-fold, while  phenobarbital pretreatment had  no effect.



Isosafrole produced a 1.8- to 2.5-fold increase in metabolism.  These in vitro



results at a high substrate concentration (2.2 pM) indicate that 2,3,7,8-TCDD can



induce its own rate of metabolism in the rat and hamster.  In contrast, 2,3,7,8-




TCDD was not able to induce its own rate of metabolism in guinea pig and mouse



hepatocytes (Wroblewski and Olson, 1985; Shen and Olson, 1987). Together, these



results indicate that  2,3,7,8-TCDD is metabolized in the liver  by a 2,3,7,8-TCDD



inducible enzyme, which  is  expressed in  the  rat and hamster, but  not  in the



guinea pig and mouse.  More recently, the kinetics of 2,3,7,8-TCDD metabolism was



investigated in  isolated  rat hepatocytes  incubated with [3H]-2,3,7,8-TCDD at




concentrations of 0.01,  0.1 and 1.0 pM (Olson et al., 1991).  Lower 2,3,7,8-TCDD



concentrations in the media result  in concentrations  in  hepatocytes which are



more similar to the levels in the liver after in vivo exposure.   For example, the



concentration of 2,3,7,8-TCDD in hepatocytes incubated at  0.01  pM are similar to



hepatic levels after in vivo exposure of rats at a dose of  -10 /jg/kg.  At 0.01
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                                       •a
and 0.1 ^iM, the rate of metabolism of [JH]-2,3,7,8-TCDD was similar in hepato-


cytes isolated from control and 2,3,7,8-TCDD pretreated rats, while at 1.0 pH,


2,3,7,8-TCDD metabolism was greater in  hepatocytes isolated from 2,3,7,8-TCDD


pretreated rats.   The results indicate that 2,3,7,8-TCDD can induce its own rate


of metabolism  in  the  rat, but only at high hepatic  concentrations,  which are


generally not attained after in vivo exposure.  A dose-dependent autoinduction


of 2,3,7,8-TCDD  metabolism is  consistent with  the  lack of  autoinduction of


2,3,7,8-TCDD metabolism and biliary excretion in the rat (Kedderis et al., 1991b;


Curtis et al., 1990).


     The metabolism of  [%]-2,3,7,8-TCDF was also investigated in isolated rat


hepatocytes incubated at  concentrations of 0.01,  0.1 and 1.0 pM  (Olson et al.,


1991).  At  all concentrations, hepatocytes from 2,3,7,8-TCDD pretreated rats


metabolized 2,3,7,8-TCDF at a rate  from 4- to 25-fold greater than that observed


in hepatocytes from control rats.   The results  indicate that 2,3,7,8-TCDF is


metabolized in rat liver by a 2,3,7,8-TCDD inducible enzyme,  possibly cytochrome


P-4501A1 or 1A2.   These in vitro results  support the in vivo autoinduction of


2,3,7,8-TCDF metabolism and biliary elimination observed in the rat (McKinley et


al., 1991).


     There is in vivo and in vitro data suggesting that autoinduction of 2,3,7,8-


TCDD and  2,3,7,8-TBDD  metabolism  does not occur in the  rat after exposure to


sublethal  doses  of these agents.    This  is  in  contrast to  2,3,7,8-TCDF and


2,3,4,7,8-PeCDF where in vivo and in vitro results  support the autoinduction of


metabolism and biliary elimination of these compounds in the rat.


1.3.4.   Excretion in Animals.  Data regarding the excretion of 2,3,4,7-TCDD and


related compounds  after exposure to a single  radiolabeled congener (see Table


1-8) support the assumption of a first-order elimination process consisting of


one or more components.  These studies show that 2,3,7,8-TCDD was excreted slowly


from all species tested, with half-lives ranging  from  11  days  in  the hamster to


2120 days in humans.  2,3,7,8-TCDD is exceptionally persistent in humans relative


to other animal models.   Elimination data in  tissues (see Tables 1-5 and 1-6)


also indicate that 2,3,7,8-TCDD and related compounds  are exceptionally persis-


tent in nonhuman  primates (Bowman  et  al., 1989;  Neubert et al.,  1990).  These




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differences may also be in  part related to the dose-dependency of the excretion



of these  compounds.    In general,  the congener and  species specific  rate of



elimination of 2,3,7,8-TCDD and related compounds from major tissue depots (see



Table 1-5) is similar to the excretion data summarized in Table 1-8.



     In the Syrian Golden hamster, the mammalian species least sensitive to the



acute toxicity of 2,3,7,8-TCDD, excretion occurred readily through both the urine



(35% of administered dose,  41% of total excreted radioactivity) and feces (50%



of the administered dose,  59% of total excreted radioactivity)  (Olson et al.,



1980b).  A similar excretion pattern was observed  in  mice,  although there was



significant strain variability (Gasiewicz et al., 1983;  Birnbaum, 1986).  In all



the other species,  excretion occurred mainly through the feces,  with relatively



minor amounts of 2,3,7,8-TCDD metabolites  found in the urine (Piper et al., 1973;



Allen et al., 1975; Olson,  1986; Rose et al., 1976; Gasiewicz  and  Neal, 1979;



Pohjanvirta  et  al.,  1990).   Results in  Table  1-8 also indicate  that fecal



elimination was the primary route for the  excretion of 1,2,3,7,8-PeCDD, OCDD,



2,3,7,8-TBDD, 2,3,7,8-TCDF, 1,2,3,7,8-PeCDF, 2,3,4,7,8-PeCDF, and 3,3',4,4'-TCB.



Only Piper et al.  (1973) reported the excretion of metabolites in  the expired



air.  During  21 days  following administration of  a single oral dose of [  C]-




2,3,4,7-TCDD  to  rats,  3.2%  of  the  administered  radioactivity  (4.6%  of  the



excreted radioactivity) was recovered in  the expired  air.



     Studies  in the  rat,   guinea pig,  hamster  and  mouse have  found  that



essentially all of the 2,3,7,8-TCDD-derived radioactivity excreted in the urine



and  bile  corresponds  to metabolites  of 2,3,7,8-TCDD  (see Table  1-8).   The



apparent absence of 2,3,7,8-TCDD metabolites in liver and  fat suggests that once



formed, the metabolites of  2,3,7,8-TCDD are excreted readily.  Thus, urinary and



biliary elimination of  2,3,7,8-TCDD depends on metabolism of the toxin. The more



limited data for other  compounds also suggest that this  relationship may be true



for  1,2,3,7,8-PeCDD,  2,3,7,8-TBDD,  2,3,7,8-TCDF,  1,2,3,7,8-PeCDF,  2,3,4,7,8-



PeCDF, and 3,3',4,4'-TCB (see Table 1-8).



     Although urine and bile appear to be  free  of  unmetabolized 2,3,7,8-TCDD,



data indicate that 2,3,7,8-TCDD and its metabolites are excreted in the feces of



guinea pigs, rats,  mice and hamsters treated with [  H]-  and/or [  C]-2,3,7,8-TCDD







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(see Table 1-8).  While 15-35% of the  2 , 3 , 7 , 8-TCDD-derived radioactivity in rat,



mouse and hamster feces represents unchanged 2,3,7,8-TCDD,  81% of the radioa-



ctivity in guinea pig feces  represents unmetabolized 2,3,7,8-TCDD  (Olson, 1986;




Neal et  al.,  1982;  Gasiewicz et  al.,  1983; Olson et  al.,  1980).   The daily



presence of unchanged 2,3,7,8-TCDD in feces and its absence in bile  suggests that



direct intestinal  elimination may be  the source  for  the  fecal  excretion of



2,3,7,8-TCDD.  Data  also suggest  that direct  intestinal elimination of parent



compound contributes to the fecal excretion for 2,3,7,8-TBDD (Kedderis et al.,



1991). While the direct intestinal elimination of parent compound  may occur for



other congeners (see Table 1-8), this conclusion cannot be  made  at  this time due



to  the  lack  of  experimental  data.   Nonetheless, the  species-specific fecal




excretion of  2,3,7,8-TCDF is very similar to that observed for 2,3,7,8-TCDD, with



>90% of  the   2, 3, 7, 8-TCDF-derived radioactivity  excreted  in guinea  pig feces



representing parent compound (Decad et al.,  1981a) .  In  addition,  the excretion



of unchanged CDDs and CDFs was detected in rat  feces after subcutaneous exposure



to a defined mixture of congeners (Abraham et al.,  1989).  Studies in lactating



rats have also found that unchanged 2,3,7,8-TCDD may be  excreted in the milk of




lactating animals (Moore et al., 1976; Lucier et al.,  1975; Nau et al., 1986).



Lactation, direct intestinal elimination, and perhaps  sebum  may serve as routes



for excretion of 2,3,7,8-TCDD, which do not depend on metabolism  of the toxin.



These data suggest that the in vivo half -life for elimination of  2,3,7,8-TCDD and



related compounds only provides  an  approximation  of the rate of metabolism of



these compounds  in  a given  animal.   The results  in Table  1-8  do  suggest that



2,3,7,8-TCDF, 1, 2 , 3 , 7, 8-PeCDF,  and  3,3 ' ,4,4'-TCB  are  metabolized  and excreted



more rapidly that 2,3,7,8-TCDD, 2,3,7,8-TBDD,  1,2, 3, 7, 8-PeCDD, 2,  3, 4, 7, 8-PeCDF



and OCDD.



     The rate of excretion of 2,3,7,8-TCDD and related  compounds is species- and



congener-specific (see Table 1-8).  2,3,7,8-TCDD is most persistent in human and



nonhuman primates.   In the  hamster, the least sensitive  species  to the acute




toxicity of 2,3,7,8-TCDD, the mean ti was 10.8 days (Olson et al.,  1980a,b) , and
in the guinea pig, the most sensitive species to  the  acute toxicity of 2,3,7,8-
                                     1-59                             08/11/92

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                          DRAFT—DO NOT QUOTE OR CITE






TCDD, the mean ti^ was 94 days (Olson, 1986).  2,3,7,8-TCDF was also most persis-




tent in the guinea pig, with a t!/6 of 20-40 days (Decad et al., 1981a; loannou




et al., 1983).  Furthermore, results indicate that the relatively limited ability



of the  guinea  pig to metabolize 2,3,7,8-TCDD and -TCDF  may contribute to the



greater persistence and greater acute toxicity of these congeners in the guinea



pig.




     The time distribution, metabolism and excretion of 2,3,7,8-TCDD were also



investigated in Han/Wistar and Long-Evans rats,  which were, respectively, more




resistent (LD50>3000 /jg/kg) versus more susceptible  (LD50 -10 /Lig/kg) to the acute




toxicity of 2,3,7,8-TCDD (Pohjanvirta et al., 1990).  The results suggest that



the metabolism  and disposition  of  2,3,7,8-TCDD do  not  have a major  role in



explaining the strain differences in toxicity.




     The intraspecies  differences in  the  ti^ of 2,3,7,8-TCDD  in three mouse




strains may  be due to  the finding that the DBA/2J strain  possesses  ~2-fold




greater adipose tissue stores than the  C57BL/6J  and  B6D2FJ/J strains (Gasiewicz




et al., 1983b).   The sequestering  of  the  lipophilic toxin  in adipose tissue



stores of the DBA/2J mouse may contribute to the  greater persistence of 2,3,7,8-



TCDD in this strain.   Birnbaum (1986) examined the effect of genetic background



on the distribution and excretion of 2,3,7,8-TCDD in two sets of congenic mouse



strains in which the congenic pairs differed only at the Ah locus.  The Ah locus



had no effect on the tissue distribution or excretion of 2,3,7,8-TCDD.  Thus, the



distribution and excretion of 2,3,7,8-TCDD were  primarily governed by the total



genetic background  rather than  the allele  present at the  Ah locus.   These



findings are consistent with the  in  vitro results of  Shen and Olson (1987), who



found that the hepatic  uptake and metabolism of 2,3,7,8-TCDD do not correlate



with genetic differences at the  murine Ah  locus.  However,  it is important to




note that  all of  these are relatively high-dose studies, which may not allow for



detection of Ah receptor-mediated effects on disposition.



     Although the dose-related tissue distribution of 2,3,7,8-TCDD and related



compounds has been described  recently, very  limited data are available on the



dose-related excretion of these compounds.  Rose et  al. (1976) investigated the









                                     1-60                             08/11/92

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                          DRAFT—DO NOT QUOTE OR CITE






elimination of [14C]-2,3,7,8-TCDD in rats given repeated oral doses of 0.01, 0.1




or 1.0 pg/kg/day Monday through Friday for 7 weeks or a single dose of 1.0 ^g/kg.



In the single-dose study,  no ^C was excreted in the urine or expired air; in the




repeated-dose study,  however, 3-18% of the cumulative dose was excreted in the



urine by 7 weeks.  This study indicated that steady-state concentrations will be



reached  in  the  bodies of rats  in  -13 weeks.   The rate constant defining the



approach to steady-state concentrations was independent of the dose of 2,3,7,8-



TCDD  over the range  studied.   Relatively small  changes in the excretion of



2,3,7,8-TBDD were also observed after exposures at 1 and 100 nmol/kg (Kedderis



et  al.,  1991).    These  results are consistent with  the in vivo and  in vitro



evidence suggesting that autoinduction of 2,3,7,8-TCDD  and 2,3,7,8-TBDD metabo-



lism  does not occur  in the rat  after  exposure  to  sublethal doses  of these



compounds (Kedderis et al.,  1991b;  Curtis et al.,  1990;  Olson et al., 1991).  In



contrast to these compounds, 2,3,7,8-TCDF and 2,3,4,7,8-PeCDF can induce their



own rate of metabolism  and biliary  excretion  (Brewster and Birnbaum,  1987;



McKinley et al.,  1991; Olson et al., 1991).   Autoinduction of metabolism would



suggest  that  these compounds may  exhibit dose-related excretion,  with longer



half-lives for elimination at lower doses, which are not associated with enzyme



induction.  Further data  are needed to test this hypothesis.



1.3.5.   Excretion in Humans.   Poiger  and  Schlatter  (1986)  investigated the




excretion of 2,3,7,8-TCDD in a  42-year-old man (92 kg)  after ingestion of 105 ng



(1.14 ng/kg) [3H]-2,3,7,8-TCDD in  6 mL corn oil (see Table 1-8).  The half-life




for elimination was estimated to be 2120  days.  Table 1-9 summarizes additional



half-life estimates for 2,3,7,8-TCDD and related compounds in humans, based on



serum  and/or  adipose tissue concentrations  at two or more  time points.   In



another  study, the half-life of 2,3,7,8-TCDD  in  humans was estimated to be -7



years on the basis of 2,3,7,8-TCDD levels  in serum samples taken in 1982 and 1987



from 36 of the Ranch  Hand personnel who had 2,3,7,8-TCDD levels >10 ppt in 1987



(Pirkle et al.,  1989).  These studies  indicate that 2,3,7,8-TCDD  is exceedingly



persistent  in humans.   Estimated  half-lives for  other congeners in  Table 1-9



range from 0.8-10 years.  The half-life values  in  Table 1-9 are rough estimates



based on  a  small  number  of  individuals and based  on  analysis  at  as few as two






                                     1-61                             08/11/92

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TABLE 1-9
Half-Life Estimates for 2,3,7,8-TCOD and Related Compound in Humans
Chemical
Exposure Incident
Number of
Individuals
Sample
Time Period
Between First and
Last Analysis
CDDs
2,3,7,8-TCDD
1,2,3,6,7,8-HxCDO
1,2,3,4,6,7,8-HpCDD

OCDD
Ranch Hand
Vietnam veterans
technical pentachlorophenol in
wood of home
technical pentachlorophenol in
wood of home
technical pentachlorophenol in
wood of home
36
1
1
1
serum
adipose tissue
adipose tissue
adipose tissue
CDFs
2,3,4,7.8-PeCDF
1,2,3,4,7,8-HxCDF

1,2,3,6,7,8-HxCDF

1,2,3,4,6,7,8-HpCDF

2,3,4,7,8-PeCDF
1, 2,3,4, 7,8-HxCDF
1,2,3,4,6,7,8-HpCDF

Binghamton, New York, state
office building
Binghamton, New York, state
office building
Binghamton, New York, state
office building
Binghamton, New York, state
office building
Yu-Cheng
Yu-Cheng
Yu-Cheng
1
1
1
1
4
3
2
4
3
2
4
3
2
adipose tissue
blood
combined
adipose tissue
blood
combined
adipose tissue
blood
combined
adipose tissue
blood
combined
blood
blood
blood
5 years
28 months
28 months
28 months
Number of
Time Points

2
2
2
2

initial 43 months
final 29 months
total 6 years
initial 43 months
final 29 months
total 6 years
initial 43 months
final 29 months
total 6 years
initial 43 months
final 29 months
total 6 years
initial 2.9 years
final 2.7 years
total 5.6 years
initial 2.9 years
final 2.7 years
total 5.6 years
initial 2.9 years
final 2.7 years
total 5.6 years
4
4
7
4
4
7
4
4
7
4
4
7
2
2
3
2
2
3
2
2
3
Half-Life
(years)
Reference

7.1a
3.5
3.2
5.7

4.7
7.2
4.5
2.9
4.4
4.0
3.5
4.3
4.9
6.5
4.1
6.8
1.3
2.9
1.7
2.1
5.1
2.4
1.6
6.1
2.4
Pirkle et
al., 1989
Gorski et
al., 1984
Gorski et
al., 1984
Gorski et
al., 1984

Schecter et
at., 1990
Schecter et
al., 1990
Schecter et
al., 1990
Schecter et
al., 1990
Ryan, 1989
Ryan, 1989
Ryan, 1989
                                                                                                                                                                                                                    8
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time points.   Phillips (1989) discusses this issue.   Estimates also assume a



simple, single compartment, first-order elimination process.  Recent data suggest



a  biphasic  elimination of 2,3,7,8-TCDD, with a  half-life  >7 years  (Birnbaum,



1992).




     Ryan and Masuda (1991)  reported on their continuing investigation into the



elimination of CDFs in humans from the Yusho and Yu-Cheng rice oil poisonings.



Yu-Cheng individuals had CDF blood levels on a lipid  basis of 1-50 pg/kg, while



Yusho patients had  levels of  0.1-5  pg/kg.   In the Yu-Cheng individuals, half-



lives for three CDFs were 2-3 years, while elimination from Yusho  individuals was



more variable  and slower, with  half-lives >5 years (see  Table  1-9)  and,  in



several cases,  no measurable elimination during the 7 years in which samples were



available.  The limited results suggest that clearance of these CDFs in the human



is biphasic, with faster elimination at higher exposure. Schecter et  al. (1990)



and Ryan (1989) also reported longer half-life values  for CDFs in  humans at later



time points  after  exposure,  when concentrations are closer  to  the background



levels of individuals with no unusual exposure.




     Due  to the  lipophilic  nature  of  milk, milk  secretion  can  provide  a



relatively efficient mechanism for decreasing the body burden  of 2,3,7,8-TCDD in



females.  As discussed  by Graham et al.  (1986), this elimination of 2,3,7,8-TCDD



through mother's milk can result in high exposure levels in the infant.  Since



both milk  and the  fatty  tissues of  fish  are  essentially providing  an  oily



vehicle, it would be likely that these sources would provide 2,3,7,8-TCDD in a



form that is readily bioavailable.




     Several investigators have guantified the levels of 2,3,7,8-TCDD in human



milk samples. Many of the milk samples were pooled (Jensen,  1987).  Rappe et al.



(1984)  reported levels  of 1-3 ppt 2,3,7,8-TCDD in milk fat (lipid adjusted) from



five volunteers  in  West  Germany, and  in  a later report,  Rappe  et al.  (1985)



reported  an average  level  of  0.6 ppt  2,3,7,8-TCDD  in  milk  fat  from  four



volunteers in northern  Sweden.  Furst et al. (1986) reported an average level of



9.7 ppt 2,3,7,8-TCDD in milk fat from three individuals in the Netherlands and



<1.0 ppt 2,3,7,8-TCDD in milk fat from two individuals in Yugoslavia.  Nygren et



al. (1986) reported average levels of  2,3,7,8-TCDD  in  human  milk samples from



four subjects in Sweden to be  0.6 ppt  in  milk fat,  in  five subjects from West




                                     1-64                             08/11/92

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                          DRAFT—DO NOT  QUOTE  OR  CITE






Germany to be 1.9 ppt in milk fat,  and in four subjects from Vietnam to be <0.5



ppt in milk fat.



     High  levels  of 2,3,7,8-TCDD  have  been  detected  in the milk  of mothers



exposed to  high levels of 2,3,7,8-TCDD in  the  environment.  Reggiani  et al.



(1980) reported levels between 2.3  and 28.0  ppt 2,3,7,8-TCDD in whole milk from



mothers in  Seveso.   Baughman  (1975)  reported  levels  between 40.0 and 50.0 ppt



2,3,7,8-TCDD in whole milk from mothers in South Vietnam.  Schecter et al. (1987)



also  found  high ppt levels of  2,3,7,8-TCDD in  human milk  samples  from South



Vietnam.  These authors found that samples taken in 1985 from South Vietnamese



mothers were comparable to the level of 2,3,7,8-TCDD  presently  found in North



American human milk  samples (5 ppt).



1.4.   PHYSIOLOGICALLY BASED PHARMACOKINETIC MODELS



     PB-PK  models have  been developed for 2,3,7,8-TCDD in C57BL/6J and DBA/2J



mice  (Leung et al., 1988), rats  (Leung et  al.,  1990) and  humans (Kissel and



Robarge,  1988).   PB-Pk  models incorporate  known  or  estimated anatomical,



physiological  and physicochemical parameters to describe  quantitatively the



disposition of  a  chemical in  a given species. PB-Pk  models can assist in the



extrapolation of high-to-low dose kinetics within a species, estimating exposures



by different routes of administration, calculating effective doses and extrapo-




lating  these values  across  species  (Scheuplein et  al.,  1990).   Table 1-10



summarizes  the  pharmacokinetic parameters  for 2,3,7,8-TCDD that  were used in



developing these PB-Pk models.  In many cases, these parameters were estimated



from in vivo experimental data.



     A five-compartment (blood, liver, fat,  muscle/skin,  viscera), flow-limited



PB-Pk model for 2,3,7,8-TCDD  was developed for the Ah-responsive C57BL/6J mouse



and the Ah-nonresponsive  DBA/2J mouse  (Leung et al., 1988).   The  model  also



included binding in the hepatic cytosol and hepatic microsomes and first-order



hepatic metabolism.  There was general agreement  between  the simulated descrip-



tion generated by the model and the experimental disposition data of Gasiewicz



et al.  (1983).   The greater  accumulation of  2,3,7,8-TCDD in  the liver of the



C57BL/6J mouse, compared to the DBA/2J mouse, was  not attributable to the 2-fold



greater total  fat content in  the  DBA/2J  strain.  The authors  suggested  that



strain  difference in  hepatic disposition  was  due to differing  affinity of




                                     1-65                             08/11/92

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TABLE 1-10
Pharmacokinetic Parameters for 2,3,7,8-TCOD Used in PB-Pk Models

PARTITION COEFFICIENT (TISSUE/BLOOD)
Liver
Fat
Richly perfused (kidney)
Slowly perfused (skin)
Slowly perfused (muscle)
BIOCHEMICAL CONSTANTS
Binding capacity to hepatic cytosolic protein (nmol/liver)
Binding affinity to hepatic cytosolic protein (nM)
Binding capacity to hepatic microsomal protein (nmol/liver)
Noninduced binding capacity to hepatic microsomal protein (nmol/liver)
Induced binding capacity to hepatic microsomal protein (/unol/liver)
Binding affinity to hepatic microsomal protein (nM)
First-order metabolic rate constant (per hour per kg liver)
Absorption constant from gastrointestinal tract into liver (per hour)
Binding to blood
C57BL/6J
Mouse3
DBA/2J
Mouse9
Sprague-Dawley
RatD
Human0

20
350
20
250
250
20
350
20
250
250
20
350
20
40
40
25
300
7-10
30
4
Female C57BL/6J Miced
Naive

10
300
10
200
3
Pretreated

10
300
10
200
3

0.0042
0.29
20
-
-
20
3.25
0.02
2.5
0.0042
2
20
-
-
75
1.75
0.02
2.5
0.054
0.015
-
25
175
7
2.0
0.2
2.5
-
-
-
-
-
-
-
-
-
0.0042
0.29
1.75
-
-
20
1.0
0.04
1.0
0
0.29
20
-
-
20
3.0
0.15
3.0
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       \eung et al.  (1988)



       bLeung et al.  (1990)



       GKissel and Robarge (1988)

       i                                                 1 OC
       Leung et al.  (1990) modeled the disposition of [ "l]-2-iodo-3,7,8-TCDD,  an analog of  2,3,7,8-TCOD,  following a single exposure (0.1 nmol/kg)

       in  naive female C57BL/6J mice and in mice pretreated  3 days earlier with an inducing dose of 2,3,7,8-TCDD (0.1 /unol/kg).
o
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                         DRAFT—DO NOT QUOTE OR CITE






2,3,7,8-TCDD for the microsomal binding protein in  the two strains, and proposed



using a different microsomal dissociation constant  for  each strain.   Alterna-



tively, the strain difference in hepatic disposition may  be due to the different



doses of 2,3,7,8-TCDD needed to induce cytochrome  P-4501A2  in the two strains.



In  contrast to  the  high  capacity/low  affinity   hepatic  microsomal  binding



proteins, the low capacity/high affinity hepatic cytosolic  binding protein (Ah



receptor) did not play a major role in determining the overall tissue distribu-




tion pattern of 2,3,7,8-TCDD in this model.



     A similar five-compartment PB-Pk model was developed to  describe the tissue




disposition of 2,3,7 8-TCDD in the Sprague-Dawley rat (Leung et al.,  1990).  This



description included  blood,  liver (cytosolic receptor  and  microsomal binding



protein), fat, muscle/skin  and visceral tissue compartments.  The authors found



generally good agreement between the PB-Pk model simulated data and the experi-



mental data for the  single-dose  study  of  Rose et  al.  (1976)  and the  7- and



13-week  multiple-dose studies  of Kociba et al.  (1978).    The  model was not



satisfactory for  the  2-year  feeding  study of Kociba et al.  (1978),  underpre-



dicting  the 2,3,7,8-1000  concentration  in  the  fat  at the  low  dose  (0.001



pg/kg/day)  and overestimating the concentration achieved at the high dose (0.1



pg/kg/day).   The model  found  the hepatic  disposition  of   2,3,7,8-TCDD  to  be




dependent on the high capacity/low affinity hepatic microsomal binding protein



with a dissociation  constant of 7 nM and a basal and induced concentration in the



liver of 25 and 175  nmol/liver,  respectively. As discussed earlier, Voorman and



Aust (1987, 1989)  and Poland et al. (1989a,b) provided evidence that this binding



species is cytochromg P-4501A2.  Induction of the microsomal  binding protein was



necessary in order to account for  the differences  in hepatic disposition at low



(0.01  /jg/kg)  and high  (1.0  ^g/kg)  daily  doses  of 2,3,7,8-TCDD.    The  dose-



dependent tissue distribution of 2,3,7,8-TCDD was also discussed  earlier.  As in



the mouse  PB-Pk model  (Leung  et  al.,  1988),  the  low  capacity/high affinity



hepatic  cytosolic binding protein  (Ah receptor)  was  not  a major  factor  in



directly influencing the hepatic disposition of 2,3,7,8-TCDD.  The dissociation



constant of the cytosolic  Ah receptor  in  vivo was estimated  to be  15  pM  by



fitting enzyme induction data from McConnell et al. (1984).









                                     1-67                             08/11/92

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                          DRAFT—DO NOT QUOTE  OR CITE






     A PB-Pk model was also developed for female C57BL/6J mice for [125I]-2-iodo-




3,7,8-TCDD, an analog of 2,3,7,8-TCDD (Leung et al., 1990). Mice were pretreated



with 0.1 fjmol/kg of 2,3,7,8-TCDD or the vehicle only, followed by 2-iodo-3,7,8-



TCDD  (0.1  nmol/kg)  3 days later.    Naive mice had liver/fat 2-iodo-3,7,8-TCDD



concentration ratios of 0.17-0.38,  while the  2,3,7,8-TCDD pretreated mice had



ratios of 2.0-6.1.  This is in agreement with the  dose-dependent tissue distribu-



tion of  2,3,7,8-TCDD described earlier (Abraham et al.,  1988;  Poiger et al.,



1989).   As  with 2,3,7,8-TCDD,  the model found  that the  2-iodo-3,7,8-TCDD



concentration in the liver was most sensitive to the  binding capacity of the



hepatic  microsomal  protein.    Whole-body elimination  of  2-iodo-3,7,8-TCDD



approximated first-order kinetics, and induction by pretreatment with an inducing



dose of 2,3,7,8-TCDD almost doubled the rate  of excretion (ti^ of 14.2 days in




naive versus 8.0  days  in  induced  mice) (see  Table 1-8).  The distribution in



naive and  pretreated mice was described by a PB-Pk model  in which  induction



(2,3,7,8-TCDD pretreatment) increased the amount of hepatic microsomal binding



protein from 1.75-20 nmol/liver and increased  the rate constant for metabolism



of free  2-iodo-3,7,8-TCDD from 1-3 hours/kg  liver.   Although the more rapid



elimination of 2-iodo-3,7,8-TCDD in 2,3,7,8-TCDD pretreated mice suggests that



the rate of metabolism of 2-iodo-3,7,8-TCDD was induced by pretreatment, no data



were provided on the  effect of this pretreatment  of body weight and composition,



which may in turn alter the rate of  elimination.  2,3,7,8-TCDD pretreatment may



also alter deiodinase activity.   Furthermore,  in vivo  and in  vitro studies



suggest that the autoinduction of  2,3,7,8-TCDD  metabolism may not occur under



these conditions.  Kedderis et al. (1991b) and Curtis et al.  (1990)  found no



autoinduction of 2,3,7,8-TCDD metabolism and biliary excretion in the rat.  In



addition,  Shen and Olson  (1987) found  that while 2,3,7,8-TCDD pretreatment of



C57BL/6J mice increased the uptake  of 2,3,7,8-TCDD by hepatocytes in suspension



culture, pretreatment did  not increase the rate of metabolism of 2,3,7,8-TCDD by



hepatocytes.   Therefore,   this PB-Pk  model may  not  accurately  describe the



metabolism of  2,3,7,8-TCDD for exposures  which result in  varying degrees of



induction  of the  hepatic  monooxygenase  system.   While the  dose-dependent



pharmacokinetics of 2,3,7,8-TCDD may not include autoinduction of 2,3,7,8-TCDD







                                     1-68                             08/11/92

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                          DRAFT—DO NOT QUOTE OR  CITE






metabolism, this may not be the  case for other CDDs, HDDs, CDFs, BDFs, PCBs and



PBBs.  For example, the autoinduction of metabolism has been reported for CDFs



(Brewster and Birnbaum, 1987; McKinley et al.,  1991; Olson et al., 1991).



     Andersen et al.  (1992) recently derived a receptor-mediated PB-PK model for



the tissue distribution and enzyme inducing properties of 2,3,7,8-TCDD. The data



used for this analysis were  from  two previously  published  studies with Wistar



rats (Abraham et al.,  1988; Krowke  et al., 1989).   The model was used to examine



the tissue disposition of 2,3,7,8-TCDD and the induction of both a dioxin-binding



protein (presumably cytochrome P-4501A2)  and cytochrome P-4501A1.



     Kohn et al. (1992) recently developed a mechanistic model of the effects of



dioxin on glue expression  in the rat liver (referred to as the NIEHS model).  The



model includes the tissue  distribution of 2,3,7,8-TCDD in the rat and its effect



on the concentrations  of CYP1A1 and CYP1A2,  and the effects of 2,3,7,8-TCDD on




the  Ah,  estrogen  and  EGF  receptors  over   a  wide  2,3,7,8-TCDD dose  range.



Experimental data  from Tritscher  et al.   (1992) and Sewall  et  al.  (1992) were



incorporated into the  NIEHS model.   Female Sprague-Dawley rats were  injected with



an  initiating  dose of diethylnitrosamine,  and after  20 days, the  rats were



exposed biweekly to 2,3,7,8-TCDD  in  corn  oil by  gavage at  doses equivalent to



3.5-125 ng/kg/day for 30 weeks.  The NIEHS model predicts a linear relationship



between administered  dose and the  concentration  in the liver over  this dose



range, which  is in agreement with  the data  of Tritscher et al.  (1992).   The



biochemical response  curves for all these proteins were hyperbolic,  indicating



a proportional relationship between target tissue dose and protein concentration



at low administered doses of 2,3,7,8-TDCDD.



     A fugacity-based PB-Pk model for the elimination of 2,3,7,8-TCDD from humans



was  developed  by Kissel  and Robarge (1988).  Transport within the  body was



assumed to be perfusion-limited  (flow-limited).   2,3,7,8-TCDD was assumed to be



uniformly distributed within each  tissue  or fluid  phase,  and tissue levels were



considered  to be  in   equilibrium  with  exiting  fluids   (blood,  bile,  urine).



2,3,7,8-TCDD  appears  to  be  poorly metabolized  in  humans,  thus  reducing the



necessity  of  modeling  the  fate  of metabolites.   2,3,7,8-TCDD also  seems to




exhibit fugacity-based partitioning behavior in  humans as evidenced by relatively



constant lipid-based tissue distribution (Leung et al., 1990; Ryan et al., 1987),




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although this is not the case in  rodents (Leung et al., 1988,  1990).   With a



daily human background  intake of  2,3,7,8-TCDD  in North America of  -50 pg/day



(Travis and Hattemer-Frey,  1987),  the steady state adipose tissue concentration



predicted by the model,  assuming no metabolism,  was 7.7  ppt.  This is similar to



the lipid-based blood tissue levels reported in the general population with no



known unusual exposure.   The model was also used to predict the elimination of



2,3,7,8-TCDD from Ranch Hand Vietnam veterans.   The model simulation assumed a



background exposure of  50  pg/day  and no metabolism.   Under  these  conditions,



apparent half-lives of 4.4, 5.2,  5.9,  7.2,  9.1  and 20 years were estimated for



individuals with adipose tissue concentrations of 100, 50, 30,  20, 15  and 10 ppt,



respectively.  The model predicted half-lives  are  similar  to the  experimental



value of 7.1 years, based on analysis of 2,3,7,8-TCDD in  blood  lipids of veterans



with adipose burdens greater than  10 ppt  (Pirkle et al., 1989) (see Table 1-9).



The apparent half-lives derived from the model  increased as the adipose tissue



concentrations  approached  the steady-state  level  associated with  background



exposure.  Ryan  and Masuda  (1991)  also reported  a similar relationship for CDFs,



with experimentally derived half-lives increasing in individuals with lower body



burdens of the compounds.   Finally, the model was also found to approximate the



elimination  of  2,3,7,8-TCDD  from one  volunteer  as  reported  by   Poiger  and



Schlatter (1986).   Taken together, the comparisons described above suggest that



a fugacity-based PB-Pk model for 2,3,7,8-TCDD in humans can provide one method



for describing the elimination of 2,3,7,8-TCDD  from humans.



     Kedderis et al.  (1992a,b) recently developed a PB-PK model for 2,3,7,8-TBDD



in the rat.  The model  is  based on previously  developed physiologically-based



models for 2,3,7,8-TCDD (Leung et al., 1990; Poland et al., 1989)  and utilizes



published data on the disposition of a single exposure to 2,3,7,8-TBDD at a dose



of  1 or 100  nmol/kg,   intravenous   (Kedderis  et  al.,  1991a,b)   and dermal



disposition data  (Jackson  et al., 1991).   In  the model, the dose- and time-



dependent  accumulation  in  the  liver was  attributed  to  specific  binding of



2,3,7,8-TBDD with  the  inducible  protein,   CYP1A2.   The  model also   includes



diffusion-limited tissue uptake of  2,3,7,8-TBDD, transluminal excretion of parent



compound via the gut into the feces, growth of tissue compartments and a  separate



skin compartment.  This  model provides further validation of the model structure




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originally  developed to  describe  important  dispositional  determinants  for
2,3,7,8-TCDD.
     A five-compartment  (blood, liver,  fat, skin, muscle) flow-limited physiolog-
ical model was developed to  describe  the  tissue  distribution and excretion of
2,3,7,8-TCDF-derived material in  rats,  mice and monkeys  (King  et  al.,  1983),
based on experimental data  reported earlier  (Birnbaum et al., 1980, 1981; Decad
et al., 1981b).  Partition coefficients (tissue/blood distribution ratios) and
metabolic  clearances were  estimated  from in  vivo  experimental data  and are
summarized in Table 1-11.   All pharmacokinetic  parameters  for 2,3,7,8-TCDF were
based on  in vivo data  after a single intravenous  exposure  at a  dose  of 0.1
pmol/kg (30.6 pg/kg).   Therefore, the model  is limited  in not considering the
potential  dose-related  distribution  and  excretion of  2,3,7,8-TCDF.   Recent
studies indicate that 2,3,7,8-TCDF is  able to induce its own rate of metabolism
and biliary excretion at higher  doses  (McKinley et al.,  1991;  Olson  et al.,
1991).  This model will need to be  revised as additional data on the dose-related
distribution and excretion of 2,3,7,8-TCDF become available.
     PB-Pk  models  are primarily  limited  by the availability  of  congener and
species-specific date that  accurately  describe  the dose- and time-dependent
disposition  of  2,3,7,8-TCDD  and  related   compounds.     The  pharmacokinetic
parameters summarized in Tables 1-10 and 1-11 were derived from available in vivo
and in  vitro experimental  data.   As  additional data become available, partic-
ularly on the dose-dependent disposition of these compounds, more accurate models
can be  developed.    Jn  developing a  suitable  model in  the human,  it  is also
important to consider that the half-life estimate of 7.1 years for 2,3,7,8-TCDD
was based on  two se?um values  taken  5  years  apart, with the  assumption of a
single  compartment,  first-order elimination process (Pirkle et al., 1989).  It
is likely that  the excretion of 2,3,7,8-TCDD  in  humans is  more  complex, involving
several compartment,  tissue-specific  bonding  proteins and a continuous daily
background exposure.  Furthermore, changes in  body weight  and body composition
should also be  considered in developing PB-Pk models for 2,3,7,8-TCDD and related
compounds  in humans.
     An empirical model  of  dioxin  (toxic equivalents) disposition in animals and
humans  has also been recently  developed  by Carrier and  Brodeur  (1991).   The
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TABLE 1-11
Pharmacokinetic Parameters for 2,3,7,8-TCDF Used in the PB-Pk Model
Described by King et al. (1983)

C57BL/6J
Mouse
DBA/2J
Mouse
Fischer 344
Rat
Rhesus
Monkey
PARTITION COEFFICIENTS
Liver
Fat
Skin
Muscle
130
25
8
2
100
40
12
4
100
35
4
2
30
30
7
2
CLEARANCES
Metabolism
Km (mL/minute/kg)
Metabolism excretion ratio K^/K^*
0.07
2.8
0.14
0.06
2.4
O.27
1.0
4.0
0.03
2.25
0.45
O.19
aUrinary clearance/biliary clearance
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kinetic analysis  begins  with the  observation that the  tissue distribution of



dioxin-like HPAH  in humans  and in animals is  dose-dependent  (or, alternately,



body-burden dependent).  As  total body burden of TCDD equivalents  increases, the



proportion  of  the body  burden associated with  the  liver  increases  toward a



maximum value.   The data were then analyzed with an empirical,  saturable binding



isotherm equation:
                   liver fraction (fH)  =
If the body burden— Cj^y  (pg/kg)— is considered a surrogate for liver concentra-




tion, this  equation can  be  loosely interpreted  as  the induction  of binding



species in the liver as dose increases.   In the analyses, Kd was found to be very



similar for people and experimental animals, indicating similar protein induction



dynamics in various  animal species. This model, however, is not physiologically-



based and the  terms,  Cj^,, and f^x, are difficult to interpret in biological




terms.   In  working  with different isomers,  fmax  and  K^ values vary somewhat,




presumably due to binding affinities in the liver.



     This empirical model is successful in providing a description that "fits"



the observed data in various species.  It still is  largely a fitting exercise to



a particular equation, not an examination of biology by computer modeling.  In



addition, there  are at  least  two assertions that seem incorrect.   First, the



assumption that the  limit of the hepatic fraction at very low  doses  is  zero.  It



seems more  likely that  the  limit is some  finite value, determined  by liver



partitioning of dioxin and the binding parameters of  the Ah  receptor, and the



dioxin binding species in the liver in the linear, low-dose region.  Secondly,



that metabolism of dioxin becomes  saturated with the maximum induction of liver



sequestration  of dioxin.   There  is no  justification  for  this  at  present.



Nevertheless, the model  indicates clearly that with  respect  to dosimetry and



induction of hepatic  binding  species for dioxin,  people and  rodents  are very



similar.   Furthermore,  the empirical model  of  Carrier and Brodeur  (1991)  is



generally consistent with the PB-PK models.






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1.5.   PHARMACOKINETICS IN SPECIAL POPULATIONS



1.5.1.   Pregnancy and Lactation (Prenatal and Postnatal Exposure of Offspring).




The  distribution  and excretion  of  [14C]-2,3,7,8-TCDD  (30 pg/kg)  and  [14C]-




2,3,7,8-TCDF  (800  /t/g/kg)  were studied  in pregnant  C57BL/6N mice  after oral



exposure on gestation day 11 (Weber and Birnbaum,  1985).   The distribution and



excretion of 2,3,7,8-TCDD and 2,3,7,8-TCDF in pregnant mice were similar to that



of males of the same strain (Gasiewicz et al., 1983; Decad et al., 1981b) (see



Tables 1-5 and 1-8), although elimination rates were higher in the pregnant mice



for both congeners.  For 2,3,7,8-TCDD, liver,  urinary and fecal elimination were



3.0, 3.4 and 14.4  times  faster than that reported for males.  For 2,3,7,8-TCDF,



liver, urinary and  fecal elimination were 1.3, 1.8 and 1.8  times faster than



observed for males.  Elimination data from pregnant mice was based on only three



time  points  (gestation days  12,  13  and  14)  and  thus  represents  only  rough



estimates.   In addition,  the greater fecal  excretion could have been due to



incomplete  absorption of 2,3,7,8-TCDD  after  oral  exposure.   Although  these



results  need further substantiation, it  is  conceivable  that  the  sex of the



animal, pregnancy and/or the route of exposure could have a significant impact



on the pharmacokinetics of these compounds.



     In a related  study, Krowke  (1986) compared the 2,3,7,8-TCDD concentrations



in the liver of pregnant and nonpregnant NMRI mice exposed subcutaneously to 12.5



or 25 nmol/kg/day  on gestation days 9-11.  At 7 days after  exposure to the lower



dose, the hepatic  2,3,7,8-TCDD concentrations were 7 and 32 ng/g in pregnant and



nonpregnant  mice,   respectively.   At the higher exposure,  5.5  times  lower



concentrations of 2,3,7,8-TCDD were found in the livers of pregnant animals on



gestation day 18.   A similar effect on hepatic  2,3,7,8-TCDD levels was observed



also in combined exposure, which contained 1,2,3,7,8-PeCDD, 1,2,3,4,7,8-HxCDD or



2,3,7,8-TCDF.  The decreased hepatic levels of 2,3,7,8-TCDD in pregnant mice are



consistent with the Weber and Birnbaum (1985)  observation of more rapid elimina-



tion of 2,3,7,8-TCDD in pregnant mice. Further investigations are necessary to



better  characterize the apparently  significant effects  of pregnancy on the



disposition  of 2,3,7,8-TCDD and related compounds.
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     Weber and  Birnbaum (1985)  also  investigated the distribution  of  [14C]-




2,3,7,8-TCDD  (30 ^g/kg)  and [14C]-2,3,7,8-TCDF  (800 ^g/kg) to the  embryos of




pregnant C57BL/6N mice after oral exposure on gestation  day 11.   On gestation



days 12,  13  and 14,  the percent of the  maternal dose in  the  embryo remained



constant at 0.032-0.037%/ embryo, while  the  concentrations in  the embryo were



0.34, 0.17 and 0.15% of the dose/g embryo, respectively.   Embryos had approxi-



mately  11-fold  higher concentrations of 2,3,7,8-TCDD than  2,3,7,8-TCDF when



exposed on a percent of total dose/g tissue basis.   This may be due to the more



rapid  metabolism  and excretion  of  2,3,7,8-TCDF  compared to  2,3,7,8-TCDD.



Assuming that all radioactive material found  in embryos was parent compound, at



most, 2.6 ng  (8 pmol) of 2,3,7,8-TCDD and 6.4 ng  (21 pmol)  of 2,3,7,8-TCDF/g




tissue were detected under these conditions.



     The transfer of [14C]-2,3,7,8-TCDD to the embryo during early gestation was




assessed in NMRI mice given a dose of 25 pg/kg by intraperitoneal injection on



either days 7, 8, 9,  10, 11 or 13 of gestation (Nau and Bass, 1981).  The mice



were sacrificed after 48 hours,  and 2,3,7,8-TCDD concentrations were determined



by liquid scintillation counting of solubilized tissue and  by GC-ECD and GC/MS.



Similar results were given by these methods, suggesting that  2,3,7,8-TCDD derived




[  C] in maternal and embryonic tissue was the parent compound.   The maternal




liver contained from 4-8% of the dose/g or 40-80 ng/g.  2,3,7,8-TCDD in embryonic



tissue from gestation days 11-15 ranged from  0.04-0.1% of the dose/g or 0.4-1.0




ng/g.  In contrast, higher levels were found  earlier in gestation, with 10 ng/g



embryo on gestation day 9 and 2 ng/g on day 10.  The higher levels may be related



to placentation, which occurs at approximately gestation days 10-11 in this mouse



strain.   The  affinity of fetal liver for 2,3,7,8-TCDD was relatively low, as



compared to maternal liver; however,  2,3,7,8-TCDD  levels in fetal livers were 2-4



times  higher  than levels  in other fetal  organs.   Nau  and Bass  (1981) also



attempted to  correlate 2,3,7,8-TCDD  levels  in  the fetuses with  the observed



incidence of  cleft palate.   Three groups of mice were  given  either a  single



intraperitoneal exposure to 25 /jg/kg  2,3,7,8-TCDD on gestation  day 7 or 10 or 5



pg/kg/day, intraperitoneally,  on gestation days  7-11.   On gestation day 13,



2,3,7,8-TCDD  concentrations in maternal tissues were very similar in the three





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exposure groups.  At day  13, however, the  embryo  contained 0.038±0.011% (0.36
ng/g), 0.096±0.027% (0.92  ng/g)  and 0.12±0.05%  (1.1 ng/g) of the dose (mean±SD)
in the 7-,  10-  and 7-  to 11-day exposure groups, respectively.   Cleft palate
incidence on gestation  day 18 was 16,  84 and 65% for the 7-,  10- and 7- to 11-day
exposure groups,  respectively.    Although  further studies are  needed,  these
results suggest that cleft palate incidence is generally related to the 2,3,7,8-
TCDD concentration  in  the embryo.   In a related study, Couture  et  al. (1990)
found that  gestation day 12 was the peak period of sensitivity for 2,3,7,8-TCDD-
induced cleft palate in C57BL/6N mice; however, tissue levels were not investi-
gated .
     In the same laboratory, Abbott et al. (1989) investigated the distribution
of 2,3,7,8-TCDD  in the C57BL/6N  mouse  fetus  following  maternal exposure on
gestation day 11 to 30 pg/kg.  2,3,7,7-TCDD  was  detected in the gestation day-11
embryo at 3 hours post-exposure and was equally distributed between the embryonic
head and body.   At  72 hours post-exposure,  0.035% of the total dose was in fetal
tissues, and 1% of  the 2,3,7,8-TCDD  in the fetus  (1.4-3.5  pg was found in the
palatal shelf.
     Krowke  (1986)  also  measured the concentration  of  2,3,7,8-TCDD  in  the
placenta, amniotic  fluid  and fetus  of  NMRI mice exposed  to  2.5  nmol/kg by
subcutaneous injection on days  9-11  of  gestation.  Similar concentrations of
2,3,7,8-TCDD were observed in the placenta,  amniotic fluid and fetus  (-0.5 ng/g)
on day 16 of gestation.  Fetal  liver 2,3,7,8-TCDD concentrations were at least
five times greater  than other  fetal  tissue.   Krowke  (1986) reported slightly
lower 2,3,7,8-TCDD  levels  in the fetal head  relative to other extrahepatic fetal
tissue, while Weber and Birnbaum  (1985)  found a  slightly  higher 2,3,7,8-TCDD
concentration in the head relative to other extrahepatic  fetal  tissue.
     Nau et al.  (1986) investigated the transfer of 2,3,7,8-TCDD via the placenta
and milk in NMRI mice exposed to 25  /^g/kg on day 16 of gestation.  The authors
confirmed the  relatively  low fetal  tissue levels with  prenatal exposure to
2,3,7,8-TCDD (Nau and Bass,  1981)  and found that postnatally,  2,3,7,8-TCDD was
transferred efficiently to mouse  neonates and  offspring by lactating mothers.
During the  first 2 postnatal weeks, the pups were given  doses of 2,3,7,8-TCDD via
the milk that were, on a body  weight basis,  similar  to  those  that  had been
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administered prenatally to  their mothers.  2,3,7,8-TCDD levels in the tissue of



lactating mothers decreased within the first 3 postnatal weeks by two to three



orders of magnitude  to reach levels  that were only -2% of  the corresponding



levels in the pups that these mothers  had nursed.  Thus in mice, excretion into



milk represents a major pathway for maternal  elimination of 2,3,7,8-TCDD and for




the subsequent exposure of pups.



     The disposition of 2,3,7,8-TCDD in rat pups was  assessed  after the prenatal



(via placental  transfer)  and/or postnatal  (via milk) exposure  from pregnant



Wistar rats given a single  dose of 3, 30 or 300 ng/kg,  subcutaneously, on day 19



of gestation (Korte et al., 1990).  Lactation resulted in the rapid elimination



of 2,3,7,8-TCDD from maternal tissues, with the half-life of 2,3,7,8-TCDD in the



liver of lactating rats estimated to be -7 days.  This compares to a half-life



of  13.6  days in  the  liver of nonlactating rats  (Abraham  et al.,  1988).   At



postnatal  day 7,  exposure via the  milk resulted  in pup  liver 2,3,7,8-TCDD



concentrations that were greater than the corresponding levels in maternal liver.



In cross-fostering experiments,  the concentrations of  2,3,7,8-TCDD in the liver



of offspring at postnatal day 7 were 0.47, 2.59 and 4.16 ng/g in the 300 ng/kg



groups exposed  through the  placenta  only,  via the  milk only  and  through the



placenta  and via the  milk,  respectively.   These results support  the earlier



observations that the placental transfer of 2,3,7,8-TCDD in rats  and mice is



relatively  limited compared  with the efficient transfer via maternal milk.



     Van den Berg et  al.  (1987)  investigated  the transfer  of CDDs and CDFs to



fetal and neonatal rats.  Prenatal exposure of the fetus was assessed  in pregnant



Wistar rats fed a diet containing a fly ash extract from  a municipal incinerator



on days 10-17 of gestation.  Postnatal exposure of 10-day-old pups was assessed



through  feeding  lactating  mothers  the same  contaminated diet for the first 10



days after  delivery.   Although the fly ash extract  contained almost all of the



136 tetra-  to octa-CDDs and  -CDFs, only 17 CDD and  CDF congeners were detected



as major compounds in the tissue of fetuses,  pups and dams. All of the congeners



were 2,3,7,8-substituted with the exception of 2,3,4,6, 7-PeCDF.  2,3,7,8-TCDD had



the highest retention  (0.0092% of the dose/g)  in the fetus, while 2,3,7,8-TCDF,



1,2,3,7,8-PeCDF  and hepta-  and octa-CDDs  and -CDFs were not  detected in the



fetus.  In the liver of offspring,  the highest retention  was  found for 2,3,7,8-




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TCDD,  1,2,3,7,8-PeCDD and  the three  2,3,7,8-substituted HxCDDs  (0.74-1.13%



dose/g).  The 2,3,7,8-substituted penta-  and hexachlorinated congeners  showed the



highest retention  in the livers of  dams  (2.05-5.17% of  dose/g  liver),  while



2,3,7,8-TCDF, 1,2,3,7,8-PeCDF and 2,3,4,6,7-PeCDF had the lowest retention.   A



linear relationship  was  found between the  retention  of CDDs and CDFs  in the




livers of pregnant and lactating rats.   Furthermore, a linear relationship was



found between the retention  of CDDs and CDFs in  the livers  of the lactating rats



and livers of the offspring.




     In a related study,  Hagenmaier et al. (1990)  investigated the transfer of



CDDs and CDFs through the  placenta and via milk  in  a marmoset monkey.  A defined



mixture of  CDDs and  CDFs was  given as a  single  subcutaneous injection  to a



pregnant marmoset  monkey  at the end of the organogenesis period (week  10  of



gestation, 11 weeks prior to delivery).   Transfer  of CDDs and CDFs through the



placenta was investigated in a newborn 1 day after birth,  and transfer through



the placenta and via milk was assessed in an infant of the same litter after a



lactation period  of  33  days.   Tissue  concentrations  of the offspring  were



compared with those of the mother at the end of the lactation period and with



data from other adult marmosets obtained at this time of maximum absorption (1



week after injection) and 6  weeks after  injection.   Deposition of CDDs and CDFs



into the  newborn liver was very  low,  suggesting very little  transplacental



transport  and hepatic  accumulation of these compounds.   2,3,7,8-TCDD  and



1,2,3,7,8-PeCDD were  found  at the highest  concentration  in  the liver of the



newborn (-0.15% of dose/g).   For all other congeners, the concentrations in the



liver of the newborn  were <10% of  the corresponding concentrations  in adults.



In contrast to  liver, concentrations of 2,3,7,8-substituted  congeners  in the



adipose tissue of the newborn were  at least 33% of the levels in adults, and in



the case of OCDD and OCDF, levels were 3-fold higher in the newborn than in the




adult.   The adipose  tissue/liver concentration ratios for 2,3,7,8-substituted



congeners in the  newborn  ranged  from 2.2  for 1,2,3,4,6,7,8-HpCDF to 10.9 for




2,3,7,8-TCDF.  Furthermore,  the concentration of these congeners in the newborn



was highest in the adipose tissue,  followed by  the skin and liver.   This  is  in



contrast to the  relative  distribution  in  the adult where the  liver  generally



contains  the  highest levels of these  congeners.    The results indicate  that




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hepatic concentrations in  the  fetus  may not be representative of  the rate of



placental transfer  of CDDs  and CDFs.   In the  marmoset monkey,  substantial



placental transfer into  fetal  adipose tissue  can be observed for  most of the



2,3,7,8-substituted congeners during  the  fetal period.  As expected from rodent



studies, the  transfer of  CDDs  and CDFs via  mothers'  milk  was  considerable,



resulting  in  hepatic concentrations of  2,3,7,8-TCDD,  1,2,3,7,8-PeCDD  and



1,2,3,6,7,8-HxCDD in the  suckled infant  (postnatal day 33) higher than those in



the dam. The  hepatic concentration of 2,3,7,8-TCDD  in the 33-day-old infant was



-0.9% of the  dose/g tissue.  Transfer of hepta-  and octa-CDDs and CDFs to the



suckled infant was rather low, only -10% of the levels in the dam.  When total



exposure of the mother and  offspring at the end of the 33-day  nursing period was




assessed in terms  of I-TE factors (U.S. EPA,  1989),  the liver  of the mother



contained 2494 pg I-TE/g,  while  the  offspring  liver contained 2022 pg I-TE/g.



This approach is necessary  to assess total exposure due to the congener-specific




transfer via  lactation.



     The pre- and postnatal transfer  of 2,3,7,8-TCDD to the offspring of rhesus



monkeys was  investigated by Bowman  et  al. (1989).   Animals were  fed a diet




containing 2,3,7,8-TCDD at concentrations of 5 or 25 ppt for -4 years and were



on  a 2,3,7,8-TCDD-free diet  for -18 months  prior  to parturition.   Maternal



2,3,7,8-TCDD levels (mean±SE) in adipose tissue were  49±11 (n=7) and 173±81 (n=3)



ppt  in  the 5  and  25 ppt  groups,  respectively.   Corresponding  levels  in the



adipose tissue of offspring at weaning (4 months) were 187±58 an 847±298 ppt in



the  5 and 25  ppt groups,  respectively.  From these data, a 2,3,7,8-TCDD BCF of



4.29 was estimated from mother to nursing infant.   This value  is similar to that



observed for 2,3,7,8-TCDD in the  marmoset monkey (Hagenmaier et al.,  1990).  The



milk of the  rhesus  monkeys  in  the  25  ppt group  contained  from  4-14  ppt of



2,3,7,8-TCDD,  which  corresponds  to 150-500 ppt on  a lipid basis.  The authors



calculated that  the  three  mothers  in the  25 ppt  group excreted from 17-44% of




their  2,3,7,8-TCDD  body burden  by lactation.   They  also concluded  that the




results are generally consistent  with overall triglyceride movement as mediating



the  excretion of 2,3,7,8-TCDD in milk.




      In a subsequent study, Bowman et al.  (1990)  reported the relative persis-



tence  of  2,3,7,8-TCDD in  the offspring of rhesus  monkeys  that  were exposed




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earlier to  5 or  25  ppt of  2,3,7,8-TCDD  in the diet.   The  concentration of



2,3,7,8-TCDD in  adipose tissue  was measured in offspring  at -4-5,  12  and 24



months of age.   The decrease of 2,3,7,8-TCDD levels in adipose tissue of seven



young monkeys departed somewhat from first-order,  single-compartment kinetics,



but with the limited data and an assumption of first-order kinetics, a half-life



of 121 days was estimated.  When the data were adjusted within each animal for



body weight  gain and for average fat content  at  each age,  the  adjusted data



apparently followed first-order, single-compartment kinetics, with a half-life



of -181 days.  Thus, young monkeys apparently eliminate  2,3,7,8-TCDD from adipose



tissue at a  faster rate than adult rhesus  monkeys,  which had individual half-



lives ranging from 180-550 days (Bowman et al., 1989).




     Furst et al. (1989) examined  the  levels of CDDs and CDFs in human milk and



the dependence of these levels on  the period of lactation.  The mean concentra-



tions of CDDs in  human milk  (on a fat basis) ranged  from 195 ppt for OCDD to 2.9



ppt for 2,3,7,8-TCDD, with  the  levels of the other congeners  decreasing with



decreasing chlorination.  This is in contrast to the generally lower levels of



CDFs in human milk, which range from 25.1 ppt for 2,3,4,7,8-PeCDF to 0.7 ppt for



1,2,3,7,8-PeCDF.   An evaluation of the  CDD and CDF levels in  relation  to the



number of breast-fed children found that the concentrations  in milk generally



decreased with the greater number of children.   The CDD and CDF levels in milk



from mothers nursing their second child are on average 20-30% lower than those



for mothers  breast-feeding  their  first child.  CDD and CDF  levels  were also



analyzed in one mother over  a period of 1 year after delivery  of her second baby



to assess the effect of duration of lactation.   After breast-feeding for 1 year,



the mother had CDD and CDF levels that were 30-50% of the starting concentration.



Levels in milk fat (ppt) at 1,  5 and 52 weeks after delivery were 251, 132 and



119 for  OCDD,  7.9,  5.9  and 1.4  for  2,3,7,8-TCDD  and  33.1,  24.5 and  10 for



2,3,4,7,8-PeCDF,  respectively.  The results suggest  a more rapid mobilization of



CDDs and  CDFs  and excretion into  human milk during the first  few weeks post-




partum.  Although further studies are necessary,  the limited data suggest that



there are time-dependent, isomer-specific differences in the excretion of CDDs



and CDFs in human milk.








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     Although data  are more  limited  for the  coplanar PCBs,  3,3',4,4'-TCB,



3,3',4,4',5-PeCB and 3,3 ' ,4,4',5,5'-HxCB have been detected in human milk from



Swedish mothers,  at  concentrations  of 16-32, 72-184  and 46-129 ppt on  a fat



basis, respectively (Noren  et al., 1990).  Therefore,  lactation appears to be an



effective means  for  the excretion of  coplanar  PCBs  from mothers  and  a major



source of postnatal  exposure  of nursing  infants.  Since 3,3',4,4',5-PeCB and



other coplanar PCBs are present in human  milk at  concentrations up to 60-fold



higher than 2,3,7,8-TCDD, it is important to consider  the relative toxic potency



of these  dioxin-like compounds and  their potential  health  impact on nursing




infants.



1.5.2.   Aging.  The  influence of aging on the intestinal absorption of 2,3,7,8-



TCDD was studied  in 13-week-, 13-month- and 26-month-old (senescent)  male Fischer



344 rats  (Hebert and Birnbaum,  1987).  Absorption was  measured by an in situ



intestinal recirculation perfusion procedure.  When absorption was calculated in



terms of ng 2,3,7,8-TCDD absorbed/g mucosal dry weight/hour, the decrease between



the senescent rats and the  two younger age groups,  from 544  ng/g/hour  (young) to



351  ng/g/hour (senescent), was not  statistically significant  (p<0.05).   The



results indicate that, as with other molecules that depend on diffusion for their



absorption, aging does not affect the intestinal absorption of  2,3,7,8-TCDD.



      Banks  et al. (1990) studied the  effect  of age  on the dermal absorption and



disposition of 2,3,7,8-TCDD and 2,3,4,7,8-PeCDF  in male Fischer 344 rats.  When



rats  were administered the  same  dose per  body weight,  dermal absorption of



2,3,7,8-TCDD, at 3 days after  exposure,  decreased from  17.7±2.7%  (mean±SD) to



5.6±2.5%  of the  administered dose in  10- and  36-week-old rats, respectively.



Dermal absorption in the 96-week-old  rats  was similar to that of the 36-week-old



rats.   Dermal absorption  of  2,3,4,7,8-PeCDF also decreased  from  22.2±0.2 to



14.7±3.8% of  the administered  dose  in 10- and 36-week-old rats, respectively.



Dermal absorption of  both  compounds  was also decreased  in  older rats given the



same  total  dose  per  surface area.  Older  animals may have  decreased blood flow



in the upper  dermis,  which will decrease  the clearance  of  these compounds from




the application site. Potential age-related changes in the intercellular stratum



corneum  lipids may also play a role in the decreased  dermal absorption observed



in older animals.  Changes in the percentage of the  administered dose detected




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in various depots reflected age-related changes in dermal absorption, while age-


related changes in the tissue distribution of the absorbed dose reflected changes


in the total mass of these tissues at various  ages.  Overall elimination of the


absorbed dose was not affected by age.  Although this investigation was conducted


using a  lipophilic  solvent  system and  an animal model with skin that is more


permeable than  human  skin,  the results  suggest  that  systemic  bioavailability


after dermal exposure to 2,3,7,8-TCDD or 2,3,4,7,8-PeCDF may be reduced in older


age groups.


     In a similar study,  absorption, tissue distribution  and  elimination were


examined 72  hours after  dermal application of  a lower dose of  200  pmol (111

       2
pmol/cnr) 2,3,7,8-TCDD to weanling  (3-week-old), juvenile (5-week-old), pubescent


(8-week-old),  young adult  (10-week-old) and  middle-aged (36-week-old)  rats


(Anderson et al.,  1992). Dermal absorption using acetone as vehicle was greatest


in 3-week-old rats  (129 pmol; 64%  of the administered dose),  decreasing to -80


pmol (40%)  in 5-, 8- and  10-week-old rats and to 45 pmol  (22%)  in 36-week-old


rats.  The results  indicate  that  2,3,7,8-TCDD is absorbed to  a  greater degree


through skin of very young animals and that a significant decrease in potential


for systemic exposure may occur during  maturation and again during aging.


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Abraham, K.  R.  Krowke and  D.  Neubert.   1989.   Absorption  of TCDD following



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Banks, Y.B. and L.S.  Birnbaum.   1991b.  Kinetics of 2,3,7,8-tetrachlorodibenzo-



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Couture, L.A., M.W. Harris and  L.S.  Birnbaum.   1990.   Characterization  of the



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Curtis, L.R.,  N.I.  Kerkvliet, L.  Baecher-Steppan and H.M.  Carpenter.   1990.


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