Ambient Water Quality Criteria
              Criteria and Standards Division
              Office of Water Planning and Standards
              U.S. Environmental Protection Agency
              Washinaton, D.C.

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                        CRITERION DOCUMENT



                               ZINC




CRITERIA




                           Aquatic Life




     For zinc the criterion to protect freshwater  aquatic  life  as



derived using the Guidelines is "e < ° • 67 ' ln ( hardness )  +




0.67)" as a 24-hour average (see the figure  "24-hour  average




zinc concentration vs. hardness") and the  concentration  should  not



exceed "e(0.64•ln(hardness) + 2.46)» (see  the  figure




"maximum zinc concentration vs. hardness") at  any  time.



     For saltwater aquatic life no criterion for zinc can  be




derived using the Guidelines,  and there are  insufficient data  to



estimate a criterion using other procedures.



                           Human Health




     For the prevention of adverse effects due  to  the organoleptic



properties of zinc, the current standard for drinking water of  5




nig/I was adopted for ambient water criterion.

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Introduction



     Zinc is a bluish-white metal which dissolves readily



in strong acids.  Its principal uses include electroplating



and the production of alloys.  Zinc is never, found free



in nature, but occurs as the sulfide,  oxide, or carbonate



(Lange, 1955).



     In the aquatic environment zinc is acutely toxic to



freshwater organisms at concentrations as low as 90 ug/1



(Rabe and Sappington, 1970) and the lowest reported chronic



effects lie between 26 and 51 ug/1 (Spehar, 1976).  In marine



waters comparable values are 141 ug/1 in acute tests (Calabrese,



et al. 1977)  and 220 ug/1 in chronic tests  (Reish, et al.



1976).



     Water quality has been shown to affect zinc toxicity.



The best-studied of these is the protective effect exerted



by water hardness, which has been incorporated into the



freshwater criterion for the protection of aquatic life.



     Because zinc is an element it can be expected to persist



in the environment indefinitely in some form.



     In humans zinc ingestion has produced no clinical symptoms



at daily intakes of 150 mg/day for as long -as six months



(Greaves and Sillen, 1970).  Brown,  et al.  (1964)  reported



food poisoning from ingestion of a meal estimated to contain



nearly 1,000 ppm of zinc and another case among people who



had drunk punch containing zinc at a concentration of 2,200



ocm.
                              A-l

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                          REFERENCES








Brown, M.A., et al. 1964.  Food poisoning involving zinc



contamination.  Arch. Environ. Health. 8: 657.








Calabrese, et al. 1977.  Survival and growth of bivalve



larvae under heavy-metal stress.  Mar. Biol. 41: 179.







Greaves, M.W., and A.W. Sillen.  Effects of long-continued



ingestion of zinc sulphate in patients with venous leg ulcera-



tion.  Lancet. Oct. 31, 1970.







Lange, N.A. 1956.  Handbook of Chemistry.  Handbook Publishers,



Inc., Sandusky, Ohio.






Rabe, F.W., and C.W. Sappington. 1970.  Biological productivity



of the Couer D'Alene river as related to water quality.



Water Resour. Res. Inst. Univ. Idaho, Moscow, Idaho.  Project



A-024-IDA. 15 p.






Reish, D.J., et al. 1976.  The effect of heavy metals on



laboratory populations cf two polychaetes with comparisons



to the water quality conditions and standards in southern



California marine waters.  Water Res. 10: 299.






Spehar, R.L. 1976.  Cadmium and zinc toxicity to flagfish,



Jordanella floridae.  Jour. Fish. Res. Board Can. 33: 1939.
                             A-2

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AQUATIC LIFE TOXICOLOGY*



                       FRESHWATER ORGANISMS




Introduction



     Zinc is one of the most commonly occurring heavy  metals  in




natural waters, and is an essential element for most plants  and



animals.  Zinc is used principally for alloys and galvanizing.




     Predicting the toxicity of a .given total zinc  concentration



in water is complicated by numerous physical-chemical  factors




which alter the form of the zinc and hence change its  avail-



ability, rate of uptake, and toxicity.  Seasonally  and locally,




toxicity may be altered by the presence of naturally occurring




chelating, complexing, and precipitating agents.  While  there are




many such factors which may alter zinc toxicity,  the only  factor



for which the effect is well documented is hardness.   Therefore




the criterion for zinc is expressed as a function of water  hard-



ness.  However, as evidenced by the criteria derived herein,  con-



centrations required for survival, growth, and reproduction  of  the




more sensitive aquatic species may at time be below ambient  total




zinc concentrations in some surface waters of the United States
*The reader is referredfto the Guidelines  for Deriving  Water



Quality Criteria for the Protection of Aquatic  Life  [43 FR  21506



(May 18, 1978) and 43 FR 29028  (July 5, 1978)]  in  order to  better



understand the following discussion and recommendation.  The



following tables contain the appropriate data that were found  in



the literature, and at the bottom of each  table  are  the calcula-



tions for deriving various measures of toxicity  as described  in



the Guidelines.
                             3-1

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This results,  in  large  part,  from  the  current  inability to corre-



late quantitatively  the effects  on  zinc  toxicity  of  physical-chem-



ical factors other than hardness.



Acute Toxicity



     One hundred  and  thirty 96-hour  LC50  values  for  21  species  of



freshwater fish are  listed in  Table  1,  including  34  for the  rain-



bow trout, 31  for the fathead  minncw,  and 20 for  the bluegill.



The 96-hour LC50  values for all  species  ranged  from  90  to 40,900



ug/1.  Approximately  one-half  of the values were  based  on flow-



through tests with measured zinc concentrations;  the range of



values from these tests was 93 to  35,500  ug/1.



     Because there are  no studies  which  directly  compare  static



and flow-through  results, the  Guideline  factors  for  converting



static to flow-through  LC50 values  are  used.   Similarly,  the



Guideline factors for adjusting  unmeasured  to  measured  values  and



less than 96-hour to  96-hour values  were  used.  The  resultant  ad-



justed acute values  ranged from  49  to  48,266 ug/1-   The use  of  the



Guideline factors did not produce  an appreciable  change in the



range of 96-hour  LC50 values.



     Data on interspecific variability  in zinc  sensitivity are



provided by several  studies.   Holcombe ^and  Andrew (1978)  found



that rainbow trout are  two- to four-times more  sensitive  to  zinc



and six to seven  times  less sensitive  than  the  fathead  minncw.



     Following the Guidelines, the  mean  intercept, adjusted  by  the



species sensitivity  factor, for  all  20  fish species  is  3.93.



Since results of  flow-through  tests  with  measured concentrations



for Chinook salmon are  lower  than  this,  the data  for chincok



salmon are used to derive the  Final  Fish  Acute  Value which is






                              B-2

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e(0.67-ln(hardness) + 3.63)^

     The effect of hardness on zinc toxicity  is  not  as  well
documented with invertebrate species as with  fish; however,  the
data of Cairns and Scheier  (1958) and Wurtz and  Bridges (1961)
indicate that zinc is more  toxic to the snail, Physa
heterostropha, in soft water than in hard water.
     Sufficient data are available for Physa  heterostropha  to  fit
a hardness regression equation.  The slope  (0.64)  is similar to
that for fish thus lending  additional support  to  this  approach.
The calculated mean intercept for the 16  invertebrate  species  is
5,50, indicating that invertebrate species are slightly less
sensitive than fish.  The range  (1,937 times)  of  adjusted LC50
values for invertebrate species  (33 to 63,910  u.g/1)  is  somewhat
greater than that for fish, with cladocerans  being more sensitive
than any fish.
     Daphnia hyaline, the most sensitive  species' (intercept  =  +
1.49), is approximately 55  times more sensitive  to zinc than
indicated by the mean sensitivity.  At least  3 invertebrate
species are more sensitive  than Chinook salmon.   The most
resistant adult insects, however, have not been  tested  in
hardnesses higher than 40-50 ug/-l •
     Using the Guidelines,  the adjusted mean  intercept  is 2.46,
which is adequate to protect all species  except  possibly Daphnia
hyalina.  Only a single acute value, run  under static  conditions
with unmeasured zinc concentrations, is available  for  this
species.  The adjusted mean intercept thus appears adequate  for
invertebrate species.  The  Final Invertebrate  Acute  Value is
e(0.64-ln(hardness) + 2.46).  since this  value is  lower
than that for fish, it becomes the Final  Acute Value.
                             B-3

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Chronic Toxicity



     Chronic toxicity  values  for  five  fish  species  ranged  from 36



to 852 ug/1  (Table  3).   All chronic  tests were  conducted  in  soft



water  (25-46 mg/1 as CaCC^);  no acceptable  hard water  chronic



tests  are found in  the  literature  to compare  with  the  soft water



data.  A life-cycle test with  the  fathead minnow in hardwater



(Brungs, 1969) observed  adverse effects  at  all  exposure



concentrations (as  low  as 180  ug/1)  (Table  7).   However,  it  is



felt to be  inappropriate to estimate a chronic  value using that



concentration and the  much lower  average control concentration of



30 ug/1.



     Since  no other appropriate fish data were  available  to



establish a  significant  relationship between  chronic toxicity



values and  hardness, a  relationship  was  estimated  by using the



slope  (0.67) from fish  acute  values.   Calculated intercepts  for



the five species tested  ranged from  1.05 for  flagfish  to  4.20  for



brook  trout, with a nean of 2.57.  The adjusted mean intercept'



(0.67) is below that for all  species.  Thus  the Final  Fish Chronic



Value  is obtained from  e(° • 67*ln(hardness)  +  0.67).



     Only one invertebrate chronic test  result  is  available  (Table



4).  This test with Daphnia magna  was  conducted in  soft water, and



the resulting chronic  value is 3.3 tines lower  than the acute



value  (280  ug/D for the same  species  in the  same  water.   Daphnids



are the most sensitive  invertebrate  organisms tested in the  acute



exposures;  therefore,  it seems reasonable to  assume that  the



chronic zinc value  for  Daphnia magna would  be equal to or  lower



than most ether invertebrate  chronic values.   Thus, it would



appear to be inappropriate to  use  the  species sensitivity  factor



                              B-4

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(5.1) with the chronic data for Daphnia magna,  since  it  is  one  of
the most sensitive invertebrate species.  Consequently  the  sensi-
tivity factor was not used in the calculations  to  derive the  Final
Invertebrate Chronic Value.  It is also interesting  to  note that
the Daphnia magna chronic value for zinc  is  relatively  close  to
the fish chronic value (Table 3).  Even though  invertebrate
chronic tests have not been conducted  in  hard water,  it  again
seems logical to assume that a similar relationship  probably
exist^ between chronic zinc toxicity and  water  hardness  for inver-
tebrate species as is demonstrated for acute and chronic exposures
of fish.
     Since appropriate invertebrate data  are not available  to
establish a relationship between chronic  toxicity  values and
hardness, a relationship i.s estimated  by  using  the slope (0.64)
from invertebrate acute values and the zinc  value  and water
hardness from the Daphnia magna chronic "test.   Thus  the  Final
Invertebrate Chronic Value is from e(°•64'In(hardness)  +
2.00)^
     $ince the Final Fish Chronic Value is lower than that  for
invertebrate species, it becomes the Final Chronic Value.
Plant Effects
     Tests with five species of plants, including  four  species  of
algae, are listed in Table 5.  Zinc concentrations from 30  to
21,600 ug/1 have been shown to reduce  the growth of  various plant
species.  .The significance of short-term  growth inhibition  in
algae has not been established; however,  since  many  algal  tests
are conducted in artificial media which may  complex  zinc more
                             B-5

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than most natural waters,  the  existence of  low  effect  levels

should be considered  as  a  potential  important ecological  effect.

     The lowest plant value  (30  ug/1)  is  similar  to  the  chronic

values for  fish and  invertebrate  species, so  sensitive algal

species will probably be protected by  criteria  for the protection

of other sensitive freshwater  organisms.

Residues                                                        fe
	                                                        1
     Table  6 contains the  zinc bioconcentration factors  for  two

fish species and two  invertebrate species.  The bioconcentration
                                                                »
factors for fish are  low (8  and  12.2), whereas  the factors  for
                                                                r
invertebrate species  are one or  two  orders  of magnitude greater- <

(106 and 1,130).

     Dietary zinc at  a level of  2,000  mg/kg has been shown  to

produce stillbirths  and  inhibition of  postnatal growth in rats

(Ketcheson, et  al. 1969).  Assuming  a  diet  of invertebrate

organisms which could bioconcentrate zinc by a  factor of  l,13o£-*it

would require a zinc  water concentration  of 1,800 ug/1 (the

Residue Limited Toxicant Concentration) to  produce this effect.

This concentration is well above  chronically  toxic levels for

freshwater  fish and  invertebrate  species; therefore  biocon-

centration  does not  seem to  be a  critical factor  in  establishing a

freshwater  criterion  for zinc.

Miscellaneous

     Table  7 contains other  data  on  the effects of zinc on

freshwater  organisms.  With  the  exception of  the  avoidance data of

Sprague (1968), no data  are  found which would appear to  influence

the criterion for zinc.  Sprague  (1968) found that rainbow  trout
                              B-6

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would avoid a zinc concentration of 5.6 ug/1  in  a  laboratory



behavior test in water with a hardness of 14  mg/1  as  CaCO3.   The



final chronic value for zinc at a water hardness of  14  mg/1  is  7.6



ug/1 (Figure 1), and may or may not protect against  significant



av.oidance behavior.
                             B-7

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CRITERION FORMULATION
                         Freshwater-Aquatic  Life
Summary of Available Data
     All concentrations  herein  are expressed  in  terms  of  zinc.
     Final Fish Acute Value  = e<°•67*ln(hardness)  +  3.63)
     Final Invertebrate  Acute Value  = e(°•64'ln(hardness)  +  2.46)
          Final Acute Value  = e <° • 64 " ln( hardness )  +-2.46)
     Final Fish Chronic  Value = e°•67*ln(hardness) + 0.67)
     Final Invertebrate  Chronic Value = e(°•64'ln(hardness)  +  2.00)
     Final Plant Value = 30  v.g/1
     Residue Limited Toxicant Concentration =  not  available
          Final Chronic  Value = e<°•67'ln
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    lOO.Op
    40.0
O

O  20.0
O
O
N  a>
UJ  S
§  OT 10.0
o: ^
UJ
            24-HOUR AVERAGE
            ZINC CONCENTRATION
            VS.
            HARDNESS
cr
a
4.0
     2.0
     1.0
       10
            20        40            ICO
                  TOTAL HARDNESS (mg/l)
                         In scale
200
4CO
                              B-9

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    2000
    1000
MAXIMUM ZINC CONCENTRATION
             VS.
         HARDNESS
cc
H-
z:  w  200
8 —
o
z;
M

5    ICO
1
X
     40
     20
       10
      20
100
                       TOTAL HARDNESS (mg/l)
                              In scale
200
400
                              B-10

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                            Table  1.  Freahwiiter fi:;h acute  values for zinc
03
 I
u
Orj.ir.ir.ni M
American eel.
An^ui 1 la rosirata
American eel .
Anruilla ro.stratu
Coho salmon,
Oiicorhynclms ki sutch
Coho salmon.
Oncorlivnuhii;; kisutch
Sockeye salmon.
OiK'orhynchui; nerka
Sockeye salmon,
Onrorhynchus norka

Chinook salmon,
Oiicorhynchu:; tnhawy tscha
Chinook salmon,
Oncorhyrichiiii tyhawy_tscha
Chinook salmon.
Oncorliynchus tshawytscha
Cut.lhroat trout.
Sal mo clarki.
Cm throat Trout ,
5i:iliuo el at k i.
Rainbow trout,
Sal mo £,aj rilnori
Ka i nbow trout ,
Sa Inio jj;.ii rdneri
Ka i nbow 1 rout ,
Sal mo «ni r Jneri
itainl.ow trout.

OthOiI'.'--
S

S

FT

FT

FT

FT


1;"l

FT

FT

S

FT

S

FT

S

FT
llct illness
y Tost (in. |/ 1 oS
o>iiO»* CaC()n)
M 53

M 55

M 89-99

M 25

M 34

M 13


M 24

M 2 A

M 24

M 24

M 24

M 320

M 500

II 5

M
Time
Jura)
96

96

96

96

96

96

X
96

96

06

96

24

48

48

96

96
l.t"jO
Jn^/JJ
1.4.600

14.500

4 . 600

905

749

1.000


97

701

463

90

420

3,500

4 , 700

2.80

550
Adjusted
l.i.'.'jO
ili-J/tJ 	
10.366

10.295

4 , 600

005

740

770


97

701

463

49

277

2.012

3.807

153

550

hi.-l 11 fiicf
Kehwoldt, et al
1971
Rehwoldt, et al
1972
l.o r z & McPheruoi
1976
Chapman & Stevei
197K
Chapman, 197fia

Boyce & Yamada ,
1977

Chapman. 1.978b

Chapman, 19731,

Chapman, 19781)

Rabc k
Sappington, 197i
Rabe f«
Scippington, lOV'i
Brown, 1968

Solbe, 1974

McLcay, 1976

Hale. 1977
                   en l r (Inert

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                            Table   1 .    (Continued)
                                                   llarunesu
                                                   (m«i/ !  JH  Time
Ol'U.lliJ. Hill
           Adjunfed
LCSU       J.OU
(»>|/1 )     JiiU/il	   !• ct C-i 0111:1;











CO
1
1 — '
M















Rainbow tr-out,
S a 1 mo j;ai rdner i
Rainbow trout,
S.'i lino j;.ai rdner i.
Rainbow trout ,
Salmo ^ai rdner i
Kainbow trout,
Salmo gairdnei'L
Rainbow trout ,
Salmo gai rdneri.
Rainbow trout ,
Salmo £,ai. rdner i
Ra i nbow trout ,
Salmo jjairdneri.
Rainbow trout,
Sri lino ^a i rdner i
Kainbow trout.
Salmo ^airdneri
Kainbow trout,
Salmo gai.rdneri
Kainbow trout,
SalniO ga.ir drier i
Rai.nbow trout ,
Salmo j'.ai rdnori
Rainbow trout,
Salmo gairdnerl
Rainbow trout ,
Salmo i?.ai rdneri
FT M

FT M

R M

S M

S M

S M

S U

FT M

S II

FT _ M

FT M

FT M

FT M

FT M

333

26

240

36

36

36

320

83

320

47

47

44.4

178

179

96

96

48

24

24

24

48

96

. 72

y«,

96 v

96

96

96

7



4

2

1

2

2

t:

3







2

o

,210

430

,000

,800

.560

,100

,460

.755

,500

370

517

756

,510

,960

7,210

430

2 , 300

1 ,312

731

984

1,089

1,755

1 . 760

370

517

756

2.510

2,960

Sinley , ct al .
1.974
Sinley, et al.
1974
I'rown &
Da It on, 1970
Cai vn s , et a 1 .
1978
Cairns, et al.
1978
Cairns, et al.
1978
Herbert &
Van Dyke, 1964
Cbapman & Stevens
1978 :
Lloyd, 1961

llolcombe £>
Andruw, 1978
llolcombe &
Andrew, 1978
llolcombe &
Andrew, 1978
llolcombe &
Andrew, 1978
llolcombe &
Andruw. 1978

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                                   Table   1.   (Continued)
09
I

U)
Hardness
Bicassay Test (me,/ 1 as Time
Orqanism Method* Cone.** CaCCK) furs)
— — — — .NT • ••- j ' — -* — T
Rainbow trout, .FT M 170 96
Salmo gairdneri
Rainbow trout,
Salmo gairdneri
Rainbow trout,
Salmo gairdneri
Rainbow trout,
Salmo gairdneri
Rainbow trout,
Salmo gairdneri
Rainbow trout,
Salmo gairdneri
Rainbow trout.
Salmo gairdneri
Rainbow trout,
Salmo gairdneri
Rainbow trout (yearling) ,
Salmo gairdneri
Rainbow trout
(fingerling) ,
Salmo gairdneri
Rainbow trout
(fingerling) ,
Salmo gairdneri
Rainbow trout
(fingerling) ,
Salmo gairdneri
Rainbow trout ,
Salmo. gairdneri
FT
FT
FT
FT
FT
FT
FT
FT
FT
S
S
FT
M
M
M
M
M
M
M
M
U
U
U
M
333
333
26
26
26
26
26
365
320
320
44
23
96
96
96
96
96
96
96
96
48
48
48
96
LC50
1,910
4,520
1.190
560
240
810
410
830
5,340 .
3.860
2.400
910
93
Adjusted
LC1>0
iiia/iL_
1,910
4,520
1.190
560
240
810
410
830
5.340
2.407
1.063
403
93
1
FeteLfcii
ice
Hoi combe &
Andrew, 1978
Goettl, et al.
1972
Goettl. et al.
1972
Goettl, et al.
1972
Goettl, et al.
1972
Goettl, et al.
1972
Goettl, et al.
1972
Goettl. et al.
1972
Watson, 1975
Herbert &
Shurben, 1964
Herbert &
Shurben, 1964
Herbert &
Shurben, 1964
Chapman, 1978b
Rainbow trout,
Salmo gatrdneri
                                     FT
                                              M
                                                         23
96
                                                                               136
136    Chapman, 1973b

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                                     Table   1.   (Continued)
03
I
            Organism
Rainbow trout,
Salmo gairdneri

Atlantic salmon.
Salmo salar

Atlantic salmon.
Salmo salar

Atlantic salmon,
Salmo salar

Atlantic salmon,
Salmo salar

Brook trout,
Salvelinus fontinalis

Brook trout,
Salvelinus fontinalis

Brook trout,
Salvelinus fontinalis

Brook trout,
Salvelinus fontinalis

Brook trout,
Salvelinus fontinalis

Brook trout,
Salvel'inus fontinalis

Goldfish,
Carassius auratus

Goldfish.
Carassius aura'tus

Goldfish.
Carassius auratus

Goldfish,
Carassius auratus
                        Bioassay  Test
                        Metl)on*_  Cone... **
                   Hardness
                   (mo/1  as  Tipie      LC50
                   CaCOj)
                                                                                       Adjusted
                                                                                       LOO
.FT


 FT


 FT


 FT


 FT


 FT


 FT


 FT


 FT


 FT


 FT


 S


 S


 S


 S
M


M


M


M


M


M


M


M


M


M


M


M


M


M


U
 23        96


 14        96


352        96


 20        96


 14        96


 47        96


 47        96


 44        96


178        96


179        96


170        96


 36        24


 36        24


 36        24


 20        96
                                                                                815


                                                                                740


                                                                              3,130
   -v.420


  1.550


  2,120


  2,420


  6.140


  6,980


  4.980


103.000


 40.000


 24,000


  6.440
              815    Chapman, 1973b
              740    Carson &
                     Carson, 1972

            3,130    Hodson &
                     Sprague, 1975

             •x.600    Sprague, 1964
  i420    Sprague &
          Ramsey, 1965

 1.550    Holcombe &
          Andrew. i978i.

 2,120    Holcombe &
          Andrew. 1978

 2.420    Holcombe &
          Andrew, 1978

 6,140    Holcombe &
          Andrew, 1978

 6,980    Holcombe &
          Andrew, 1978

 4,980    Holcombe &
          Andrew, 1978

48,266    Cairns, et al.
          1978

18.744    Cairns, et al.
          1978

11.246    Cairns, et al.
          1978

 3.521    Pickering &
          Henderson, 1966

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                             Table   1 .   (Cuiitifiued)
11
ic-abi;ay Test
H jcciness
(tin;/ ! .is
Oi 'Jjiiii sin He tin id '•'•' I'niic:.** CaCO.,)
Goldfish,
Carass lit';; aural. us
Car p.
Cyprinus carpi o
Carp,
Cypri.mis carpio
Golden shiner.
Hoi fini jjonus crysol eucus
Golden shiner.
Hotemi ^onus cr^soleucus
Golden shiner,
tp Nol emi i^onus eryjuil eucus
1 "" ~
I—1 Golden shiner,
01 Notemiftonus crysoleucus
Fathead minnow,
I'imephalcs promelas
Fathead minnow,
1'i nienhjl es prciinel as
Fathead minnow,
IMmephales nromclas
Fathead minnow,
JM.mephal.es promelas
Ful.head minnow,
1'imephalet; nrome las
1'athead minnow,
IMmephales promelas
Fathead minnow,
IMniepha 1 e.s promelas
Katliuad ininnov/,
S U

S M

S M

S H

S M

S M


S IJ

FT M

FT M

FT M

FT M

FT M

FT M

FT M

FT M
50

53

55

36

36

36


50

50

50

100

100

200

200

50

50
Tune
Jt.tij)
96

96

96

24

24

24


96

96

96

96

96

96

96

96

96
I.CSu
Ad i us Led
i.C'jO


Jtii(/i) ('"I/-1) 1- c- 1 --I c.i» :tr
7

7

7

11

7

8


6

12

13

18

25

29

35

13

6
. 500

,800

,800

,400

.760

,330


,000

, 500

.800

,500

,000

.000 .

,500

,700

,200
4. 100

5.538

5.538

5,342

3.636

3,903


3.280

1.2.500

13.800

J8.500

25,000

29,000

35,500

13,700

6,200
Cairns ,
1969
et al .

Rehwoldt, et al
1971

Kehwoldt, et al
1972
Cai rns ,
1978
Cairns ,
1978
Cai rns ,
1978

Cairns ,
1*69
Mount ,

Mount ,

Mount ,

Mount ,

Mount ,

Mount,

Hout t ,

Mount ,

et al.

et al .

e t a 1 .


et al .

1966

1966

1966

1966

1966

1966

1966

1966
''iDii'I'Llril^ii promts las

-------
                                     Tame  1.    (continued)
03






CTi

Organism
Fathead minnow,
l'imepj)a les promelas
Fathead minnow,
I'i merlin les promelas
Fathead minnow,
1'i me nil u 1 es jiromelas
Fathead mLnnov;,
Vimojihalos promelas
Fathead minnow,
Pimephales promelas
Fathead minnow,
Pimuplial os promelas
Fathead minnow,
I'imepha les promelas
Falhuad minnow,
I'imepha] es promo la. i
Fathead minnow,
I'imepha les promelas
Fathead minnow,
1'imephales promelas
Fathead minnow,
I'inii-pjialcs p_romelas
F;ithu;id minnow,
Hmephales promelas
Fathead minnow,
1'imephales promelas
Fathead minnow,
I'imepha les promelaa
Fathead minnow,

iliCxiSSay
Method*
FT
1'T
FT
1-T
FT
FT
FT
FT
FT
FT
FT
FT
S
S
FT

Test
Cone .**
M
M
M
M
M
M
M
M
M
M
M
M
U
U
M
lUtiiriess
(in«;/l .is
CaCO.j)
100
100
200
200
50
50
100
100
200
200
203
203
203
203
46

Time
96
96
96
96
96
96
96
96
96
96
96
96
96
96
96

LC50
J'w/ijL
12,500
12,500
1 9 , 000
13,600
4 , 700
5,100
8.100
9,900
8,200
15,500
8,400
10.000
12.000
13,000
600
Ad j us red
l'"J/i] 	
12,500
12,500
19,000
13,600
4 .700
5,100
8 . 100
9 . 900
8,200
15.500
8.400
. 10,000
6,560
7.107
600

hereifc
Mount ,
Mount ,
Mount ,
Mount ,
Mount ,
Mount ,
Mount ,
Mount ,
Mount ,
Mount ,
llrungs
Hrungs
Brunts
Orungs
Benoit

,K:C
1966
1966
1966
1966
1.966
1966
1966
1966
1966
1966
. 196
. 196
. 196'
, 196
& Ho
            Lim£Pnilli^ promclag
1978

-------
                                      TaLae  I.   (Continued)
 I
-J
l-'athead minnow  (embryo) ,
I'imeplwileu promelas

Tathead minnow  (embryo),
Pinivphiilcs promelas

Kalhoiid minnow  (Cry),
Pimcplialc£ Iiri2!ni:]jl:i

Fathead minnow,
P i nig 1> h .• 11_ u s prome la a

(•'ill head minnow,
j'iniepluileji premie las

Kathcad miiinou,
PiiiiL'piiales proniolas

I'aLhead iniiinuw.
Piuionluilcs promelas

l-'alheail minnow,
I'inu:p_hal_es pronielas

Handed  klllifisli.
I'undidiiu d_iaphanua

Han.led  kill il'ish,
Kiiniliil us tliaphanus

Flagfish,
Jiirdanel la I'Loridae

Uuppy,
Poeci^l ia rot iculatus

Southeirn platyfish,
X_i ['^'P.liHHl'l macul atua

White perch,
llurone  aiiio
While  perch,
Morone  americana
Aliiiiay
I:OQ*
Ff
FT
FT
s
S
S
0
s
s
s
FT
S
*
-'>
S
Test
Cone.**
M
M
M
U
U
U
U
U
M
M
M
I)
U
M
M
Hardness
(in.;/ 1 js
CaC03) _
174-198
174-198
174-198
20
20
20
360
166
55
53
44
20
166
53
55
Time
iius)
96
96
96
96
96
96
96
96
96
96
96
96
96
96
96
Juu/iL
1,850
1 ,820
870
960
780
880
33,400
7.630
19,200
19.100
1.500
1.270
1.2,000
14,300
14,400
Adi us ted
l'U/i) 	
1 .850
1.820
870
525
426
481
18,260
4,171
13.632
13.561
1.500
694
6.560
10.153
10.224
l-.i.-ti-i 4:m:t;
Pickering ft Vi.goi
1965
Pickering & Vigoi
1965
Pickering -It Vigoi
1965
Pickering &
Henderson , 1966
Pickering &
Henderson, 1.966
Pickering &
Henderson , 1966
Pickering 6.
Henderson, 1966
Kach I in 6
Pcrlmutter, 1963
Rehwoldt, et al.
1972
Rehwoldt. et al.
1971
Spehar, 1976
Pickering &
Henderson, 1966
Kachlin ft
Per limit cer, 1968
Rehwoldt, et al.
1971
KehwoLdt, et al.
                                                                                                        1972

-------
                         Table  I.    (Continued)
UiCviuoay Test
Ot'Hanj :'ifi M  Cuiic.**
Si:r ipcd bass , S M
Mornne s.'ixati lis
Striped bans, S M
Mornne saxaL il is
Striped bass (embryo), ;; M
Mortinu sax.aL~i.lis
Siripod bass (fry), i! M
Mortinu .saxat.i J i s
Scriped bass, S 11
Mo rone saxatilis
r~.unpkinsi.~uJ, S M
l.epomis j-.ibbosuu
g-j .._
jL I'uiiipkJn.seeiJ, S M
°° L^L'L-L'L'-i ti-5!.^^!1!!
Ill u eg ill, I-T M
l.eponii s inacrochi rus
Bluegill, S U
I.cpomi s iiiacrochirus
IHuegill, S (I
I.c|>omi s iiiacrochirus
liluogill , S U
I.epomi.s ni.'icrochirus
BUicgilJ, • S U
l.t:~_ioini a mucrorh-i rus
liluugill, S M
l.ojioinis niacrochirus
liluetjill. S M
l.epciin i s iiiacrochirus
lilueKill, .S M
(in.:/! .f.i Tlint.' LCiiU U"<0
CaCOj) (liia) •(••ti/11 (•••J/Jl I't-tt-'i I'lK-
55 96 6,800 4,828 'Kehwoldt:
1972
53 96 6.700 4 757 Keliwoldt
1971
137 96 1.850 1.313 O'Ku.ir.
137 96 1.180 837 O'Kear.
96 100 54 llughus,
53 96 20.000 14,200 Keliwoldt
1971
55 96 20,100 14,271 KcLwoldt
1972
46 96 9,900 9,900 Cairns,
. 1972
10 48 5,200 2,302 Cairns.
1965
96 7.450 4,072 Ca i.rns &
Schcior,
96 7,200 3,936 Cairns &
Scheiur,
96 6,910 1./77 Cairns f<
Schoier ,
36 24 23,000 10.77B Cairns.
1978
36 24 19,100 8,950 Cairns.
1978
36 24 8,850 4.14V .Cairns,
0.
, CL al.
, ci ai
1972
1972
1973
. OL al
, ot a 1
c L a 1. .
e t a 1 .
1959
1959
1959
cl al.
u t a 1 .
,c L a 1 .
l.i.'oini:; macrochi rus
1978

-------
                                      1.    (Continued) '
1)1 u.II: 1 Sill
                             lliG,it;:j;iy   Test
                             Mv thud'"    OHIO.
(nui/ 1  .1:;  Timo
C.-iCO.)     jiu.
... .	
                                                                               LC!»0
Ad jus led
!.<--, 0
-lii'Jil.i.1 __  I- et t-i em ;e
Hiuej'.i 11,. s u
l.i-|n>iiii.s macrochi rus
liluei'.ill . S II
1 .e])i mi i s iiiacroclii.ru:;
Kliu-j'i 11. S U
I.t.-j)onii s macroch i rus
IUuc^il.1. S U
I.ejioni i s macroch i rus
liluc^ii 1 , S U
l.c[ioiiii s iiiacrochirus
m UlucKill, S 1)
1 I.L-jioini u ni.icrochi rus
<^ UlllC|M 11 , S 11
l.«:|iciini s inae.roch i rus
lUuei'i.l 1 . S U
I.L'noini .-> iiiacrochirus
IllllCjM 11, S 11
I.t.-poin i :; mac rochi rus
11 1 in.-,-, i 1 1 , S U
1 .c[x mi i s rn.ic roch i rus
llluec.i 11. , S 'l)
I.c|ioiiii :; macroch i I us
IJIiu:(.,i 11. . .S U
l.r '[111111! s ma croc hi rus

20 96
20 96

20 96

20 9b

360 96
45 96

'.5 96

4/i 96

V, 96

171 96

1 7 1 96


2.860-
3.780
5.460. .
4,8')0

5.820

5,370

40.900
8.020

4 , 900

2 860-
3 , 780
1.930-
3.630
10,130-
12, 500
10,150-
1 2 , 300

2^067
2,985
2,631

3,182

2,936

22.360
4.385

2.679

1 ,560-
2.06/
1 055-
1 /J85
5.538-
6.834
5.549-
6,724

Patrick, OL al .
1968
Picker inj'. iSc
lleiulorson , 1966
lleiulorson , 1966
Pickering, &
Henderson, 1966
Picker in g fir
Hendei son , 1966
Pi eke riii); ft
Henderson , 1966
Cairns ,S,
.Scheier. 1957a
Cairns 6,
Scheier, 1957a
Cairns 6
.Schoier. 1957b
Cairns &
Sc.-hci.er. 19571)
Cairns f,
Scheier. 1957|j
Cairns &
Scheier, 195 7b

    S -  static,  K  - renewal,   IT =  flow-1 hrouf.h

•'.-'•  |-| rj  inca jurutl.  D —•  unineasuted

-------
                                  T
-------
2.   FreshwuLor invertebrate acute values for zinc

— iil'JLUI;;!!!
Uorm,
Na[s sp.
Snail (egg).
Amnicola sp.
Snail (adult).
Anmir.nl a sp.
Snail .
Coniobasis livescens
Snail,
rymnca emarginata
CO Sna i 1 .
1 1'hysa heterostropha
t-j
1—1 Snail ,
Physu heterostropjia
Snail,
Pbysa heterostropha
Snail,
1'liy s a he t e ros ( ropha
Snail ,
Pliysa heterostropha
Snail ,
1'hysa heterostropha
Snail .
Pliysa herorostropha
Snail.
1'hysa heterostropha
Snail,
I'hvsa hcteroKtroplia
Snail,

H«.'thOd>';
S

S

S

S

S

S


S

S

S

S

S

r>

s

s

s
y Tout
Court ^i
M

M

M

(I

I)

U


U

U

11

U

U

U

U

U

U
( in. i / 1 i\a
CjCO..)
50

50

50

137-171

137-171

4-'.


44

44'

44

171

171

171

171

100

20
Time
llil£)
96

96

96

48

48

96


96

96

96

96

96

96

96

96

96
1-CLiU
(im/n
18,400

20.200

1 4 , 000

13,500

4 , 150

790


1,270

620

780

2,660

5.570

2 . 360

6,360

14 ,000

4,900
Ad jus Led
l.Cb 0
(U'J/l)
20,240

22.220

15.400

4.916

1,511

669


1,075

525

660

2,253

4,717

1 ,998

5.386

11,860

4,150

I'etej frnc
Rehwoldt
1973
Rehwoldt
1973
Kehwoldl
1973
Cairns ,
1976
Cairns ,
1976
Cairns &
1958

Cairns &
1958
Cairns &
1958
Cairns 61
1958
Cairns &
1958
Cairns &
1958
Cairns &
1958
Cairns &
1958
Wurtz &
1961
Uurtz &

:o
, et al.

, et al.

, et al .

et al'.

et al.

Schulcv


Scheier

Scheier

Scheier

Scheier

Scheier

Scheier

Scheier

Bridges ,

Bridges ,
                                                               1961

-------
TaLie  2.   (Continued)
UicxifcSuy Ti.-iit











Tl
UJ
1
K)
1-0

















( >L (] jn i : :in
Snail ,
Hivsa heterostropha
Snail ,
Physa intej^ra
Cladoceran ,
D.'iphnia hyalina
Cladoceran ,
Daphnia niagna
C] adocoran ,
Dapjinia magna
CM adoceran ,
Daphnia niagna

Cladocoi'an,
D.ipjmia magna
Copepod,
?.y£*-9P5. ahyssorum
predpjjius
Copepod,
Fudi apl.omus padainis
p. ida mis
Sowbug ,
Ascllus commnnis
Scud ,
Clanunartis up.
Damsel f ly ,
Unidentified
Miiljie,
Clii ronomus sp.
CaddisCly,
IJniilenti fled
Mi flux:
S

S

S

S

U

R


S

S


S


S

S

S

S

S

I-'-' (..'oiic'-V*
U

U

U

U

M

M


U

U


II


•U

M

M

M

M


-------
                         TaLle  2.   (Continued)
                                                       Haroness
                                                                                     Adjusted
CD
I
K>
U)
Bioa'&say Test
Organism Method* •" Cone.**

Rotifer, . SI)
Philodia acucicornus
Rotifer, . S U
Philodi.a acuticornus
Rotifer, S U
Phi.lodla acuticornus

(mq/1 as Time
CaC03) (nrs)

81 24

25 96

25 96

LCbO LCi-0
(uq/1) (uq/1)

4.100 902

1,500 1,270

1,200 1,016


hetcceiice
"
Buikema, et al.
1974
Buikema, et al.
1974
Buikema, ec al.
1974
*  S = static, R = renewal

** u = unmeasured, M = measured

Adjusted LC50 vs. hardness:

  Snail, Physa heterostropha: slope = 0.64. intercept =• 4.80, r = 0.48, Not significant, N = 11

  Geometric mean slope = 0.64 (only value available)

  Mean intercept for 16 species =5.50

  Adjusted mean intercept = 5.50 - ln(21) = 2.46
             Final Invertebrate Acute Value
                                               (0.64'ln(hardness) + 2.46)

-------
         Table  3.  Freshwater fish chronic values for zinc
CO
to
*>.
Qj.gjni.sm
Chinook salmon,
Oncorhynchus tshawytscha
Rainbow trout,
Snlmo gairdnori
Brook trout ,
Salvelinus fontinalis
Fathead minnow,
Pimephales uromelas
Flagfish,
Jordanella floridae

Limits
Teat* (uq/1)
E-L 280-500
E-L 140-260
LC 534-1,360
LC 78-145
LC 26-51
* LC = life cycle or partial life
Chronic Value vs. hardness:
No hardness relationship could
cycle; E-L -
be derived for
Chronic
Value

187
95
852
106
36
embryo- larval
any fish species
Hardness
( ITUJ / 1 as
CaCO.,)
22
26
45
46
44

Reference
Chapman, Manuscript
Sinley, et al. 1974
Holcombe, et al . 1978
Benoit & Holcombe, 1978
Spehar. 1976


  Slope =0.67 from Fish Acute Values
  Mean intercept for 5' species = 2.57
  Adjusted mean intercept = 2.57 - ln(6.7) = 0.67
  Final Fish Chronic Value = e(0.67-ln(hardnesS) + 0.67)
                                    Application Factor Values
Species
Brook trout ,
Salvelinus fontinalis
Fathead minnow,
Pimephales promelas
Flagfish,
Jordanella floridae

96 hr LC50
(v.g/1)
2.000 '
600
1,500
Hardness
(mg/1 as
CaC00)
45
46
44-
MATC
MR/1
534-1.360
78-145
26-51
A.F.
.43
.18
.02
Reference
Holcombe, et al.'
Benoit & Holcombe
Spehar, 1976
1978
. 1978

Geometric mean A.F. = 0.12
Geometric mean LC50 = 1,216 ug/1

-------
                    Table  /i.  Freshwater  invertebrate  chronic vnlues for zinc (Biesinger & Chiri .stensen,  1972)




                                                             Chronic
Of Ian ism
Cladoceran,
Daphnia magna
Limit n Value (imj/l as
Teat* (iui/1) I"1!/1! CaCO.,)
l.C 70-102 84.5 45

           * ).C = life cycle or partial  1 i.Ce  cycle


             Chronic Value vs. hardness:



             Mo harJneus relationship could he  derived for any invertebrate species.



             Slope =• 0.64 from invertebrate acute value.



             Intercept for Daphntn ma^.na  « 2.00 (only upccies tested).


             ...  . ,    .  .      „.    .  „ ,       (0.64-ln(harduess) + 2.00)
             1-inaL InvertebraLe Chronic Value » e  •


CO


to

ui

-------
                         Table 5.  Freshwater plant effects  for zinc
                                                   Concentration
                                   Kttect
                                                                       Kfetert-nce
          Alga.
                  la.  -
CD
 I
i-o
cr>
          Alga.
          Ch 1 oc 1
          Alga,
          Chlorell a  vulgari s
          Chloi'el la  vulgaris
          Alga,
          Scenedesnuis
507. inhibition    5,100
of cell division

DxLendecl lag      7,500
Lime to 7 days
Alga,
S\	
c.'ipr icornuT uni

A1 ga .
Se K; na s truni
Capricornuturn

Alga,
Selenast ruin
- '21'£ 1 cor ri u f uin

Eurasian waterniilfoil,
Hyri^(.j)hy_l_li.im spica turn


Eurasian waterniilfoil,
Ilyri  npliyl 1 um spica i urn
          Eurasian  watenniIfoil,
                   i iuin y'™
Decrease
chlorophyll a

507,, reduction
in growth rate
96 hrs

Threshold
toxicity
Alpicldal
                                   Total p.i-owth
                                   inhi hi I:ion
  7,500


  2,400



1,000-1.400



    700



    120
          Ui. ..I Com,
          Ni L:'.'.;{. li i a  1 incur i s
                                   Incipient- growth     30
                                   inhibition
507., root         21,600
weight reduc-.
tion

50% root         21,600
length reduc-
tion

50Z reduction    20,900
in shoot
length

LC50 12.U hrs      A, 300
                                    Rosko S, ttachlin.  1977
                                    llosko & Kachlin,  1977
                                    Rcsko & Uachlin.  1977
                                                                       Rachlin & Farran,  1974
                                    Bringmann & Kuhn,  1959
                                    bartlett, et  al.   1974
                                    Ilartlett, ct  al.   1974
                                    llartlett. et  al.   1974
                                                                       Stanley,  1974
                                                                       Stanley,  1974
                                    Stanley, 1974
                                    Patrick, et  al.   1968
          Lowest  plant  value - 30 pg/1

-------
               TaLle
                         Freshwater residues for  zinc
i)t >jani SHI
Mayfly.
Kpjiemerol la grand i s
SLi>nef ly ,
I'toronarcys cal i forn
Carp,
O/nrinus carpi o
Stickleback,
G.u'.t crosLeiis aculcat


Organ i.sm
W
1 White Kilt
K>
'J'lnie
DiocunceiiC.r ution FdCI 01 (days)
1 . 1 30 1 4
106 I.-'.
. 8 60
12.2 0 . £

Maximum Permissible Tissue Concentration
Concentration
Action Level or ICffect ing/k^
stillbirths and 2,000
postnatal growth
inhibit ion
                                                                               -t (.-1 er.co
                                                                             Nelirin;;,  1976
                                                                                  infi.  1976
                                                                             l.ebedova d Ku^neC.sova, 1969
                                                                     0.66    Matthieascn f, Hraficld,  1977
                                                                              Re Corenee





                                                                              Ketchuson.  ot al.   1969
bi.oconccnt ration  factor - 1,130



Lowest re:;iiliio  concentration = 2,000  mg/lq;



      -  1.77  m;./kK = 1.800 ,,g/l

-------
Table
(Continued)
Oruaniii.,,
I.ejiomi :> niacrochi rus
UluiijjiH.
I.epoini s niacrochirus
Bluep/ili ,
I.opornis macrochirus
Pond snail ,
P h v s a 1 1 c; Lc r o s t raplia
Pond snai 1 ,
Physa heterostropha
Pond snail,
DO Pliy.sn heterostropha
1 ~" ~ "
^ Pond snail,
Pliys.-i hetcrost ropjia
Pond snail ,
Physa heterostrogha
Pond snai 1 ,
Physa heterostropha
Eluegi 11 ,
Leponii!) niacroctii rus


I.op'jinis macrochirus
Test
OUI'cl t 1 Oil
20 days
20 days
20 days
96 hrs
96 hrs
96 hrs
96 hrs
96 hrs
96 hrs
96 hrs


96 hrs

LC50
I.C50
1.C50
LC50 ' - ••
soi't water
I.C50
hard water
1.C50
soft water
LC50
hard water
I.C50
soft water
1.C50
hard water
LCO


LCI 00
Hardness
(mj',/1 as
CaCO,
370
370
370
20
100
20
100
20
100
46


A6
KfcSUit.
(UU/U
10,500
12.000
10,700
303
ilV>
1,700
350
1 . , 1 00
13,500 -
32,000
i nsol uble
zj no
18,000 •
soluble
l«jt ei riict.-
Pickering, 1968
Pickering. 1968
Pickering. 1968
Wurt2, 1962
Wurt:'., 1962
Uuruz. 1962
Wurtz, 19b2
Wurt:;:. 1962
Wurc;:, 1962
Cairns, et al. 1971


Cairns, et al . 1971
                                         zinc

-------
                        SALTWATER ORGANISMS



Acute Toxicity




     The mummichog was'the only non-anadromous  saltwater  teleost



used for acute toxicity tests for zinc  (Table 8).  The  unadjusted



96-hour LC50 value was 60,000 ug/1  (Eisler and  Hennekey,  1977).




Longer exposure to zinc (Tables 12) did not significantly change




the result; the 168-hour LC50 was 52,000 ug/1 (Eisler and Hennekey,



1977) and the 192-hour LC50 was 66,000 ug/1 (Eisler, 1967).   Smolts




of Atlantic salmon, Salmo salar, acclimatized to  70 percent  salt



water, were more sensitive to zinc  than yearling  rainbow  trout, S_.



gairdnerii, at the same salinity under- flow-through conditions,




with unadjusted 48-hour LC50 values of 27,000 ug/1 and  35,000  ug/1/



respectively (Herbert and Wakeford, 1964).  Both  species  were  more-



resistant at 30 to 40 percent salt water; LC50  values were 39,000




ug/1 for the salmon and 82,000 ug/1 for the trout.



     Application of the adjustment  factors to the fish  acute  toxic-



ity data gives a geometric mean of  33,450 ug/1  which, when adjusted




by the species sensitivity factor (3.7), results  in a Final  Fish




Acute Value of 9,000 ug/1.  No fish acute toxicity data from  Table



8 is below 9,000 ug/1/ indicating the procedure allows  protection



for at least 95 percent of the species.




     Saltwater invertebrate species are more sensitive  to acute



zinc toxicity/ as shown by data on various life stages  of annelids,




bivalve and gastropod molluscs, arthropod crustaceans,  and echinc-




derms (Table 9).  Among oolychaete annelids, adults are more  toler-



ant than young of the species.  Adult Capitella capitata  and  Neanthes




arenaceodentata had adjusted 96-hour LC50 values  of 2,965 and  1,524




ug/1 zinc, respectively (Reish, et al. 1976).  While the  level for
                              B-29

-------
larvel C. capitata is 1.440 ug/1 and that for juvenile N. arena-


ceodentata is 762 ug/1  (Reish, et al. 1976).  As with fish, salin-


ity affected zinc sensitivity of adult polychaetes.  Nereis


diversicolor in 17.5 °/oo had an adjusted 96-hour LC50 value of


46,585 ug/1 while a salinity of 3.5 °/oo, the LC50 was 9,317


(Bryan and Hummerstone, 1973).


     Larval bivalve molluscs were the most susceptible invertebrate


species to zinc.  Forty-eight-hour LC50 values were 141 ug/1 for


Mercenaria mercenaria larvae  (Calabrese, et al. 1977) to 287 ug/1


for Crassostrea virginica (Calabrese, et al. 1973).  Acute toxicity


values for adult pelecypods ranged from 2,640 ug/1 for Mytilus


edulis planulatus (Ahsanullah, 1976) to 6,522 ug/1 for Mya arenaria


(Eisler and Hennekey, 1977).  Among gastropod molluscs, the ad-

                                                            i
justed 96-hour LC50 value for Nassarius obsoletus was 42,350 ug/1


(Eisler and Hennekey, 1977).


     Among crustaceans, susceptibility to zinc varied between


species and development stages.  The adult crab, Carcinus maenas


was the most resistant  of those studied, with adjusted 96-hour LC50


values of 5,281 (Conner, 1972) and 4,370 ug/1 (Portmann, 1968).


Larvae of this species  were more sensitive with an adjusted 96-hour


concentrations of 847 ug/1  (Conner, 1972).  The copepod, Acartia


tonsa was the most sensitive crustacean species tested, with a


96-hour LC50 value of 246 ug/1 (Sosncwski, et al. 1979).  Among


echinoderms, Eisler and Hennekey (1977) showed that the adult


starfish, Asterias forbesi, was rather insensitive to zinc, with an


adjusted LC50 value of  33,033 ug/1.


     Toxicity studies of longer duration with invertebrate species


(Table 12) resulted in  lower lethal zinc concentrations.  Minimum



                               B-30

-------
LC50 values were 195 ug/1 (12 days) for'larvae of the clam,
Mercenaria mercenaria, (Calabrese, et al. 1977) and  200 ug/1  (168
hours) for adult hermit crab, Pagurus longicarpus,  (Eisler and
Hennekey, 1977).  The 168-hour LC50 value for adult  polychaete,
Nereis virens, was 2,645 ug/1 (Eisler and Hennekey,  1977).
     The Final Invertebrate Acute Value of 41 ug/1 was calculated
from the geometric mean of 2,026 ug/1 and a species  sensitivity
factor of 49.  This value does not exceed the adjusted LC50 value
for any life stage of any invertebrate species (Table 9) thus af-
fording 95 percent protection for invertebrate species.  Since this
level is lower than the Final Fish Acute Value (9,000 ug/1),  41
ug/1 is the Final Acute Value.
Chronic Toxicity
     No whole or partial life cycle chronic toxicity data are
available for zinc and saltwater fish or invertebrate species.
Plant Effects
     The minimum zinc concentration which inhibited  growth among
five species of microalgae (Table 10) was 50 ug/1; Skeletonema
costatura was the most sensitive species tested (Bryan, 1964).  At
this concentration, zinc also interacted with copper to affect
growth (Braek, et al. 1976).   Maximum tolerance to growth inhibi-
tion among algae was 25,000 ug/1/ as' shown by Jensen, et al.  (1974)
with Phaeodactylum tricornutum.  .The most sensitive  kelp species
was La'minaria digitata, with  growth inhibition occurring at 100
ug/1 (3ryan, 1964).
     The Final Plant Value is 50 ug/1.
Residues
     Algal bioconcentration of zinc includes data for both micro-
algae and macroalgae (Table 11).  The maximum BCF value for the
                              B-31

-------
macroalgae, Fucus serratus, was 10,000 after  140 days exposure  to



9.5 ug/1  (Young, 1975).  Among the microalgal species examined,



Thallossiosira pseudonana, accumulated zinc 12,400  times over



ambient water concentrations of 250 ug/1  in 13 days  (Jensen, et al.



1974).



     Whole body concentration in adult Crassostrea Virginica was



2,703 mg  zinc/kg wet weight after exposure to 0.1 mg/1 for  140-



days, resulting in a BCF of 27,080 (Shuster and Fringle, 1969).



Shuster and Pringle  (1968) reported a BCF of  15,240  for C.



virginica exposed to 0.1 mg/1 for 140 days.   Among  the soft-shell



clams, adult Mya arenaria were poor concentrators of zinc,  accumu-



lating only 43 times over a water concentration of  500 ug/1 after



112 days  (Eisler, 1977b).  Similarly, the hard shelled clam,



Hercenaria mercenaria, had a bioconcentration factor of 85  (Shustjer



and Pringle, 1968) while mussel, Mytilus edulis accumulated zinc up



to 500 times (Pentreath, 1973c).



     Bioconcentration factors for crustaceans ranged from 266  in



the mud crab (Duke, et al. 1969) to 9,000 for adult  Carcinus maenas



(Bryan, 1971).



Miscellaneous



     Various saltwater phyla are well represented in studies of



sublethal effects of zinc (Table 12).  After a 14-day exposure  to



10,000 ug/lf liver aminolevulinate dehydrase enzyme  activity in-



creased in the adult mummichdg, Fundulus heteroclitus, (Jackim,



1973).  Although no larvae of oysters, Crassostrea virginica, died



during 48 hours in 75 ug/1 (Calabrese, et al. 1973), C_. gigas



larvae did exhibit abnormal shell development in 70  ug/1 after



immersion for 48 hours (Nelson, 1972).  Oyster larvae showed
                              B-32

-------
reduced development in a slightly higher level of 125 ug/1



(Brereton, et al. 1973).  Adult bivalve molluscs were more resis-



tant to zinc toxicity; Crassostrea virginica showed no significant



mortality in 200 ug/1 after 140 days (Shuster and Pringle, 1968;



1969).   A small increase in temperature doubled toxicity  to adult



Mya arenaria.  The 168-hour LC50 value at 20° C was 3,100 ug/1



(Eisler and Hennekey, 1977) while at 22° C it was 1,550 ug/1



(Eisler, 1977a).  Larval stages of crustaceans were again the most



sensitive to zinc, as shown by delayed development in crab,



Rhithropanopeus harrisi, during a 16-day exposure to 50 ug/1



(Benijts-Claus and Benijts, 1975).  Polychaetes were generally



tolerant of zinc; Reish and Car (1978) reported reduced survival



after 21 days in 1,750 ug/1 for Ophyryotrocha diadema and in 10,000



for Ctenodrilus serratus.  Growth of the protozoan, Cristigera  sp.,



was reduced in 125 ug/1 after 4 to 5 hours (Gray, 1974).
                              B-23

-------
CRITERION FORMULATION



                      Saltwater-Aquatic Life



Summary of Available Data



     The concentrations below have been rounded to two significant



figures.  All concentrations herein are expressed in  terms of



zinc.



     Final Fish Acute Value = 9,000 ug/1



     Final Invertebrate Acute Value = 41 ug/1



          Final Acute Value = 41 ug/1



     Final Fish Chronic Value = not available



     Final Invertebrate Chronic Value = not available



     Final Plant Value = 50 ug/1



          Final Chronic Value = 50 ug/1



          0.44 x Final Acute Value = 18 ug/1



     CRITERION:  No saltwater criterion can be derived for zinc



using the Guidelines because no Final Chronic Value for either fish



or invertebrate species or a good substitute for either value is



available, and there are insufficient data to estimate a criterion



using other procedures.
                              B-34

-------
                               Table  7,   Other freshwater data for zinc
CD
I
U)
Ul
            Organism
 Protozoa,
 Chilomonas- sp.

 Protozoa,
 Chilomonas sp.

 Protozoa,
 Telrahymena sp.

 Protozoa,
 Tetrahymena sp.

 Protozoa,
 Parameclum caudatum

 Protozoa,
 Paramecium caudatum

 Protozoa,
 Paramecium multi-
 micronucleaturn

 Protozoa,
 Paramecium multi-
 tnicronucTeatum

 Protozoa,
 Blcphartsma sp.

 Protozoa,
 Blepharisma sp.

 Cladoceran,
 Daphnia magna

 Mayfly,
 Ephemerella grandis

 Mayfly,
 Ephemerella subvaria

 Stonefly,
.Acroneuria lycortas

 Stonefly,
 Pceronarcys
 caTTfornica
                                    Test
                                     3  hrs


                                    10  mint


                                     3  hrs


                                    10  mins


                                     3  hrs
                                     3  hrs
                                     3  hrs


                                    24  hrs
Etfect
LC100
LCO
LCI 00
LCO
LC100
LCO
LC100
LCO
LC100
LCO
LG50
LC50
LC50
LC50
LC50
Hardness
(mg/1 as
CaCO,)
51-68
51-68
51-68
51-68
51-68
51-68
51-68
51-68
51-68
-
-
30-70
44
44
30-70 •
Result
9.200
16,000
32,000
>13,200
 Retereiicfc


 Ruthven & Cairns.  1973


 Ruthven & Cairns,  1973


 Ruthven & Cairns.  1973


 Ruthven & Cairns,  1973


 Ruthven & Cairns.  1973


 Ruthven & Cairns.  1973


 Ruthven & Cairns.  1973



 Ruthven & Cairns,  1973



 Ruthven & Cairns,  1973


.Ruthven & Cairns,  1973


 Bringmann & Kuhn.  1977


 Nehring.  1976


 Warnick & Bell,  1969


 Warnick & Bell,  1969


 Nehring.  1976

-------
                               Table  7.  (Continued)
OJ
Organism
Caddisfly,
Hydropsyche betteni
Coho salmon,
Oncorhynchus kisutch
Sockeye salmon
(embryo- smolt) ,
Oncorhynchus nerka
Cutthroat trout,
Salmo clarkii
Rainbow trout,
Salmo gairdneri
Rainbow trout,
Salmo gairdneri
Rainbow trout,
Salmo gairdneri
Rainbow trout,
Saimo gairdneri
Rainbow trout,
Salmo gairdneri
Rainbow trout,
Salmo gairdneri
Rainbow trout ,
Salmo gairdneri
Rainbow trout,
Salmo gairdneri
Rainbow trout,
Salmo gairdneri
Brown trout,
Salmo trutta
Test
Duration
11 days
96 hrs
18 mos
14 days
7 days
2 hrs
48 hrs
7 days
14 days
20 mins
5 days
7 days
21 days
21 days
Hardness
(mg/1 as
Effect CaCO,
LC50 44
WBC-T 3-10
counts
depressed
No effect 20-90
on survival
or growth
LC50 48
Gill tissue 44-55
damage
Increase in 66
ventilation
rate
Increased 320
swimming
velocity .
increased
toxicity to
Zn
Hyper- -374
glycemia
LC50 48
Threshold 13-15
avoidance
level
LC50
LC50 - 280 '
Median 14
survival
time
Median 14
survival
Result
fuq/1)
32,000
500
242
670
40,000
40,000
1,680
214
410
5.6
4,600
560
500-1.000
-vl.OOO
Reference
Uarnick & Bell, 1969
McLeay, 1975
Chapman, 1978a
Nehring & Goettl. 1974
Skidmore & Tovell. 1972
Hughes & Adeney, 1977
Herbert & Shurben, 1963
Watson & McKeown, 1976
Nehring & Goettl, 1974
Sprague, 1968
Ball, 1967
Lloyd, 1961
Grande, 1967
Grande. 1967
                                              time

-------
                             Table   7.   (Continued)
CD
I
OJ
-J
Organism

Brown trout,
Salmo trutta

Atlantic salmon
Salmo salar
Atlantic salmon,
Salmo salar
                                  Test
                                  Duration   Effect

                                  14 days    LC50
                                  182 hrs
                                  Incipient
                                  lethal
                                  level
                        21 days   Median
                                  survival
                                  time
Brook trout,            14 days   LC50
Salvelinus fontinalis
Golden shiner,
Notemigonus
crysoTeucas

Fathead minnow,
Pimephales promelas

Channel catfish,
Ictalurus nunctatus
          Guppy,
          Poecilia reticulatus
                        96 hrs    Avoidance
                                             Hardness
                                             (mg/1 as
                                              GaC03	

                                                 48
                                                 14
                                                            14
                                                           44
                                                           51
                        10 mos
                                  12 hrs
                                  Reproduction  203
                                  reduced
                                  Serum  -
                                  osmolarity
                                  decrease .
                        30 days   Growth
                                  inhibition
          Stickleback,             3 days   Gill damage   282
          Gasterosteus aculeatus
Stickleback,           200 hrs
Gasterosteus aculeatus
                                            Increased
                                            oxygen
                                            uptake
Bluegill,
Lepomis macrochirus

Bluegill,
Lepomis macrochirus

Bluegill.
Lepomis macrochirus

Bluegill.
Lepomis macrochtrus

Bluegill,
Legomis_ macrochirus

BlueRill.
Lepomis macrochirus
                                   7 days   Increased      51
                                            breathing rate
                                  96 hrs
                                  24 hrs
                                  LC50 (swimming 46
                                  stress)
                                  Increased
                                  cough response "
                                  20 days   I.C50


                                  20 days   LC50


                                  20 days   LC50
                                                           Result
                                                            (uq/i)    Reterencfe
    640     Nehring & Goettl, 1974


150-1,000   Zitko & Carson. 1977



100-500     Grande, 1967



    960     Nehring & Goettl. 1974


  3,640     Waller & Cairns. 1972



    180     Brungs. 1969
                                               206-236    12.000     Lewis & Lewis. 1971
                                                 80        1,150     Crandall & Goodnight, 1962
                                                         500-1,000   Matthiessen & Brafield, 1973
                                                282        1.000     Brafield & Mattheissen. 1976
                                                           8,700     Cairns & Sparks, 1971
                                                           3,200     Burton, et al.  1972
                                                          40.000     Sparks, et al. 1972
                                                370        7.200     Pickering, 1968
                                                370        7,500     Pickering. 1968
                                                370       10,700     Pickering, 1968

-------
                         Table  8.  Marine  fish acute values  for  zinc
00
                                                                           Adjusted
Bioassay Test Time LC50 iXTSO
Orqanism Method- Cone.** (hrs^ (uq/ll (uq/1) Keference
Mummichog (adult) . S U
Fundulus heteroclitus
Rainbow trout (yearling) , FT M
Salmo gairdnerii
Rainbow trout (yearling) , FT M
Salmo gairdnerii
Atlantic salmon (smolt) , FT M
Salmo salar
Atlantic salmon (smolt) , FT M
S.ilmo salar
•
96 60,000 32,802 Eisler & Hennekey, 197.?
48 35,000 28,350 Herbert & Wakeford, 1964
48 82,000 66,420 Herbert & Wakeford, 1964
48 27.000 21,870 Herbert & Wakeford, 1964
48 39,000 31,590 Herbert & Wakeford, 1964
            * S = static,  FT = flow through
           ** U = unmeasured, M = measured
              Geometric mean of adjusted  values = 33,450   33.450 = 9,000ug/l

              Lowest value from flow-through test with measured concentrations = 21,870 ug/1

-------
                        Table  9.   Marine invertebrate acute values for zinc
Bioassay Test
Organism MetJiod* Cone.**
Polychaete (adult) , S
Capitclla capitata
Polychaete (larvae). S
Capitella capitata
Polycahete (adult) . S
Neanthes drenaceodentata
to
1
Ul
vo
Polychaete (juvenile),
Neanthes arenaceodentata
Polychaete (adult) ,
Nereis diversicolor
Polychaete (adult),
Nereis diversicolor
Polychaete (adult) .
Nereis diversicolor
Sandworm (adult)
Nereis virens
Oyster (larva) ,
Crassostrea virginica
Oyster (larva),
Crassostrea virginica
Hard-shell clam (larva) ,
Mercenaria mercenaria
Hard-shell clam (larva) ,
Mercenaria mercenaria
Soft-shell clam (adult),
My a arenaria
Soft-shell clam (adult),
S
S
S
S
S
S
S
S
S
S
S
U
U
U
U
U
U
' U
U
U
U
U
U
U
U
Time
(hrs)
96
96
96
96
96
96
96
96
48
48
48
48
96
96
LC50
tug/1)
3,500
1.700
1.800
900
1.500
55.000
11,000
8,100
310
339
166
195
5,200
7,700
Adjusted
LC50
2,965
1.440
1.524
762
1,270
46,585
9,317
6.245
262
287
141 '
165.
4,404
6.522
Reterence
Reish. et al. 1976
Reish. et al. 1976
Reish. et al. 1976
Reish. et al. 1976
Bryan & Hummerstone, 1973
Bryan & Hummerstone, 1973
Bryan & Hummerstone, 1973
Eisler & Hennekey, 1977
Calabrese, et al. 1977
Calabrese, et al. 1973
Calabrese, et al. 1977
Calabrese & Nelson, 1974
Eisler. 1977a
Eisler & Hennekey. 1977
Mya arenaria

-------
                                 Table  9.   (Continued)
         Organism
                        Bioassay  Test
                        Method*   cone.*"
Time
(hrs)
03
*»
O
Mussel,                    S
Mytilus edulis planulatus

Mud snail (adult),          S
Nassarius obsoletus

Copepod (adult),            S
Acartia tonsa

Copepod (adult),            S
Apartla claust

Copepod (adult),            S
Pseudodiaptomus coronatus

Copepod (adult),            S
Eurytemora affinis

Copepod (adult),            S
Tigriopus japonicus

Crab (larva).      •         S
Carcinus maenas

Crab (adult),               S
Carcinus maenas

Crab (adult),               S
Carcinus maenas

Hermit crab (adult).       S
Pagurus longicarpus

Starfish (adult),          S
Asterias -forbesi
                                             M


                                             U


                                             U


                                             U


                                             U


                                             U
                                             U


                                             U
 96


 96


 96


 96


 96


 96


 96


 48


 48


 48


 96


 96
           Adjusted
 LC50      LC50
 (uq/l>     (ug/1)     Reference

 2,500     2,640     Ahsanullah, 1976
50,000    42,350     Eisler & Hennekey, 1977
                                         f

   290       246     Sosnowski. et al. 1979


   950       805     Sosnowski. et al. 1979


 1,783     1.510     Sosnowski, et al. 1979


 4,090.     3,464     Sosnowski. et al. 1979


 2,160     1,830     Sosnowski, et al. 1979


 1.000       847     Conner. 1972


14.500     5.281     Conner, 1972


12,000     4,370     Portmann, 1968


   400   ,    339     Eisler & Hennekey, 1977


39.000    33.033     Eisler & Hennekey. 1977
*  S = static, FT = flow- through
** U = unmeasured, M = measured        .       ,
   Geometric mean of adjusted values = 2,026 ug/1
                                                                026
                                                                 — =
                                                                      41 wg/1

-------
                         Table  10.  Marine  plant  effects  for  zinc
           Organism
                                   Effect
               Concentration
               (ug/1)	
                                                                      Reference'
CD
           Alga,                    Growth
           Amphldinium carteri     inhibition
                   400
           Alga.
           Amphidinium carteri

           Alga.
           Dunaliella tertiolecta
Interaction with   100
copper on growth

Reduction in  .gs 6..JOO
potassium content KM
           Kelp,                    Growth
           Laminaria hyperiborea   inhibition

           Kelp,                    Growth
           Laminaria digitata      inhibition
           Kelp.
           Macrocystis pyrifera.
                   250


                   100
Photosynthesis  10,000
inhibition
           Alga,                    Growth
           Phaeodactylum           inhibition
              tricornutum
                25,000
                Braek, et al.  1976


           ; V   Braek. et al.  1976


                Overnell, 1975


              -  Hopkins & Kain. 1971


                Bryan, 1964


                Clendenning & North, 1959


                Jensen, et al.  1974
           Alga,
           Phaeodactylum
              tricornutum

           Alga,
           Skeletonema costal:urn

           Alga,
           Skeletonema costatum

           Alga,
           Skeletonema costatum
Interaction with 1,000
copper on growth.
Growth
inhibition

Growth
inhibition
 50
200
Interaction with    50
copper on growth
                Braek. et al.  1976
Bryan, 1964
Braek, et al.  1976
                Braek, et al.  1976
           Alga.
           Thalassiosira
              pseudonana
Growth
inhibition
500
           Alga,
          'Thalassiosira pseudonana
Growth inhibition  400
Braek, et al.  1976
                Braek. et al.  1976

-------
03
I
•U
to
                          Table 10. (Continued)


                                                   Concentration
            organism                Etrect         (ug/i)	       Reference


            Alga,                    Interaction with   200             Braek, et al.  1976
            Thalassiosira           copper on growth
               pseudonana
            Lowest marine plant value = 50 ug/1

-------
              Table
                          Marine residues  for  zinc
Organism
Dioconceiitration Factor
                                                                            rttreience
Alga (live tip) ,
Ascophyllum nodosum
Alga (dead tip),
Ascophyllum nodosum
Alga.
Cladophora sp.
Alga,
Cladophora sp.
Alga.
Fucus serratus
Algae (mixed) ,
Five genera
« Alga.
j^ Laminar ia digitata
OJ
Alga.
Phaeodactylum tricornututn
Alga.
Skeletonema cost a turn
Alga,
Thalassiosira pseudonana
Polychaete (adult) ,
Nereis diversicolor
Scallops (adult) ,
Aequipecten irradians
Oyster (adult)',
Crassostrea virginica
Oyster (adult) ,
Crassostrea virginica
Gastropod (adult) ,
55
950
1.785
4,680
10.000
1.900
3,000
8.100
1
12.400
55
321
27,080
146
670
4
7
12
34
140
90
30
14
13
13
9
15
140
15
50
Skipnes, et al. 1975
Skipnes, et al. 1975
Baudin, 1974
Baudin, 1974
Young. 1975
Cross, et al. 1971
Bryan, 1964
Jensen, et al. 1974
Jensen, et al. 1974
Jensen, et al. 1974
Bryan & Hununerstone, 1973
Duke, et al. 1969
Shuster & Pringle, 1969
Duke, et al. 1969
Young, 1975
Littorina obtusata

-------
              Table   n>  (Continued)
Organism
Hard-shell clams (adult) ,
Mercenaria tnercenaria
Hard-shell clams (adult).
Mercenaria mercenaria
Soft-shell clam (adult),
Mya arenaria
Soft-shell clam (adult).
Mya arenaria
Mussel (adult) ,
Mytilus edulis
Mussel (adult),
Mytilus edulis
Mussel (adult),
y Mytilus edulis
**
•U Mussel (adult),
Mytilus edulis
Amphipod,
Gamma rus locusta
Crab (adult).
Carcinus maenas
Crab (adult) .
Carcinus maenas
Mud crab (adult) .
Bioconcentr ation Factor
22
85
85
43
460
500
105
330
400
9.000
5.400
266
Time
(days)
15
70
50
112
13
21
20
35
27
32
42
15 .
Kfcterence
Duke, et al. 1969
Shuster & Pringle. 1968
Pringle. et al. 1968
Eisler. 1977b
Phillips. 1977
Pentreath. 1973
Van Weers. 1973
Phillips, 1976
Fowler, et al. 1975
Bryan. 1971
Bryan, 1966
Duke, et al. 1969
Panopeus herbstii

-------
                   Table   12. Other marine data for zinc
Organism

Muuunichog (adult),
Fundulus heteroclitus

Mumiuichog (adu 11) ..
Fundulus heteroclttus

Mumnichog (adult),
Fundulus heteroclitus
Test
Duration  Etfect
  96 hrs    LC28
  24 hrs    No  histological
           damage

  24 hrs    Histological  damage
oa
Ul
Mummichog (adult),.
Fundulus heteroclitus
Mummichog (adult).,
Fundulus heteroclitus
Mummichog (adult) ,
Fundulus heteroclitus
Mummichog (adult),
Fundulus heteroclitus
Mummichog (adult) ,
Fundulus heteroclitus
Mummichog (adult),
Fundulus heteroclitus
168 hrs
168 hrs
168 hrs
14 days
48 hrs
48 hrs
LCO
LC50
LC100
lucre*
ALA*D
LCO
LC100
Mummichog  (adult)>
Fundulus heteroclitus

Mummichog  (adult),
Fundulus heteroclitus

Protozoan,
Cristigera sp.

Protozoan,
Cristinera sp.

Protozoan,
Euplotes vannus
                        Result
                        (uq/11     Reterencfc

                        60,000   Eisler & Gardner, 1973


                        36,000   Eisler & Gardner, 1973


                        60,000   Eisler & Gardner, 1973


                        10,000   Eisler & Hennekey, 1977


                        52,000   Eisler & Hennekey, 1977


                       120,000   Eisler & Hennekey, 1977



ALA*D enzyme activity   10,000   Jackim, 1973

                        10,000   Thomas, 1915
 192 hrs     LCO


 192 hrs     LC50


 4-5 hrs     Reduced, growth


  —        Growth  reduction


  48 hrs     EC10  (reproduction)
                       157,000   Eisler. 1967


                        43,000   Eisler. 1967


                        66,000   Eisler. 1967


                          125    Gray. 1974


                          125    Gray & Ventilla. 1973


                        10,000   Persoone & Uyttersprot. 1975

-------
                    Table 12.   (Continued)
 Organism
  Test
  Duration  Ett'ect
                         Result
                         fuq/lL
                                                                      Reference
 Polychaete,
 Ctenodrilus serratus

 Sandworm (adult),
 Nereis virens

 Polychaete,
 Ophryotrocha diadema

 Polychaete,
 Ophryotrocha labronica

 Oyster (larva),
 Crassostrea gigas

 Oyster (larva),
 Crassostrea gigas

 Oyster (larva),
 Crassostrea gigas

 Oyster (larva),
 Crassostrea gigas

 Oyster (larva),
 Crassostrea virginica

 Oyster (larva),
 Crassostrea virginica

 Oyster (adult),
 Crassostrea virginica

 Hard-shell clam
 (embryo),
 Mercenaria mercenaria

 Hard-shell clam
 (larva),
.Mercenaria mercenaria
 21 days


 168 hrs


  21 days


  13 hrs


   5 days


  48 hrs


 '  6 days


  48 hrs


  48 hrs


  48 hrs


 140 days
..'•42-48
   hrs
Reduced survival         10,000
LC50                      2,600
Reduced survival          1,750
LC50                      1,000
Substrate attachment        125
inhibition

Reduced development         125
Growth inhibition           125
LCO
LC100
       Reish & Carr, 1978
       Eisler & Hennekey, 1977
       Reish & Carr, 1978
       Brown & Ahsanullah, 1971
       Boyden, et al. 1975
       Brereton, et al. 1973
       Brereton, et al. 1973
Abnormal shell development   70    Nelson, 1972
 75    Calabrese. et al. 1973
500    Calabrese, et al. 1973
No significant mortality    200    Shuster & Pring'le, 1968, 1969
LCI 00
279    Calabrese & Nelson. 1974
 ,12 days   LC5
                             50
       Calabrese, et al.  1977

-------
Table  12. (Continued)
Organism
Hard-shell clam (larva)
Mercenaria mercenaria
Hard-shell clam (larva)
Mercenaria mercenaria
Soft-shell clam (adult)
Mya arenaria
Soft-shell clam (adult)
Mya arenaria
Mussel (adult) ,
Mytilus edulis
Coot clam (adult) ,
Mulinia lateralis
7 Mud snail (adult).
•*» Nassarius obsoletus
Mud snail (adult),
Nassarius obsoletus
Mud snail (adult) ,
Nassarius obsoletus
Isopod (adult) ,
Idoten baltica
Barnacle (adult) ,
Balanus balanoides
Crab (larva) ,
Carci.nus maenas
Hermit crab (adult) ,
Pagurus longicarpus
Crab (larva),
RhiLhropanopeus harrisi
Test
Duration
, 12 days
. 12 days
, 168 hrs
, 168 hrs
14 days
14 days
72 hrs
72 hrs
168 hrs
120 hrs
5 days
0.22 hrs
168 hrs
16 days
Res
Ettect (u'l
LC50
LC95
LC50 @ 20°C 3
LC50 @ 22°C 1
Decrease in cadmium
uptake
Decrease in cadmium
uptake
No effect on behavior
Decreased oxygen consump-
tion
LC50 7
LC40 @ 34°/oo S 10
],cyo 8
LC50- 33
100
LC50
Delayed
development
ult
/il
195
341
.100
.550
500
500
100
200
,400
,000
,000
.000-
,000
200
50
Ret ereiiCfe
Calabrese, et al. 1977
Calabrese, et al. 1977
Eisler & Hennekey, 1977
Eisler, 1977a
Jackim, et al. 1977
Jackim, et al . 1977
Maclnnes & Thurberg, 1973
Maclnnes & Thurberg, 1979
Eisler & Hennekey, 1977
Jones, 1975
Clarke, 1947
Conner. 1972
Eisler & Hennekey, 1977
Benijts-Claus & Benijts, ]

-------
03
I
          Organism
                             Table  12.  (Continued)
Test
Duration  Ettec
Result
 (uu/ll
          Sea urchin  (spennatozoa), A mins
          Arbacia puctulata

          Sea urchin  (spermatozoa), A mins
          Arbacia puctulata

          Sea urchin  (spermatozoa), A mins
          Arbacia puctulata
           Decreased motility
           Decreased motility
           Decreased motility
163-817   Young & Nelson. 197A
   81     Young & Nelson. 197A
1,635     Young & Nelson. 197A
          Sea urchin  (egg),
          Arbacia puctulata

          Starfish  (adult),
          Asterias  forbesi

          Starfish  (adult).
          Asterias  forbesi
 15 hrs    Abnormal development    1,250     Waterman, 1937
168 hrs    LC50
 2A hrs    Equilibrium loss
2.300     Eisler & Hennekey. 1977


2.700     Galtsoff & Loosanoff, 1939
00

-------
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Press, Seattle, Washington:  319.








O'Rear, C.W., Jr.  1972.  The toxicity of zinc and copper



to striped bass eggs and fry with methods for providing



confidence limits.  Paper presented at 26th meeting of Souther:



Assoc. of Game and Fish Commissioners.  Knoxville, Tenn.



Oct. 15 p.








Overnell, J.  1975.  The effect of heavy metals on photo-



synthesis and loss of cell potassium in two species of marine



algae, Dunaliella tertiolecta and Phaeodactylum tricornutum.



Mar. Siol.  29: 99.








Patrick, R., et al.  1968.  The relative sensitivity of



diatoms, snails, and fish to twenty common constituents



of industrial wastes.  Prog. Fish-Cult.  39: 137.







Pentreath, R.J.  1973b.  The accumulation from water of



65Zn, 54Mn, 58Co and 59Fe by the mussel, Mytilus edulis.



Jour. Mar. Biol. Assn. U.K.  53: 127.
                              B-64

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Persoor.e, G. ,  and G. Uyttersprot.  1975.  The influence of



inorganic and organic pollutants on the rate of reproduction



of a marine hypotrichous ciliate: Euplotes vannus Muller.



Rev. Intern. Oceanogr. Med.  37-38: 125.








Phillips, D.J.H.  1977.  Effects of salinity on the net



uptake of zinc by the common mussel Mytilus edulis.  Mar.



Biol.  41: 79.








Phillips, J.H.  1976.  The common mussel Mytilus edulis



as an indicator of pollution by zinc, cadmium, lead and



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of metals.  Mar. Biol.  33: 59.








Pickering, Q.H.  1968.  Some effects of dissolved oxygen



concentrations upon the toxicity of zinc to the bluegill,



Lepomis macrochirus Raf.  Water Res.  2: 137.








Pickering, Q.H., and C. Henderson.  1966.   The acute toxicity



of some heavy metal to different species of warm water fishes,



Air/Water Pollut.  10: 453.








Pickering, Q.H., and W.N.  Vigor.  1965.  The acute toxicity



of zinc to eggs and fry of the fathead minnow.  Prog. Fish-



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Portmann, J.Z.  1968.  Progress report on a programme of



insecticide analysis and toxicity-testing in relation to



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                               3-65

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Pringle, B.H., et al.  1968.  Trace metal accumulation by


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                                      0


455.






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A-024-IDA.  16 p.






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Prog. Fish-Cult.  30: 203.






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                              B-66

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                  •




Reish, D.J., et al.   1976.  The effect of heavy metals on




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Rosko, J.J., and J.W. Rachlin.   1977.  The effect of cadmium,




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Protosool.  20: 127.








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                               3-67

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Sosnowski, et al. 1979.








Sparks, R.E., et al.   1972.  Monitoring zinc concentrations



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                               B-68

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Sprague, J.B.  1968.  Avoidance reactions of rainbow trout



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Res. Board Can.  22: 425.








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movement patterns to monitor zinc in water.  Water Res.



6: 257.
                              B-69

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Warnick, S.L., and H.L. Bell.  1969.  The acute toxicity



of some heavy metals to different species of aquatic insects,



Jour. Water Pollut. Control Fed.  41: 280.








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Bull.  73: 401.








Watson, T.A.  1975.  The effect of sublethal concentrations



of zinc on histological, histochemical, growth, and blood



parameters in rainbow trout  (Salmo gairdneri Richardson)  .



Masters Thesis, Univ. of Guelph.








Watson, T.A. , and 3.A. McKeown.  197.6.  The effect of sub-



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Jour. Wildl.  Dis.  12: 263.








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Bull.  147: 236.
                               S-70

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Young, M.L.  1975.  The transfer of ° Zn and   Fe along



a Fucus serratus  (L.)     Littorina



obtusata (L.) food chain.  Jour. Mar. Biol. Assn. U.K.



55: 583.
Zitko, V., and W.G. Carson.  1977.  Seasonal and developmental



variation in the lethality of zinc to juvenile Atlantic



salmon (Salrno salar) .   Jour. Fish. Res. Board Can.   34:  139.
                              B-71

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Mammalian Toxicology and Human Health Effects

Introduction

     More than 100 years ago it was shown that zinc was essential for the

growth of Aspergillus niger.   It was then shown that it was an essential metal

for plant life.   In the 1930's, the essentiality of zinc for the growth of

rats was shown.   Zinc has for a long time been regarded as an essential element

for human beings but not until the 1960's was it shown that zinc deficiency

could cause a certain syndrome and that therapy with zinc salts could alleviate

or even cure the symptoms of zinc deficiency.  During the recant past some

other disease states including congenital diseases have been related to zinc.

Zinc therapy has attracted the interest of clinicians.  The evergrowing interest

in the metabolism of zinc and the relationship between zinc and certain diseases
        *
has, during the last decades, been reflected in a large number of reviews and

books  (Brewer and Prasad, 1977; Halsted et al., 1974; National Research

Council, 1978; Pories et al., 1974; Prasad, 1966; Prasad, 1976; Prasad, 1978;

Sandstead, 1975; Sandstead 1973; Vallee, 1959; Underwood, 1977).  The National

Research Council (NRC) report contains 1,855 references and gives information

not only on metabolism and essentiality of zinc for human beings but also much

information on occurrence of zinc, analytical methods, and human health hazards

form excessive exposure to zinc.  Since this chapter to a large extent  relies

on the NRC report, reference will be given to chapters or page numbers  in that

report whenever it is quoted in this or following sections.

     The information given will mainly rely on the above mentioned references

and specific references will only be given when there is information which

might add to the understanding of the metabolism and effects of zinc, esp-

cially in human beings.
                                   C-l

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                                   EXPOSURE







Ingestion from Water



     The National Research Council (NRC) (1978) (Chapter 2 pp. 25-28 and



Chapter 11 pp. 269-271) summarized available data on zinc in drinking water



and concluded that generally the concentrations were well below 5 mg/1. •, In a



study by the Department of Health, Education and Welfare (HEW) (1970) 2595



water samples were tested and of them 8 had zinc concentrations above the 5



mg/1 level.  The highest concentration found was 13 mg/1.  The average zinc



concentration was 0.19 mg/1.  In water leaving treatment plants, Craun and



McCabe (1975) found that all samples contained less than 5 mg/1 of zinc, but



that in cities with soft acidic water the concentration increased in the



distribution system.  Tapwater could thus have concentrations around 5 mg/1.



In a study by EPA (1975) it was found that in 591 water samples all had zinc



concentrations below 4 mg/1.



     Uncontaminated fresh water generally contains less than 0.01 mg of zinc/1



(NRC, 1978).  Analysis of filtered surface waters in the U.S. revealed that of



714 samples only 7 had concentrations exceeding 1 mg/1 and that 607 (85 percent)



had concentrations below 0.1 mg/1 (Durum et a!., 1971).



     The concentration of zinc in both natural waters and in drinking water



are generally low, but may increase due to pollution of water systems or  ..,



release of zinc from distribution systems and household plumbing respectively.



Ingestion from Food



     In the NRC document the content of zinc in different foodstuffs is listed



in detail (Appendix A-I pp. 313-326).  It was noted that meat products contain



relatively high concentrations of zinc, whereas fruits and vegetables have



relatively  low concentrations and contribute little to the daily intake.  Zinc
                                   C-2

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concentrations in milk are generally low, but at a high intake, milk can make


an important contribution to daily intake of zinc.


     Additional data are provided by Mahaffey et al.  (1975) who calculated


that meats, fish, and poultry on an average contained 24.5 mg/kg of zinc,


whereas grains (and cereal products) and potatoes only provided 8 and 6 mg/kg,


respectively.   These data were obtained from Food and Drug Administration


market basket studies which are based on the diets of teenage males, 15 to 20


years old.  In the years 1973 and 1974 it was calculated that the daily intake


in this age group was 18 and 18.6 mg/day of zinc, respectively.  Greger (1977)


calculated the daily intake of zinc in subjects living in an institution for


the aged, with an average age of 75 years, and found that on an average the


intake was 18.7 mg/day.   In girls 12 to 14 years old, Greger et al. (1978)


found that the average intake of zinc Was 10 mg/day.


     In the "recommended dietary allowances" the National Research Council


(National Academy of Sciences, 1974) recommended that adults should have a


zinc intake of 15 mg/day;,but pregnant women should have an intake of 20
                         / "* V  .

mg/day and lactating women an intake of 25 mg/day.  As a requirement of pre-


adolescent children, 10 mg/day was recommended.  In infants up to 6 months


old, 3 mg/day was recommended and for children aged 0.5-1 year 5 mg/day was


suggested.  Based on body weight the requirement for zinc would be about 0.5



mg/kg for the infant and about 0.2 mg/kg in the adult.


     A bioconcentration factor (BCF) relates the concentration of a chemical


in water to the concentration in aquatic organisms.  A recent survey on fish


and shellfish consumption in the United States (Cordle et al., 1978) found


that the per capita consumption is 18.7 g/day.  From the data on the nineteen


major species identified in the survey, the relative consumption of the four


major groups can be calculated.
                                   C-3

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     At least one BCF from an exposure of 28 days or more is available for

each of the four major groups:
        Species

        	fish
   Carp,
   Cyprinus carpio

o  Saltwater fish

   Plaice (adult)
   Pleuronectes platessa

o  Saltwater molluscs

   Hard-shell clams (adult)
   Mercenaria mercenaria

   Soft-shell clam (adult),
   Mya arenaria

   Soft-shell clam (adult),
   Mya arenaria

   Soft-shell clam (adult),
   Mya arenaria

   Clam (adult),
   Tapes jaoonica

   Scallops  (adult),
   Aeouipecten irradians

   Oyster (adult),
   Crassostrea virginica

   Oyster (adult),
   Crassostrea virginica

   Oyster (adult),
   Qstrea edulis

 •  Mussel (adult),
   Myti1 us  edulis

o  Saltwater decapods

   Crab (adult),
   Carcinus  maenas

   Crab (adult),
   Carcinus  maenas

  . Lobster  (adult),
   Homarus  vulaaris
      BCF



       8



     373



      85


      85


      43


    52-78  t


     500


   282-321


15,290-27,080


    15,240


      450


   130-310



 8,000-9,000


    5,400


      142
    Reference
Lebedeva &'•' """'
Kuznetsova, 1969
Pentreath, 1973
Shuster & Pn'ngle,
1968

Pringle et al.
1968

Eisler, 1977
Eisler, 1977


Kameda et al.  1970


Duke et al.  1969


Shuster & Pringle,
1S69

Shuster & Pringle,
1968
Romeri1, 1971


Philips, 1976
Bryan, 1971
          i
Bryan, 1966

Bryan, 1964
                                    C-4

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     From these data the geometric mean bioconcentration factor for each group
can be calculated.
                                 Consumption           8 i concentration
         Group                    (Percent)            	factor	
Freshwater fishes                    12                       8
Saltwater fishes                     61                     373
Saltwater molluscs                    9                     306
Saltwater decapods                   18                     980

Using the data for consumption and BCF for each of these groups, the
weighted average BCF for zinc is 432 for consumed fish and shellfish.

Inhalation Via Ambient Air
     Air quality data compiled in the NRC document (1978) show that zinc
concentrations throughout the U.S.A. generally are less than 1 ug/m  (Chapter
3 p. 42-43).  In 1975 and 1976, EPA (1979) observed zinc concentrations at
approximately 50 National Air Surveillance Network sites .-throughout the U.S.
Zinc concentrations in most areas were below 1 pg/m , quarterly average.
     The air levels of zinc are, in most areas, fairly constant.  As an
example, Lioy et al. (1973) presented data on zinc concentrations in New York
City during the years 1972 to 1975 where the annual averages varied from 0.29
to 0.38 pg/m .  Much higher concentrations have been reported near smelters.
About 1.5 miles from a smelter in Kellogg, Idaho, Ragaini et al. (1977) found
in ambient air a yearly mean zinc concentration of 5 ug/m .  The 24-hour
values ranged from 0.27 to 15.7 ug/m .  It should be mentioned that the average
                                   C-5

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lead and cadmium concentrations were 11 and 0.8 ug/m , respectively, indicating



very severe environmental pollution.  The U.S. data may be compared to data



from 15 cities in a heavily industrialized European country, Belgium  '



(Kretzschmar et a!., 1977).  During the period May 1972 to April 1975 the



average concentrations in 15 locations were from 0.22 to 3.05 ug/m .  The



highest value recorded during 24 hours was 57 ug/m .



     These data from industrialized countries may be compared to background



levels of zinc which have been measured at the South Pole and over the Atlantic



Ocean.  At the South Pole an average concentration of 0.03 ng/m  was found.



In the air over the Atlantic Ocean concentrations were from 0.3 to 27 hg/m



(Dues, 1975; Maenhaut, 1977; Zoller, 1974).



Exposure Via Smoking



     In cigarettes and other tobacco products zinc concentrations have been



reported to vary from 12.5 - 70 ug/g.   (Menden et al., 1972; Dermelj et al.,



1973; Franzke et al., 1977).  In the studies by Menden et al.  and Franzke et



al. the amount of zinc in the mainstream smoke was determined by simulated



smoking in a smoking machine.  Menden et al. found in two brands of cigarettes



that 0.06 and 0.36 ug, respectively, was in the mainstream leaving the cigarette,



whereas Franzke et al. found in 16 brands that from 0.12 to 0.92 ug was in the



same fraction.  These data indicate that by smoking 20 cigarettes up to 20 ug



of zinc might be inhaled.  There might have been some differences in experimental



techniques, since Menden et al. found that about 85 percent of the zinc remained



in the ash, whereas Franzke et al. found that in some cigarettes only about 10



percent remained in the ash.
                                   C-6

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Quantification of Total  Intake;  Relative Contribution From All Routes of Exposure

     The major source of zinc for the general  population in the U.S.  is food.

The average intake is generally  above 10 mg in adults.   An individual inhaling

air with an average concentration of 5 ug/m ,  would have an additional daily

intake of 100 ug, assuming that  he inhales 20  m  of air per day.   Smoking

would contribute even less than  that.   Compared to the intake via food, airborne
                                                                               0
exposure is insignificant.

     The intake via drinking water might be of more significance.  Levels

around 1 mg/1 are not uncommon and levels around 5 mg/1 have been reported.

Assuming a daily intake  of 2 liters of water this might result in daily intakes

of 2 and 10 mg, respectively.  The latter amount might double the intake for

people on a low dietary  intake,  but the total  intake will still be within

recommended limits.  In  people with recommended daily intakes of zinc, i.e.,

15-20 mg, the additional intake  via water will result in total daily intakes

of 25-30 mg.   As discussed later, the homeostatic regulation of zinc ensures

that such amounts and even larger amounts can  generally be well tolerated.
                                   C-7

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                               PHARMACOKINETICS








Metabolism and Homeostatic Regulation



Inhalation



     The fate of inhaled particles containing zinc will depend on particle



size and solubility as well as functional state of the lungs.   The quanti-



tative features of the deposition patterns of particles have been reviewed by



the Task Group on Lung Dynamics (1966) and the Task Group on Metal Accumulation



(1973).  There are no quantitative data on the deposition and absorption of



zinc compounds, but experiments on human beings by Sturgis et al. (1927) and



Drinker et al. (1927) indicated that both zinc oxide fumes and zinc oxide



powder with very small particle size were deposited in the alveoli.   That



inhaled zinc  is absorbed is shown by the finding of increased serum and plasma



levels of zinc in exposed workers.  It should be pointed out, however, that



part of the inhaled material will be transported to the gastrointestinal tract



via ciliary activity and some zinc may also be absorbed that way.



Gastrointestinal Absorption



     The absorption of ingested zinc will depend mainly on the zinc status of



the organism.  The presence or absence of other nutritional constituents may



also influence absorption.



     Spencer  et al. (1965) showed in human beings that   Zn as the chloride



was rapidly taken up, with plasma peak values within 4 hours.   It was calculated^



that about 50 percent was absorbed, but with a wide range (20 to 80 percent).



In that study it was not possible to show that the amount of calcium in the



diet influences the uptake of zinc from the gut.  There are difficulties
                                   C-8

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in assessing the absorption of zinc,  since there is also considerable excretion



of absorbed zinc via the gastrointestinal  tract .   There are also several



other earlier studies which show that there are wide variations in the absorp-



tion rates of ingested zinc (NRC Chapter 6 pp.  145-154).



     The protein content of the diet  has been shown to influence the uptake of



zinc.  In studies done on people with zinc deficiency it has been noted that



the effect of zinc therapy is enhanced by a simultaneous administration of



protein.   It has also been shown that the absorption of zinc will be reduced



if the diet contains large amounts of phytate .especially in the presence of



large amounts of calcium (NRC Chapter 7 pp.  183-187).   S-ince phytates are



found in cereals, zinc in vegetable diets including large amounts of unleavened



bread may be less available for absorption.   Arvidsson et al.  (1978) found



that the average absorption of   Zn added to bread during baking was 25 percent



ranging from 12.2 to 39.1 percent in  11 subjects.   The study was repeated



after one month and the same average  absorption was found.   In this study, the



influence of phytate seems to have been small.   The fiber content of the diet



may influence the uptake of zinc (Sandstead et al., 1973).   Zinc in anima-1



proteins seems to be easily available and thus meat is a good source of zinc.



     The influence of oral contraceptive agents on the absorption of zinc was



studied in 14 women and compared to 8 who did not take contraceptive pills



(King et al., 1978).  All were of similar age.   Zinc was administered as a



stable isotope,   Zn, and the absorption was determined from the difference



between intake and fecal output of the stable isotope which was measured by



neutron activation analysis.  Among the women taking the contraceptive agents,



the average absorption was 33 percent and in the control group it was 46
                                   C-9

-------
percent.  The difference, however, was not statistically significant, and the



authors concluded that there was no difference in absorption.



     The mechanisms for absorption of zinc are homeostatically controlled, and



data from animal experiments suggest that several proteins and low molecular



weight compounds may be involved in the absorption process.  There is evidence



that metallothionein, a low molecular weight, metal-binding protein, in the



intestinal mucosa may bind zinc (Richards and Cousins, 1977).  Zinc binding



ligands with molecular weights lower than metallothionein have been found in



animals.  Evans et al. (1975) proposed that such a compound .was produced in



the .pancreas and through the pancreatic secretions could bind zinc in the



gastrointestinal tract and enhance absorption.



     Of special interest is a zinc binding ligand which occurs in human milk,



but has not been found in bovine milk.  In 1976, Eckhert et al. (1976) reported



that gel chromatography of cow's milk and human milk showed that in cow's milk



zinc was associated with high molecular weight fractions, whereas in human



milk it was mainly associated with low molecular weight fractions.  This



species difference was taken by these authors as an explanation for the



congenital disease acrodermatitis enteropathica which usually occurred when



infants were weaned  from human breast milk.   Similar results were reported by



Evans  and Johnson  (1976) who thought  that the low molecular weight zinc binding



ligand in milk  was similar to the ligand  found in pancreatic secretions from



the  rat.  During the  last years several studies  have been  performed to isolate



and  identify this  ligand (Song and Adham, 1977;  Evans and  Johnson, 1977;



Shricker  and Forbes,  1978; Lonnerdal  et al.,  1979; Evans and Johnson, 1979).



The  data  are controversial and at present no  certain conclusions can be drawn



regarding the  nature of  the  ligand or ligands.   It has  also  been sho.wn by
                                    C-10

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Cousins,  et al.  (1978) that degradation products of  intestinal



proteins  including  metallothionein  r.ay crrur  as low  molecular



weight zinc binding complexes in  rat intestine.  The role  of.



ligands in  zinc absorption  has recently been  discussed by



Cousins (1979).







 Other Absorption Routes




      Zinc  salts will be absorbed through  intact skin of the  rat as  shown by




 Keen and Hurley  (1977).  According to  these authors, the  amount of  zinc absorbed



 was  higher in zinc-deficient animals and  was of a magnitude  which might be



 clinically significant.




      Hallmans (1978a, 1978b) showed  that  in rats with excisional wounds there



 was  a high absorption of zinc from gauzes containing zinc  sulfate.  At a




 concentration of 20 percent there were even systemic effects;  Hallmans concluded



 that the absorption from zinc sulfate  was higher than from zinc oxide.  Hallmans



 (1977) also  showed that in humans treated for burns  with  gauzes containing



 zinc oxide,  there was absorption of  zinc.




      Anteby  et al. (1978) reported that  in women using an  intrauterine device



 containing copper and zinc a slight  rise  in serum zinc could be shown, but no



 abnormal values were found.



 Transport  and Deposition




      Zinc  is found in erythrocytes mainly due to the presence  of the zinc




 metallo enzyme carbonic anhydrase and  in  leucocytes  where  several zinc metallo




 enzymes are  present.  In plasma, zinc  is  mainly bound to  albumin and it is




 thought that the binding is to one of  the histidine  moieties of the albumin



 molecule.   About one third of the serum zinc is bound to  an  a?-macroglobulin




 and  a few  percent to ami no acids.   In  the albumin and the  ami no acids there is
                                  C-ll

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an exchange of zinc, whereas there is no exchange with zinc in the (^-macro-



globulin.  The zinc bound to amino acids constitutes the diffusible serum zinc



(Giroux, 1975; Giroux 1976; NRC, 1978).



     Of special interest is the relationship between zinc and histidine.  It



has been shown in human beings that oral administration of histidine will



cause decreases in serum zinc and an increase in urinary zinc excretion (Henkin



et a!., 1975).  This observation has also been made in experiments on rats



(Freeman and Taylor, 1977) and dogs (Yunice et al., 1978).   The latter authors



also showed that cysteine caused a considerable increase in excretion of zinc.



This is thought to be one explanation for the losses of zinc seen in patients



given parenterally hyperalimentation, since the fluids given usually contained



large amounts of essential amino acids,  without sufficient amounts of essential



metals (Agarwal and Henkin, 1978; Kumar, 1976).



     In the tissues, the highest concentrations of zinc are found in the male



reproductive system where the prostate has the highest content.  Other organs



with high concentrations of zinc are the muscle, bone, liver, kidney, pancreas,



and some endocrine glands, especially the thyroid.  The largest amounts of



zinc are found in the muscles and the bone.  Within tissues there may be



variation; in the human prostate gland the highest zinc concentrations are



found in the lateral prostate and the lowest in the interior and inner prostate.



Also significant is the finding that semen has a high zinc content.  In most



organs there are relatively small variations in zinc levels during a lifetime



except that in the newborn, zinc concentrations generally are higher than



later in life.  It should also be pointed out that the zinc content of the



kidney and liver will, to a large degree, depend on the cadmium concentrations



and renal zinc concentrations will vary with age (Elinder et al., 1978; Piscator
                                   C-12

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and Lind, 1972; Schroeder et al., 1967).   Regarding the form in which zinc is



stored in different organs, zinc is generally an essential component of many



enzymes (see section on essentiality).   Zinc is also found in metallothionein



(see special section on metallothionein).



Excretion



     Zinc is mainly excreted via the gastrointestinal tract but part of that



zinc is reabsorbed.   Urinary excretion of zinc is relatively small and during



certain conditions,  i.e., extreme heat or exercise, much larger quantities may



be excreted in sweat (Cohn and Emmett,  1978; Kohnadel et al. , 1973).  Zinc is



also excreted via hair and milk, and in the female there is a placenta! transfer



to the fetus.



     Losses of zinc may also occur via menstrual blood losses and skin.  Molin



and Wester (1976) determined by neutron activation the zinc content of epidermis.



They calculated that the daily losses by desquamation would be about 20 to 40



(jg, only about one tenth (1/10) of the urinary excretion.



Biological Half-time



     The long-term biological half-time of zinc will depend on the zinc status;



it has been shown that after oral intake or injection of   Zn to human beings,



the half-time may vary from about 200 to about 400 days, depending on the zinc



status (NRC Chapter 6 pp. 151-154).  Arvidsson et al. (1978) gave eight subjects



single injections of   Zn.  After the injection, measurements were taken for



84 to 190 days.  The slow component for the half-time of the injected zinc for



this group was on an average 247 days.   Kennedy et al.  (1978) found that the



average half-time was 412 days in 19 female patients undergoing treatment for



rheumatoid and osteoarthritis who were given an oral dose of   Zn .   In certain
                                   C-13

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body compartments, e.g., bone, the half-time may be considerably 1onger'(NRC


Chapter 6 pp. 149-154).


Metal!othionein


     Metallothionein was briefly discussed in previous reports and books


concerning zinc, but during the last several years there has been an enormous


increase in the number of papers on this protein.  Recently a very comprehen-


sive report on metallothionein has been prepared (Nordberg and Kojima, 1979).


Mammalian metal!cthionein is a protein with a molecular weight of 6,000 to


7,000 which is characterized by a very special amino acid composition, a high


cysteine* content, but  lack of aromatic ami no acids and histidine.  Metal! othionei'n


was first discovered in equine renal cortex by Margoshes and Vallee (1957) and


has now been shown to  occur in most mammalian tissues, and also  in lower


organisms.  Total metal content of metallothionein can reach 5 to 7 g atoms


per mole.  The metals  generally found in metallothionein are zinc, copper, and


cadmium.  The relative occurrence of these metals will depend on a number of


factors.  In fetal liver metallothionein, zinc and copper are the major con-


stituents, whereas in  animals exposed to cadmium, cadmium will be the dominat-


ing metal especially in the renal protein.  A number of factors  can induce the


synthesis of metallothicnein.  In addition to administration of  the above-


mentioned metals, metallothionein synthesis seems also to be indirectly.induced


by factors that might  influence zinc metabolism.  Thus, environmental stresses


of different kinds may induce the synthesis.
                                                                    •

     With regard  to zinc metabolism, it  has been shown that parenteral or


dietary  administration of zinc will cause an  increase of the synthesis of


matallothionein  (Bremner and  Davies, 1S75; Richards and Cousins, 1975a;;Richards


and Cousins, 1975b; Richards  and Cousins, 1977).  Recently, it was shown that
                                    C-14

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hepatic zinc was increased and metallothionein synthesis stimulated in response



to several environmental  stresses,  such as cool  and hot environments, burns,



and exercise (Oh et al.,  1978).   Food restriction and bacterial  infections



have been shown to cause  such changes (Bremner and Davies, 1975; Richards and



Cousins, 1976;  Sobocinski  et al.,  1978).   Failla and Cousins (1978) demonstrated



that glucocorticoids j_n  vitro stimulated the uptake of zinc in liver parenchymal



cells, a process that required synthesis of metallothionein.  Such findings



indicate that metallothionein may serve as a regulator of plasma zinc levels



and constitute an easily  available  pool for acute replacements of zinc in



certain situations.   Also of interest is the finding of large amounts of



metallothionein containing zinc and copper in fetal livers reported by several



investigators (Bremner et al., 1977;  Hartmann and Weser, 1977; Ryden and



Deutsch, 1978), which gives similar indications.  Much is still  unknown about



the biological  function  of metallothionein, but there is no doubt that this



protein must play a very  important  role in the regulation of zinc in the



mammalian body (Nordberg  and Kojima,  1979).



Normal Levels in Tissues  and Fluids



     In the National Research Council (NRC) report (1978), extensive informa-



tion is given on concentrations of  zinc in blood, urine and tissues (Chapter 6



pp. 123-145).  The NRC report concluded that the mean serum-zinc concentra-



tion in humans is approximately 1 mg/liter, the same in healthy men and



women.  The zinc content  of whole blood will be about 5 times higher than the



serum level, since the concentration in the red cells is about 10 times the



amount found in serum.   A lowering of the serum concentrations of zinc may be



seen in women who take contraceptive pills, during pregnancy, and as a result



of certain stresses such  as infections.  In the same individual  the zinc
                                   C-15

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concentration in serum will be higher than in plasma mainly due to the release



of zinc from platelets (Foley et a!., 1968).   In 14 subjects the mean serum



level was 1.15 mg/1 and the mean plasma level 0.98 mg/1,  the average difference:



being 16 percent.                                                    '



     The influence of age and sex on plasma zinc levels was studied by Chooi



et al. (1976).  They found that in both males and females there was a'decrease



in plasma zinc from age 20 to age 90.  Between men and women below the age of



50 no difference in plasma zinc levels could be noted between the sexes.



However, females using contraceptive agents had lower zinc levels than women



who did not take contraceptive agents.  Average plasma levels in the groups



studied were around 0.7 mg/1.



     In a recent report, Hartoma (1977) stated that men had higher serum zinc,



levels than women.  The average concentration in 154 male blood donors was



1.24 mg/liter (range 0.74 to 2.2 mg/1), and in 95 women it was 1.11 mg/liter



(range 0.64 to 1.82 mg/1).  The difference was highly significant according to



the author.  It was not stated to what extant the women took contraceptive



pills.  Hartoma also found that there was a slight tendency to a lowering of



the serum concentration of zinc in men with increasing age, and that there was



a significant correlation between serum zinc and serum testosterone in, males



aged 36 to 60 years.  In men 23 to 35 years of age, there was a negative



correlation, which was not significant.  In these two studies plasma and serum



levels,; respectively, were lower and higher than earlier reported data which



indicates -that methodological problems in sampling and analysis may still



exist.  In both  studies samples were taken in the morning aftar overnight



fasting.
                                   C-16

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     In the NRC report (Chapter 6 p.  129) it was stated that approximately 0.5



mg of zinc is excreted in the urine every 24 hours by healthy persons.   Addi-



tional data have been provided by Elinder et al. (1978) who studied the urinary



excretion of zinc in different age groups.   They found that there was a



tendency towards a higher zinc excretion in smokers than in non-smokers.



Among non-smokers there was a tendency to decreased zinc excretion from



about age 20 to higher ages (See Table C-l).  The tissue concentrations of



zinc are generally higher in the newborn.  After the first year of life there



are fairly small changes in the zinc levels in most organs except the kidney



where the zinc concentrations are dependent on the accumulation of cadmium



(Elinder et al., 1977; Piscator and Lind, 1972; Prasad, 1976).  In the  liver



the zinc level is constant during a lifetime.   In the pancreas there is a



decrease in zinc levels with increasing age on a wet weight basis, whereas if



the pancreas values are calculated on an ash weight basis that decrease is not



seen (Elinder et al., 1977).  This is in agreement with Schroeder et al.



(1967).  In the study by Elinder et al. (1977), the average concentrations of



zinc in liver and pancreas were 45 and 27 mg/kg wet weight, respectively.   The



highest concentrations of zinc are found in the prostate, where the concen-



tration is about 100 mg/kg wet weight.  In  human semen concentrations of 100



to 350 mg/1 have been reported.  The zinc concentrations in hair will vary



depending on age and geographical location  (NRC Chapter 6 pp. 140-141).



Sorenscn et al. (1973) found that in 13 communities in the U.S. the average



zinc concentration in hair from adults varied from 148 to 210 mg/kg.  The



newborn has zinc levels in hair similar to  levels in the adult, but at  age 1-4



the levels are  lower than in adults (Hambidge et al., 1972; Petering et al.,



1971).  Zinc concentrations in hair will decrease during pregnancy (Baumslag
                                   C-17

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             TABLE C-l.   ZINC CONCENTRATIONS IN THE URINE  OF SWEDISH PEOPLE
Number of
Group persons
Men, non-smokers
(age in years)
2 to 9
17 to 19
20 to 29
30 to 39
40 to 49
50 to 59
60 to 69
70 to 79
80 to 89
Men, smokers
(age in years)
40 to 49
50 to 59
66
75 .
Women, non-smokers
(age in years)
3
40 to 49
50 to 59


4
10
10
10
16
15
9
11
9


5
5
1
1


4
10
10
Zinc, average (a)a
(mg/g of creatinine)


0.86
0.38
0.32
0.29
0.25
0.32
0.27
0.40
0.35


0.35
0.39
0.32
0.27


1.23
0.23
0.47
Standard Zinc,
Deviation calculated
(a) average (mg/24 hr)


0.23
0.19
0.13
0.10
0.16
0.09
0.17
0.18
0.12


0.19
0.09
.
—


0.21
0.17
0.38


0.33
0.71
0.59
0.49
0.39
0.45
0.35
0.46
0.35


0.55
0.55
0.41
0.31


0.37
0.20
0.34
a, arithmetic averages.
                                        C-18

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et al., 1974; Hambidge and Droegemueller, 1974).   The determination of zinc in



hair has been used as a screening tool for zinc deficiency (Hambidge et al.,



1972).   The total body store of zinc in adult humans has been estimated to be



2.3 mg for a 70 kg man (NRC Chapter 6 p.  123).



The Homeostatic Regulation of Zinc



     The homeostatic regulation of zinc absorption in the rat was studied by



Evans et al.  (1973).  Rats fed an optimal intake of zinc were compared to rats



which had been on a diet for 7 and 13 days, respectively, containing less than



1 mg/kg of zinc.   Whereas, in the controls the absorption was about 15 percent



measured by examining the radioactivity in the carcass 1 hour after a gastric



dose of   Zn, it was about 35 and 50 percent, respectively, in the two experi-



mental groups.



     Weigand and Kirchgessner (1973) studied the homeostatic mechanisms for



zinc absorption in 36 weanling rats, where in groups of six they were given a



diet with the following zinc contents:  5.6, 10.6, 18.2, 38, 70, and 141



mg/kg.  After 6 days the animals had adjusted to the respective intakes and



the absorption of zinc was from 100 to 34 percent in inverse relation to the



intake of zinc.  The true zinc absorption and the fecal excretion of endogenous



zinc could be determined by measuring the turnover of radioactive zinc which



had been injected at the start of the experiment.  The figure of 100 percent



seems surprisingly high, but these were weanling rats which were growing



rapidly.  This may also explain the relatively high absorption figure for the



group receiving 141 mg/kg feed of zinc.  The daily zinc retention was the same



in the groups receiving 38, 70, and 141 mg/kg, whereas it was lower in the



groups receiving 5.5, 10.'5, and 18.2, indicating that in this study this



supply was not sufficient.  In the three highest exposure groups both total
                                   C-19

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absorption and total fecal excretion of endogenous zinc increased in proportion



to the daily intake.



     The homeostatic regulation of ingested zinc was also studied by Ansari



et al. (1975).   Male rats were given a diet containing 53 ppm zinc, and at



different times groups were given a diet with 600 mg/kg of added zinc



beginning 7, 14, 21, or 42 days before sacrifice.  One week before sacrifice



each rat was given, by gavage, an oral dose of   Zn as the chloride.:  Feces



were collected for 7 days.  The elimination of fecal zinc was similar in all



groups except the control group irrespective of  length of exposure, 'whereas



the fecal elimination of   Zn increased with length of exposure.  Also, analysis



of tissues revealed that the longer the exposure to the high zinc.level in the



diet the more rapidly   Zn was eliminated.  Tissue levels of stable 'zinc were



only slightly influenced by the high zinc content of the diet.  Only in the



liver could a significant increase in the zinc level be noted.  Levels in



kidney, muscle and heart did not differ from controls.  These results also



show the extreme capacity of the organism to handle excess zinc in the diet.



They also show how rapid the exchange will be between absorbed zinc and tissue



stores of zinc.



     Ansari et al. (1976) gave male rats dietary zinc at levels of from 1200



to 84QO ppm zinc for 3 weeks.  One week before sacrifice each rat was given



  Zn  as the chloride by gavage and after that feces were collected for one



week.  The high zinc content of the diet did not affect weight gains or feed



consumption or produce any obvious signs of toxicity.  In controls 65 percent



of the   Zn was eliminated in one week in contrast to 86 percent in the rats



given 1200 ppm zinc  in the diet.  At still higher levels of dietary zinc there



was no further increase of fecal   Zn.  Rats given 1200 ppm zinc in the diet
                                    C-20

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had significantly higher levels of stable zinc in liver, kidney, and tibia



than controls,  whereas there was no change in concentrations in heart and



muscle.   No further increase was seen at levels of 2400 to 7200 ppm in the



diet, but at 8400 ppm level  a new increase was seen, also in heart but not in



muscle.   The amount of radioactive zinc was, at all exposure levels, only a



few percent of the amount found in the controls.   There were no obvious changes



with increasing dietary zinc, except in tibia where, at the highest levels,



there occurred an increase compared to the previous levels.   In heart and



muscle there was a slight but continuous decrease.  In liver and kidneys there



was no change.   The authors  concluded that the data indicated that there was a



good homeostatic control in  the range 2400 to 7200 ppm.  The authors also



concluded that the homeostatic regulation of zinc was much more effective in



the rat than in calves.  Stake et al. (1975) found that calves given a diet



containing 600 mg/kg of zinc after one week had considerably higher zinc



levels in liver, kidney, and pancreas than calves fed a diet containing 34



mg/kg.  There was, however,  no change in heart or muscle zinc levels.



Essentiality of Zinc. Zinc Metal!oenzymes and Zinc Deficiency



     The topics of zinc essentiality and zinc deficiency have been extensively



treated in the National Research Council (NRC) report (1978) and also in a



recent review by Prasad (1973).  In 1934, it was  shown by Todd et al. (1924)



that zinc was necessary for the growth of rats and since then many studies



have been made on the essentiality of zinc, including studies of human beings.



     In human beings zinc is necessary for normal growth and for normal



development of the gonads.  Prasad et al. (1963)  found that in certain villages
                                   C-21

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in Egypt many subjects exhibited a syndrome characterized by dwarfism and



anemia, hypogonadism, hepatosplenomegaly, rough and dry skin, and mental



lethargy.   These young persons had a very low intake of animal proteins with



bread as their main food.  Zinc deficiency was demonstrated by the finding



that zinc concentrations in plasma, red cells, and hair were decreased; that



subjects had a higher turnover of radioactive zinc than normal, and that the



excretion of zinc in feces and urine was less than in controls.  Improvements



were seen after oral administration of zinc with a still greater effect observed



upon additional protein supplementation.



     Similar syndromes have been reported in other parts of the world.   There



are, however, studies that show that zinc deficiency with less pronounced



symptoms may be more common than thought earlier.   In the U.S., evidence of



symptomatic zinc deficiency has been found in Colorado by Hambidge et al.



(1972).  Zinc concentrations in hair were used as an index of the zinc status.



Hambidge et al. found that in 132 children ages 4 to 15, 10 children had hair



zinc concentrations below 70 rag/kg, whereas most children had concentrations



above 125 mg/kg.  Eight out of 10 of these children were found to have heights



at the lower range  for their age group.  Poor appetite and a low intake of



meat was thought to be one reason for trie zinc deficiency.  In these children



hypogeusia (impaired taste acuity) was also found.  After zinc supplementation,



this condition was  normalized.  An increase in hair zinc could be shown



parallelling the supplementation with zinc.  In five children with hair zinc



levels of 10 to 63  mg/kg before therapy, the levels were 67-170 mg/kg after 4



months of therapy.  There are studies in other parts of the U.S. showing that



low zinc levels in  children's hair is not an uncommon finding  (Prasad, 197S).
                                   C-22

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     The reason for the signs and symptoms caused by the zinc deficiency is



not clear, but it is known from a number of studies in a variety of organisms



including human beings (NRC Chapter 8) that zinc is an essential constituent



of many metal!oenzymes.   Typical examples of such metalloenzymes are alcohol



dehydrogenase, carboxypeptidase, leucine aminopeptidase, alkaline phosphatase,



carbonic anhydrase, RNA polymerase and DNA polymerase.  Also, thymidinekinase



is thought to be a zinc dependent enzyme.  Zinc may be involved in the synthesis



and catabolism of RNA and DNA.



     In addition to nutritional zinc deficiency, which is caused solely by a



low dietary zinc intake, there are instances of zinc deficiency which are



thought to have other causes.  These are:



     (1)  zinc deficiency in dialysis patients, which has been attributed tc



depletion of bcdy zinc stores (Atkin-Thor et al., 1978);



     (2)  zinc deficiency after intravenous hyperalimentation, which might



lead to increased excretion of zinc because of the large amounts of ami no



acids in the infusion fluids (Bernstein and Leyder, 1978; Freeman et al.,



1975);



     (3)  zinc deficiency after excessive alcohol ingestion (Ecker and Schroeter,



1978; Weismann et al., 1978); and



     (4)  zinc deficiency after operations such as intestinal bypass surgery



(Atkinson et al., 1973; Weismann et al., 1978).  The signs noted are generally



changes in the skin and hypogeusia.



     There is also a rare congenital disease called acrodermatitis enteropathica



which generally occurs in children after weaning.  As has been discussed



earlier, human milk seems to contain a factor or factors necessary for the



absorption of zinc.  Signs in this disease may come from many organs, among
                                   C-23

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them the skin, central nervous system, and the gastrointestinal tract.  As in



other zinc deficiencies in children, there will be retarded growth and



hypogonadism.  Large oral doses of zinc will correct the condition.



     Prasad et al. (1978) have recently reported on experimental zinc deficiency



in humans.   They studied four male volunteers who were hospital patients with



various diseases.  They were given a diet containing about 3 mg Zn/day for



several weeks.  In order to decrease the zinc intake it was necessary to give



subjects cereal protein instead of animal protein during the study.   In all



subjects considerable weight losses occurred during the zinc depletion period.



The plasma zinc level decreased significantly in all subjects and in three of



four subjects there was a decrease in zinc excretion.   Connective tissue was



analyzed in two patients; during the period of low zinc intake thymidinekinase



activity could not be detected, whereas after zinc supplementation it became  '



close to the normal values.  Also, plasma alkaline phosphatase activity



decreased along with a decrease in plasma lactic dehydrogenase activity during



the zinc depletion.  In the connective tissue the RNA and DNA ratio showed



changes during the restriction period.
                                   C-24

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                                   EFFECTS







     Zinc deficiency will  not be  covered in this section since it has been



discussed in a previous  section;  the emphasis will  be on the effects caused by



excessive exposure to zinc via inhalation or via ingestion.   The literature on



such adverse health effects is limited.   One probable reason for the limited



information is that zinc has generally been accepted as a beneficial substance



and adverse effects have neither  been expected nor looked for.



Inhalation of Excessive  Amounts of Zinc



     Effects on the lungs  and systemic effects after inhalation of zinc compounds



have only been reported  from occupational settings.   A special case is the



lung damage seen after inhalation of zinc chloride from smoke bombs.  As will



be discussed later, not  only zinc chloride but also the hydrochloric acid



formed are of importance for the  development of such effects.  Health effects



observed in workers exposed to zinc and the results of some studies on animals



will be discussed.  Information on the health hazards of zinc will also be



found in most textbooks  on occupational hygiene and in the recent National



Institute on Occupational  Safety  and Health (NIOSH) criteria document on zinc



oxide (NIOSH, 1975).



Acute Effects



     Most of our knowledge about metal fume fever and its relationship to



exposure to zinc oxide fumes comes from the beginning of the century when



there was extensive research on this acute type of poisoning (Drinker et a!.,



1927; Drinker et al., 1928; Sturgis, et al., 1927).   Reviews on metal fume



fever, often also containing case reports, have been published in large numbers



(Anseline, 1972; Hegsted et al.,  1945; Kehoe, 1948; Rohrs, 1957).  Metal fume
                                   C-25

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fever is described in all textbooks on occupational hygiene.  It should also



be mentioned that metal fume fever has not only been associated with inhalation



of zinc oxide fumes, but with many other metal fumes which may produce similar



symptoms.



     Metal fume fever only appears after exposure to freshly produced metal



fumes (McCord, I960; Rohrs, 1957) which can penetrate deep into the alveoli.



Zinc oxide dust or other metal dusts are not capable of producing the disease.



Typical for metal fume fever is symptom occurrence within a few hours after



exposure.  The symptoms may persist for 1 to 2 days and are characterized by



influenza-like symptoms such as headache, fever, hyperpnea, sweating, and
    %


muscle pains.  Among the laboratory findings leukocytosis is the most prominent.



There have never been any fatalities from metal fume fever.  Metal fume fever



generally occurs at the beginning of the working week when the worker has not



been exposed for a couple of days and further exposure will not cause new



symptoms, indicating a type of immunity.  This disease has also been given the



name "Monday fever."  It has been suggested by McCord (1960) that there is an



allergic basis for the mechanism of metal fume fever.  Several theories have



been put forward, but there is no definite evidence for any of the proposed



different mechanisms for this reaction.  One reasonable theory is that the



metal fume penetrates deep  into the alveoli, and combines with proteins which



might act as sensitizing agents.  There is a lack of data on the  levels of



zinc oxide fumes in air that might cause the disease.•  The only available



information  is from experiments on human beings in 1927 by Sturgis et al.



(1927), who  exposed 2 subjects to zinc  oxide fumes at a level of  600 mg zinc/m  .



It  was  calculated that the  subjects inhaled 48 and 74 mg zinc, respectively.
                                    C-26

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     There was a report on acute emphysema in cattle reported to have been



exposed to zinc oxide fumes (Hilderman and Taylor,  1974).   This episode occurred



in a barn where oxy-acetylene cutting and arc welding of galvanized pipe were



done during remodelling of the barn.   Three heifers were severely affected.



Within a short time all three died.   Autopsy showed severe changes in the



lungs with edema, emphysema, and hemorrhages.  Zinc concentrations in liver,



kidney, and lungs were not above normal values in two animals examined.  In



this case, a galvanized material was  suspected but the extremely severe condi-



tion caused by the fumes showed either that cattle are extremely sensitive to



zinc oxide fumes or that other metals (such as cadmium) might have been respon-



sible.



     Acute pulmonary damage and even  death may occur after the inhalation of



zinc chloride which is the major component in smoke coming from so-called



"smoke bombs" which are often used in military exercises.   Accidental inhala-



tion of such smoke in confined spaces may rapidly lead to severe disease, but



it should be pointed out that the toxic action may not only be due to the



zinc.  The hydrochloric acid component in the smoke may contribute.  Further



details on exposure to zinc chloride  are provided by Mil liken et al. (1963).



     The effects of inhalation of zinc chloride in smcke from smoke bombs have



also been described by Schmal (1974)  who reported on 11 cases, of which two



had very severe  reactions  including edema of the lungs.  However, no severe



sequelae were seen.  In one case, however, it was almost 2 years before the



lung function was normalized.



Chronic Effects



     Batchelor et al.  (1925) made an extensive investigation of workers exposed



to zinc in a smelter in New Jersey.  The authors pointed out that this smelter
                                   C-27

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was «ell  suited for studies on chronic effects of zinc since the aaounts of
lead-/ cad»iia»,  and arsenic in the ore were very  low ccsg>ar*d with other types
«•
of zinc ores processed in other parts of the U.S.  Of a total work fores of
1,520 aen, a nuaber of workers w*re selected fro*s different work areas for the
special studies.   Twelve »en *ere selected from  bag rccas where zinc oxide was
tetiKHed.  Fro»  a zinc oxide packing house five i»en were selected; four of thea
never wore respirators.   Fro* another zinc oxide plant t*o sen were selected
arsd two asen were selected frc* a plant handling  setallic 2lnc.  Finally, three
workers fro* a  Hlhopone packing house were selected,  A m»ber of deterarina-
tio*>s of zinc concentrations in air were sade.   Jn the bzg house an
concentration of 14 JKJ/SI  was observed.  In other workplaces ^e«an
were generally be'lcw 35 jag/ai.   In the zinc dust plant a maxi#i*i concentration
of 130 ss/»  was measured.   The  24 subjects underwent a tmfcber of
•tefhich included .x-rays, physical exa»inat1ons, Interviews, blood pressure
E»asur*»ents, and *»easuresients of zinc in blood, urine and feces.  Regarding
the laboratory findings,  It »sy b* noted that 14 Of the 24 wen shov&d a slight
leijkocytosis; hewc^lobin  was  reported to range between 72 and 97 percent with
an average of 81 percent  (100 percent is assi»ed to be ISO §/l).  Twenty-four
ho«r zinc elimination via feces in controls was reported to vary froa about 4
to 20 sag, with an average of  9.32 ag, which is in good agreement with present
daily values.  In the exposed subjects, 24-hour excretion of zinc via feces
averaged 46,8 wg which indicates an exposure via the $a$lroiniesUr»al tract or
esassive excretion into the Intestine.  The conclusion of the euthors was that
the workmen could be exposed  to zinc compounds in a spelter for ttecades without
any syfcptods or chronic disease.
                                   O28

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     Chmielewski  et al.  (1974a,  19745)  reported on the examination of 60



shipyard workers  who were exposed to zinc oxide in different operations.  As a



control  group,  10 healthy subjects who  did not work in the shipyard and 10



shipyard workers  not exposed to  zinc oxide were used.   Interviews showed that



most of the workmen had experienced metal fume fever several times.   Exposure



levels varied between 1.7 and 18 mg/m  of zinc oxide,  but a maximum value of



58 mg/m  was found during welding on one occasion.  Laboratory investigations



showed a tendency to leukocytes is, but  other laboratory investigations gave no



conclusive results.  Some enzyme activities were determined before work and



after work.  Also in control groups changes were noted during the workday.  It



is obvious that in this study many of the workers must have been exposed to



substances other than zinc oxide.  For  example, levels of nitrogen oxides were



high in some workshops, the highest being 120 mg/m , with mean concentrations



varying from 2-20 mg/m .   Also,  the total dust was high in some workplaces



with levels around 100 mg/m  in  several places.



     Pistorius (1976) studied the effect of zinc oxide on rat lungs in an



34-day study.  The rats were divided into groups so that they were exposed for



1, 4, or 8 hours a day to a concentration of 15 mg/m  of zinc oxide, at



particle size less than 1 micron.  A number of lung function tests were performed



after 2, 4, and 7 weeks and at the end of the experiment.  For most parameters



there was  no difference between  controls and exposed animals, but in specific



conductance and difference volume there was a significant decrease after  two



weeks.  Further exposure resulted in all three exposure groups getting  closer



to the control values.  Paradoxically the animals with the 1-hour exposure per



day  had the lowest values and the 8-hour exposure animals the highest values.



The  results were interpreted as  a bronchial constriction.  The author also
                                   C-29

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explained the improvement in lung function with extension of exposure as a



result of an increased elimination from the lung due to an increase in



macrophages.



     Pistorius et al. (1976) exposed male and female rats for 1, 14, 28, and



56 days to zinc oxide dust at a concentration of 15 mg/m  4 hours a day, 5



days a week.  Animals were killed 24 hours after the last exposure and the



zinc content of lungs, liver, kidney, tibia, and femur was measured.  After a



single exposure the total zinc content of the lung in males and females was



about 46 and 49 ug, respectively.  In the male rats similar amounts were found



after the longest exposure, whereas  in female rats the zinc content after



repeated exposure was lower in all groups than at the first exposure.   Zinc



concentrations were highest in the lung after 1 and 14 days of exposure.  In



liver and kidney there were no major changes during the experiment, but it  .



should be pointed out that a non-exposed control group was not followed.  No



differences could be noted in bone.  Histclogical examination of the lungs



showed infiltration of leukocytes and inflammatory changes; after 28 and 55



days of exposure, an increase in macrophages could be shown.  These studies



indicate that there is a rapid elimination of inhaled zinc from the lungs, and



that the absorbed zinc is rapidly eliminated from the body through the hcmeostatic



mechanism.



     Zinc stearate is a compound other than zinc oxide which is often encountered



in the plastic industry and is suspected of causing lung disease. "Vctila and



Noro (1957) reported on a fatal case involving a worker employed for 29 years



in a rubber plant.  The autopsy showed the cause of death was a diffuse fibrosis



of the lungs with histochemical examination of the lungs showing increased



deposits of zinc.  However, no quantitative determinations of the zinc content
                                    C-30

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of the lung were made.   The role of zinc stearate as a cause of chronic lung



disease has since then been discussed by Harding (1958) and by Weber et al.



(1976).  Harding gave rats intratracheal instillations of 50 mg of zinc stearate



which caused about half of the animals'  deaths.  In the survivors (living up



to 259 days after instillation of the compound) fibrosis could not be detected.



Harding also found that the zinc stearate had disappeared from the lungs



within 14 days.   Weber et al.  described autopsy findings in a man who was



employed for the last 8 years  of his life in a plastics industry and who was



exposed to zinc stearate.  Fibrosis was found in the lungs with the zinc



content of 62 mg/kg of lungs on a dry weight basis (Weber et al., 1976).  The



same authors found that thirty persons from the same area had concentrations



between 3.3 to 69.3 mg/kg of zinc in lungs.  The man had also had other occupa-



tions, but his exposure to silica quartz in another occupation could not



explain the fibrosis.  The authors concluded that zinc stearate could not have



caused the fibrosis, one reason being that the zinc content of lungs was



within the normal limits.  However, as pointed out by Harding (1958), zinc



stearate is relatively rapidly cleared from the lungs, so a normal content of



zinc in the lungs does not exclude the possibility that zinc stearate might



have contributed to this disease.



     Tarasenko et al. (1976) exposed rats to a single intratracheal administra-



tion, of zinc stearate in a dose of 50 mg, and found, like Harding, that 50



percent of the animals died after that dose.  In animals that survived,



pathological changes were seen in the lungs 2 months later.  Still later a



picture of chronic alveolar emphysema and bronchitis was seen.  According to



the  report, doses of 10 mg and 5 mg were also given but the results were not



presented.
                                   C-31

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Ingestion of Excessive Amounts of Zinc



     The hazards of keeping food or liquids in galvanized containers are



illustrated by a report by Brown et al. (1964) on two outbreaks of food poison-



ing assumed to be caused by zinc in California in 1961.  In one instance the



food poisoning was caused by keeping chicken with tomato sauce and spinach in



galvanized tubs.  In the other instance a punch drink had been kept in galvanized



containers.  Zinc content of the food was estimated by repeating the preparation



of the meal.  After 24 hours of storage the mixture of chicken and tomato



sauce contained close to 1000 ppm of zinc.  The other poisoning was caused by



punch containing 2200 mg/1 of zinc.  It was calculated that the doses of zinc



would be 325-650 mg.  In the first instance symptoms occurred 3 to 10 hours



after ingestion.  Severe diarrhea with abdominal cramping was the main symptom.



Vomiting was not common, whereas after drinking the punch the first symptoms



were nausea and vomiting which occurred within 20 minutes after ingestion.



Diarrhea was also noted in the latter instance.  No after effects were observed.



It may be noted that in the first instance zinc was ingested with food and the



delay in symptoms may have been caused by a simultaneous occurrence of vegetables



and meat, whereas in the second instance a more acute effect occurred, since



only drinks were served.  Cadmium was not determined in either of these studies.



Galvanized materials often contain relatively large amounts of cadmium.



     Murphy (1970) reported on a 16-year-old boy who tried to promote wound



healing by ingesting a large amount of zinc, 12 g of elemental zinc mixed with



peanut butter.  The zinc was ingested over a two-day period in doses of 4 and



8 g per day.  He became lethargic, had difficulties in staying awake, experi-



enced a slight  staggering of gait, and noted problems in writing legibly.
                                   C-32

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Nine days after the irigestion of the first dose of zinc, he was admitted to a



hospital.  Neurological  and laboratory examinations did not reveal anything



abnormal, except a slight rise in serum-amylase and lipase.  Zinc in whole



blood was slightly elevated whereas serum zinc was within the normal range.



There was no increase in the zinc level of cerebrospinal fluid.  He was treated



with dimercaprol and there was a rapid decrease of whole blood levels of zinc



to subnormal values.   This treatment removed his lethargy.   The author's



conclusion was that this case showed symptoms indicating an influence of zinc



on the pancreas and the cerebellum, but that these effects were easily reversible



and no sequelae were seen.



     Chunn (1973) studied a group of hospitalized children with anemia.  There



were 3 children who had levels of zinc in urine above 1 mg/1, but it was not



stated by which method the zinc concentrations were determined.  The author



attributed the common factor for anemia and high zinc excretion in these



children to the fact that all 3 children played with metal cars made from an



alloy containing zinc.  The author also suggested that the zinc could have



been ingested by the children imbibing water when they were in the bath tub



playing with toys.  In a test it was found that placing a toy car in warm



water resulted in zinc levels of 1.8 mg/1 in water.  However, it does not seem



likely that significant amounts of zinc could have been taken up by exposure



via that route.



     Greaves and Skillen (1970) reported on 18 patients who were given daily



doses of zinc sulfate corresponding to 150 mg zinc per day for between 16 and



26 weeks as treatment for venous leg ulcerations.  Before treatment the plasma



zinc levels varied between 0.68 and 1.2 mg/1, and after completion of treatment



the levels were between 0.84 and 1.92 ;ng/l.  During the study a number of



laboratory  investigations were undertaken on several occasions, but copper
                                   C-33

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levels were not determined.  No ill effects could be noted from the treatment



with zinc and there were no changes in hemoglobin or serum enzymes.   •



     In animal experiments it has been shown that zinc may interfere with



copper metabolism and that when the intake of copper is low, excessive zinc



may induce a copper deficiency and anemia (NRC Chapter 9 pp. 256-257; Underwood,



1977; Hamilton et a!., 1979; Murthy and Petering, 1976).  The animal data



indicate that prolonged excessive intakes of zinc may constitute a hazard in



patients treated with oral zinc supplements.



     During the last years there have been some reports on copper deficiency



in human beings after treatment with zinc.  Prasad et al.  (1978) and Porter et



al. (1977) have reported hypocupremia after a long-term treatment with zinc



sulfata in doses of 660 mg/day, i.e., 150 mg zinc per day.  In both cases it



was easy to correct the hypocupremia.  No chronic effects of the treatment



were seen, but Porter et al. pointed out that the daily doses of 650 mg zinc



sulfate may be toe high for long treatment.  It should be noted that in both



studies patients with severe diseases were treated (sickle-cell anemia and



coeliac disease).



     Zinc poisoning has occurred in cattle.  In the outbreak described by



Allen (1968), the zinc poisoning of cattle was caused by dairy nuts which had



been contaminated by error with zinc so that the zinc concentration was- 20



g/kg. ' It was stated that  the cows had an intaKe of about 7 kg/day of these



dairy nuts, which would correspond tc an intake of 140 g of zinc per cow per  .  .



day.  Exposure was only for a couple of days but it resulted in severe enteritis.



On one farm 7 out of 40 cows were so severely affected that they died or had



to be slaughtered.  The post-mortem findings showed severe pulmonary emphysema



with changes  in both myocardium, kidneys, and liver.  There were also some
                                    C-34

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indications that copper levels were lower than normal.   Zinc concentrations in



li'ver were extremely high,  measured on a dry matter basis, 1,430 and 2,040



mg/kg in two analyzed livers.



     Lead poisoning has occurred in horses living near lead-zinc smelters.  In



foals, some symptoms, lameness and joint afflictions especially, have been



described and related to exposure to zinc in areas near smelters.  Willoughby



et al. (1972) gave foals a diet containing 5,400 mg/kg of zinc and another



group received, in addition, lead in the amount of 800 mg/kg.  The groups were



compared with a control group and a group given only the excessive amount of



lead.  It should be mentioned that the groups consisted of only two or three



animals each.  In three animals given excessive amounts of zinc, bone changes,



especially in the epiphyseal areas of the long bones, were noted as a first



sign; later the animals had difficulties in standing and walking.  In animals



given lead and zinc the symptoms associated with exposure to zinc dominated.



There were less effects from the exposure to lead and zinc than in animals



given only lead.  It should be noted that in this experiment exposure to zinc



was extremely high but taken together with the above-mentioned reports on



actual findings in animals living near smelters it is obvious that exposure to



zinc in high amounts may constitute a hazard to horses.



     Aughey et al. (1977) gave zinc (as the sulfate) to mice for up to 14



months in drinking water at a concentration of 500 mg/1.   The concentrations



of zinc in feed for controls and exposed animals were not stated.  That zinc



is readily absorbed was seen by a rapid rise in plasma concentrations of zinc



during the first days of exposure.  During 6 months no difference between



controls and exposed animals could be shown regarding zinc concentrations in



liver, spleen, and skin nor was there any difference between the sexes.
                                   C-35

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Histological examination showed that several endocrine glands were affected by



the administration of zinc.  Hypertrophy was found in the adrenal cortex; in



the pancreatic islets and  in the pituitary gland changes consistent with



hyperactivity were noted.



     Kang et al.  (1977) gave rats, by pair-feeding, diets containing 1.3, 55,



and 550 mg zinc/kg of feed for 4 weeks.  The animals were killed after that



time and tissue concentrations of zinc and a number of other metals were



determined.  The low zinc  diet gave typical signs of zinc deficiency, whereas



there was no difference in weight gains and food efficiency ratios in the two



groups given higher amounts of zinc; this fact, according to the authors,



suggested that the highest level (550 mg/kg) was not toxic.   Liver and kidney



concentrations of zinc were slightly higher in the group given the largest



amount of zinc, but no difference was noted in the heart.  Iron concentrations



in liver were inversely related to the intake of zinc,-whereas no difference



in copper concentrations or magnesium concentrations in the liver could be



seen between the two highest zinc levels.  In the kidney there was also a



tendency for decreasing iron concentrations with increasing zinc intakes as



well as for copper, but there was practically no difference between the two



highest dose levels, nor was there a difference in magnesium.



     In pigs given zinc in the diet in concentrations ranging from 500 to 8000



mg/kg, Brink et al. (1959) found that signs of toxicity in the form of weight



gain and feed intake were  seen at levels above 1000 ppm.  In pigs, given from



2000 ppm and higher, deaths occurred as soon as 2 weeks after exposure and



severe gastrointestinal changes were seen with hemorrhages.   There were also



signs of brain damage due  to hemorrhages.  Changes in the joints were also



seen, mainly in the form of swollen joints.  In liver samples from these pigs



levels of  zinc above 1000  mg/kg wet weight were found.
                                   C-36

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Effects Caused by Exposure Via Other Routes



     In a woman given total parenteral nutrition after an operation, acute



zinc poisoning occurred due to an error in prescription.   During a period of



60 hours she received 7.4 g of zinc sulfate.   She became acutely ill with



pulmonary edema, jaundice, and oliguria,  among other symptoms.  The serum zinc



concentration was 42 mg/1.  In spite of treatment she remained oliguric and



hemodialysis did not improve renal function.   She died after 47 days of illness



(Brocks et al., 1977).



     It has been reported that zinc and copper could be introduced in excessive



amounts into the blood during hemodialysis (Blomfield et al., 1969).  Petrie



and Row (1977) described nine cases of anemia in dialysis patients due to the



release of zinc from a galvanized iron tubing in the dialysis system.  Copper



levels were not measured in these cases but there was a rise in hemoglobin



concentrations after removal of the source of the zinc.



     Acute effects of hemodialysis have been described by Gallery at al.



(1972).  A woman on home dialysis used water stored in a galvanized tank and



two hours after the first dialysis at home she had symptoms including nausea,



vomiting and fever.  Similar severe symptoms were experienced by her at two



subsequent dialyses, but subsided between dialyses.  Dialyses at the hospital



were then done without any symptoms, but she had symptoms again when she



started dialysis at home.  At new admission to the hospital she was found to



be severely anemic.  It was then found that the zinc concentration in the tank



water was 6.25 mg/1.  The patient's zinc concentration in red cells was 35



mg/1 and after 6 weeks dialysis in the hospital it was reduced to 12 mg/1.



During the same period plasma levels decreased from 7 mg to 1.58 mg/1.  Slood



copper was not decreased.
                                   C-37

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Carcinogenesis, Mutagenesis,'and Teratogenesis



     The relationship between zinc and cancer has been reviewed earlier by the



NRC (1978) (Chapter 7 pp. 208-209, Chapter 9 pp. 231-234 and Chapter 10 pp.



258-261) and by Sunderman (1971).  It was concluded that during certain experi-



mental conditions, injections of zinc- salt into the testes could induce testicular



tumors.  There was no evidence that zinc given via the oral route or parenterally



could cause tumors.  However, zinc is of interest with regard to cancer since



zinc seems to be indirectly  involved by being of importance for the growth of



tumors.  As discussed earlier zinc is necessary for DNA and RNA synthesis. *It



has been shown that in zinc-deficient rats tumor growth was reduced (Petering



et al.-, 1967; DeWys et a!.,  1970).  These earlier findings have recently been



confirmed in other studies.



     The effect of different levels of dietary zinc on the development of



chemically-induced oral cancer in rats has recently been studied by Wallenius



et al. (1978) and Mathur et  al. (1978).  In the study by Wallenius et al.



(1978), three groups of female rats were fed diets for 3 weeks which contained



15 mg/kg, 50 mg/kg, and 200  mg/kg of zinc, respectively.   The palatal mucosa



was then painted with the carcinogen 4-nitro-quinoline-n-oxide three times a



week.  The animals were killed after cancer could be observed macroscppically



in the oral cavity.  It was  found that in animals given the diet with the



highest level of zinc, the macroscopical signs of cancer appeared earlier, as



compared with animals given  lower amounts of zinc.  In the study by Mathur et



al. (1978),a similar design  was used but the levels of zinc in that experiment



were 5.9, 50, and 250 mg zinc/kg diet.  Three, 9, 13, and 23 weeks after the



beginning of exposure the groups of animals were sacrificed and blood, liver,



and palatal mucosa were sampled.  Control animals were killed at the same
                                   C-38

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time.   The carcinogen had been applied 3 times a week.   It was found that



after 3 weeks the animals with the lowest zinc intake,  which was regarded as



producing zinc deficiency, showed more advanced histological changes than



animals given 50 or 260 mg/kg diet of zinc.   After 20 weeks' application of



the carcinogen, there was no difference in the development of tumor between



zinc deficient and zinc supplemented groups.   It may be noted that both in the



low and high level zinc groups, carcinoma i_n situ and fully developed carcinomas



were found, whereas in the group given 50 mg zinc/kg diet, regarded as an



adequate level, even after 20 weeks only moderate dysplasia was seen.  The



groups studied were quite small and thus did not allow any detailed statistical



analysis.  The results were interpreted to mean that zinc deficiency made the



animals more susceptible to the induction of cancer but at the same time



caused a slower growth rate of tumors and that a high zinc intake initially



gave some protection against the development of tumors but that later excessive



zinc intake promoted tumor growth.



     Another example of the importance of zinc deficiency for the development



of cancer is the study by Fong et al. (1978).  One group of rats was fad a



diet containing 60 mg/kg of zinc and one group of rats was fed a diet contain-



ing 7 mg/kg of zinc.  After 12 weeks on these diets the carcinogen methylbenzyl-



nitrosamine was administered by intragastric intubations twice weekly in doses



of 2 mg/kg body weight for 12 weeks.  In another experiment the design was



similar but the carcinogen was administered after 4 weeks with the length of



exposure of 9 weeks.  Some animals were killed at the end of exposure and some



animals were killed 5 weeks later.  In a third experiment the carcinogen was



given for 4 weeks and animals were sacrificed 63 days after the start of



exposure.  Finally, there was one experiment where the exposure was only for 2
                                   C-39

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weeks for a total  of  four  doses of the carcinogen.  As expected, zinc levels



in the esophagus were lower in zinc deficient animals than in controls, but



they were also  lower  in  animals on an adequate  intake of zinc, but which were



given the carcinogen.  A general  finding was also that in zinc-deficient



animals more carcinomas  of the esophagus were found than in animals fed an



adequate intake of zinc.   It was  also noted that in the groups given the



lowest doses of the carcinogen, the difference  between groups was most



significant; a  total  of  eight doses gave figures of 79 and 29 percent,



respectively, for  tumor  incidence and at a total of four doses the correspond-



ing figures were 21 percent and zero (0) percent.                     '



     Regarding  human  beings, there is no definite evidence that zinc deficiency



in itself has any  etiological role in human cancer.  However, many studies



have been performed on the levels of zinc in both malignant and non-malignant



tissues  in human beings.   The zinc concentrations have been found to be both



lew and  high and no definite pattern has occurred (NRC (1978) Chapter 9 pp.



231-234  and Chapter 10 pp.  259-251).  As an example it has been shown that in



cancer of the esophagus  in human  beings zinc concentrations were lower than



normal which is in accordance with the above mentioned experiments on rats



(Lin et  a!., 1977).   However, there  is one organ in the human being where



there  seems to  be  a more consistent pattern, the prostate gland.  It has been



discussed earlier  that zinc concentrations in the prostate normally are very



high;  there has been  a consistent finding that  in cancer of the prostate there



is a decrease  in zinc in the carcinomatus tissue of the prostate.



     In  the study  by  Habib et al. (1976), zinc  concentrations in the neoplastic



tissue were less than half of the concentrations in normal tissue or in hyper-



trophic  prostates. These  authors also reported that the cadmium levels were
                                    C-40

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higher in the carcinomatous  tissues than in the normal  or hypertrophic tissue.



High industrial  exposure to  cadmium has been implicated as a possible cause of



prostatic cancer and since there are interactions between cadmium and zinc,



this might have  some bearing on the problem of the relationship between zinc



and cancer of the prostate.   Habib (1978) has reviewed the role of zinc in the



normal and pathological  prostate.



     Regarding hyperplastic  prostatic tissue, it may be noted that most reports



have stated that there are the same concentrations of zinc in the hyperplastic



tissues as in normal tissue.   There is one exception; the study by Gyorkey et



al. (1967) found considerable increases in zinc levels in hyperplastic tissue—



more than three  times the normal.



     The mutagenic effects of zinc have been discussed by the National Research



Council (Chapter 10 p. 261)  which could not find literature that suggested



that zinc is mutagenic in animals and human beings nor have any new data



appeared on this subject.  The same conclusions are made with regard to



teratogenesis.  The greatest risk is related to zinc deficiency which might



cause malformations.  However, it is reasonable to assume that indirectly zinc



might have an effect since long-term supplements with large amounts of zinc



will cause disturbances in copper metabolism.



     In a study by Cox et al. (1969), it was shown that if rats were fed a



diet containing 4,000 ppm of zinc during gestation, copper levels were reduced



in the fetal body and liver whereas zinc concentrations increased.  Ketchescn



et al. (1969) fed rats diets containing up to 5,000 mg of zinc/kg during



gestation.  Even at that level malformations were not observed, but there was



a  reduction in the copper concentrations of the fatal liver.
                                   C-41

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     A brief statement in a report by Kumar (1976) states that in a small



group of women supplements of zinc administered during the third trimester of



pregnancy in a dose of 100 mg of zinc sulfate per day (23 mg zinc per day)



caused premature births and one still-birth in four consecutive subjects.



Kumar then made studies in rats and gave them a daily supplement of 100 ppm



zinc orally (it is not quite clear hew the dose was calculated, but it is



stated in the report "received additionally 150 ppm zinc as a 2% zinc sulphate



solution").   The concentration of copper and other nutrients in the diet was



not stated.   In the zinc-supplemented animals there was a significant increase



in the number of resorptions of the inplantations.  Supplementation for pregnant



women has been recommended, but due to the known interaction between zinc and



copper, excessive zinc intakes during prolonged times could have an adverse



effect on the fetus.  It is well documented in animal experiments that zinc



deficiency during pregnancy might have an adverse effect on the fetus (NRC



Chapter 7 pp. 179-180).
                                    C-42

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                   INTERACTIONS  OF  ZINC  WITH  OTHER METALS







     As has already been discussed  in  the section concerning effects of excessive



intakes of zinc,  interactions  between  zinc and other metals may occur.   It was



demonstrated that excessive  intakes of zinc could influence the metabolism of



iron and copper,  but it is also  possible that excessive intakes of other



metals may also have an influence on the metabolism of zinc.  Such metal-metal



interactions have recently been  discussed at an international meeting and



reported (Nordberg, 1978).   Interactions between zinc and other metals have



also been reviewed by Underwood  (1977) and NRC (Chapter 7 pp. 186-187).



Cadmium



     Interactions between cadmium and  zinc we-.'e extensively discussed in the.



NRC report (Chapter 10 pp.  251-268) and the literature up to 1974 was reviewed



and discussed.   It was concluded that  exposure to cadmium would cause changes



in the distribution of zinc with increases in liver and kidney where cadmium



also, accumulates.  In animals  on marginal zinc intakes there could be a zinc.



deficiency in certain organs parallel  with the increase in  liver and kidney.



It has also been shown that in both human beings and horses the increase in



renal concentrations of zinc is  parallel to the increases in cadmium and that



this increase is nearly equimolar up to cadmium concentrations of about 60



mg/kg wet weight.  These earlier findings have recently been confirmed in new



studies both in human beings and in horses (Elinder and Piscator, 1977; Elinder



and Piscator, 1978).  The increase in  renal zinc is also related to the occurrence



of cadmium in metallothionein.  It has recently been shown  that whereas at  low



levels of cadmium in the kidney there are about equimolar amounts of zinc and



cadmium in metallothionein, with increasing cadmium concentrations the ratio
                                   C-43

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of cadmium to zinc will increase.  It was also shown that at a level of about

200 mg/kg wet weight of cadmium the amount of zinc in metal!othionein would be

close to zero (Nordberg et al., In Press 1979) and that corresponds to the

critical level which has been estimated for renal cadmium related to the

occurrence of renal tubular dysfunction (Friberg et al., 1974).
                                                                        X
     Although a large number of animal studies have been performed, there

might be some difficulties in drawing conclusions with regard to the human

situation.  A review of the literature by Elinder and Piscator (1978) showed

that there are clear differences between some large mammals (e.g., man, horse)

compared to small  laboratory animals.  In the rat especially (the most commonly

used laboratory animal), exposure to cadmium will result mainly in an increase

in hepatic zinc, whereas the increase in renal zinc is rather small.  On the

other hand, exposure to cadmium causes increases in renal copper concentrations.

Such differences make it reasonable to conclude that one must be cautious when

drawing conclusions from experiments done with rats.  The differences between

species are illustrated in Figure C-l.  Zinc deficiency a-lone is known to

cause effects on the fetus.  If animals are exposed to cadmium during the

gestation period,  this may also influence the mineral distribution in'the

fetus.  Pond  and Walker (1975) showed that both low zinc concentrations and

copper  concentrations and decreases  in birth weight were found in rat pups

that had been given cadmium orally.  Since cadmium does not pass the placenta!

barrier to any  significant extent, this is thought to be due to retention of

zinc in the dam parallelling the accumulation of cadmium as mentioned above.

Data by Choudhury  et al. (1978)  indicate that in the rat fetus a decrease of

copper  and iron occurs before the zinc levels are affected.
                                    C-44

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                HUMAN
                LAMB
                PIG
                HORSE
                BOVINE
                GOAT
                RAT
                RABBIT
                GUINEA PIG
                MOUSE
                CHICKEN
                          Cd LEVEL,
Figure C-1.  Increase of zinc as a function of increasing cadmium
concentration in kidney of 11 different species. (Courtesy Elinder
and Piscator, 1978.)
                               C-45

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     Lai (1976) found that oral exposure to cadmium could cause testicular and



pulmonary lesions in rats en a marginal intake of zinc, 5 mg/kg feed, whereas



such lesions were not seen when the diet contained 40 mg zinc/kg.   The exposure



to cadmium in that experiment was 17.2 mg/1 of drinking water.  Zinc concentra-



tions in the testes of zinc-deficient animals were 104 mg/kg, compared to 143



mg/kg in the animals at the higher level of exposure.



Copper



     It has been mentioned earlier that excessive intakes of zinc may cause



copper deficiencies in human beings and result in anemia, which can be easily



corrected by decreasing the intake of zinc and giving copper supplementation.



It has also been suggested by Klevay (1975) and Klevay and Forbush (1976) that



the ratio between copper and zinc in the American diet contributes to coronary



heart disease.  The main reason for this may be that the copper content of the



typical American diet is less than the requirement.  These theories have not



been substantiated, even though Klevay (1973) found that in rats hypercholes-



terolemia occurred with an increasing zinc-copper ratio in the diet.  It has



since been shown that it is the copper status tnat is the main factor with



regard to cholesterol' levels (Petering et al., 1977; Murthy and Petering,



1976; Allen and Klevay, 1978)



     Evans et al. (1974) found that in zinc deficient rats excessive amounts



of copper did not influence the uptake of   Zn from the gut, but in zinc-



supplemented rats excess copper had an influence on the uptake of   Zn.  The



authors tried to explain the findings by suggesting that in the zinc deficient



rats a  larger number of zinc binding sites on plasma albumin would be available



and that at such sites there would be no competition with copper.
                                    C-46

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     Kinamon and Bunce (1965) fed groups of rats a basic diet containing 18



mg/kg of copper, 70 mg/kg of zinc and less than 1 mg/kg of molybdenum.   To



these diets zinc, copper, or molybdenum and combinations of these metals were



added in amounts of 100 mg/kg of copper, 1,800 mg/kg of molybdenum, and 5,000



mg per kg of zinc.   The length of the experiment was 7 weeks.  At the and of



the experiment all  animals were given an injection of radioactive zinc.   After



4 days the animals  were killed.   As in other studies, it was found that an



increase in dietary zinc resulted in a decreased retention of the isotope, but



that even the very  high level of copper or molybdenum did not influence the



retention of the isotope.  These data indicate that the influence of zinc on



copper metabolism is probably of greater importance than the opposite,  i.e.,



influence of copper on zinc metabolism.



Calcium



     The influence  of calcium on absorption of zinc from the gut was discussed



by NRC (1978) (Chapter 7 pp.  184-185).   It was concluded that calcium levels



in the diet do not  influence zinc absorption except for some indications that



calcium could have  an influence when zinc intake is marginal.  Also Underwood



(1977) has reviewed the relationships between zinc and calcium.   The study by



Hurley and Tao (1972) shows an interesting example of interaction between :inc



and calcium.  Beginning on the first day of gestation, female rats were given



either a zinc-deficient diet containing 0.4 mg zinc per kg or a zinc-deficient



and calcium-deficient diet which contained the same amount of zinc but 15



mg/kg feed of calcium.  The animals were killed on the 21st day of gestation,



and the fetuses were removed and examined.  The results showed that in females



deficient in both calcium and zinc the resorption rate in the uterus was lower
                                   C-47

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and there was a larger number of live births per litter than among the rats



given only the zinc-deficient diet.  Eighty-three percent of the fetuses from



females on the zinc-deficient diet showed malformations whereas the corresponding



figure for zinc-deficient and calcium-deficient group was 57 percent.  Analysis



of maternal bone showed that there was a reduction in both ash weight and



total calcium content of the femur in the females given the zinc-deficient and



calcium-deficient diet.  This was interpreted as calcium being withdrawn from



the bone during pregnancy to provide calcium to the fetus.  There was also



lower zinc content in the bones of rats on the calcium-deficient diet.  This



suggested that zinc was released from bone during the release of calcium.



This zinc could then be available and transported to the fetus, whereas in



animals on a zinc-deficient diet and high calcium intake there would be no



release of zinc from bone and thus the large amount of zinc stored in bone



would net be available to the fetus.  This study shows how two essential



metals can interact with each other.



Iron



     As mentioned earlier, high intake of zinc may affect iron metabolism, but



much less is known about the effects of iron on zinc.  Sherman et al. (1977)



gave pregnant rats diets containing 5, 29, and 307 mg/kg of iron.  Eighteen



days after parturition both the dams and pups were killed and examined.  It



was found that the zinc to copper ratio in spleen increased in dams but tended



to decrease  in the pups as a result of iron restriction.  In the pups the zinc



to copper ratio was considerably lower in the liver of iron-deficient animals



but in the dams no differences were seen between groups with high and low iron



intake.  In  the iron-deficient pups increased levels of serum lipids were



associated with decreased ratio of zinc to copper in the tissues.
                                   C-48

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     Hamilton et al.  (1978) studied the intestinal absorption of zinc in



iron-deficient mice and found that zinc uptake from the gut was inhibited by



adding iron to the duodenal loop system used.   It was concluded that there



were some common mucosal  binding sites for both iron and zinc.



Lead



     It was mentioned earlier that in horses there can be simultaneous



exposure to lead and zinc and there seem to be some interactions; there was a



lower uptake of lead in animals with high intake of zinc.  Cerklewski and



Forbes (1976) studied the influence of three dietary levels of zinc (8, 35,



and 200 mg/kg) on rats given 50 and 200 mg lead per kg feed.  They found that



with higher dietary zinc concentrations the symptoms of lead toxicity decreased.



The lead concentrations in tissues were lower in animals with high zinc intake,



but also the hematological changes were less.   It was concluded that the main



interaction was in the gut.



     Lead will also have an influence on the zinc concentrations in tissues as



was shown by El-Gazzar et al. (1977) in rats given drink-ing water containing 5



and 50 mg/1 of zinc and 100 mg/1 of lead.  Lead exposure decreased the plasma



zinc in the low level zinc group but increased erythrocyte zinc.  Further



exposure caused reduced plasma zinc levels also in the high zinc level group.



There were also reductions in the zinc levels in liver and tibia of both



groups.  There was no change in the brain concentration of zinc.



     An effect which has attracted great interest the last years is the effect



of zinc on the activity of ALA dehydratase, a zinc dependent enzyme, in blood.



In a number of studies both ij} vivo and j_n vitro it has been shown that zinc



is antagonistic to lead regarding the ALA dehydratase activity, and that zinc



decreases the excretion of ALA seen in lead-intoxicated rats (Abdulla et al.,
                                   C-49

-------
1976; Border et al. , .976; Finelli et al., 1975; Thawley et al., 1978; Thomasino



et al., 1977).



     Thawley et al.  (1977) gave rats a basic diet containing 30 mg/kg of zinc



and 7 mg/kg of lead and then groups were given additions of 5,000 mg/kg of



lead or 6,300 mg/kg of zinc and combinations thereof.  These diets were also



combined with two levels of calcium in the diet, 0.9 and 0.1 percent respectively.



The findings indicate that the increase in ALA excretion caused by lead was



reduced by the additional exposure to the high level of zinc.   The exposure to



zinc'caused larger reductions in serum iron than lead exposure.  The most



severe anemia was seen in animals on a high lead and a high zinc intake together.



Interactions Between Zin.c and Drugs



     In the previous chapters it has been mentioned several times that contra-



ceptive pills have an influence on zinc metabolism.  The influence of oral



contraceptives on the excretion of zinc in women on a low intake of zinc,



copper, and iron was studied by Hess et al. (1977).  Urinary zinc excretion



decreased in women both on contraceptives and not on contraceptives.  The



greatest decrease was in the contraceptive group with a decrease of^3 percent



and a 62 percent decrease for those not on contraceptives.



     The usual intake of zinc in these women before the study started was



estimated to be about 10 mg/day.  During the study the intake averaged only



0.17 mg/day.  At the beginning of the study, before the zinc intake'was lowered,



the average excretion of zinc in urine was 0.36 and 0.4 mg, respectively, for



the group on contraceptives and for the control group.  These data indicate



that whereas contraceptives will have relatively little influence on zinc



metabolism during normal zinc intake, they may have a more profound influence



when  the zinc intake is  low.  In this study the zinc  intake was extremely low.
                                    C-50

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     Many other drugs,  especially drugs with chelating properties, may
influence zinc metabolism.   Thiazids and penicillamine can increase the
excretion of zinc.   Substances in food such as phytate can influence the
absorption.   Also,  alcohol  will  have an influence on zinc metabolism
especially if a state of chronic alcoholism has been reached with cirrhotic
changes in the liver.   Such cases often have low serum levels of zinc and an
increased excretion.
                                   C-51

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                    CRITERION FORMULATION



Existing Guidelines and Standards



     The National  Institute of Occupational Safety and Health



(NIOSH, 1975) has  recently reviewed the occupational hazards



of exposure  to zinc oxide and no changes were suggested



regarding the existing standard for zinc oxide of 5 mg/m  .



The American Conference of Government Industrial Hygienists



(ACGTH, 1976) has  an adopted threshold limit value  (TLV)



for zinc oxide of  5 mg/m  and the Occupational Safety and



Health Administration  (OSHA, 1978) has a workplace standard



for zinc oxide of  5 mg/m , eight-hour time-weighted average.



The TLV value has  also been adopted in other countries. :



For zinc chloride  a limit of 1 mg/m  has been adopted by



ACGIK and OSHA also adopted a standard of 1 mg/m  for zi'nc



chloride.



     The present standard for drinking water, 5 mg/1, is



based on organoleptic effects, i.e.., some people will recog-

                               o

nize the bitter taste caused by zinc present at such levels.



The World Health Organization (WHO) has also proposed that



the level should be 5 mg/1; however, the USSR has established



a limit for zinc at i mg/1 for other than health reasons



(National Academy  of Sciences (NAS), 1977).



     There is no acceptable daily intake for zinc in food.



As mentioned earlier zinc is an essential nutrient and there
   i


has been no reason to restrict the zinc levels in food.  .



     In 1974, the  National Academy of Sciences recommended



that adults should have an intake of 15 mg  of zinc per day,



that pregnant women should have an intake of 20 mg/day and
                                r-52

-------
 that pre-adolescent children  should have  10 mg/day  of  zinc

 (National Academy of Sciences, 1974).

 Current Levels of Exposure

     It has been well established  in several  studies that

 the present intake of zinc via food for the adult U.S. popula-

 tion is from 10 to 20 mg.  For the majority of  the  population

 the intake of zinc via drinking water will be only  a few

 percent of the intake via food, but for some  individuals

 the zinc concentration in tap wat-er may cause an additional

 daily intake of 2 to 10 mg of zinc.  The  average exposure

 to zinc via ambient air will, even in the vicinity  of  zinc

 emitting industries, be in the order of only  a  few  tenths

 of a milligram.  Smoking will contribute  even less.

 Special Groups at Risk

     Since zinc may interfere with copper and other minerals,

 excessive intakes of zinc by people with  a tendency to copper

 deficiency might cause reversible health  effects.   Patients

 treated for months or years with large oral doses of zinc

 salts,  about ten times the intake via food, for curing of
 r
 various diseases caused by zinc deficiency or to promote

 wound healing may constitute a group at special risk.  Infants

with copper deficiency or low intakes of copper may constitute

another risk group.   Occupational exposure to zinc oxide

 fumes may cause acute reversible reactions which may put

persons subjected-to such exposure at special risk.

Basis and Derivation of Criterion

     Zinc is an essential element and is not a carcinogenic

agent.   Studies on  experimental animals and on human beings
                               C-53

-------
given zinc for therapeutic purposes together with observations



of occupationally exposed persons show that large doses



of zinc can be tolerated for long periods, provided that



the copper status is normal.



     Daily ingesticn of about 150 mg of zinc as the sulphate



has not resulted in adverse effects in most patients even



after several months of treatment.  A reduction of copper



levels has been reported in patients with diseases such



as sickle cell anemia and coeliac disease.  A reduction'



of the dose of zinc and copper supplementation corrected



the copper deficiency.



     Laboratory animals have been shown to tolerate zinc



concentration in the range of 100 to 300 rug/kg food and



even higher for long periods when the intake of copper has



been adequate.  Copper deficient animals have been shown



to be more susceptible.  In many animal experiments zinc



concentration in the diet of 1000 'to 2000 mg/kg have been



reported to be without effect.  These concentrations should



be compared to the average zinc content of human food, which



is about 10 mg/kg.



     The water•quality criterion for zinc in water based



on available data on effects of ingested zinc would be about



10 mg/1 for the adult U.S. population.  Assuming a water



intake of 2 liters per day, this exposure would not cause



more than an additional intake of 20 mg which can be well



tolerated.  This concentration is above the present standard



for drinking water which is 5 mg/1 based on organoleptic



effects.
                                C-T.4

-------
     There.are some indications that infants and small children



may have a high intake of water and an additional intake



of 10 to 20 mg might have an influence on copper metabolism



in children with low copper intakes or with copper deficiency



due to, e«g. intestinal diseases.   However, due to insuf-



ficient amount of information available for this special



groups at risk, derivation of criterion lower than the current



standard would be difficult to justify.  Therefore, it is



recommended that the current level be maintained for water



quality criteria purposes (5 mg/1).   As additional information



becomes available reconsiderations of appropriateness of



the current standard should be performed.
                               r-55

-------
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Petering, H.  G.,  L.  Murthy, and E. O'Flaherty.  Influence  of  dietary copper
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                     ADDITIONAL REFERENCES

k. *^yan,  G.W.  1964.  Zinc regulation in the lobster Homarus
a^ nericanus.  Tissue zinc and copper concentrations.  Jour.
 :-iar.  Biol.  Assn.  U.K. 4.4:  549.

 Bryan,  G.W.  1966.  The metabolism of Zn and   Zn in  crabs,
 lobsters and freshwater crayfish. In:  Radioecological Concen-
 tration Processes. Proc. Inter.  Symp., Stockholm, Apr.  25-
 29.  Sym. Pub.  Division. Pergamon Press, New York: 1005.

 Bryan,  G.W.  1971.  The effects of heavy metals (other than
 mercury) on marine and estuarine organisms.  Proc.  Roy.
 Soc.  London B.  177: 389.'

 Cordle, F.,  et al. 1978.  Human  exposure to polychlorinated
 biphenyls and  polybrominated biphenyls. Environ. Health
 Perspectives 24:  157.

 Duke,  T., et al.  1969. Influence of environmental factors
 on the  concentrations of zinc-65 by an experimental community.
 Proc.  2nd Natn.  Symp. Radioecol., Ann  Arbor, 1967:  355.

 Eisler, R.  1977.  Toxicity  evaluation of complex metal mixture
 to the  softshell clam Mya  arenaria. Mar. Biol.  43:  265.

 Kameda, K.,  et al. 1970. On the  uptake of   Zn  and  concentra-
 tiongfactor of Zn in marine organisms. II. Changes  in Zn
 and   °Zn concentration in  rearing water. Jour.  Radiation
 Res.  11: 44.

 Lebedeva, G.D.,  and G.A. Kuznetsova. 1969. Absorption of
 radioactive zinc by freshwater (an experimental investigation)
 Gig.  Sanit.  34:  151.

 Pentreathe4R.J.,  1973. The accumulation and retention of
   Zn and   Mn  by the plaice, Pleuronectes platessa  L. Jour.
 Exp.  Mar. Biol.  Ecol. 12:  1.

 Phillips, J.H.  1976. The common  mussel Mytilus  edulis as
 an indicator of  pollution  by zinc, cadmium, lead and copper.
 I. Effects of  environmental variables  on uptake of  metals.
 Mar.  Biol.  38:  59.

 Pringle, 3.H.,  et al. 1968. Trace metal accumulation by
 estaurine mollusks. J. Sanitary  Engineer. Div.  94 SA3:  455.

 Romeril, M.G.  1971. The uptake and distribution of    Zn
 in oysters.  Mar.  Biol. 9:  347.

 Shuster, C.N.,  Jr., and B.H. Pringle.  1968. Effects of  trace
 metals  on estuarine molluscs. Proc. First Mid-Atl.  Indus.
 Waste Conf., 13-15 Nov. 1967: 285. Available from Dept.
 Civil Engineering, Univ. Delaware, Newark, Del.

 Shuster, C.N.,  Jr., and B.H. Pringle.  1969. Trace metal
 accumulation by the American oyster, Crassostrea virginica.
 1968 Proc.  Nat.  Shellfish. Assoc. 59:  91.
                                C-7C                 GPO 943-122

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