EPA/600/8-87/022 F
                                  JULY 1987
 Summary Review of Health Effects
Associated With Zinc And Zinc Oxide

       Health Issue Assessment
  ENVIRONMENTAL CRITERIA AND ASSESSMENT
                OFFICE
   OFFICE OF HEALTH AND ENVIRONMENTAL
              ASSESSMENT
   OFFICE OF RESEARCH AND DEVELOPMENT
  U. S. ENVIRONMENTAL PROTECTION AGENCY
    RESEARCH TRIANGLE PARK, NC 27711

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                           Disclaimer
    This document has been reviewed in accordance with U.S. Environmental
Protection  Agency policy and approved for publication.  Mention of trade
names or commercial  products  does not constitute endorsement  or
recommendation for use.

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Preface

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                              Abstract

    Zinc is  a dense, bluish-white, relatively soft metal  used extensively in
the galvanizing of iron and steel.  Zinc oxide, the most valued of the variety of
compounds  formed  by zinc is  used principally  in rubber  products as  an
activator in the vulcanization process and in the treatment of burns, .nfections,

3nd Snncdoccu?seSnaturally in the environment; however  zinc may also enter
the environment as the result of mining and processing the production of z me
oxide and the manufacture and use of products contaming zinc oxide,  he
combustion  of coal  and oil, the production of iron  and steel, and  the
       man              exposed  to  zinc  through  the ingestion of food
 (between 8 and 18.6 mg/kg/day)' and drink (averaging up to 10 rng/day^
 Based on annual average airborne zinc concentrations ,n areas throughout the
 United States  without  mines  or smelters  of  generally  <1mg/m3,  the
 contribution, of zinc  from inhaled air  represents an  ms.gnificant amount of
 daily zinc exposure, averaging approximately 20 yg.
     The literature on the toxic  effects of z.ne is lim.ted.  The most widely
 known systemic effect resulting from acute inhalation of freshly formed I zinc
 oxide fumes is a disease called  "metal fume fever."  Metal fume fever occurs
 fn  certain  occupational  settings  and  the exposure level at which toe fever
 occurs is not known. Also, the ingestion of zinc levels above 400 parts per
 million (ppm) produces acute gastrointestinal distress.
     There  is inadequate evidence to evaluate the carcinogen.c  potential of
 zinc or zinc oxide and  no evidence  suggesting  that zinc  is teratogen.a  A
 definite conclusion regarding the possible reproductive or mutagemc  effect of
 zinc cannot be drawn because of the lack of adequate studies.
                                     IV

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                          Table of Contents
  Preface  	
  Abstract  	'.'.".'.'.' i 1	   .'"
  Authors, Contributors, and Reviewers	   !,!
  List of Tables   .		   v!
  1.  Summary and Conclusions  "......' ........ .".'.	    V"

  2.  Background Information
      2.1   Chemical Characterization and Measurement	   5
      2.2   Sources and Emissions  	                        5
      2.3   Environmental Release and Exposure ".'.'.	  K
           2.3.1 Environmental Release                 	   a
           2.3.2 Exposure ..	  	   *
      2.4   Environmental Effects  	'.'.'.'.'.'.'.'.'.'.'.'.'.	   Q

 3. Health  Effects	
      3.1    Pharmacokinetics and Metabolism  !	  IQ
           3.1.1 Absorption  	             	  in
           3.1.2 Distribution   ...           	    o
           3.1.3 Elimination   	'.'.'.'.'.'.'.'.'.'.'.	  ,3
     3.2    Essentiality and Biochemical Role  ....'.'.'.	  14
     3.3    Clinical Manifestions of Zinc Deficiency   	  1 s
     3.4    Effects in Animals  	      	    7
          3.4.1Acute Toxicity 	'.'.'.'.'.'.'.'.'.'.'.	  17
              3.4.1.1 Inhalation  . .              	  17
              3.4.1.2 Oral  	'.'.'.'.'.'.'.'.	  ,9
          3.4.2Subchronic Toxicity           	  pn
              3.4.2.1 Inhalation   .       	  ™
              3.4.2.2 Oral  	.'.'	  go
          3.4.3Chronic Toxicity   	      	 22
     3.5   Carcinogenesis  	    	 22
     3.6   Mutagenicity  	   	 2^
     3.7  Teratogenicity   	  	 04
     3.8  Reproduction	 04
     3.9  Neurotoxicity  .           	 oc
     3.10 Effects in Humans   	'.'.'.'.'.'.'.'.'.	 ?S
         3.10.1 Inhalation Toxicity             	  oc
         3.10.20ral Toxicity  	.'.'.'	  £3
         3.10.3Other Routes of Exposure  	'.'.'.'.'.'.	  27
         3.10.4Epidemiology  	   	  2/

4. References  	                              „

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          Authors, Contributors,  and Reviewers

    This  document  was prepared by  the Environmental  Criteria  and
Assessment Office  EPA, Research Triangle Park, North  Carolina (Beverly

Wafts' otthis^mL have been reviewed for scientific and technical
merit by the following scientists:  Dr. Paul Mushak, Div,s,on of Environmental
Pathology University9 of North Caro.ina, Chape.  ^-.^^S^JSSSS
Piscator  Department of Environmental  Hygiene, the Karolinska.InsMute.
S ockho m Sweden; and Robert D. Putman, Environmental  Health  ConsuKant,
7 Maple Street. Weston. Connecticut.  In addition, it  has been reviewed by
members of the Carcinogen Assessment Group (CAG). Reproductive Effects
Assessment Group (REAQ), and the Ensure  Assessment Group W of
the Office  of Health and  Environmental Assessment (OHEA),
Washington, DC.
                                  VI

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No.

2-1
2-2
3-1
3-2
3-3
3-4
                           List of Tables
Atmospheric emission factors  	      Q
Acute toxicity values for fish  	  9
Typical zinc concentrations of normal tissues in four species  14
Recommended dietary allowances for zinc  	  15
Zinc metalloenzymes  	     j Q
Groups involved, age, duration of work and timing of work
of the 66 workers exposed to the effect of zinc oxide-seen for
medical examination  	            29
                                 VII

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                  1.  Summary and Conclusions

  «f «fli7C 'ia den!f ' bluish-wnite- relatively soft metal with an atomic weight
  of 65.37.  Zinc oxide, the most valued of the variety of compounds formed by

              '
     In 1984, the U.S. mine production of zinc totaled 252,768 metric tons
  Domestic production of zinc oxide in 1984 totaled 150,623 metric tons  Zinc
  !t-n^   .f*6"5^ in the Salvanizing  of iron and steel.  Zinc oxide is used
  prmcipa ly in rubber products as an activator in the vulcanization process

     skin diseases   e$ °f ^ OXide '* '" the treatment °f burns> Dions',

                                   fr°m 10 to 30°    k- Uncontaminated
                                                                Content
                    6 natural|V ^"^ing  levels of zinc in the environment,
                    sources which enter  the environment as contaminants.
 Such sources include  m.nes, smelters, production of zinc oxide and the
 ma.±d «?*   U!f ? Pr°,dUCtS Containin9 2inc oxide-  the combustion of
 coal and oN, the product,on of iron and steel, and the incineration of refuse
 howeZ rt ^ I'6 ^ ar'e on ambient air levels around mines or smelters;
 however, it has been  estimated that  100 g  of  zinc is  emitted to the
 atmosphere per metric  ton of zinc mined  and milled.   Air concentrations of
 zmc have been reported  to range  from  0.27  to  15.7 yg/m3  over 24-hr
 periods  proximal to one U.S. smelter in 1977.  The annual average around
 that smelter m 1977 was 5.0 Vg/m3.  However, average yearly  or quarterty

 aeTsw^m2^    6H °f <' V9/m3 have been ^ported" for several other
 areas with smelters; and m areas without mines or smelters, ambient air levels
 of zinc generally average < 1 yg/m3.
     High levels of zinc in  surface waters represent  industrial  and  urban
 poHution from such sources as galvanized  pipes, dumpings of plating baths

 as 210 mnH9',hSurfeCt ^ haS bee" found to «>ntain zinc levels as high
 frLtm T9   f    feSf °f the dlsposal of zinc minin9 waste- Water leaving
 treatment plants generally contains < 5 mg/L of zinc

 i««.i?nC|'S  tOXi(;-t0 aquatiC or9anisms and other wildlife at  high exposure
 ESS; J»n^UH   °r9anism,s- zinc toxicity  depends  largely on the  water
 hardness and pH, as well as the exposure level
     Several quantitative  methods may  be used for  determining the
 atmospheric and soil levels of zinc and  zinc  compounds.   The analytic
 JmS"68 fre?uentV "sed are  X-ray fluorescence  spectrometry  (X-ray
 emission  spectrometry), neutron  activation analysis,  mass  spectrometry
 voltammetry, absorption  spectrophotometry, atomic absorption spectrometry
 atomic fluorescence spectrometry, and optical emission spectroscopy.  The

      e                                              in Water ******
    The body of a 70-kg man typically contains approximately 1 4 to 2 3 q
of zinc. Humans are mainly exposed  to zinc through the ingestion of food

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and drink   The zinc content of the average daily diet ranges from 8 to 18.6
ma/kq  The ingestion of 2 liters of water per day could contribute up to 10
mq Jnc per  dly   The contribution of zinc from inhaled a,r represent an
SiqnmcanT amount of the daily zinc exposure, averaging approximately -20
uo  Z nc may also be absorbed through skin during the adm.mstrat.on of
ointments Xining zinc oxide or from skin contact with dust containing jzmc
    Inhaled zinc is absorbed across the alveolocaP.llary membrane; however
the fate of inhaled zinc will depend on the particle size and solubility as wen
as the functional state of the  lungs.  There are no quantrtative  data on the
deooltion and absorption of  inhaled  zinc  compounds, but experiments on
SmansinSe that both zinc oxide dust  and fumes of very small particle
sizSare deposited in the alveoli. That inhaled zinc is absorbed was shown by
me finding of widespread distribution of zinc in the soft tissue and hver of a
man  aSenta^ly  exposed to radio.abled  zinc  dust  from  an  expenmental
reactor and increased plasma and serum zinc levels in exposed workers
re O Jy aSstered zinc  is absorbed at several loci  in the gastrointes-
tinal tract  particularly in the second portion of the duodenum   The rate of
absorption depends  on the level and  form of zinc  adm.nistered  and the
 oresence or absence of other substances.                     .
     Zinc  is mainly excreted via the gastrointestinal tract; approx.mately 70 to
 80 percent of the ingested zinc is found in the stool. To a .lesser extent zinc
 is eliminated via urine, sweat,  hair, and skin. Urinary excret.on of zinc may be

 SUbS^s6slu^S StaTSl the body attempts to control  the zinc
 balance homeostatically  by regulating  zinc absorption and fecal Breton.
 The  mechanism governing this homeostat,c regu ation is not well understood
 however,  available data  suggest that several  protems  and  some low
 molecular-weight compounds may be involved.
     Zinc  is essential for the growth and development  of both plants and
 aninS and Seen included in the list of recommended dietary allowances
 ?RDA) for humans. A daily intake of 15 mg/day has been recommended for
 adults and 10 mg/day for preadolescent children.  In children ages 0.5 to 1.0
 yea   5 mg/day has been recommended and 3 mg/day for infants ages 0 1 tc ,6
 monhs   A daily zinc intake  of 20  and  25 mg/day is recommended for
 pregnant and lasting women, respectively.  Zinc deficiency  in people can
 result in dwarfism, anemia, hypogonadism, hepatosplenomegaly, rough and
 dry  sk in. and mental lethargy.  From a  public health perspective .much
  greater concern generally exists in regard to zinc defiaency associated wrth
  insufficient daily intake of the metal in contrast to toxic effects less often seen
  in association with excessive intake resulting from higher level exposures to
                 re0        effects resulting  from exposure to zinc is very
  limited. The most widely known systemic effect resulftng from ^inhala-
  tion  of freshly  formed zinc oxide fumes is a disease called metal fume
  fever " Metal fume fever occurs in certain occupational settings and generally
  strikes at the beginning of the work week when the worker  has not been
  exoosed for several days.  It is characterized by headache, fever, hyperpnea,
  naSS swealng  andymuscle  pains, which occur within a few hours after
  exposu e and per-sist for 1 to  2 days.   The exact acute exposure  eve  a
  wh?ch  metal  fume fever occurs is not known, but it has been  estimated that
  metal  fume  fever generally does  not occur  at zinc oxide levels below 15
  mgm3 aTthough some Eastern European literature reports the occurrence of
  mete!  ume  fever in workers  repeatedly  exposed to  «nc ox.de  leves
  averaging  as low as 5 mg/m3  but ranging  up to 58 mg/m3.  Chrome

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  respiratory infections,  dermatitis,  conjunctivitis,  and  gastritis  were also
  reported for the same workers. Other Eastern European literature reported an
  increase  in  respiratory  illnesses such as chronic  bronchitis and  diffuse
  pneumosclerosis in workers exposed to zinc oxide levels of up to 5.1  mg/m3
  However,  in  both reports,  contributions from  other  substances  in  the
  workplace air cannot be ruled out.   Hypocalcemia was  reported  in workers
  exposed to zinc oxide levels ranging from 2.44 to 7.15 mg/m3.
      The National Institute for Occupational Safety and Health  (NIOSH) has
  sought to protect workers exposed to zinc oxide fumes by  recommending  an
  exposure standard.  Occupational  exposure to zinc oxide fumes shall  not
  exceed concentrations greater than 5 mg zinc oxide/m3 determined as  a TWA
  exposure for up to a 10-hour workday, 40-hour workweek, with a ceiling  of
  15 mg zinc oxide/m3 as determined by a sampling time  of 15 minutes  The
  Occupational  Safety and Health Administration  (OSHA) established an  8-
  nour TWA  permissible  exposure  limit of 5  mg  zinc  oxide/m3 and the
  American Conference  of Governmental Industrial  Hygienists  (ACGIH) has
  adopted a threshold limit value (TLV) of 5 mg/m3.
     Acute  effects also  result from exposure  to  zinc chloride,  the  major
  component of smoke bombs.  Inhalation of this smoke in confined areas has
  resulted in severe pulmonary disease and death.  No  information is available
  on the concentrations of zinc chloride which causes these  effects.
     The  ingestion of zinc levels above 400 ppm is  known to cause acute
 gastrointestinal distress.  Such conditions usually result from the ingestion  of
 food and/or drink which  has been stored in galvanized containers.  However
 epigastric pain has been reported in subjects chronically exposed to mean
 zinc  oxide  levels of 5  to 18 mg/m3 in an occupational setting.   Available
 information also suggests that the administration  of 150 mg  elemental
 zinc/day for 6 weeks may have an  adverse effect on the immunologic and
 cardiovascular systems.
     Zinc oxide has been shown to cause chromosomal damage in the form of
 an increased frequency of hyperdiploid cells in the bone marrow of noninbred
 white rats at concentrations  of 0.1  and 0.5 mg/m3.  An increase in  the
 frequency of structural aberrations of the chromosomes and hyperdiploid cells
 was seen when human lymphocytes at the G0  stage  of the cell cycle were
 exposed  to  zinc  acetate  at  concentrations of 7.0  to  200  pg/mL    An
 interpretation  of this report is  difficult because the category of aberrations'
 referred to as hyperdiploid cells is not one generally used by cytogeneticists
 in discussing this type of study.  Additionally, the frequency  of  structural
 aberrations  at  20  ug/mL  was slightly less  than the frequency  at 7 yg/mL
 Zinc  oxide  was not mutagenic at levels  of  100 to 5,000 jjg/plate in the
 Salmonella reversion assay.
    There are no data which suggest that a zinc level over that required for
 normal growth and  development  is  teratogenic.   A greater  risk of
 malformations is expected in regard to zinc  deficiency.  Zinc also appears to
 offer a degree of protection against the teratogenic effect of cadmium. There
 are several  animals studies and one human  study  which suggest that the
 ingestion of high levels of zinc may have an adverse impact on reproduction
 Three premature births and one stillbirth occurred in a small  group of women
 ingesting 40.5 mg zinc/day during the third trimester of  pregnancy.  However
 no adverse effects on the outcome of pregnancies were observed in a group
of women supplemented with  81  mg zinc/day during  the third  trimester of
pregnancy.
    There is no evidence suggesting that inhaled zinc or orally or parenterally
administered  zinc induces tumor formation.   The only  positive carcinogenic

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response resulting from zinc exposure occurs following injection of zinc salts
into the testes of fowl and rats. Since this route of exposure is not likely to be
encountered by humans, the predictive value of these results for humans is
limited given the lack  of carcinogenicity  testing and epidemoologic studies.
The available evidence for zinc is considered to be inadequate to assess the
carcinogenic potential equivalent to a Group D weight of evidence. There are,
however, data which indicate that zinc is indirectly involved in tumor formation
as a  growth promoter or inhibitor.  In some animal studies, zinc-deficient
diets  have been  found to promote the development of  chemically induced
cancers, whereas zinc-adequate and  zinc-supplemented diets  provide a
protective  barrier against tumor formation.   In other animal studies,  zinc-
adequate or zinc-supplement diet facilitated the development of chemically
induced  cancers. Also, examinations of cancerous  tissues  in humans have
shown that the zinc level deviates from that found in noncancerous tissue.

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                   2.   Background Information
  healthpffprnf                  Summary of the data  ava«able on  the
  health  effects  of  exposure to  zinc/zinc  oxide.   Emphasis  is  olaced  on
  dressed  inn, H           ,
addressed, including  general
States
wth
                                                                   are
                              toxicity,  teratoqenicitv
                              health effects d*»3£i    Perspe his
                             qU3lity aSpSCtS °f Zinc/zinc °*ide inPfhe United
                          distnbution' fate- a"d concentrations  associated

                             ^
 2.1 CHEMICAL CHARACTERIZATION AND MEASUREMENT
                                                 ' bluish-white'
                                            '           '              ,
 formed   vzinr'f     Z"l?f 'S ^ m°St  valued of a" the Compounds
 powder wfththPmnL  ,   white or yellowish white, odorless, and  tasteless
 powder with the molecular formula ZnO and atomic weight of 81 37

 soil ?eeve1s  oqfUa±tatiVHmeih°dS may be used to -determine atmospheric and
 em,8S,on speolroscopy  (National  Research Council, 1978)  The
                                    ol 2inc  in ™aier
 2.2 SOURCES AND EMISSIONS
 or J" tF!f U2'ted States there are over 25 mines and smelters where zinc is
 The  U I awidhPrOCeSSfHd' J" 1984' 252'768 metric tons of 2inc werf mined n
 me  U.S., with  a worldw.de mine production  of 6,419000  metric tons
 Domestic production of zinc oxide in  1984 totaled 150623 me  c tons'
             t        Smelter Produ^on totaled  331.245 metri^tons (JoNy '

       horizon Si SrfrtT HI", baSlC typ6S °' primary  2inc smelters  "  the
        °              d'stl lat'on units- verti'al retort  distillation units,

                                           (L'°yd and Showak-
    Because  of  its electrochemical nature,  zinc  is used extensively  to
galvamze  iron and steel.  The element also readily combines wlhothe°
metals  .mpartmg the characteristics  of  workability at low  temDeratC Ss-
COrrOSIOn  resistance;  and pleasing fmishes  for use 2 SLasZg

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brass and other common alloys.  Zinc displays a vigorous reducing power,
liberating hydrogen from  sulfuric and hydrochloric acid. This property is the
basis for the use of zinc dust  or mossy zinc in many commercial  organic
chemical processes (National Research Council, 1978; Nriagu, 1980a).
    Zinc oxide is principally used to activate the vulcanization  of rubber.  It
also helps protect rubber by its opaqueness to ultraviolet light and  its  high
thermal conductivity.  A newer  use of zinc oxide utilizes its photoconductive
and electrostatic properties in office photocopying  applications (National
Research Council, 1978; Nriagu, 1980a).  One of the oldest uses of zinc oxide
is in  the  treatment of burns,  infections, and skin diseases (McKay, 198.};
National Research Council, 1978; Nriagu, 1980a).  It is also used to give white
paints good  concealing  power, in the manufacture  of opaque and certain
types of transparent glass, and in the manufacture of porcelain enamels for
sheet iron and  vitreous,  enamels for cast iron (National  Research  Council,
1978; Nriagu, 1980a).
2.3  ENV4RONMENTAL RELEASE AND EXPOSURE

2.3.1 Environmental Release
     Although zinc is  a moderately  abundant element in  nature,  it does not
occur in the free state but instead  is found as a salt or  oxide.  Zinc levels
occur around 70pg/kg in the earth's crust.  Some zinc is present in part in
igneous and metamorphic rock as  the sulphide sphalerate. In sedimentary
rock zinc is concentrated notably in  shale and clays.  It  is also  quite
concentrated in marine  phosphorites (National  Research Council,  1978;
 Nriagu, 1980a). In soils, the zinc concentration ranges from 10 to 300 yg/kg^
 Naturally occurring levels of zinc in fresh water and  sea  water are  <10 and
from 1  to 27 vg/L, respectively (National Research Council, 1978; Lloyd and
 Showak, 1984). Background ambient levels of zinc have been measured over
 the South Pole and  the Atlantic Ocean.  An average concentration of 0.03
 nq/m3  was found over the South Pole.   Zinc levels  over the Atlantic Ocean
 ranged from  0.3 to 27 ng/m3  (U.S. Environmental Protection  Agency,  1980;
 Nriagu 1980a). In addition to the naturally occurring  levels of zinc in air, zinc
 is  also' emitted to the atmosphere from such man-made sources as:   zinc
 mining milling, and concentrating; metallurgical processing; the production of
 zinc compounds; and the  manufacture and use of  the  products containing
 zinc (National Research  Council,  1978;  U.S. Environmental Protection
 Agency,  1980; Lloyd and Showak, 1984; Nriagu, 1980a).
      Loss of zinc from mining is small, but some does occur during blasting,
 ore  handling, crushing,  and wind loss from tailings.   Only limited data were
 found on the concentrations of atmospheric zinc near mines;  however,  it has
 been estimated that 100 g of zinc is emitted to the atmosphere per metric ton
 of zinc mined and  milled (W. E. Davis and Associates, 1972; Lloyd and
 Showak  1984; Nriagu,  1980a).  On the basis of the 1984 total of 252,768
 metric tons of  zinc mined and milled in the U.S., the total zinc emissions to
 the atmosphere from this process would be 25 metric tons.
      During  the smelting process zinc  may be released to the atmosphere
 during concentrate handling,  open storage,  and conveying.   Roasting  could
 also create large amounts of zinc  dust, but  since this operation is enclosed,
 the  dust may be readily collected  using particulate  collecting devices  which
  recover  >95 percent of  the  particulate matter (National Research Council,
  1978-  Nriagu 1980a; Lloyd and Showak, 1984).  There are only limited data
  on levels of atmospheric zinc near  smelters. In 1977,  a yearly mean zinc
  level of 5 yg/m3 was found approximately 1.5 miles from  a smelter in Kellogg,

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  Idaho.   The  24-hour values  ranged  from 0.27  to  157  pg/m3 (US
  Environmental Protection  Agency, 1980).  The U.S. Environmental Protection
  Agency (Hunt et al.,  1984) reported  average yearly or quarterly zinc
  concentrations of < 1  yg/m3 in  several areas with smelters.  Table 2-1 lists
  other emission factors and sources of zinc.
      Available data on atmospheric levels of zinc have shown a general
  decline. The National  Air  Sampling  Network reported annual average airborne
  zinc concentrations in  areas throughout the U.S. without mines or smelters of
  generally  <1  yg/m3  (U.S.  Environmental Protection Agency,  Hunt et al
  1984;  National Research  Council,  1978).  Atmospheric zinc  levels in  the
  Washington, D.C. area ranged  from 0.05 to 0.1 yg/m3 (Kowalczyk et al
  1982).  Lee and von  Lehmden  (1973)  reported atmospheric zinc  levels in
  urban  are^s throughout the  U.S. of 0.1 to 1.7 pg/m3.  |n 1970, the average
  atmospheric zinc  level in urban  areas in the U.S. ranged from 0 1 to  17
  yg/m-i  (Lee et al.,  1972).   Dyson and Quon  (1976)  reported  average
  atmospheric zinc levels in  urban air in 1966 of 0.7 ng/m3.
     Zinc levels in water are generally very low. High levels of zinc in surface
  water  represent industrial  and urban  pollution from  such sources  as
  galvanized water pipes, dumping of  planting baths, and zinc mining  (National
  ,oo^\    Counci1- 1978= u-s- Environmental Protection Agency, 1980; Nriagu
  1980a).  In a 16-month study, Mink et  al. (1971) found that  a section of
  Idaho s Couer d'Alene River system contained  zinc levels  of up to 21 mg/L as
  the result of the disposal of  zinc mining waste for a number of years  The
  U.S^ Department of Health, Education, and Welfare (currently the Department
 of Health and Human Services) found that, of 2,595 drinking water samples  8
 samples contained zinc levels above 5 mg/L, Water leaving treatment plants
 generally contains less  than 5 mg/L of zinc, but in cities with soft acidic water
 the level of zinc increases in the distribution system.  Therefore tap water
 could contain zinc levels of  around 5 mg/L (U.S. Environmental  Protection
 Agency, 1980).
     Atmospheric workplace concentration limits have been established for
 zinc  oxide.   The Occupational Safety and Health Administration  (OSHA)
 established an  8-hour  time-weighted average (TWA) permissible exposure
  imit of 5 mg zinc oxide/m3 and the American Conference of Governmental
 Industrial Hygienists (ACGIH) has adopted a threshold limit value (TLV) of 5
 mg/m-i.  The National Institute for Occupational  Safety and Health (NIOSH)
 has recommended the following  standard.  Occupational exposure to zinc
 oxide fumes shall not exceed  concentrations greater than 5 mg zinc oxide/m3
 determined as  a  TWA exposure for up to a 10  hour  workday  40  hour
 workweek, with a ceiling of  15 mg/m3 as determined by a sampling time of 15
 minutes.

 2.3.2 Exposure

    Humans are exposed  to  zinc  through the  inhalation  of  air and the
 mgestion of food and water. Zinc levels in air are generally < 1  yg/m3 (U S
 Environmental Protection Agency, 1984;  National Research Council  1978)
Assuming an individual  inhales 20 m3 of  air per  day  with an average  zinc
concentration of 1  jig/m3, the daily zinc contribution from this source would
be 20 \tg.
    There is a wide range  of values published in'the  literature  on the  zinc
content  of  various foods; however, in general, meat,  milk products  eqqs
shellfish  (Halsted  et  al.,  1974;  National Research  Council,  1978- US
Environmental Protection Agency, 1980; Nriagu,  1980b)  and wheat germ

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        TABLE 2-1.   Atmospheric Emission Factors
Source
Mining (Zn + Cu + Pb)
Primary metal production
Zinc
Lead
Copper
Nickel
Aluminum
Secondary metal production
Zinc
Copper
Lead
Iron and steel
Ferroalloys and iron foundaries
End uses of zinc products inadvertent
sources
Coal combustion
Oil combustion
Wood combustion
Waste incineration
Rubber tire wear
Phosphate fertilizers
Grain handling
Emission Factor
100 g/metric ton

17,600 g/metric ton
110 g/metric ton
845 g/metric ton
845 g/metric ton
1 1 g/metric ton

9,000 g/metric ton
500 g/metric ton
300 g/metric ton
27 g/metric ton
54 g/metric ton

4.8 g/metric ton
0.025 g/metric ton
58 g/metric ton
500 g/metric ton
4.5 g/tire
15 g/metric ton
0.5 glmetric ton
          Source: Nriagu (1980a).
(National  Research Council,  1978) are the best sources of dietary  zinc.
Halsted et al. (1974) reported a  zinc content of standard hospital  diets
(breakfast, lunch, and dinner) of 11.3 mg.  The U.S. Environmental Protection
Agency (1980) reported a zinc dietary intake of 18 and 18.6 mg/day for males
ages 15 to 20 years old, respectively, whereas the daily dietary intake of girls
12 to 14 years old was 10 mg.  Nriagu (1980b) reported daily zinc dietary
intakes of 8 to 14 mg.
    Zinc levels in water are usually very low;  however, due to contamination,
levels of 5 mg/L have been reported (U.S. Environmental  Protection Agency,
1980). Assuming an individual  ingests 2 liters of water per day  containing 5
mg zinc/L, the daily intake of zinc from drinking water would be 10 mg.

2.4  ENVIRONMENTAL EFFECTS

    Zinc levels above those needed for maximal plant growth  may produce
toxic  effects.  Buchauer  (1973)  reported  that the vegetation  around  two
smelters  in  Palmerton,  PA  was scrubby, with  red and  yellow foliage  and
interveinal chlorosis. Depressed yield and leaf damage ranging from marginal

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 necrosis to death was seen in legumes exposed to 3.2 and 6.25 pM zinc in a
 !^9HCtUJ'fe  SyStem (Carro" and Loneragan, 1968).   Nriagu (1980a)
 reported  hat excessive levels of zinc curtails growth in  plants by inhibiting
 root development through restraint on both cell division and elongation
 ««, JS"« *toXiaty 3PP?rS }°, depend Iar9ely on the water hardness and PH,
 Mnl   10™e,exP°sure level 
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                        3.  Health Effects


3.1 PHARMACOKINETICS AND METABOLISM/

3.1.1 Absorption
    The absorption of zinc in humans and other mammals is similar.  The site
of absorption depends on the form of presentation.  Inhaled zinc is absorbed
across the alveolocapillary  membrane; however, the fate of inhaled zinc wiM
depend on the particle size and solubility as well as the functional state of he
lungs  Orally administered zinc is absorbed across the gut mucosa with the
major site of absorption in the second portion of the duodenum.  Absorption
across the  tissue and  organ membranes normally  follows gastrointestinal
absorption or parenteral administration.  Zinc may also be absorbed across
the  broken  and unbroken epithelial membrane (National  Research Council,

     f rJr'eTre no quantitative data on the deposition and absorption of inhaled
zinc compounds,  but experiments on humans indicate that both zinc  oxide
dust and fumes of very small particle size are deposited in the a veoh (Bonne
and Bridges  1983;  U.S. Environmental  Protection  Agency,  1980).   That
inhaled zinc is  absorbed was shown by the finding of widespread distribution
of zinc  in  the  soft  tissue  and  liver of  a man  accidentally  exposed  to
radiolabeled zinc  dust  from  an experimental  reactor (Newton and Holmes,
 1966)  and  increased plasma  and serum zinc  levels in  exposed workers
 (Chmielewski et a!.,  1974a,b; Hamdi, 1969; Klucik and Koprda, 1979; U.S.
 Environmental  Protection Agency, 1980).                          *•„„•„,
     The absorption of  orally ingested and parenterally administered  zinc  is
 affected by several  factors, some of which  include:  the amount of zinc
 ingested,  the  zinc  status of  the  organism,  and the presence  of  other
 substances (Lykken  et at., 1986; Song  and Adham, 1985; van  RIJ ;and HaM.
 1985; Prasad.  1978;  National Research  Council, 1978, Nriagu, 1980b;  Rckel
 et al' 1986; Furchner and Richmond, 1962).
     A significant  decrease in plasma, erythrocyte, and leukocyte zinc levels
 has been seen after experimentally induced zinc  deficiency.   Following oral
 zinc supplementation,  values close to normal were obtained (Prasad et  al.,
 1978)   Spencer  et al. (1966) found that intravenously administered zinc is
 rapidly distributed.  Using radiolabeled zinc as an indicator, the zinc retention
 after 30 days was  >80 percent.  The zinc status of the subjects was  not
 obtained prior to administration of the radiolabeled zinc.   Istfan et al.  (19BJ)
 found  that absorption of  radiolabeled  zinc increased linearly with  an
 increasing level of available zinc.                             .       .
     Valberg et al (1985) studied the rate of absorption and retention of zinc in
 20 healthy subjects. Subjects ingested 25 mg radiolabeled zinc in  metal free
 water or in ground white turkey meat after overnight fasting.  The absorption
 and retention of radiolabeled zinc after 7 days was 42 percent for both
 methods of administration.  However, the rate of absorption, as shown by the
 average increase in  plasma zinc levels  over a 4-hour period was significantly
                                    10

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  lower when zinc was administered in the solid  test meal.   The authors
  believed that this finding was the result of the binding of zinc to food and the
  slower rate of gastric emptying of the solid meal.
      Hyperzincuria is associated  with the consumption of alcohol.  Dinsmore
  et al. (1985) after orally  administering alcoholic and nonalcoholic volunteers
  50 mg zinc supplements via diet found significantly higher serum zinc levels
  in the nonalcoholic  volunteers.   Under normal physiological conditions  a
  mutual inhibition also exists between zinc and folic acid (Ghishan et al   1986)
  Zinc absorption  is reduced if the diet contains large amounts of phytate or
  phytic acids  (Lowy  et  al.. 1986;  Solomons et  al., 1979;  Reinhold  1971-
  Remhold et al..  1973, 1974; Turnlund et al.. 1984; Morris  and Ellis   1980)'
  Since phytic acid and phytates are found in plants and seeds, zinc from
  plants is considered to  be less  available to monogastric animals than zinc
  derived from animal protein. This was suggested to be a contributing  factor
  in the zinc  deficiency seen in  Iranian villagers who consumed a substantial
  amount of unleavened bread high in phytate.
      A biological  antagonistic  relationship exists  between  zinc  and several
  other metals.  Generally calcium does not affect zinc absorption except  in the
  presence of phytate  (Spencer  et al.. 1984; Snedeker et  al., 1982- National
  Research Council, 1978; U.S.  Environmental Protection Agency  1980) by
  forming  an  insoluble  calcium-zinc-phytate  salt at the  site  of intestinal
  absorption (Halsted et al., 1974;  Forbes et al., 1983). There are, however
  indications that high levels of calcium may affect zinc absorption when dietary
  V^-fo of zmc are mar9'nal (Halsted et al.. 1974; National  Research Council
  1978; Spencer et al., 1984). As such, the high level  of calcium (18.6 percent)
 in  clay ingested  by  Iranians with a history of geophagia may have been a
 contributing  factor to  the zinc deficiency  seen  in that  group  (National
 Research Council, 1978).  Calcium has also been  implicated in the formation
 of  irreversible sickle  cells  in  sickle  cell anemia patients.   Data on the
 interactions of zinc with calcium suggest that zinc may competitively inhibit
 calcium leakage  into the red  blood cells and inhibit the formation of the
 irreversible sickle cells (Prasad, 1978).  Klucik and  Koprda  (1979) reported
 that exposure to levels of,zinc ranging from an average of 0.5 mg/m3 to 7 14
 mg/mJ produced  signs of hypocalcemia in exposed workers.  High levels of
 orally administered zinc decreases the retention of copper and if administered
 over an extended period  of time will induce  copper deficient  anemia and
 neutropenia  (Festa et  al.,  1985;  Fischer  et  al.,  1883,  1984- L'Abbe  and
 Fischer, 1984).  Mulhern et al. (1986) reported that excess dietary zinc (2000
 ppm zinc/day) produced copper deficiency in the offspring of C57BL/6J mice
 The offspring also developed alopecia by 5  weeks of age.  In addition  the
 «m  u  reported tnat excess zinc  causes alopecia in the monkey  and mink
 Whether  excess zinc administered at certain  stages of  development will
 produce alopecia  in  humans has not been determined.  An increased
 mgestion of zinc will offer protection against some of the toxic effects of  lead
 absorption (Nriagu, 1980a; Cerklewski and Forbes,  1976;  EI-Gazzar et al
 1977) by inhibiting lead  absorption at the intestinal level (Cerklewski  and
 Forbes, 1976).   A  nonheme iron and  zinc ratio of 2:1 slightly inhibits  zinc
 absorption (Solomons, 1986; Solomons and Jacob, 1981) by competing  with
 ?«oo!n     upper Smal1 intestine  and delaying its absorption (Meadows et al
 1983). However, Solomons (1986)  suggested that there are sufficient sites for
 both  zinc and  iron absorption  when the total  ion concentration  does  not
exceed 25 mg.  Cadmium, a nonessential and toxic metal is associated  with
zinc .in both  geological and biological matter.   The interaction between
cadmium  and  zinc has  not been  fully  demonstrated;  however  renal
                                   11

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concentrations of zinc have been shown to parallel those of cadmium up to
concentrations of 50 to  70 yg/g.  There are also  equ.moar  amour, s  of
cadmium  and zinc  in the kidney when  cadm.um  levels are low, but  as
cadmium  levels increase, the  ratio of cadmium and zinc increases  (U.b.
Environmental Protection Agency, 1980).
    Zinc  may also  be absorbed  through  both  broken  and  unbroken  sk.n
(Hallmans 1977; Derry et at.. 1983; Anteby et al., 1978; Hallmans and Lasek,
1985)   Hallmans (1977) found that  serum  zinc levels increased in burn
patients treated  with gauze containing zinc oxide. An increase in serum zinc
levels was seen  in healthy subjects treated with a zinc oxide ointment, but the
increase was not statistically significant. It was theorized that  zinc applied to
subjects topically with normal serum zinc concentrations is bound in the  hair
follicules  and slowly absorbed and stored or excreted resulting in no increase
in serum  zinc concentrations. (Derry et al., 1983). A slight rise in serum zinc
has been seen  in women using an intrauterine device containing copper  and
zinc (Anteby et  al.,  1978).
     Numerous  studies indicate that the body attempts to control the  zinc
balance  homeostatically according  to need  by regulating  the  extent of
absorption of dietary zinc and  the  rate of fecal excretion  of stable  zinc
 (National Research Council, 1978; Evans et  al., 1973; Ansan  et al.,  975,
 1976- Weigand and Kirchgessner,  1978; Nriagu,  1980b; Cousins,  1985.
 Dinsmore et al  1985).   The  exact  mechanisms  involved  in  homeostatic
 regulation have not been determined; however, recent  information suggests
 that zinc absorption across the brush border surface of  the small intestine
 may be  partly  regulated by a carrier-mediated diffusion mechanism which
 responds homeostatically to the dietary zinc supply  (Cousins, 1986; Menard
 and  Cousins  1983b).   It has also  been  reported  that many  brush border
 proteins  are increased during  zinc depletion (Menard et al.,  1983); however,
 this finding has not been confirmed by other researchers (Park et al.  1985).
 Numerous other studies suggest that several  proteins  and low-mqlecular-
 weiqht compounds may be involved in the absorption of zinc  and other heavy
 metals (Seal and  Heaton. 1987; Wapnir  and Stiel, 1986; Song and Adham,
  1985- Wapnir et al., 1983; Lonnerdal et al., 1982; Menard and  Cousins, 1983a;
  Freeman and  Taylor,  1977; Smith  et al., 1978; Blakeborough  et al.,  1983;

   °° In examining  the reason  for the accumulation of metals in mammalian
  tissue a protein was discovered and termed metallothionem  (Cousins, 1985).
  This low-molecular-weight protein is  characterized by  a  very  special ammo
  acid  complex  consisting  mainly of  cysteine and a  lack of  aromatic ammo
  acids and histidine (Nordberg  and Kojima, 1978; Kojima et al., 1976). A more
  detailed discussion of the  physical  properties of  metallothioneins are
  contained in Kagi and Nordberg (1979) and Cousins (1985).  Metallothipnems
  have been isolated from  intestine, liver,  and kidney  (Margoshes  and Vallee,
  1957- Kadi and Vallee 1960).  More recently, a metallothionein-like protein
  was 'isolated  in the  rat brain (Ebadi, 1984).   The  exact  function of
  metallothionein has not been determined;  however, several functions  have
  been suggested.  These  include absorption and  detoxification and hepatic
  storage of heavy metals (Jackson et al.,  1986;  Bell,  1979; R-chards and
  Cousins  1976;  Cousins.  1985; Ebadi,  1984;  Swerdel  and Cous.ns,  1982;
  Menard et al., 1981; Olafson, 1983;  Kern et al., 1981; Quinones and Cousins,
  1884; Gallant  and Cherian, 1986; Banerjee et al., 1982).
                                     12

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  3.1.2  Distribution


  
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         TABLE 3-1.    TYPICAL ZINC CONCENTRATIONS OF
                     NORMAL TISSUES IN FOUR SPECIES
Tissue
Adrenal
Brain
Heart
Kidney
Liver
Lung
Muscle
Pancreas
Prostate
Spleen
Testis
Human
v&g
12
14
33
55
55
15
54
29
102
21
17
Monkey
V9'9
16
—
22
29
51
19
24
48
—
21
17
Rat
V9/9
—
18
21
23
30
22
13
33
223
24
22
Pig
V9/9
33
—
—
40
40
—
~
45
—
28
—
          Source: Underwood (1971)

1978).   Also,  Binder et al.  (1978) found  that urinary  excretion of zinc
decreases after the age of 20 years.
    In addition to fecal and urinary excretion, zinc is also excreted in sweat
under conditions  of  extreme heat or  exercise, via  hair and milk, through
placental transfer to the fetus, and via skin sloughing (National Research
Council  1978).   Molin  and Wester (1976) found the zinc content  of the
epidermis to be  about  40  pg/g dry tissue by neutron  activation analysis.
They estimated the daily loss of zinc by desquamation to be from 20 to 40
yg.  The mean loss of zinc in sweat has been reported to be 4 percent of the
average daily intake (Jacob et al., 1981).

3.2  ESSENTIALITY AND BIOCHEMICAL ROLE

    Over a hundred years ago zinc was shown  to be an essential element in
the nutrition of Aspergillus niger.  It was not until  some  years later that the
first indications of a function for zinc in plants  and animals was uncovered.
Zinc is necessary for the growth and development of  humans and is included
in the  list of recommended dietary allowances (National Research Council,
1978;  Krebs and  Hambidge, 1986; U.S. Environmental  Protection Agency,
1980)  (Table 3.2).                                       .
     The essential nature of zinc is based on its role as an integral  part of
some metalloenzymes, a cofactor in regulating  the activity of zinc dependent
enzymes (Nriagu, 1980b). and as a structural  and functional component of
biomembranes  (Bettger   and  O'Dell,  1981).   More  than  20  zinc
                                   14

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            Table 3-2. Recommended Dietary Allowances for Zinc

Infants
Children
Men
Women
Pregnant
Lactating
Age
(years)
0.0-0.5
0.5-1.0
1-10
11-51 +
11-51 +


Zinc
(mg)
3
5
10
15
15
20
25
           Source: National Research Council (1978).
  metalloenzymes have been identified (Nriagu, 1980b) and over 100 enzymes
  require zinc for maximum catalytic function  (Cousins, 1986) (Table 3-3 lists
  some  of the zinc  metalloenzymes).   Zinc  plays an important role  in the
  metabolism of proteins and nucleic acids and is essential for the synthesis of
  DNA and  nbosomal RNA.  It also serves  to stabilize the structure of some

  ™±L0enzymeS" ,T^US the level of  available  zinc  maV Control metabolic
  processes through the formation and/or regulation  of  the activity  of zinc-
 dependent enzymes (Nriagu, 1980b).

 3.3 CLINICAL MANIFESTATIONS OF ZINC DEFICIENCY
  .       metabolic and biochemical defects responsible for the symptoms of
 zinc  deficiency are not fully understood.   However, the manifestation  of
 ^wt^2'"*      i!ncy.SVmptoms mav be associated  with  the reduced
 SlnL n ?T 6r   ZmC C0ntainin9 enzymes.  Typical symptoms of zinc
 deficiency include:   anorexia, pica, impaired taste acuity, mental lethargy
 delayed  sexual  maturation  in  adolescence (Nriagu,   1980b)  immune
 dysfunction  (Fraker  et  al.,  1986; Sandstead et at  1982),  dermS
 emaciation, alopecia, ocular lesions, and retarded growth  (Yamaguchi. 1984,:
 Haisted et al  1974).  Chronic, severe, and untreated zinc deficiency can be
 fatal (Evans 1986).  Prasad et al. (1963) found that in certain villages in Egypl
 many  people  exhibited a  syndrome  characterized by dwarfism  anemia
 teCv^in?; hePatosPlenome9aly, rough  and dry  skin,  and  mental
 5«SSy'«?K? deflc|ency was indicated by an abnormally  low zinc content in
 piasma, red blood cells, and hair.
    LessPron
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       Table 3-3.  Zinc Metalloenzymes
Enzyme
RNA polymerase
RNA polymerase
DNA polymerase
Nucleotide pyrophosphatase
5'-Nucleotidase
Cyclic phosphodiesterase
Phosphomannose isomerase
Phosphoglucomutase
oc-D-Mannos/dase
3-i.acfamase
Protease
5'-Adenosine monophosphate
aminohyrrolase
Collagenase
Neutral protease
Dipeptidase
Phospholipase C
Dipeptidase

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      Experimentally  induced  zinc-deficient subjects  experienced
 considerable weight loss.  During the zinc depletion period thymidinekinase
 activity was not detected and  there was a  reduction in plasma alkaline
 phosphatase and plasma lactic dehydrogenase activity. Changes were also
 noted in the RNA and DNA ratio in the connective tissue (Prasad et al  1978)
     Whether zinc deficiency  causes human  reproductive or teratological
 effects has not been established; however, the possibility has been suggested
 based  on the results of a number of animal studies (Lytton and Bunce 1986-
 Styrud et al., 1986; Dreosti et  al., 1986;  Hurley and Swenerton, 1966- Hurley
 and Mutch, 1973; Hurley  et al., 1971; Apgar, 1971; Hurley and Shrader 1972)
 Lytton  and Bunce (1986) reported that female  rats maintained on a low zinc
 diet  starting on  day 10  of gestation usually experienced  a  prolonged fetal
 delivery period with  prolonged periods of abdominal straining.   Also  many
 pups were either stillborn or died shortly after birth. Hurley and Mutch (1973)
 found  that rats  maintained on zinc-deficient  diets from  day 6 to 14  of
 pregnancy exhibited an increased number of stillbirths and a high incidence
 of congenital malformations.  Similar results were reported by Hurley et  al
 (1971).  After  maintaining rats on a zinc-deficient diet  from day  0 to 21  of
 pregnancy, they  found that about half of the fetuses were  resorbed and that
 almost all of the remaining fetuses showed gross malformations.
     A number of studies  on the effects of zinc deficiency indicated that zinc
 is necessary for normal neurological development and function (Dreosti et al
 1986; Hurley et al., 1971; Hurley and Swenerton, 1966; Gordon et al   1982:
 Lokken et al., 1973; Hurley and Shrader, 1972; Halas et al., 1979- Halas and
 Sandstead, 1975; Golub et al.,  1985; Sandstead,  1986).  Hurley et al  (1971)
 reported severe neurological effects  in the  form  of  hydrocephalus
 anencephalus,  hydranencephalus and exencephalus  in litters of  zinc-
 deficient mothers.  Gordon et  al. (1982) found that zinc-deficient rats were
 slower  to explore the observation area and only  explored a small portion  of
 the area. Marginally zinc-deficient infant primates showed  signs of lethargy
 apathy, and hypoactivity (Golub et al., 1985).  Similar findings have also beeri
 reported in humans suffering from zinc deficiency  (Prasad et al  1963- Henkin
 et al., 1975).
    Certain evidence suggests  zinc is essential for immune  function (National
 Research Council,  1978;  Sandstead et al., 1982; Bach, 1981; Beisel  1982-
 Moynahan, 1975; Nriagu,  1980b).  Successful  results have  been reported  in
 infants  with acrodermatitis enteropathica after zinc  therapy (Chandra  et al
 1983; Eckhert  et al., 1977; Ecker and  Schroeter,  1978;  Nriagu  1980b)'
 Patients with  latrogenic zinc deficiency  have developed a clinical  picture
 similar to that of acrodermatitis enteropathica which has been alleviated with
 zinc therapy  (Sandstead et al.,  1982; Nriagu, 1980b).  Chandra et al (1983)
 reported that zinc deficiency increases vulnerability  to  Listeria Salmonella
 Coxsackie virus, and other pathogens.
    It has also been suggested  that zinc deficiency stimulates the  production
 of endogenous free  radicals in lung microsomes.  The endogenous free
 radicals may then react with tissue components  initiating lipid  peroxidation
 and/or cross-linking of proteins leading to cell damage (Bray et al., 1986).

 3.4 EFFECTS IN ANIMALS

3.4.1    Acute Toxicity

3.4.1.1   Inhalation.  Lam et al. (1985)  found  functional, morphologic and
biochemical changes  in the respiratory tract of guinea pigs exposed'to  5
                                  17

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mg/m3 zinc oxide for 3 hours/day for 6 days.  Vital capacity, functional
residual capacity,  and alveolar volume were decreased  following  the last
exposure. Microscopic lesions in exposed animals consisted of f'™t'™
of the proximal portion of the alveolar ducts and adjacent alveoli charactenzed
by interstitial thickening, increased pulmonary macrophages and neutrophiis
in adjacent airspaces, and replacement of the alveolar squamous epithel urn
with cuboidal cells.  In an earlier study, Lam et al. (1982) found that ventilation
and lung mechanics in guinea pigs exposed to 7.8 mg/mS zinc ox.de  or a
single 3-hour exposure  period were not significantly different  from  controls.
A significant decrease was, however, seen in the functional residual volume.
    The pulmonary  response to  zinc  oxide fumes of  23 guinea pigs was
studied by Amdur et al. (1982). The animals were exposed to approximately
1 mq/m3 of freshly formed zinc oxide.  Respiratory measurements were made
every 5 minutes for a 30-minute preexposure  period, a 1-hour  exposure
and a  1-hour postexposure period.   Pulmonary  response  measurements
included resistance, compliance, frequency, total volume, and minute volume.
The only statistically significant effect noted  by the end of  the  exposure
period was a 9 percent decrease in  compliance.   One hour postexposure,
compliance had decreased  16 percent below  control values.  To further
examine the decrease in  compliance,  the experiment was repeated using  /
quinea pigs  The animals were again  exposed  to approximately 1 mg/m^ of
freshly formed  zinc oxide for 1  hour, followed by a 2-hour postexposure
observation  period.  Unlike the first  experiment,  a statistically  significant
decrease in compliance was not noted by the end  of the exposure period.
 However by the end of the first hour postexposure period, the compliance
 had dropped 16 percent below control  values.  At the end of the second hour
 postexposure period, the  compliance had decreased  to  27  percent below
 control values.  The decrease in compliance without a change in the airway
 resistance noted in these experiments reflects a response in the periphery of
 the lung, the primary site of deposition of submicron aerosols.       ....
     The ability  of zinc oxide to alter pulmonary defenses was evaluated by
 Hatch et al (1985).  Ninety mice were treated with an intratracheal injection of
 10 or 100 ug zinc oxide followed by exposure  to group C Streptococcus sp.
 The  severity of the infection was quantitated by the resulting mortality over a
 15 day period.  A significant number of mortalities  was  noted  in both
 exposure groups (73 and 55 percent, respectively).                     .
      An intratracheal injection of 0.5 mg zinc oxide produced morpho ogical
 changes in pulmonary alveolar macrophages (RAM) in rats.  One week after
 exposure  PAM contained a prominent nucleolus within a vagmated nucleus.
 The resident  pulmonary macrophages contained many  electron dense
  structures  some of which were homogeneous and membrane bound, while
  others of  varying  electron densities were  in the proximity to  lamellar
  configurations.   Membrane-bound  electron dense structures  were also seen
  in the intercellular spaces among interstitial  macrophages.   The authors
  hypothesized  that the  presence  of  electron  dense structures along with
  lamellar membranous formation  in  proximity to and within  the  intersti jal
  macrophages suggested a transfer of paniculate matter from alveolar to the
  resident interstitial macrophages.  Accumulation of particulate matter within
  the  macrophages may interfere with the normal phagocytic function of these
  macrophages, resulting  in the  metal  fume fever  (see Section  3.10.1)
  associated with zinc toxicity (Migally et al., 1982).
      Fischer et al. (1986) reported that zinc  oxide  is cytotoxic.  Using the in
  vitro bovine pulmonary  macrophage assay  system, the EC50  (effective
                                     18

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  concentration  required  to  reduce phagocytosis to  50 percent  of  control
  values) was 22 yg/ml.
      Gupta et al. (1986) observed no signs of toxicity or symptoms of gross
  morphological changes in the lungs of guinea pigs 7, 15, or 30 days after a 50
  mg intratracheal injection of zinc oxide dust.  However, an increase in alkaline
  phosphatase activity was noted in  the  lung mitochondrial supernatant  and
  serum.   A decrease  in the  activity of  lactate dehydrogenase in the lunq
  mitochondrial supernatant was  noted on days 7 and 15 postexposure  but
  became normal after 30 days.   No significant change was observed in the
  activity of this enzyme in serum.
      Conner et al. (1985) studied the irritancy  potential of a combination of
  zinc oxide and  sulfur dioxide.  Guinea pigs were exposed to 6 mg/m3 zinc
  oxide  mixed with 1  ppm sulfur dioxide for 3 hours a day for 6 days   Total
  lung capacity, vital capacity, functional residual volume, alveolar volume and
  diffusing capacity were decreased following exposure and had not returned to
  normal 72 hours after exposure.  Morphological changes in  the lungs were
  limited to the centnacinar alveolar ducts and associated alveoli and consisted
  of interstitial cellular infiltrate, increased numbers of macrophages in alveolar
  ducts  and alveoli,  and replacement  of  squamous  alveolar epithelium  with
  cuboidal cells.  The severity and frequency of such lesions were lessened by
  72 hours postexposure.  Similar but more severe changes were seen after a
  S!n9™"«hour exposure of 25 m9/m3 2inc oxide  and sulfur dioxide (Conner et
 T   ,A *;?n™?f 3-?ute emPhVsema '" cattle was  reported by  Hilderman  and
  layior (1974).  The episode occurred  in a barn that was being remodeled
 The cattle were exposed to  zinc oxide fumes emitted during oxyacetylene
 cutting and arc welding of galvanized  pipe.  Three heifers  were severely
 affected, and  died  within a  short time.  Autopsy findings showed  severe
 changes in the lungs  with edema,  emphysema, and  hemorrhages    Zinc
 concentrations in liver, kidney, and lungs were not above normal values in the
 two animals examined.  In this case, a galvanized  material was  implicated  but
 the extremely severe condition caused by the  fumes  indicated either 'that
 cattle are highly sensitive to zinc  oxide fumes, or that other metals such as
 cadmium,  may have been involved.
     Harding (1957)  administered  intratracheal instillations of 50 mg of zinc
 stearate to rats.  Approximately 50 percent mortality was noted after dosinq
 buryivmg animals were  sacrificed up to day 259 after  instillation.  Fibrosis
 could not be detected.  Harding also found that the zinc stearate disappeared
 from the lungs of the survivors within 14 days after administration
     Unlike Harding, Tarasenko et al. (1976) found  pathological changes in  the
 lungs of surviving animals  in the  form of widespread plasmorrhagia  in  the
 walls of small arteries  and alveolar atelectasis foci alternating with foci of
 chronic alveolar emphysema 2 months after a single  50 mg intratracheal dose
 of zinc stearate.  Still later, chronic alveolar emphysema and bronchitis were
 S66P.

 3.4.1.2   Oral.   In an outbreak  described by  Allen  (1968), cattle were
 poisoned with dairy nuts which had been accidentally contaminated with zinc
 oxide.  The zinc content of the nuts was 20 g/kg.  Based on a dairy nut
consumption of 7 kg/day, it is estimated that the  cows consumed 150 g of
zinc/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 postmortem examination revealed severe
pulmonary  emphysema,  a flabby myocardium, blood spotting  in the cortex
                                  19

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and medulla of both kidneys, and marked degenerative changes in the liver.
The zinc cncentrations in the two livers analyzed were extremely high,  1,430
and 2,040 mg/kg (dry matter basis), and there were indications that copper
levels were lower than normal.
    Breitschwerdt et al. (1986) described the clinical and laboratory findings
of three cases of acute oral zinc toxicosis in dogs.  In two of the cases the
source of zinc was a metal nut  high in zinc content (>98 percent).  In the
third case, the animal had ingested a large amount of zinc oxide  ointment
which had been applied to the perianal and scrotum areas to prevent moist
dermatitis secondary to fecal contamination.  While only one dog succumbed
to the zinc toxicosis, all of the animals exhibited a loss of appetite, weakness,
depression, and  vomiting.   The zinc content in plasma and urine  was also
elevated over that  routinely found in healthy animals.  Necropsy findings in
the  dead animal  were  pulmonary peribronchial  artenolar thrombosis,
enlargement of the right side of  the heart, and various lesions of the kidneys.
The zinc content of the liver and kidney was 369 (average 26.2) and 295 ppm
(average 14.6 ppm), respectively.

3.4.2 Subchronic Toxiclty
3 4 2.1    Inhalation.  In  a study designed  to  determine  the  effect of
 inhalation of zinc oxide particles of < 1 micron in size on  rat lungs, Pistorius
 (1976) exposed test animals to  15 mg/m3 zinc oxide for 1, 4, or 8 hours/day
 for 84 days. There were no differences in lung function between controls and
 exposed animals except for a decrease in  specific conductance  and  another
 lung function parameter termed "difference  volume"  (A-TGV-Vt)  in the
 exposed groups at the end of  the second week  of  the  experiment.  The
 conditions  improved  as  the length of exposure  increased.   The  author
 believed the improvement in lung function  with the extension of exposure to
 be  the  result of an  increase in macrophages, which in  turn increased the
 elimination of zinc from the lungs. In another study rats were exposed to 15
 mg/m3  zinc  oxide dust for  4 hours/day 5  days/week for  1, 14, 28, and 56
 days   Histological  examination of the  lungs showed core-shaped fresh
 leukocytic inflammatory changes with numerous small leukocyte plugs in the
 bronchus clearings and intraalveolar edema. After  14 days exposure isolated
 foam and round cell cores appeared.  The inflammatory changes decreased
 by day 28 and 56;  however,  there  were  numerous alveolar macrophages
 (Pistorius et al., 1976).                                       .          ,
      Oberdorster and Hochrainer (1979) evaluated the effect of inhalation of
 zinc oxide aerosol on the lung clearance mechanisms. Rats were exposed to
  submicron zinc oxide aerosol  (1 mg/m3)  for 6  weeks followed by a  1-hour
  exposure to  11.5 mg/m3 59pe  as  Fe203  (used as a marker).  The rate of
  clearance of 59Fe from the lungs of the  zinc  oxide exposed  animals was
  found to be twice  that of the controls. On day 38 postexposure, 62 percent of
  the initial lung 59pe was still present in the lungs of the  zinc oxide  exposed
  animals  The authors postulated that exposure to the zinc oxide aerosol over
  the 6 week period affected the bronchial and alveolar clearance mechanism.
  3422  Oral.  Animals can tolerate high dietary levels of zinc without any
  signs of a toxic effect. Ansari  et al. (1976) administered  from 1,200 to 8,400
  ppm zinc oxide to rats via their diet for 21  days. No clinical signs of toxicity
  were noted in any of the exposed groups. At the 1,000 ppm feeding level,
  Sutton and Nelson (1937) found no adverse effects in rats or their offspring.
  The National Research Council (1978) reported that dietary administration of
  4000  to 7,500 ppm  zinc produced a condition resembling iron deficiency
                                     20

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 anemia in young  rats.  Supplements  of  iron and  copper  increased the
 hemoglobin concentration to normal levels.
     In 1937, the University of Illinois was asked to identify a disease in two
 suckling colts on a farm located near a zinc smelter.  Autopsy examination of
 the colts revealed parasitism, a form of arthritis,  and abnormal amounts of
 zinc in bone, liver, and urine. An abnormally  high amount of zinc was also
 found in the mother's  milk.   Based on these findings, Graham et al. (1940)
 initiated a  study to determine the effect of dietary zinc on pregnant mares and
 mares nursing colts.  Mares were administered 3.5 and 35 g of zinc lactate via
 diet over a period of up to 2.5 years. These feeding levels were based on the
 zinc content of the feed assumed to have been  consumed by the mares while
 suckling the affected foals.  The results of the study did not demonstrate that
 zinc, at the levels administered, would produce harmful effects in pregnant
 mares or mares suckling colts. This led the authors to believe that the effects
 seen in the two colts were caused by something other than zinc. However, it
 should be pointed out  that the zinc content in  the milk  from the experimen-
 tal animals was Jess than that from the mares suckling the two infected colts.
     The effects of subchronic exposure to zinc have also been studied in
 several commercial  animal species.  Sampson et al. (1942) evaluated the
 effect of ingestion of zinc lactate in pigs. In the first experiment shoats were
 fed a basal diet plus  100 g of zinc lactate for 3 months.  At the conclusion of
 the experiment, none of the pigs showed any sign of an adverse effect. In the
 second experiment weanling pigs were fed  a basal diet  plus  17.5 g of zinc
 lactate for 9.5 months.  The zinc-fed  weanling  pigs  began losing  their
 appetite after only a few weeks on the diet.   Symptoms of stiffness and
 lameness were also noted.   Autopsy findings revealed pathologic  lesions in
 the joints and  an  increased  liver zinc content.  This arthritic condition was
 confirmed  by Brink et al.  (1959) and Hill et al. (1983) after feeding  pigs from
 500 to 8,000 mg/kg zinc.  In addition to the arthritic condition characterized by
 swollen joints,  at  feeding levels of 2,000 mg/kg  and above, test animals
 exhibited depressed weight gain and food  consumption.  There was also a
 dosage-related increase in  deaths (Brink et al.,  1959).  Postmortem
 examination revealed extensive  hemorrhaging   in  the axillary  spaces  and
 intestine and marked gastritis with some ulceration.
    In sheep,  the  ingestion of 240  mg zinc/kg  as  zinc oxide or zinc sulfate
 administered three times a week for 4 weeks produced pancreatic damage in
 all exposed animals.  Animals ingesting zinc sulfate also experienced severe
 diarrhea which commenced after a week of dosing and persisted throughout
 the experiment.  All  animals in  the zinc sulfate group  died after day 13.
 Postmortem examination revealed a reduction of the papillation of the rumen
 wall and edema of the fundic folds of the abomasum.  The  liver had a finely
 mottled surface and an orange brown color (Smith and Embling, 1984).
    Dewar et al. (1983) studied the effects of excessive dietary zinc as zinc
 oxide in chicks and hens.  Chicks were maintained on a diet  containing 2 000
 4,000, or 6,000 mg/kg for 42 days or 1,000, 2,000, or 4,000 mg/kg for 28 days
 while hens  received 10,000 or 20,000 mg/kg for 4 days. Mortality was high in
 chicks receiving 4,000  and  6,000  mg  zinc/kg.  Postmortem  examination
 revealed macroscopic abnormalities of the alimentary tract.   In five  chicks in
the 6,000 mg/kg group there was internal hemorrhaging from the descending
aorta or the thoracic  aorta.   Histological examination revealed gizzard  and
pancreatic lesions in all  exposed groups.  There  was no mortality reported for
the exposed hens; however,  gizzard and pancreatic lesions were  found in
both exposed groups.
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3.4.3 Chronic Toxicity
    No information was found on the effects of chronic inhalation exposure to
zinc/zinc oxide in animals.  However, a study on the oral administration of
subtoxic  levels of zinc  indicates a possible  effect  on the endocrmological
balance.  Mice were administered 0.5 g/L zinc sulfate in drinking water for up
to one year.   The animals maintained a healthy outward appearance during
the length of the study.  Analysis of liver, spleen, and skin samples of zinc
supplemented animals did not show a significant increase in zinc content over
that of the controls.  Histological examination  revealed hypertrophy of the
adrenal cortex and the  pancreatic islets.  Since hypertrophy of the adrenal
cortex has been seen  with  an  increased  plasma level  of  certain  pituitary
hormones, it was suggested that the administration of zinc over an extended
period of time may also cause  hyperactivity of the pituitary (Aughey et al.,
1977)  In an  earlier study, Drinker et al. (1927b) found no evidence of toxic
effects in rats administered from 0.5 to 34.4 mg zinc/day as the oxide, citrate,
acetate, and malate for a period of 35 to 53 weeks.

3.5 CARCINCGENESIS
     Under conditions of high gonadal activity, the injection of zinc salts into
the testes of fowl has induced testicular  tumors (Sunderman, 1971; National
Research Council, 1978; U.S. Environmental Protection Agency, 1980; Nriagu,
1980b).  Seminomas, interstitial cell tumors, and teratomas have also  been
reported  in  rats after  testicular  injection of  zinc  salts (Nriagu,  1980b).
Conversely, the injection of zinc sulfate  into  the mammary glands of young
and sexually  mature  Marsh-Buffalo mice significantly delayed the onset and
incidence of mammary adenocarcinoma (Bischoff and Long, 1939).
     There is  no evidence  that the inhalation,  ingestion,  or  parenteral
administration of zinc induces the formation of tumors.  There is,  however, a
considerable  amount of  information which indicates that the  administration of
zinc is indirectly involved in tumor formation as a growth promoter or inhibitor.
 In a study  by Wallenius et al.  (1979), 4-nitro-quinoline-n-oxide-induced
cancer of the oral cavity in female rats appeared earlier in animals ingesting a
 diet containing 200 mg/kg zinc than animals fed 15 or 50 mg/kg zinc. Fenton
 and Burke (1985) found that TEPC plasmacytoma transplanted tumors were
 somewhat smaller in mice  maintained  ort a  zinc-deficient  diet (0.5  yg/g)
 compared to mice maintained on a zinc-adequate diet (50 pg/g).  Mathur et
 al. (1979) reported that zinc deficiency (5.9 mg/kg) promoted the development
 of 4-nitro-quinoline-n-oxide-induced  histological  changes  of  the  oral
 cavity  in rats.  However, at the conclusion  of the study  there  were  no
 differences  in tumor formation between the animals fed  the  zinc-deficient
 diet and the  zinc-supplemented diet  (260 mg/kg).  Only moderate dysplasia
 was seen in animals on  the zinc-adequate diet (50 mg/kg).  The authors
 concluded  that  zinc deficiency  facilitates  the development  of the  initial
 histological  changes and supplementary zinc  provides an initial protective
 barrier against tumor formation, but once the protection is overcome,  tumor
 formation is accelerated.  Fong et al. (1978) found  that a zinc-deficient diet
 (7  mg/kg)  promoted the formation of methylbenzylnitrosamme (MBN)-
 induced esophageal tumors. By the conclusion of the  study, there was an
 increased incidence of  esophageal  tumors in zinc-deficient  animals  over
 animals maintained  on the  zinc-adequate diet (60 mg/kg).  Similar results
 were reported by  Gabrial  et  al. (1982) after maintaining rats  on a  zinc-
 deficient diet.  In a  more recent work, Fong et al. (1984) found  that a zmc-
                                    22

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 deficient diet also promotes  the formation  of  benzylmethylamine  (BMA)-
 induced esophageal tumors and NaN0.2-induced forestomach tumors.   Van
 Rensburg (1981),  in a survey of 21 regions, found  that in  areas  with high
 incidences of esophageal cancer consumed diets  were deficient in  zinc,
 magnesium, riboflavin, and nicotinic acid.
     Many  human studies have documented  the  level of  zinc  in  both
 cancerous and noncancerous tissues, and the zinc content has been found to
 be both high and  low with no definite  pattern.   Mulay et al.  (1971) found a
 higher zinc content in bronchogenic carcinoma and cancerous breast tissue
 than in noncancerous bronchial and breast tissue.  Lin et al.  (1977) showed
 that zinc concentrations in the esophagus in humans  with esophageal cancer
 were lower than normal.   Zinc concentrations are normally very high in the
 prostate, but levels are consistently lower in  carcinomatous prostate  tissues
 (Lahtonen,  1985; Leake et al., 1984; Boddy et al., 1970; Feustel et al  1982-
 Gyorkey et al., 1967; Schrodt et al., 1964; Habib et al., 1976).  In the study by
 Habib et al. (1976), zinc concentrations in the neoplastic tissue of the prostate
 were less than  half of those found in normal  tissue  or  in  hypertrophic
 prostates; however, cadmium levels were higher in the neoplastic tissue than
 in normal or hypertrophic  tissue.  High industrial exposure to cadmium  has
 been implicated as a possible factor in the development of prostatic cancer.
     The  only  positive carcinogenic  resonse resulting from zinc occurs
 following injection of zinc salts into the testes of  fowl and rats.  The special
 situation with regard to  injection  site tumor has been  reviewed  by several
 authors. Gasso and Goldberg (1977)doubted the  usefulness of the technique
 if only injection site  tumors developed.   Tomatis  (1977)  reviewed  102
 chemicals reviewed by IARC that had been tested using the subcutaneous
 route.   Based  on  the  results by  other  routes, he  concluded  that
 "administration of a chemical by the subcutaneous injection route produced
 what one could call false negative results for six ( 5.6% ) of the  102 chemicals
 tested, and if we accept all the crticism of this route  of administration false
 positive results for nine ( 8.7% ) of the 102 chemicals tested."  Thus,  with this
 route a false positive  result is a more likely result  if only injection site tumors
 are observed.  Recently, Theiss  ( 1982), again using the IARC  data base
 conclued that  subcutaneous injection  was most useful  if  the compound
 produced tumors at a site distant from the site of injection.   Therefore, by
 analogy one could conclude that the testicular tumors resultimg from  injection '
 of zinc salts into the testes are of limited predictive value.  In addition, with
 zinc it is possible that the resulting testicular tumors could be influenced (i. e.
 .promoted ) by the local displacement of cadmium from  its carrier protein.
 Because the carcinogenicity data in animals  is derived from  an  artificial
 exposure route and no other animal or  human data  exists to evaluate the
 carcinogenic potential, the  available evidence for zinc  and  zinc oxide is
 considered to be inadequate, equivalent to a group O weight-of-evidence
 using EPA's Cancer Risk Assessment Guidelines.

 3.6 MUTAGENICITY

    In its review of zinc's possible mutagenic effects,  the National Research
 Council (1978) found no  literature suggesting  that zinc or  any of  its
compounds  are mutagens.  However,  Voroshilin ei al. (1978) reported
chromosomal damage in the form of an  increased frequency of hyperdiploid
cells but not structural aberrations in the bone marrow of noninbred rats  The
rats were exposed to 0.1 and 0.5 mg/m3 zinc oxide aerosol continuously for a
period of 5 months. In the same report, the  authors also found an increase in
                                  23

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the frequency of structural aberrations of the chromosomes and hyperdiploid
cells when  human lymphocytes  at  the  G0 stage of the cell  cycle  were
exposed to the action of zinc acetate at concentrations from  7.0 to 20.0
uq/mL   An interpretation of this  report is difficult because the category  of
aberrations  referred to as  hyperdiploid cells is not  one  used  by
cytogeneticists in this type of study.  Additionally, in  the in vitro  s udy  he
frequency  of structural aberrations at 20 yg/mL was  slightly less than the
frequency  at 7 yg/mL (3.6 percent versus 4.0 percent, respectively),   n a
recent study, Crebelli et al. (1985) found zinc oxide (1,000 to 5,000 yg/plate)
nonmutagenic in the Salmonella reversion assay.

3.7 TERATOGENICiTY
    There are no data indicating that zinc is teratogenic.  A greater risk of
malformations  is  expected  in regard  to  zinc  deficiency,  as  discussed  in
Section 3.3.  Zinc also appears to offer a degree of protection against the
teratogenic effect of cadmium. In a study by Perm and Carpenter (1968)  an
increase in both unilateral and bilateral cleft lips and incomplete and complete
palatal clefts was seen in the offspring of hamsters administered cadmium
 intravenously at levels of 2 and 4 mg/kg during the eighth  day of gestation.
 The  simultaneous administration of zinc sulfate was found to reduce the
 teratogenic effect of cadmium.  This protective effect was also noted when
 zinc was administered 15 minutes to 6 hours after the cadmium; however, the
 malformations were slightly increased.

 3.8  REPRODUCTION
     It  has  been  established  that zinc  deficiency  may impair normal
 reproduction or  adversely affect the outcome  of pregnancy in humans and
 lower  animal forms.  However,  excessive  dietary zinc may also adversely
 affect  fertility (Samanta  and Pal, 1986; White, 1955)  and pregnancy (Sutton
 and  Nelson, 1937;  Schlicker  and Cox, 1968; Hill et al., 1983; Kumar, 1976^
 Samanta and Pal (1986) reported that sperm motility was inhibited in rats fed
 a diet containing 4,000 ppm zinc for 30 to 32 days. Of 18 females mated with
 males from the zinc-exposure group, only  11 females conceived,  whereas all
 of the females  (15) mated  with control rats conceived.   No strNbirths or
 malformations were reported  in either group. Sutton and Nelson (1937) found
 that in most cases growth was retarded and no reproduction occurred  after
 feeding female rats 10.000 ppm zinc carbonate.  At the 5,000 ppm feeding
  level  increased stillbirths occurred.   Growth  and  reproduction were  not
  affected at the 1,000 ppm feeding level.  The original females were remated.
  At the 5 000 ppm level, no  live young were born and, after 5 months  the
  females ceased to become pregnant.   Hemoglobin values  were  found to
  decrease  with time in  the 5,000 ppm  group.   Hemoglobin  and red blood
  corpuscles were  diminished in those animals in the 10,000 ppm feeding
  qroup Schlicker and Cox (1968) reported 100 percent resorption of  fetuses
  in rats fed 4,000 ppm zinc oxide beginning 21 days before gestation.  Kumar
  (1976) found a significant number  of resorptions in  rats receiving  a  total ot
   ISO ppm  zinc daily. In a brief statement this author also reported that three
  premature births and one stillbirth occurred in a small group of women given
   100  mg zinc sulfate  (40.5  mg zinc)  daily during the third trimester of
   pregnancy.   However,  no premature births or stillbirths were reported  in a
   group of  seven women receiving 200  mg  zinc sulfate twice a  day  (81 mg
   zinc/day) during the third  trimester of pregnancy  (Nnagu,  1980b).   Also,
   adverse  effects on the  outcome of pregnancies were not reported in a group
                                     24

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 of women supplemented with 20 mg zinc sulfate per day in addition to dietary
 zinc intakes of from 9.3 to 11.3 mg/day (Hunt et al.,  1985).

 3.9  NEUROTOXICITY

     It is known that zinc deficiency may  have an adverse effect on the central
 nervous system. However, recently it has been suggested that the ingestion
 of excessive  amounts  of zinc may  also exert toxic effects on the central
 nervous system.  Kozik et al. (1980) found  morphological changes  in the
 ammonal  cortex and  basal ganglia in  the form of shrunken neurocytes
 accompanied by  proliferated  oligodendroglia,  neuronal  losses, and
 degenerative changes and considerable vacuolization of the neurocytes of the
 septum lucidum amygdaloid body in rats orally dosed with 100 mg zinc oxide
 for 10 days. A reduction in the activity of acid phosphatase (acP), adenosine
 triphosphatase (ATPase),  acetylcholinesterase   (AChE),  and
 butyrylthiocholinesterase  (BuTJ) along  with  an  increase  of thiamine
 pyrophosphatase (TPPase) and nonspecific esterase (NsE) activity was also
 noted.  The authors stated that the effects seen were  rather low grade and
 may be reversible.  In a  similar study, Kozik et al. (1981) found  that the
 ingestion  of  large  doses  of zinc  oxide increased  the  production  of
 neurosecretion in the  hypothalamus  (supraoptic  and paraventricular nuclei)
 along with an  increased  release of  antidiuretic  hormone  in the
 neurohypophysis. Histological  examination of cells of the hypothalamic nuclei
 revealed enlargement of both the cells and their nuclei.  Many neurocytes of
 the supraoptic and paraventricular nucleus were also shrunken. Motor effects
 suggestive of  neurological disturbances in pigs during zinc intoxication have
 also been reported (Hill et al., 1983).

 3.10    EFFECTS IN HUMANS

     The  literature on  adverse health effects  in  humans  resulting  from
 exposure to excessive amounts of zinc  is  limited.  One probable reason is
 that zinc has generally been accepted as a beneficial substance,  and adverse
 effects, with the exception of those incurred under occupational settings have
 generally not been expected or sought.

 3.10.1  Inhalation Toxicity

    In certain  occupational settings, the inhalation of zinc oxide fumes
 produces a disease known as metal fume fever. This disease is produced by
 the  inhalation  of zinc  oxide fumes when  zinc  is  heated in an oxidizing
 atmosphere to a temperature near its boiling point, as in smelting operations,
 galvanizing,  brass-founding, brazing, and oxyacetylene  welding  of
 galvanized iron.  Metal fume fever generally strikes at the beginning of the
 work week when the worker has not been exposed for a couple of days  and
 so it has been called "Monday Fever."  Further repeated exposure does not
 cause  any  new symptoms, suggesting some type of  adaptation.  The
 symptoms  of this disease  (headache, fever, hyperpnea,  nausea, sweating
 and muscle pains) occur within a few hours after exposure and  may persist
 for 1 to 2 days. The most prominent laboratory finding is leucocytosis.  While
 metal fume fever is most commonly caused by exposure to zinc oxide fumes
 and/or  dust, it may  also be caused by  exposure to other metals such  as
 manganese, copper,  iron, cobalt, cadmium, antimony, lead,  and beryllium
 Most of our knowledge  about metal fume fever and its relationship  to zinc
oxide fumes comes from the beginning of the century (Drinker et al., 1927a,
 1928; Sturgis  et  al., 1927).   Many reviews on  metal  fume fever, often
                                 25

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containing case reports, have also been published (Anseline, 1972; Armstrong
et al  1983; Wolf, 1975; Kemper and Trautman, 1972; Prasad, 1978; Hegsted
et al.! 1945; Kehoe, 1948; Rohrs, 1957; Summer and Haponick, 1981; Mueller
and Seger, 1985).
    There are few data on the ambient levels of zinc oxide fumes that might
cause metal fume fever in man. Sturgis  et al. (1927) exposed two people to
zinc oxide fumes at  a  dose corresponding  to 600  mg  zinc/m3.   It  was
calculated that the subjects inhaled 48 and 74 mg zinc, respectively. Both
subjects developed symptoms of metal  fume fever.  Batchelor  et al., 1926;
Kemper and Trautman (1972); and Hammond (1944) reported that metal fume
fever does not occur at zinc oxide levels below 15 mg/m3.
    Several  theories have been postulated concerning the  mechanism  of
metal fume fever, but there is no definite evidence for any of the proposed
theories.  McCord (1960) suggested that there is an allergic basis  for the
mechanism  of the fever.  Mori et al. (1975) stated  that catalytically active
metal  oxide  fumes produced by  heating the metal within  the  proper
temperature range in  the  presence of carbon monoxide causes metal fume
fever by an oxidative action in the blood.  Regardless of the mechanism of the
fever, the disease is likely caused only by  metal particles of extremely small
size.'  These penetrate deep into the alveoli, causing acute  reactions there
(National Research Council,  1978;  U.S. Environmental Protection Agency,
1980).
     Acute pulmonary damage that can  be  lethal  may occur after  the
inhalation of  zinc chloride, the major component in smoke coming from the
so-called "smoke bombs" often used  in  military exercises.   Inhalation of
such smoke  in confined spaces may  rapidly lead  to severe pulmonary
disease (Milliken et al., 1963;  Schmahl, 1974; Schenker et al., 1981).   Milliken
et al. (1963)  reported on a fire fighter who  died after being  exposed to zinc
chloride smoke from a smoke generator  during a demonstration.  The subject
experienced  difficulty in  breathing, tachypnea, epigastric  pain,  nausea,  and
fever followed by cyanosis, confusion, and coma.   Postmortem examination
revealed advanced pulmonary fibrosis, acute cor  pulmonale,  and  right
ventricular  hypertrophy.   Death  was attributed to acute  respiratory
insufficiency.
     The effects of inhalation of zinc chloride in smoke from smoke bombs
 have also been described by Schmahl (1974), who reported on 11 cases, of
 which 2 had very severe reactions.  There were no  severe sequelae; however,
 in one case it was almost 2 years before the lung function returned to normal.

 3.10.2  Oral Toxicity

     The hazards of  ingesting foods and/or liquids stored in galvanized
 containers are well known.   Callender  and  Gentzkow (1937) reported  on a
 case of two companies of soldiers that dined separately who became ill after
 consuming  limeade which had been prepared and stored in galvanized iron
 cans.   Symptoms included  gastrointestinal  distress and diarrhea  of mild
 intensity. Analysis of the limeade prepared under the same conditions as that
 in the poisoning incidents revealed a concentration of zinc oxide of 910 mg/L
 and 15.6 mg/L  of antimony.  It was concluded that the  amounts of zinc and
 antimony present in the limeade were responsible for the  poisonings. Brown
 et al. (1964) reported on two cases of zinc poisoning in California.  In the first
 case, 300 to 350 people became ill after  consuming food which had  been
 stored in galvanized containers.  By simulating the preparation and storage of
 the contaminated foods,  the  investigators estimated  that  the  zinc
                                   26

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 concentration approached 1,000 ppm (wet weight).  In the second case, 44
 people became ill with nausea, vomiting, and diarrhea within 20 minutes after
 consuming an  alcoholic punch.   Analysis of the punch revealed that it
 contained 2,200 mg/L of zinc.  A group of students in  a home economics
 class experienced chills,  dizziness,  nausea,  vomiting,  and headache after
 consuming fruit punch  which had been stored in a galvanized container
 overnight.  Punch  samples from  the  storage container contained 443 ppm
 zinc (Lapham et al., 1983).
     Hooper et al. (1980) after orally administering 440 mg zinc sulfate/day
 (160 mg  elemental zinc/day) to healthy young males for 5 weeks found a 25
 percent  reduction  in  the  high-density  lipoprotein-cholesterol
 (antiatherogenic lipoprotein) levels.  The authors speculated that excessive
 levels of  orally administered zinc may be atherogenic in man.   The effect of
 moderate  increases  in dietary  zinc on  the high-density  lipoprotein-
 cholesterol level is not known.
     In a  later  work, Chandra (1984) found a reduction  in the high-density
 lipoprotein-cholesterol level and  an  increase  in   the   low-density
 lipoprotein-cholesterol  level in healthy adult males after oral administration of
 150  mg  elemental zinc/day  for  6 weeks.   A  reduction in  lymphocyte
 stimulation to  phytomemaglutinin and a reduction in polymorphonuclear-
 migration in response  to chemotactic migration and phagocytosis of bacteria
 was also  seen in these subjects.  The results  of this study indicate that oral
 ingestion   of excessive  amounts  of zinc by  healthy  individuals over an
 extended period  of  time  may  have a deleterious  effect  on  both  the
 immunologic and cardiovascular systems.
     Murphy (1970) reported on a 16-year old boy who ingested 12 grams of
 zinc over a 2 day period to hasten healing of a minor laceration.  Three days
 after ingestion the subject  experienced difficulty in awakening after a full
 night's  sleep, light-headedness, slight  staggering  of  gait, and  difficulty  in
 writing.    Follow-up examination  1  month   later  revealed no apparent
 sequelae.

 3.10.3  Other Routes of Exposure

     Because it is an essential element, zinc is routinely added to parenteral
 nutrition  regimens;  however, care must be taken  to ensure  against  zinc
 intoxication.  Brocks et al. (1977) reported on a woman who suffered from a
 case of acute zinc poisoning while  receiving total parenteral nutrition. Over a
 period of  64 hours she received 7.4 g of zinc sulfate. The  patient became ill
 with pulmonary edema, jaundice, vomiting, diarrhea,  and oliguria.  Her serum
 zinc concentration was  4,184 pg/100 mL.  In spite of treatment, renal function
 did not improve and she  remained  oliguric.  She died after 47 days of illness
 with bronchopneumonia.
    Gallery et al. (1972)  reported on a patient who  became ill  with nausea,
 vomiting,  and fever during home  hemodialysis.  An  investigation into the
 cause of the illness disclosed that  the patient was using rain water stored in
 galvanized tanks for the dialysis.  The water contained 625 yg zinc/100 mL.

 3.10.4  Epidemiology

    In 1926, Batchelor et  al.  made an extensive  investigation of workers
exposed to zinc in  a smelter in New Jersey.   A total of  24 workers were
selected from a baghouse where zinc oxide was handled, from several zinc
oxide packing plants, from a plant handling metallic zinc, and from a lithopone
packing house.  The length of exposure ranged  from 2 to 35.5 years. In most
                                  27

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work places the mean zinc concentrations were generally below  35 mg/m3,
except in the zinc dust plant, where concentrations of up to 130 mg/m3 were
measured.
The 24 subjects underwent careful  examinations.  A slight leukocytosis was
seen in 14 of the subjects. Hemoglobin readings ranged between 72 and 97
with the average being  81.   Zinc  in  whole  blood  in  the  exposed groups
averaged  458  ug/100 mL, compared to 387 yg/100  mL  in  controls.   In
exposed groups, 24-hour zinc elimination via  feces averaged 46.8 mg, while
in controls  the average was 9.32 mg.  This finding indicated an exposure via
the gastrointestinal  tract.  The conclusion of  the authors was that  workmen
could be exposed to zinc compounds in a smelter  for  decades without any
symptoms or chronic disease.  However, more recent surveys,  discussed
below,  do  indicate  hazards  associated  with high-level exposures to  zinc
compounds in the workplace.
    Chmielewski et al. (1974a,b) examined a  group  of workers in a shipyard
consisting  of ship  smiths,  electric  welders, ship's  pipeline fitters, and
zincifying  workers  who were exposed  to  zinc  oxide (see  Table 3-4).
Exposure  levels varied and in  some cases  exceeded  the maximum
acceptable concentration (MAC) for zinc oxide in air (5  mg/m3).  The highest
concentrations of zinc oxide  during work were  found  at the stands of the
electric welders who worked  in containers (maximum  58 mg/m3,  mean  18
mg/m3), the ship's pipeline fitters working within the engine room of the ship
(maximum 40  mg/m3, mean 5 mg/m3), and  the ship smiths employed in a
superstructure (maximum 50  mg/m3, mean  12 mg/m3).  Interviews showed
that most of the smiths, welders, and fitters had experienced metal fume fever
several times.  Frequent occurrences of chronic respiratory tract  infections
were noted in  the welders and fitters during  the physical examination.  Two
cases of  an  early  stage of  welder's pneumoconiosis were  noted in  the
welders' group. Chronic conjunctivitis and dermatitis occurred in all groups
examined.   Chronic gastritis was  noted  in  all groups examined; however,
because of the lack of a  commonly  accepted objective diagnostic criterion, an
 unequivocal confirmation of this diagnosis could  not be made.  A statistically
 significant increase in  asparate aminotransferase activity was noted  in the
 welders and a statistically significant rise in alanine aminotransferase was also
 noted in the welders and fitters.  However, these workers were also exposed
 to other hazardous compounds, such as nitrogen oxides.
     Bobrishchev-Pushkin et  al. (1977) studied  the health  status of 1,018
 workers in the casting shops of three copper alloy production facilities.  Four
 hundred and fifty-one workers from the rolling shops were  used as controls.
 The average level of zinc oxide exposure in the casting shop was 2.1 mg/m3
 (range of 0.2 to 5.1  mg/m3).  Analysis of the health status of workers over a 5
 year period showed an  increased  illness rate for the respiratory organs such
 as subatrophic changes in the breathing passages, chronic  bronchitis, and
 diffuse pneumosclerosis.   The frequency  of illness  with subatrophic  and
 atrophic rhinitis, rhinopharyngitis, and rhinopharyngolaryngitis increased with
 the length of employment.  The illnesses were noted in  15 percent of those
 with an employment of 10  years, in 21  percent  with  11 to 20  years  of
 employment, and in 35 percent of those employed for over 20 years; these
 illnesses were 3 to 6 times higher than for controls.  Chronic bronchitis was
 diagnosed in  11  percent of  exposed workers compared to 6 percent  in
 controls.   However, workers  were also  exposed  to  other metals such as
 copper, lead, and nickel.
     A study of the  mutagenic potential of urine  from subjects occupationally
 exposed  to a variety of compounds, including zinc oxide in the rubber
                                    28

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 Table 3-4 Groups Involved, Age, Duration of Work and Timing of
 Work of the 66 Workers Exposed to the Effect of Zinc Oxide- Seen
 for Medical Examination


Number of
the workers
examined




20

13


15


18



Groups
examined




ship-
smiths
electric
welders

ship's
pipe-line
filters
zincifying
workers


Shop




k-3

k-3


R


I



Working
stand




super-
structure
super-
structure
container
engine-
room

zincifying
shop

Average
age of the
groups
pvstfnin&ri
C7Ad«//(//CU
(yr)


27.6

29.0


29.2


36.6



Mean
duration of
professional
work (yr)



7.0

8.0


7.9


14.5

Mean
duration of
exposure to
zinc oxide


(yr)

3.0

6.0


7.1


8.5


daily

(hr)
4.2

4.6


3.7


6.0

 Source: Chmielewski et al. (1974b)
industry, was conducted by Crebelli et al. (1985).  The urine samples were
found to not be mutagenic in the microtitre fluctuation assay with Salmonella
typhimurium strains TA1535, TA98, and TA100.
    Klucik and Koprda (1979) found that everyone exposed to zinc oxide dust
in a zinc oxide factory showed signs of hypocalcemia.  Exposure levels were
reported to average 0.5 mg/m3 for zinc melters and 2.44 to 7.15 mg/m3 for
zinc  oxide  packers;  however, it was  not indicated  how these values were
obtained. Serum calcium levels of exposed subjects were significantly lower
and serum zinc  was higher than in controls.  X-rays revealed definite signs
of osteoporosis,  loss of spongiosis in  the vertebrae  and pelvis of two of six
zinc oxide packers, of which one was thought to be due possibly to the age of
the subject (60 years). The authors suggested that with a higher zinc intake,
the zinc forces calcium from the bone,  and the latter is then eliminated.
    In a study on furnace operators exposed to zinc oxide fumes in a brass
foundry  for  a mean duration of  11   ±5 years,  Hamdi (1969) found that
workers  often complained  of epigastric  pain.  These workers  showed a
statistically significant increase in zinc concentration in  whole blood, blood
corpuscles,  and basal fasting gastric juice in comparison to  nonexposed
subjects. The author suggested that the increased zinc content of the gastric
juice may have been responsible for the gastric complaints; however, it could
also be due to the presence of other substances used  in the manufacture of
the alloys.
                                  29

-------
    Zinc stearate,  an  organic compound  of zinc encountered in the rubber
and plastics industry, is suspected of causing lung disease.  Uotila and Noro
(1957) reported on the death of a man who had been employed in the rubber
industry for 29 years.  The cause of death was determined  to be chronic
pneumoconiosis.  Histochemical  examination  of  the  lungs showed  an
increased deposit of zinc; however, no quantitative determination of the zinc
content  was  made.   The role  of zinc stearate  as  the  causative agent in
neumoconiosis has also been evaluated by Weber et al. (1976).  Weber and
co-workers,  as reported by  the U.S. Environmental Protection Agency
(1980), described the  autopsy findings in  a man who, for the last 8 years of
his life,  had  been  exposed  to zinc stearate in  the plastics  industry.
Pneumoconiosis was given as the cause  of death.   The  lungs contained  62
mg/kg zinc  on a dry weight basis,  which  was  within normal limits.  The
authors  concluded that zinc  stearate could not have caused the fibrosis.
However, as pointed out by Harding (1957), zinc stearate is relatively rapidly
removed from the lungs; thus, a normal content of zinc does not  exclude the
possibility that zinc may have contributed to the disease.
                                  30

-------
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