PRELIMINARY STUDY OF
         SELECTED POTENTIAL
 ENVIRONMENTAL CONTAMINANTS -
   OPTICAL BRIGHTENERS, METHYL
CHLOROFORM, TRICHLOROETHYLENE,
    TETRACHLOROETHYLENE, ION
          EXCHANGE RESINS
                JULY 1975

              FINAL REPORT

      U.S. Environmental Protection Agency
          Office of Toxic Substances
           Washington, D.C. 2046O

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EPA-560/2-75-002
                             Final Report
                         PRELIMINARY STUDY OF
             SELECTED POTENTIAL ENVIRONMENTAL CONTAMINANTS
                          OPTICAL BRIGHTENERS
                           METHYL CHLOROFORM
                          .TRICHLOROETHYLENE
                          TETRACHLOROETHYLENE
                          ION EXCHANGE RESINS
                        Contract No. 68-01-2657

                            Project Officer
                            Frank D. Kover
                             Prepared for


                      Office of Toxic Substances
                    Environmental Protection Agency
                        Washington, D.C.  20160

                               July 1975

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              NOTICE

This repor.t. has been reviewed by the
Office of Toxic Substances, EPA,,and
approved for publication.  Approval
does not signify that the contents
necessarily reflect the views and
policies of the Environmental Pro-
tection agency, nor does mention of.
trade names or commercial products
constitute endorsement or recommenda-
tion for use.

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                TABLE   OP-  -CONTENTS


OPTICAL BRIGHTENERS

       Summary and Conclusions                                        1

I.     Physical Properties                                            U

II.    Uses                     .                                •      U

III.   Production and Importation                                    lU

IV.    Current Practice                                              l6

V.     Enviornmental Contamination                                   17

VI.    Monitoring and Analysis                                       18

VII.   Chemical Reactivity                                 '         "22

VIII.  Biology   .    .     •                                           25
       A.  Absorption                                                25
       B.  Excretion/Elimination                                     26
       C.  Transport and Distribution                                26
       D.  Metabolism and Metabolic Effects  .                        29

IX.    Enviornmental Transport and Fate                              29
       A.  Persistence and/or Degradation                  .  .        29
       B.  Enviornmental Transport              .        ••'    ,         30
       C.  Bioaccumulation                                           30

X.     Toxicity                                                      30

       A.  Human Toxicity                                            30

       B.  Toxicity to Non-human Mammals                             32
           1.  Acute, Subacute, and Chronic Toxicity                 32
           2.  Sensitization                                         36
           3.  Teratogenicity                                        37
           k.  Carcinogenicity                                       38
           5.  Mutagenicity                                          Uo
           6.  Behavioral Effects                                    Ul

       C.  Toxicity to Lower Animals                                 Ul

       D.  Toxicity to Plants                                        U2

       E.  Toxicity to Microorganisms                                ^3

Appendix                    .                                   . •     UU.

Literature Cited                                                     ^5

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              TABLE. OF   CONTENTS (Cont'd)


CHLORINATED HYDROCARBON SOLVENTS                ..                .

METHYL .CHLOROFORM, TRICHLOROETHYLENE, -TETRACHLOROETHYLENE

       Summary and Conclusions                                       U8

I,     Physical Properties           .                                50

II.    Production                                            '   •  .   6h

       A.  Methyl Chloroform                                         6k

       B.  Trichloroethylene                                         66

       C.  Tetrachloroethylene                                       69

III.   Uses     .             -•'....      ..-              ,.           72

IV.    Current Practices                                             76

V.     Enviornmental Contamination                  "        "   • .81

VI.    Monitoring and'Analysis             .  .                 .       83

       A.  Analysis of Mixtures                  .              .      83

       B.  Trichloroethylene                                  •    .   85

       C.  Tetrachloroethylene          •  .         •                  86

VII.   Chemical Reactivity                                           87

       A.  Methyl Chloroform                                         87

       B.  Trichloroethylene                            '             88

       C.  Tetrachloroethylene                       '                89

VIII.  Biology       .                                  '        '      90

       A.  Absorption                '.                     .  .         90

       B.  Excretion                                   .        '•     90
           1.  Methyl Chloroform                                     90
           2.-  Trichloroethylene       .                  .   -..-.     .  -92.
           3..  Tetrachloroethylene                                 .93
                                 11

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             TABLE   OF   CONTENTS  (Cont'd)


CHLORINATED HYDROCARBON SOLVENTS

METHYL CHLOROFORM, TRICHLOROETHYLENE, TETRACHLOROETHYLENE

       C.  Transport and Distribution                              9^
           1.  Methyl Chloroform                                   9k
           2.  Trichloroethylene                                   9^
           3.  Tetrachloroethylene                                 95

       D.  Metabolism and Metabolic Effects                        96

IX.    Enviornmental Transport and Fate                            99

       A.  Persistence and/or degradation                          99

       B.  Enviornmental Transport •                               100

       C.  Bioaccumulation                                        100

X.     Toxicity        ..            .....    ...           101

       A.  Human Toxicity                                         101
           1.  Inhalation of Methyl Chloroform                    101
           2.  Ingestion of Methyl Chloroform                     103
           3.  Skin Contact with Methyl Chloroform                10U
           h.  Behavioral Effects of Methyl Chloroform            IQk
           5.  Inhalation of Trichloroethylene                    10U
           6.  Ingestion of Trichloroethylene                     107
           7.  Skin Contact with Trichloroethylene       '         108
           8.  Behavioral Effects of Trichloroethylene            108
           9.  Inhalation of Tetrachloroethylene                  109
          10.  Ingestion of Tetrachloroethylene                   112
          11.  Skin Contact with Tetrachloroethylene              112
          12.  Behavioral Effects of Tetrachloroethylene           112

      B.  Toxicity to Non-human Mammals                           115
           1.  Acute, Subacute, and Chronic Toxicity              115
               a.  Inhalation                                     115
               b.  Ingestion                        .   .           119
               c.  Intraperitoneal Administration                 119
           2.  Sensitization                                      120
           3.  Teratogenicity                                     120
           U.  Carcinogenicity                                    120
           5.  Mutagenicity                                       121
           6.  Behavioral Effects                                 121

      C.  Toxicity to Lower Animals and Insects                   121

      D.  Toxicity to Plants                                      122

      E.  Toxicity to Microorganisms                              122

Literature Cited                                                  123
                                  iii

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                TABLE   OF   CONTENTS (Cont'd)
                     '-....-                                 Page
ION-EXCHANGE RESINS           /              :
       Summary and Conclusions                                   131
I.     Physical Properties                ,  •   •                  133
II.    Production              '                                  136.
III.   Uses                                                      136
IV.  .  Current, Practice                                         .138
V.     Environmental Contamination                               138
VI. .   Monitoring and Analysis                                   138
VII.   Chemical Reactivity                  .
VIII.  Biology                                            .;/..
       A.  Absorption                             ,
       B.  Excretion/Elimination                      .
       C.  Transport and Distribution         .
       D.  Metabolism and Metabolic Effects
IX.    Environmental Transport and Fate
       A.  Persistence and/or Degradation
       B.  Environmental Transport
       C.  Bioaccumulation
X.'     Toxicity
     .A.  Human Toxicity                            .
           1.  Inhalation
           2.  Ingestion
       B.  Toxicity to Non-Human Mammals
           1.  Acute, Subacute and Chronic Toxicity
           2.  Sensitization     '                   .
           3.  Teratogenicity - Reproductive Effects
           4.  Carcinogenicity  -
          . 5.  Mutagenicity
           6.  Behavioral Effects
       C.  Toxicity to Lower  Animals                          .
       D.  Toxicity to Plants
       E.  Toxicity to Microorganisms
Literature Cited                       .                .
                                    iv        .       •.. -:.' . ;..

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OPTICAL BRIGHTENERS:  Summary and Conclusions




     The "optical brighteners" constitute a unique class of chemicals,  not




onjy because of their wide structural variety but also because of their




wide application range.




     In recent years, optical brighteners have become one of the more im-




portant components of laundering products in the United .States.  Millions




of pounds are used yearly for this purpose.  Virtually all clothing con-




tains brighteners; they are used extensively for the mass whitening of




synthetic polymer fibers, during which the optical brightener is added to




the spinning solution or melt.  They are also used in the finishing of




textiles, including "wash-wear" cottons, where they are applied to the




fabric along with a finishing agent.  In paper manufacture, the brighteners




can be applied to the pulp in the dipping process or during the coating



operation.  Most of the vast numbers of articles which are manufactured




from plastics contain brighteners, including wrappers and containers for




foodstuffs.




     Although the production of optical brighteners in the United States




has declined somewhat, this cannot be taken as an indication of the pre-




valence of these agents without reference to import statistics:  available




figures show that approximately 2,000,000 pounds of brighteners were im-




ported in 1972.  These import figures are broken down to the amount of




each brightener by trade name.  No such breakdown was found for the brigh-




teners which are manufactured in the United States.




     Identification of the individual structures of the molecules which




are employed as brightening agents has become increasingly difficult because




of their growing numbers and tremendous structural varieties.  Each agent,

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of course, has a characteristic spectral-absorption curve of minimum




transmittance or maximum absorption.  Reliable identification,  however,




would depend on a detailed examination by chroma tography, absorption spec-




troscopy, and comparison of the infrared spectra to determine the parent




structure and the substituents.




     Nothing is reported on the fate of these compounds when their sub-




strates decompose, i.e., deterioration from use or gradual decomposition




after being discarded, or following incineration of the substrate.  They




certainly have a direct route  into the water supply, being carried in the




effluent from manufacturing plants and in household laundry waste water.




The stilbenedisulfonic acid salts are water soluble when released as the




free molecule (not attached to a substrate) into aquatic systems.




     Considering the inertness of the optical brighteners towards other




chemicals which they .contact during application, and their stability under




rigorous processing conditions, it would seem that they should remain




stable in the environment.  Those brighteners which are incorporated into




enzyme-containing detergent formulations would probably resist biodegradi-




bility becuase of their enzyme-stability.  This would certainly raise the




question of bioaccumulation, on which no specific studies under natural



conditions (accumulation in fish, for instance) have been reported.  The




few tissue-affinity studies which have been published report a rapid




excretion of the brighteners into the bile or the urine.  Long-term studies




showed no changes in the organs of the test animals.  These results, of




course, are valid only for those compounds which were selected for the




studies.




     All studies reported in the literature on the toxicity of  the optical




brighteners toward humans and  the lower animals- gave negative results.   The

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studies on animal reporduction, including teratogenicity and mutagenicity




studies, also gave negative results.




     One specious report of the carcinogenic interaction of the optical




brighteners and ultraviolet light appeared in the recent literature and




reported positive results.  However, this work has been highly criticized




because it was conducted under unrealistic conditions and thus had no




practical value.  The authors of this report have conceded to their critics




and have announced that further work is in progress.  All other studies




on carcinogenesis have reported negative results.




     In summary, it would seem that introduction into environmental waters




would be the most probable source of pollution by the optical brightening




agents.  There are no data in the literature reporting on the fat-solubility




of any brightener molecules.  This property would have bearing on bioaccu-




mulation.  While these compounds may be chemically inert in vitro, no




conclusions can be drawn from the information in the literature as to what




biological activity they might exhibit if they gained entrance into human




systems to any extent.

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                       Optical Brighteners






1.  PROPERTIES AtiD USES




     The literature abounds with synonyms alluding to the properties of




the optical brighteners:  optical whiteners, fluorescent white dyes, or-




ganic fluorescent dyes, fluorescent whitening agents, fluorescent brighten-




ers, and optical bleaching agents.  Optical brighteners, however, are in




no way comparable with bleaching agents; their only common property is




the improvement of the whiteness of the substrate; even in this they




differ in the means by which the desired effect is attained.




     In all other properties the optical brighteners are closely related




to dyes.  They are dyes, in fact, in the sense that they change the visual




appearance of the substrate to which they adhere, although they differ




from dyes in the way that the desired effect is produced.  A dye molecule




absorbs visible light and reflects the unabsorbed portion.  A fluorescent




molecule absorbs invisible ultraviolet light and emits visible blue




fluorescent light.  It is this property that lends special status to the




optical brighteners.




     A variety of theories have been developed to explain dye-fiber inter-




action.  These same theories serve to explain brightener-fiber interac-




tion.  The main theories pertaining to brightening cellulose are the theor-




ies of direct dye mechanisms:




(1).  Hydrogen Bonding.  The brightener molecule must be capable of




forming hydrogen bonds.  It should be linear, should have aromatic nuclei




capable of coplanar configuration, and should cont.ain conjugated double




bonds.

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(2).  Van der Waal's Forces.   The brightener molecule should be planar to




allow the closest possible contact with the fiber.  The attraction is by




interaction of dipoles, between nonionic portions of the molecules.  The




attractive forces depend on the size and the mobility of the electron




clouds.  Substantivity increases with the number of conjugated double




bonds.




(3).  Aggregation Theory.  The brightener molecule must be planar to penetrate




the cellulose and enhance aggregation.  The molecules pass singly into




the fiber and then aggregate after losing their water of hydration.  Van




der Waal's forces between the dye molecules increase in strength with




increasing numbers of double bonds (Stensby, 1967).




     The main theories pertaining to brightening synthetic fibers, such




as nylon, polyester, and acetate, are the theories of dispersed dye mechan-




isms:  (1).  The solid brightener dissolves into the solid fiber, or:




(2).  The brightener molecules penetrate into "canals" between the fiber




molecules, or:




(3).  The water-insoluble brighteners may be soluble to a small extent.




The small amount of dissolved brightener, then, would be adsorbed by the




fiber, permitting more brightener to dissolve until equilibrium is reached




(Stensby, 1968).




     Further discussion on brightener-fiber interaction is given in Sec-




tion VII, CHEMICAL REACTIVITY.




     Raw textiles, papers, and plastics have a yellow tint attributable




not only to the wavelength of light which they naturally absorb, but also




to the colored impurities associated with the raw goods.  It is well known




that materials with a yellow cast can be made to look whiter by adding a blue

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tint, as evidenced by the success of the laundering "bluing agents" which




fluorished until recently.  Optical brighteners correct any off-white




appearance by reason of the blue-to-violet fluorescence which they exhi-




bit under ultraviolet light as it is present in ordinary daylight.




     To qualify as an additive in laundry products, a brightener must




be stable to heat, water, and bleaching agents (Figs. 1, 2, and 3).




     For use in the textile industry, a brightener'must be light-fast and




possess certain properties of fiber affinity (Figs. 4, 5, and 6).




     In the plastics industry, the main areas of brightener application




today are in PVC films, boards,  injection mouldings, and plastisols; poly-




styrene boards and injection mouldings; polypropylene films and injection




mouldings; polyethylene paper coatings, polyurethane coatings, thermo-




setting pressings and resins (Fig. 7).




     Following are the basic chemical structures of some optical brighten-




ers with the most important fields of application of their derivatives, as




given in Review 1973/1, by Ciba-Geigy.

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Fields of application
and substrates
Textiles, detergents
spinning solutions/
melts, plastics
polyamide (T, W)
polyester (T, W, S)
polyvinylchloride (K)
polystyrene (K)
polypropylene (K)
secondary acetate (T. S)
triacetate (T, S)
Textiles, detergents
spinning
solutions/melts
cotton (W)
polyamide (W)
polyacrylonitrile (T, S)
Textiles, detergents
spinning solutions/
melts, plastics
polyamide (T, W)
polyester (S)
polyacrylonitrile (T)
polyvinylchloride (K)
polystyrene (K)
silk (T)
secondary acetate (T)
triacetate (T)
Textiles, detergents
! wool (T)
silk (T)
triacetate (T)
secondary acetate (T)
polyacrylonitrile (T)
polyamide (T, W)
Textiles
polyester (T)
polyacrylonitrile (T)
secondary acetate (T)
triacetate (T)
Textiles
polyester (T)
secondary acetate (T)
triacetate (T)
Textiles, detergents
polyamide (T, W)
polyester (T, W)
General basic structures
R R
R R
bis- (benzoxazol-2-yl) -derivatives
£^x_£r^
R2 R,
bis- (benzimidazol-2-yl) -derivatives
i1
Coumarins
R5
"3 "4
pyrazolins
o >r~\
RK1 \i .— /
1 / \
naphthalimides
OR
^^^ OR
triazinyl-pyrenes
1 U
• 1 H ^
2-styryl-benzoxazoles and naphthoxazoles
Subsmuetiut
ii H
W
H H
1 1 f~\.
— c=c— — c=c-< y-
i i \— /
H H
CM,
-R--H.-C(CH,)»— C-/ N .— CH,
CH,
-COOsIM
~ — *L. / — . — c=c —
H
_R = _H, -CH,. -CH2CH2OH
-R, -.-H.-CH,.-CH1COOH
-R,.-H.-/^.-|T~J ^-COOCH,
-M' ^T J| -,O*»»«. -N (*»*),.- "-CO-CM
-R, =-H,-CI.-N: *— *
_R3,_R4__H, -alkyl. -^^
-R2 = -CI.-SO3H,-SO2NH2,-H
-SO2NH-. -COO alkyl
-S02CH^
-SO2 NH CH2 CH2 CH2 N (CH,),
R— U f*t
5 	 H. - U
RI ~ alkyl CH2CH2CH2N(CH,),
-R2 = - O alkyl, - SO3H. - NH CQCH3
R - alkyl

-R, = -CN, -COO alkyl. -Cl
- R4 = -H, -alkyl.— /^N
Fiel«te of application. Textiles (T). Detergents (W), Paper (P), Spinning Solutions/melts (S), Plastics (K)

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        Textiles, detergents
        paper, spinning
        solutions/melts
        cotton (T, W)
        polyamide (T. W, S)
        cellulose (T. W. P. S)
                SOjH  "                   R4

4.4' -bis- (triazinylamino)-stilbene-2,2'-disulfonic acids
                                                                                                           SO3H
                                                                                      -N(CH2CH2OH)2. -NCH2CH2OH. -NH2
                                                                                      -N(alkyl)2,-OCH3.-Cr

                                                                                      -N-CH2CH2S03H,-NHCH2CH2OH

                                                                                      H
        Textiles, detergents
                     H03S
        cotton (T, W)
        polyamide (T, W)
                              4,4'-bis-(v-triazpl-2-yl)-stilbene-2,2'-disulfonic acids
       Spinning
       solutions/melts
       polyester (S)
                                                                                     _R = -H,-OCH3,-aikyl
                                       4,4'-bis-(diphenyltriazinyl)-stilbenes
       Textiles, detergents
       paper
       spinning solutions/
       melts, plastics
       cotton (T, W)
       cellulose (T, W, P)
       polyamide (T, W, S)
       polyester (T, S)
       polyvinylchloride (K)
       polystyrene (K)
       polyurethane (K)
               H

4.4' - distyryl - biphenyls
                                                        -R = -H,-SO3H.-SO2N(3lkyl)2
                                                            -OCH3. -CN, -C(, -COQCHj

                                                            -6oN(alkyi)2
       Textiles, spinning
       solutions/melts
       polyester (T)
       polyamide (S)
                    H

                C=C

                H

4-phenyl-4'-benzoxazolyl-stilbenes
                                                                                     -R =-H,-GI.-alkyl,-SO2CH3
       Textiles, detergents
       spinning solutions/
       melts, plastics
       cotton (W)
       polyamide (W)
       polyacrylonitrile (S)
       oolyester (T, W, S)
       polyvinylchloride (K)
       polystyrene (K)
                                                        -R, =_H,-CI

                                                        -R2 =-SO3H,-SO2NC,-SO2OC6HS

                                                             -CN

                                                        -R3 = -H,-SO3H
stilbenyl - naphthotriazoles
       Textiles, spinning
       solutions/melts
       polyester (T)
       polyamide (S)
                                                                                     -R = -CN,-CONc
                              4-styryl-stilbenes
Fields of application Textiles ^T). Detergents (W), Paper (P), Spinning Solutions/melts (S). Plastics (K)
                                                   8

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                    Fig. 1.   OPTICAL BRIGHTENERS  (FLUORESCENT WHITENING AGENTS)  IN DETERGENTS
                    FLUORESCENT BRIGHTENER 9
"v
  NH
                                                                            CH = CH
                                                                       SOjNa
                       SOjNa
                                                                                               NH
                    FLUORESCENT  BRIGHTENER 28
E
                                                                CH,
                                                                                               N^     J?
                                                                                          NH-fT ~^t-NH —('
            SO,H
                                                                                   SO,H
                                                             i   CHJ


                                                            II

                                                            OH   OH
                                                                                                 OH
                                                                  NH-C'   ^VCHsaCH-C'   ^>-NH-j^ "^St- NH •











                                                             ,,   CH,                           ^C  CH,




                                                            H,





                                                                                             OH

                                                          HjC
                                                             \ x'
                                                              O
            SO,Na
                                                                                   SOjNa
                                                                                          NH—^*|—NH-
                   SOURCE:   Stensby, 1965
                                                  SOjNa
CH,  CH,



CH,  CH,



OH  OH
                                  CH,  CH,

                                  r  i
                                  CH,  CH,

                                  OH  OH

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                             Fig. 2.   COTTON BRIGHTENERS
                                       i
                     R=
     "•       r01'     r-   MO- or

          " '  r     i '  f' '  MOR'NH
             M     Oil  M


TA     DM    DMEA  DDEA   MEO
                          Fig. 3.  BLEACH STABLE BRIGHTENERS
                       BRIGHTENER BS      BRI6HTENER NTS
                                    f
                                  BRIGHTENER BBI
SOURCE:   Stensby,  1967 a
                                         10

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                  Fig. 4.  POLYAMIDE BRIGHTENERS
                    R'
                              7
                   BRI6HTENER  AC    BRI6HTENER  DP
           Fig. 5.  POLYESTER AND POLYAMIDE BRIGHTENERS
                                                  \
                                                  ,C-CH=CH-R
BRIGHTENER  BBO
                                           BRI6HTENER BOS
                                       N — N
                            BRIGHTENER  NTSA
        Fig. 6.
                    The most important properties
                    of some polyester whiteners
                    in relation to their chemical
                    structure.
X
.0-
-o
naphthyl
naphthyl
stilbyl
stilbyl
R
-C(CH3)3
-E©
-H
-COOR
-H
-COOC4H9
Thermal
stability
good
good
poor
good
poor
good
Glycol
vapour
volatil-
ity
high
moder-
ate
high
none
moder-
ate
none
Subli-
mation
high
none
high
none
moder-
ate
none
Shade
greenish
greenish
bluish
bluish-
green
bluish
bluish
SOURCES:  Figs.  4 and 5 - Stensby, 1967a

          Fig.  6 - Review,  1973/1
                                  11

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Fig. .7.   PROPERTIES  OF VARIOUS  OPTICAL BRIGHTENERS FOR USE IN PLASTICS
Structure
@CC
f^Wl
Fields
of
applica-
tion
PVC. PS.
PP. PE
PVC, PS,
PP. PE
PVC, PS,
PS
PVC, PS,
PP, PE
Migra-
tion
stability
very
good
very
good
good
moder-
ate
Light
fastness
good
good
moder-
are
good
White
build-
up
good
very
good
very
good
moder-
ate ;
SOURCE:  Review. 1973/1
                               12

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     The optical brighteners are very versatile chemical compounds; most
of them have more than one major application, as is shown in the
tables and figures  in the appendix.
     There is a lack of sufficient data in the literature to establish
which of the brighteners are most commonly used (the U. S. Tariff Commission
does not publish individual production figures for the brighteners).  Figures
1 through 7 are indicative of the major volume compounds; however, these
are all based on data from Ciba-Geigy Corp.  The amount of information
which is published on an individual brightener (compiled in the tables
given in the appendix) may be indicative of its competitive status.

     According to Chemical Economics Handbook, the following figures are
1965
1966
1967
1968
1969
: percent of
Detergents
63.6%
67.6
73.3
73.0
72.6
sales value
Paper
13.0%
9.8
7.7
7.8
8.2
by application:
Textiles
18 . 3%
16.0
13.0
13.1
12.8
Fibers/Plastics
  .   5.1%
     6.6
     6.0
     6.1
     6.4
     These figures indicate that, in 1969, approximately 29,000,000 pounds
of the brighteners produced in the United States went into detergents;
3,000,000 pounds went into paper; 4,000,000 pounds went into textiles;
and 2,000,000 pounds went into synthetic fibers and plastics.
     Sandoz, Inc. (Technical Bulletin I-C-2009 No. 5) recommends its
Aclarat 8678 as a shampoo additive—0.01% to brighten hair and 0.05% to
whiten off-white hair.  This is the only direct reference to cosmetic appli-
cation found in the literature.  Since no C. I. -Fluorescent Brightener num-
                                  13-

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her was found for this product, its properties are listed under the trade




name at the end of the appendix.   .,






III.  PRODUCTION AND IMPORTATION                  .




     While dye production gained by 8.0% in 1972 over 1971, the production




of optical brighteners fell by 8.4%.  Of the total 1972 production of all




compounds classified as dyes, the optical brighteners accounted for 10.4%.




     The United States' manufacturers of brighteners  as reported to the




U. S. Tariff Commission in 1972, are:  American Cyanamid Co.; Ciba- Geigy




Corp.; Cincinnati Malacron Chemicals, Inc.; E. I. duPont de Nemours and




Co., Inc.; GAF Corp. (Chemical Div.); Pfister Chemical Works; Sandoz, Inc.




(Sandoz Color and Chemicals Div.); Hilton-Davis Division of Sterling Drug




Co., Inc.; and Verona Corp.




     Production figures are as follows, in pounds, as published by the




U. S. Tariff Commission:






YEAR      SPECIFIC FLUORESCENT BRIGHTENERS  .    ALL OTHERS         TOTAL
1958
1959
1960
1961
1962
1963
1964
1965

1966
1967

1968



F.
F.
F.


B.
B.
B.


68
68
68
Fluorescent
F.
F.
F.
F.
F.
F.
F.
F.
B.
B.
B.
B.
B.
B.
B.
B.
68
9
28
28
9
28
9
28


63
72
100


,000
,000
,000


7,
9,
11,


429
684
746


,000
,000
,000
Brighteners are included under "ALL
31
3,749
1,515
1,240
318
1
234
1,420
,000
,000
,000
,000
,000
,410
,000
,000
16,

14,
2.1.

25,

29,
644

156
972

894

643
,000

,000
,000

,000

,000
5
7
7
9
11
OTHER
16

19
23

26

30
,900,
,000,
,492,
,756,
,846,
DYES
,675,

,420,
,212,

,213,

,297,
000
000
000
000
000
it
000

000
000

410

000

-------
254,000
1,676,000
1,593,000
1,574,000
1,604,000

37,844,000
29,731,000
28,238,000
25,717,000

39,774,000
31,324,000
29,812,000
27,321,000
YEAR      SPECIFIC FLUORESCENT BRIGHTENERS      ALL OTHERS          TOTAL
1969      F. B.  9
          F. B. 28
1970      F. B. 28
1971      F. B. 28
1972      F. B. 28

     Although the production of optical brighteners in the  United States
has declined somewhat, this cannot be taken as an indication of the pre-
valence of these agents without reference to import statistics.  Import
figures for 1972 (in pounds) are listed below.  This information was
taken from the U. S. Tariff Commission Reports.
OPTICAL BRIGHTENER     AMOUNT IMPORTED      OPTICAL BRIGHTENER   AMOUNT IMPORTED
     F. B.  28             4,180            Ecophan                 240,302
     F. B.  32             5,181            Fluorescent Red 5B          110
     F. B.  47            33,951            Hostalux NR              26,978
     F. B.  48             5,570            Hostalux PR               1,980
     F. B.  52             3,527            Leucophor PC             16,534
    J*. B.  55               220            Phorwite BHC            167,090
     F. B.  75             1,200            Phorwite DCR              5,885
     F. B. 103               220            Phorwite K                   50
     F. B. 112               250            Phorwite MAN   .             100
     F. B. 119           125,040            Tinopal CH-3511           1,875
     F. B. 121            79,210            Tinopal MSP                 220
     F. B. 134            25,792            Tinopal SFG               7,883
     F. B. 140               441            Tinopal 3751                112
     F. B. 148             5,250            Tuyacol 61F              11,023
     F. B. 184               551            Uvitex AT                 2,006
     F. B. 191            77,975            Uvitex CK                22,484
     F. B. 200            46,250            Uvitex EFT                  496
     F. B. 205           490,665            Uvitex MA                 1,058
     F. B. 229            77,160            Uvitex MES          .      2,249
     F. B. 238             1,587            Uvitex NFW             .220

                               15              ••   '

-------
OPTICAL BRIGHTENER     AMOUNT IMPORTED      OPTICAL BRIGHTENER  AMOUNT  IMPORTED
     F. B. 251               220            Uvltex 3257             332,782
     F. B. 254             1,102            Uvitex 5660               1,433
     F. B. 257             1,050            Other optical
     F. B. 265               450               brighteners            3,747
                                            TOTAL                 1,833,659

 IV.  CURRENT PRACTICE
     There seem to be no particular problems in the storage,  transport,
or handling of the optical brighteners.
     The Hilton-Davis Division of Sterling Drug Co. advises that if Hilta-
mine Arctic White products come into contact with the skin, it should be
rinsed thoroughly with water.  Precautions should be taken against entry
of these products into the eyes or respiratory tract.  By following these
precautions, the fluorescent whitening agents should offer no health
hazards in industrial handling (Hilton-Davis Technical Bulletin B-17-4/73).
Data on these Hiltamines can be found in the tables   in the  appendix
tinder C. I. Fluorescent Brighteners 9.1, 28, 126, 127, 128, 129,
130, 130:1, 131, and 132.  Those Hiltamines with which no Fluorescent
Brightener number was correlated are listed separately at the end of the
tables.
     American Cyanamid Co. (Technical Sales Bulletin 1056.) states that
all shipments of Calcofluor White RW Solution bear the following warning
label:
     CAUTION!  May Cause Irritation.
               Avoid contact with skin or eyes.
               In case of contact, flush skin or eyes with plenty of water.
     Further data on Calcofluor White RW can be found in the tables under
C. I. Fluorescent Brightener 61.

                                   \6

-------
     No other directives for special handling of the optical brighteners




was found in the literature.






V.  ENVIRONMENTAL CONTAMINATION




     The wide range of applications of the optical brighteners would make




environmental contamination a distinct possibility.




     Their incorporation into laundry products would suggest a transport




route into surface and ground waters.  During industrial production or




application, brighteners may get into the effluent.  Ciba-Geigy reports




(Review, 1973/1) that the amounts measured in domestic effluent in densely




populated areas vary between about 0.01 and 0.1 ppm (Stensby, 1968, states




that the total concentration of birghtener in the liquor of the modern




American home laundry would be only 3-10 mg/liter).  Efficient purifica-




tion plants retain more than 90% of the brighteners from industrial ef-




fluents.  In very badly polluted rivers with few adjacent purification




plants, doses can be of the order of 0.000001 grams per liter, while no




demonstrable amounts can be found in rivers with sufficient purification




plants.




     Skin contact is inevitable, largely from wearing textiles that have




been treated with these agents.  According to Ciba-Geigy Corp. (Review,




1973/1), the high affinity for natural fibers and firm fixation in synthetic




fibers do not permit the transfer of measurable amounts of FWA to the skin.




The same holds true for plastics and paper which contain amounts of brigh-




tener similar to the amounts contained in textiles (0.05% and 0.15% of ...




optical brightener).                                .




     Transference into food from brightener-treated containers and wrapping




paper may lead to unintended ingestion.  Low levels of brighteners persisting
                                   17

-------
in potable water would be another source of unintended ingestion.   If  some
amount of brightener were ingested from these sources, the amount would be
10,000 times smaller than the amounts tolerated in long-term animal experi-
ments without toxic effects (Ciba-Geigy, Review. 1973/1).

VI.  MONITORING AND ANALYSIS
     A comprehensive presentation of the analysis of optical brighteners
is given by Kiger and Bbn (1960).  The following brighteners were  studied
in this work:
TRADE NAME
 Tinopal AN
 Tinopal 2B
 Tinopal BV
 Tinopal 4BM
 Tinopal GS
 Tinopal RBN
*Tinopal SP
*Uvitex BT
 Uvitex GS
 Uvitex RBS
 Uvitex RS
 Uvitex RT
 Uvitex VR
 Celumyl BW
FLUORESCENT BRIGHTENER
       '   55' •"••'."
          24
           1
          28
          47
          59
          18
       ;..  19
          42

          41
          37
         142
    TRADENAME
Celumyl R
Celumyl S
Blankophor BA
Blankophor BBV
Leucophor B
Leucophor 2B
Leucophor BS
Leucophor R
Leucophor RG
Fluotex CBL
Fluotex CDC
Blankit 1A
*Ultraphor GPB
Pontamine White G
FLUORESCENT BRIGHTENER

        17
       113
       114
        32

        49
        30
        14
        21


       114
*These brighteners are not being currently manufactured.

     The most suitable solvent for these brighteners was a mixture of 95
parts of pyridine to 5 parts of ammonium hydroxide.  To extract the brigh-
teners from cotton fabric for assay, 2 gm of fabric (approximately 10 x 10
cm) was placed in a 100 ml flask with 30 ml of a 5% solution of ammonium
                                   18

-------
hydroxide in pyridine and was shaken for two hours.  The extract was con-:




centrated to 3-5 ml on a water bath.




     Detection methods are summarized as follows:




Circular Paper Chromatography;  Results were obtained within two hours,




but were not satisfactory enough to merit further study.  No migration




took place with dichloroethane, cyclohexanone, ethyl acetylacetate or




methylcyclohexanone.  Spots were displayed with butyl acetate and isobutanol.




Migration was quite variable with neutral or acidic acetone, with neutral




or acidic acetone, methanol, with propanol, and with dimethylformamide.




Column Chromatography:  A 5 mm alumina column was used and development took




place in approximately two hours per ml of solution.  The differences in




the fluorescence of the chromatograms were too weak to allow definite




identification of the-brighteners.




Ascending Paper^ Chromatography;  The brighteners in a pyridine-ammonia




solution were run in a mixture of butanol, acetic acid, and water in the




ratio of 80:20:100.  It was possible to classify a certain number of groups ;




from the chromatograms, but individual brighteners within the groups could




not be identified because of identical migrations.  The author gives a




tabulation of the Rf values obtained in this study.




Electrophoresis;  Microelectrophoresis under high voltage was applied




for five hours.  An exact pH of 8.6 was attained by using the following




mixture:  29.428 g of sodium veronal, 19.428 g of sodium acetate, 180 ml




of 0.1 N hydrochloric acid, and 3 L of distilled water.  The author gives




a tabulation of the Rf values obtained in this study,  both of the pure




products and of the products extracted from fabric.




Spot Fluorescence on Textiles:  One drop of a mixture of 10% sulfuric
                                  19

-------
acid, 4% sodium hydroxide, sodium hypochlorite, and hydrogen peroxide




was applied to samples of fabric and of paper which had been treated




with brighteners:  The results obtained from the fabric samples differed




from those of the paper samples.  The brighteners could be differentia-




ted by groups.  All results are' tabulated by the author.




     O'Hare (1966) gives a simple test method which is accurate to ±5%,




in which anionic brighteners are titrated with cationic Methylene Blue




G to give a water-insoluble complex which does not fluoresce.  The end-




point is observed under ultraviolet light.




     Spectrophotometric analysis of optical brighteners is described




by Weeks, Harris, and Lewis (1959).




     A 0.2500 g sample of brightener was transferred to a foil-wrapped




Erlenmeyer flask and the weighing pan was washed with 200 ml of absolute




methanol.  One ml of 40% aqueous sodium hydroxide was added to aid dis-




solution.  The mixture was heated at 55-60°C for several minutes, after




which it was transferred to a 1000 ml flask.  The Erlenmeyer flask was




rinsed with 200 ml of -water and then by 200 ml of methanol.  The flask con-




tents were diluted to 1000 ml with 67% aqueous methanol.  The resulting




solution contained 0.0250% brightener and was used as the stock solution.




     It is important that non-ionic, actinic glassware be used throughout,




and that the solution be absolutely protected from any ultraviolet radia-




tion.



     Test solutions were prepared by diluting 5, 10, 15, 20, and 25 ml




aliquots of the stock solution with 67% aqueous methanol to the mark in




250 ml actinic volumetric flasks to yield brightener concentrations of




0.0005%, 0.0010%, 0.0015%, 0.0020%, and 0.0025%.
                                  20

-------
     A Cary spectrophotometer was calibrated to zero absorbancy over




the range of 300 mu to 400 mu with 67% aqueous methanol in both the




blank cells and test cells.  It was operated at 0.6 mu per second.  The




ultraviolet absorption spectra were determined for the brightener test




solutions at 0.0010% concentration.




     Once the absorbancy characteristics of a brightener were known, the




other solution concentrations were analyzed at the wavelength providing




maximum absorbency.  After a concentration vs. maximum absorbancy curve




is made for a standard of reference brightener, it is then possible to




analyze other samples of the same type for relative purity.




     Some idea of the brightener present in an unknown detergent composi-




tion may be gained by:  1) Determination of stability of the brightener




to hypochlorite bleach; 2) Washing a spectrum of fibers to determine af-




finity characteristics of a brightener; and 3) Fluorescence spectrum of




the washed fabric.




     Functional properties of brighteners are suggested as a means to




characterize them.  It should be possible to identify unknown brighteners




by comparing their functional properties with those for knowns.




     Colorimetry in the visible range is described by Taylor (1955), using




a Spekker fluorimeter (Hilger and Watts).  This work is limited to com-




parative strength determination of chemically identical samples.  The




following brighteners were studied:




TRADE NAMES   FLUORESCENT BRIGHTENER   TRADE NAMES   FLUORESCENT BRIGHTENER
Uvitex RS
Uvitex GS
Uvitex RBS
Uvites RT
*Uvitex W
41
42
—
37
57
Uvitex WGS
Uvitex RSW
*Uvitex NA
Uvitex WS

61
: —
58
—

       *These brighteners are not being currently manufactured.





                                  21

-------
     Transmission vs. concentration values and reflectance vs. concentra-

tion values were obtained and used as standard curves.  Ethyl alcohol or

Cellusolve were the preferred solvents.

     Taylor states that no attempt should be made to obtain even a rough

comparison of the fluorescence of brightening agents which are not chemi-

cally similar, in water or in any other solvent.  Also, the fluorescence

of a product in solution gives no reliable indication of its fluorescence

when adsorbed on the substrate for which it is intended.
                                                 i                 .
     A major difficulty encountered in the fluorimetry of brighteners

in solution is the appreciably differing absorptions for ultraviolet

radiation between the cis and trans isomers of the stilbene series.

In certain cases, no steady state of equilibrium was attained and the

test had to be abandoned.



VII.  CHEMICAL REACTIVITY

     It is physical fluorescence and not chemical reactivity that is the

primary characteristic of an optical brightener.  In fact, a highly reac-

tive molecule would be disqualified as a brightener, as it must remain

stable to the rigorous conditions to which it is submitted during appli-

cation and use.

     A brightener must have certain structural features:  a series of con-

jugated double bonds to give it fluorescence; one or more solubilizing

groups (such as sulfonic acid groups); NHCO groups, or sufficiently

high molecular weight, to have affinity for the fiber  (Adams, 1954).

     Brightener-fiber interactions are discussed briefly in Section I,

PROPERTIES AND USES, and are discussed here in greater detail.

     Cellulosic fibers absorb water and swell when in  contact with water.
                                  22.

-------
Brightener molecules are then admitted to the fibers and pass through




water-filled channels by diffusion.  These brightener molecules may




interact with the fiber by either of two bonding mechanisms:




(a) A brightener molecule which is capable of forming a hydrogen bond




with the substrate will do so.  A hydrogen bond is formed when a hydrogen




atom on one molecule forms an addition bond to an electronegative atom on




another molecule, thereby creating an attractive force which holds these




interacting molecules together.  The energies of hydrogen bonds are




5 kcal/mole, well below normal bond energies, and too weak to be con-




sidered as true chemical bonds.




(b) Van der Waal's forces result in a weak attractive force between




the brightener molecules and the fibrous substrate, by dipole moment in-




teraction.  Although these forces are electrical in nature, their bonding




energies are far less than the energies of hydrogen bonds, and so are




too weak to be considered as true chemical bonds.




     Van der Waal's forces are the principal forces which bind dispersed




brightener molecules to hydrophobic synthetic fibers, such as nylon,




polyester,--and acetate.  The dispersed dyestuff .particles are relatively




small in size, have low solubility, and are neutral in character.  These




particles may either dissolve into the solid fiber, penetrate the fiber




between the fiber, molecules, or simply deposit onto the fiber.  Van der




Waal's forces then establish the attraction between the fiber and the




brightener molecules.




     Individual optical brighteners exhibit different fastness properties




and different stabilities, depending on individual chemical constitutions.




and the reactive strength of other chemicals present•during application
                                  23

-------
and use.  The fastness and stability characteristics of the individual




brighteners are given in the tables in the appendix.




     For application in the textile industry, the brighteners, after




incorporation into the fibers, must have fastness, to light; must with-




stand frequent washings in detergents or dry-cleaning; must be inert to




atmospheric gases; and must remain fast to ironing, perspiration, deo-




dorants, and friction in use (Stensby, 1967).




     To be suitable as a detergent additive, a brightener must be stable




to severe processing conditions in a strongly alkali medium at high tem-




peratures.  It must remain stable during storage of the product, re-




main stable in solution, and be inert to bleach and to other detergent




additives (Stensby, 1968; Siegrist, 1955).




     The optical brighteners selected for use in the paper industry




must be compatible with the chemicals used in paper making, including




chlorite bleach.  They must have good storage stability arid affinity




for pulps and fillers, and they should have good tolerance to sizes,




bonding agents, wet strength resins, and retention agents.  They must be




fast to alum, alkalies, and acids, and must be insensitive to hard




water (Review, 1973/1).




     Whiteners for incorporation into polymers have great demands made




on their thermal and chemical behavior during addition at the polyester




or polymerization stage with polyamide.  The whiteners must be so stable




thermally that they withstand the high temperatures necessary for polymer-




ization or polycondensation, without any noticeable degradation.  They must




not be volatile, nor must they sublime from the melt in a vacuum (Review,




1973/1).
                                   2U.

-------
     Those brighteners which are incorporated into pigmented coatings




must have outdoor durability and thermal stability.






VIII.  BIOLOGY




     A.  ABSORPTION




     Experiments with three strains of bacteria, three strains of fungi,




and three strains of yeast show that some optical brighteners are absorbed




by microorganisms and transported to new cells.  Specific names for the




brighteners tested are not given, except for 4,4'-bis[4-anilino-6-bis(2-




hydroxyethyl)amino-s-triazin-2-ylamino]-2,2'-stilbenedisulfonic acid




(Darken, 1962).  Complete data on this brightener is compiled




in  the tables  in the  appendix, under  C.  I. Fluorescent  Brightener  28.








     In those investigations during which brighteners were topically




applied to skin and mucous membrane, no toxic effects were noted.  Snyder




(1963) applied stilbene disulfonates and other common brighteners used




in detergents to the skin of mice, rats, guinea pigs, and rabbits over




a two-year period without any development of toxic symptoms from absorp-




tion.  Alexander (1964) recommends further study on the possibility of




incorporating brighteners into cosmetics, since his review of the liter-




ature indicated no toxicity from topical application.  The only direct




reference to brighteners which are actually recommended for cosmetic use




is published in Sandoz, Inc.  Technical Bulletin I-C-2009 No. 5.  Aclarat




8678 is recommended for use as a shampoo additive.  Other information on




this brightener is listed under the trade name at the end of the tables




in the appendix.                             ,




     The stilbene character of most optical brighteners might have an

-------
estrogenic effect after accumulation and resorption through the skin.




Brighteners were injected subcutaneously in doses of,100-600 mg/kg into




rats, and for three weeks brighteners were applied to the skin.  The




conclusion was drawn that the stilbenedisulfonic brighteners do not




resorb, as evidenced by a lack of estrogenic effect.  In this same ex-




periment a 1% solution of Blankophor brighteners was applied to the skin




of post-menopausal women for a period of three weeks.  No stilbene




groups were found in the urine, and Papanicolaou smears indicated no




estrogenic activity (Schneider, 1955).  Schneider does not indicate




which specific brighteners were used in this study.




     B.  EXCRETION/ELIMINATION




     Diaminostilbenedisulfonic acid derivatives of the Blankophor series




were administered intraperitoneally to cats in doses of 50 mg/kg.  The




largest amount of brightener was initially excreted in the urine, with




subsequent smaller amounts being detected over a period of time until




the total amount of brightener had been eliminated.  After an oral ad-




ministration of the same dosage, brightener could be detected for 2 days




in the urine of the cats by qualitative fluorescence, but could not be




determined quantitatively (Gloxhuber, 1962).




     A common brightener, 4-methyl-7-diethylaminocoumarin, was given




orally and intravenously to rabbits, after which the route of elimina-




tion was determined to be in the bile and in the urine.  (Gouaze, 1963).




Other data on this brightener are listed at the end of the tables in



the appendix, under the trade name Advabrite MDAC.




     C.  TRANSPORT AND DISTRIBUTION




     The tissue affinity of one hundred forty-eight optical brighteners
                                  26

-------
for the tissues of lower animals was studied by Gbuaze (1963).   Soluble




compounds were administered both intravenously and orally while insoluble




compounds were administered only orally to mice, rats, rabbits, and dogs.




     The di-sodium salt of (2-oxo-4-imidazoline-4,5-diyl)dibenzenesul-




fonic acid, a non-toxic, soluble compound, had no affinity for the spleen




or nervous system.  It gave a general fluorescence to the skin, mucosa,




intestinal tract and muscles.




     4,4'-Bis[4-anilino-6-(bis(2-hydroxyethyl)amino-s-triazin-2-yl)ami-




no]-2,2'-stilbenedisulfonic acid, anon-toxic, soluble compound, gave




general fluorescence to the skin, mucosa, intestinal tract and muscles.




It showed affinity for the spleen, fatty tissue, nervous system, pan-




creas, and glandular system.  Complete data on this compound are listed




in the tables in the appendix under C.  I. Fluorescent Brightener 28.




    7-(Diethylamino)-^-methylcoumarin,  a soluble compound having




a slight toxicity, had an affinity for the nervous system.  Other data




on this compound are listed in the tables at the end of the appendix, under




Advabrite MDAC.




     l~[p~[(2-Hydroxypropyl)sulfonyl]phenyl]-3-phenyl-2-pyrazoline also




had an affinity for the nervous system.




     Derivatives of diaminostilbenetriazine had an affinity for the spleen




and for the nervous system.




     Derivatives of bis-benzoxazole had an affinity for the pancreas,




salivary glands, thyroid, adrenals, pituitary, ovaries, and testes.




     Gouaze (1963) administered 7-(diethylamino)-4-methylcoumarin and




several pyrazole derivatives, such as l-[p-[(2-hydroxypropyl)sulfonyl[phe-




nyl]-3-phenyl-2-pyrazoline, to rabbits, both orally and intravenously.
                                  27

-------
He found that these compounds were taken up by the brain and nervous




system.




     The distribution of 7-hydroxy-4-methylcoumarin was investigated in




the rats.  Male Sprague-Dawley JCL strain rats, weighing 200 to 250 g,




were given 50 mg of methylhydroxycoumarin (1% suspension in 0.5% carboxy-




methylcellulose solution) per kg of body weight, by means of a stomach




tube.




     The cumulative amounts of free methylhydroxycoumarin recovered from




urine after 24, 48, and 72 hours were 2.96%, 3.04%, and 3.12%, respectively,
                                                 I
                                                • *


of the administered dose.




     Following are the tissue and plasma concentrations of total (con-




jugated + free) and free methylhydroxycoumarin in the rat.  A vertical




line indicates a standard error..          .
Source:  Tomura,  1971



     The distribution of free methylhydroxycoumarin was markedly different




from that  of  total methylhydroxycoumarin.   The  level of the  free form in




                                  28

-------
the brain was not statistically different from those in cardiac muscle,




lung, and skeletal muscle and was 20% to 30% of that in the plasma.




The free form of the drug was predominant in the brain.




     D.  METABOLISM AND METABOLIC EFFECTS




     The di-sodium salt of diaminostilbenedisulfonic acid inhibited the




respiration of rabbit liver homogenate 41.0% at 1.5 X 10~6 M and 62.2%




at 1.5 X 10~5 M.  Subcutaneous injection of 200 mg/kg of the di--sodium




salt of 4,4'-bis(l,3,5-triazin-6-ylamino)stilbene-2,2'-disulfonic acid




into rabbits increased urinary excretion of lactic and pyruvic acids




but did not affect excretion of citric acid (Ukita, 1960).




     The major metabolic pathway for 7-hydroxy-4-methylcoumarin is as a




sulfate conjugation (Tomura, 1971).  This was demonstrated by sulfatase




hydrolysis of the conjugated form in plasma, diluted urine, or in 10%




water homogenate of tissue after a 50 mg oral administration of methyl-




hydroxycoumarin to rats.  The free compound was determined in the




urine at levels of 2.96%, 3.04%, and 3.12% of the administered dose.




After the sulfatase hydrolysis these values increased to 85.7%, 87.0%,




and 94.6%.




     The free form of the compound was predominant in the brain, demon-




strating that free methylhydroxycoumarin, which is low in liposolubility,




penetrates through the blood brain barrier very easily.  Its lipid in-




soluble metabolite, the conjugated form, does not gain access to the brain.






IX.  ENVIRONMENTAL TRANSPORT AND FATE




     A.  PERSISTENCE AND/OR DEGRADATION




     From the information gathered on the chemical properties of molecules




which qualify them for use as optical brighteners, it would seem that -
                                  29

-------
they would persist in the environment.  Their inertness to the various




other chemicals with which they come into contact during application,




and their stability under the severe conditions to which they are sub-




jected during processing and use, would support this assumption.




     No information on the decomposition products of the brighteners




is published.  Individual stabilities to various agents are listed under




the individual compounds in the appendix.




     B.  ENVIRONMENTAL TRANSPORT




     The brighteners are carried both on and in the tremendous variety




of substrates to which they are applied.  However, water-transport would




be the main area of concern related to environmental significance.




     C.  BIOACCUMULATION




     No information was uncovered concerning the bioaccumulation of the




optical brighteners.  It would seem, however, that fat-soluble molecules




might accumulate in animal tissues.






X.  TOXICITY




     A.  HUMAN TOXICITY




     Contact or accidental ingestion would be the major pathways by which




the optical brighteners could demonstrate toxicity toward humans.  Textile




materials which are worn contain between 0.05%-0.15% of optical brighten-




ing agents.  Their fastness on the fiber substrate would argue against




transference to the skin.  The amount of brightener that might be acciden-




tally ingested, as from an .agent transferring into food from a brightener-




treated container would be negligible.  The amount of brightener persisting




in potable water, if ingested, would be approximately 1 micrdgram per




liter; this amount is 10,000 times smaller than the amounts tolerated in
                                  30

-------
long-term animal experiments without the slightest effect (Review, 1973/1).




     Ten derivatives of 4,4'-diamino-2,2'-stilbenedisulfonic acid were




used in patch tests (1%) on eight human subjects.  Seven subjects revealed




no reactions, but a transient hyperemia occurred in one case.  Intra-




cutaneous injection of the brighteners in a 1% aqueous solution caused




necrosis and infiltration.  These compounds showed no photosensitizing




effect (Gloxhuber, Hecht, and Kimmerle, 1962).  In similar patch tests,




Schneider (1955) noted no reaction unless ultraviolet light or abrasive




action was employed.  Alexander (1964) conducted patch tests on 2000




subjects, using dilutions of optical brighteners from 10 mg/L to .100




mg/L.  Readings were taken after 24 and 48 hours, and repeat applications  '




were made at two-month intervals; 53 of the 2000 subjects showed weakly    V




positive sensitization reactions after 24 hrs; 87 of the 2000 subjects




displayed erythema.  Glashoff (1963) applied washing powders and soaps.  .




containing optical brighteners to human skin in a 5% solution.  The     !




solution was reapplied for 6 days.  No sensitization was noted.  In




further investigations, 87 dermatology patients were tested, with similar




results.




     Keplinger, Fencher, Lyman, and Calandra (1974) tested the following




optical brighteners for sensitization induction in human subjects:




(I)  4-(2H-naphtho[i,2-d]triazol-2-yl)-2-stilbenesulfonic acid, sodium




     salt




     Tinopal RBS (Ciba-Geigy Corp.)




     Fluorescent Brightener 46




(II) 4,4'-Bis[[[4~anilino-6-(2-hydroxyethyl)(methyl)amino]-s-triazin-2-




     yl]amino]-2,2'-stilbenedisulfonic acid, disodium salt         ,




     Tinopal'AMS (Ciba-Geigy Corp.)







                                  31             "    ,   ••••-.-   ..•-"•• '-.'••    '

-------
(Ill)  4,4I-Bis[[[4-anilino-6-(2-hydroxyethyl)(methyl)amino]-s-triazin-2-
       yl]amlno]-2,2'-stilbenedisulfonic acid, disodium salt
       Tlnopal 5BM (Ciba-Geigy Corp.)
(IV)   2,2'-(4,4'-biphenylylenedivinylene)dibenzenesulfonic acid,
       disodium salt
     Patches containing these brightening agents were applied to human
skin, three times a weekj with a. total of ten patches being applied to
the same site.  After a rest period of 10-14 days, a challenge patch
was applied.  Examinations 24 hours and 48 hours later revealed neither
irritation nor sensitization in 50 human subjects.
     According to American Cyanamid Co. (Technical Sales Bulletin 1056),
Calcofluor White RW (C. I. Fluorescent Brightener 61) shipments bear a
warning label which states that this compound is a skin and eye irritant.
     B.  TOXICITY TO NON-HUMAN MAMMALS
     1.  Acute, Subacute, and Chronic Toxicity
     Gloxhuber, Hecht, and Kimmerle (1962) studied the following brigh-
teners in relation to animal toxicity:
    TRADE NAME                  FLUORESCENT BRIGHTENER
Blankophor R                             30
Blankophor G                             40 (not presently manufactured)
Blankophor B                             —
Blankophor BE                           115
Blankophor BH
Blankophor BBH                          121
Blankophor BGH
Blankophor BUP
Blankophor HZN                           ~
Blankophor PM                            —
Blankophor H type B
                                   32

-------
       ACUTE TOXICITY,  SINGLE ORAL ADMINISTRATION, LD50 (g/kg)
            Blankophor            Rats            Guinea Pigs
              B                   > 5.0              >2.0
              BH                    3.0               0.25
              BBH                 > 2.0              >1.0
              BGH                 > 2.0              >1.0
              G                   > 5.0        ,       2.0
              H type B            > 5.0               1.0
              R                   > 5.0               0.5
              BUP                 >10.0              >2.5
              HZN    ''           > 2.5              >2.5
              PM                  >10.0               	
     Doses higher than 1.0 g/kg were not administered to rabbits nor
cats.  At this level, these animals survived with no toxic reactions.

    ACUTE TOXICITY, SINGLE PARENTERAL ADMINISTRATION, LD50 (g/kg)
       Blankophor       Mice (iv)        Rats (ip)       Mice (sc)
         B                0.1
         BH               0.3
         BBH              	
         BGH              	
         G
         H type B         0.35
         R                0.35
         BUP              0.9
         HZN              	
         PM               0.8
     After intraperitoneal injection of 50 mg/kg  of Blankophor B to cats,
the brightener was excreted in the urine over a two-day period without
any toxic effect.
1.0
0.5
0.35
0.75
0.5
0.35
0.35
1.75
0.4
1.75
0.5
1.0
1.5
1.0
	
1.0
1.0
1-5
. 	
	
                                  33

-------
     REPEATED ORAL ADMINISTRATION
     Rats, rabbits, and cats were given oral doses of Blankophors B,
BH, BBH, BGH, G, H type B, R, BUP and HZN, over a 2-4 week period, at
levels of 0.1-0.5 g/kg.  No recognizable toxic effects were noted.
     CHRONIC FEEDING STUDY
     Male rats, weighing 50 g, were given optical brighteners in their
drinking water.  Results are given as follows:
                                           Test Time         Total Amount
Blankophor         Concentration %           (days)          Administered
   R                     0.2                  498                20.3
   BH                    0.5                  464                35.5
   BBH                   0.2                  362                18.0
   BGH                   0.2                  362                12.0
     One animal from the R group expired after 7 days; one animal from
the BGH group expired after 269 days; and one animal from the BBH group
expired after 330 days.  The weight of the survivors did not differ from
that of the controls.  During the time period of the experiment, the
survivors showed no toxic symptoms.  The average life-span of the survivors
was 700 days, calculated from the beginning of the test period.
     EFFECT ON MUCOUS MEMBRANES
     Aqueous solutions of the Blankophor brighteners produced no particular
irritation of animal mucous membranes.  A 1% solution of Blankophor BUP
produced a transient hyperemia of the rabbit conjunctival sac.  Blankophor
"BBH and BE showed no such effect.
     INTRACUTANEOUS ADMINISTRATION                             :
     The intracutaneous administration of 1 ml ,of a 1% solution of the
Blankophor brighteners to rabbits resulted in infiltration and localized

-------
necrosis.  Blankophors BUP and PM were exceptions; they produced no


adverse effects.


     CHRONIC PARENTERAL ADMINISTRATION


     Male rats were given parenteral injections of 0.5 ml of 1% solutions


of the Blankophor brighteners twice weekly for one year.  Any ulcerations


which formed healed normally after interruption of the treatment.


     PHOTOSENSITIZATION


     Control mice were given subcutaneous injections of"Hypericin in


doses of 25 mg/kg.  A rapid onset of toxic symptoms appeared when these


animals were placed in sunlight, and 4 of the 5 animals treated expired


within 12 hours.  Similarly treated control animals survived in the dark.


     The test mice were given doses of 0.25 g/kg of Blankophors R and BH,


subcutaneously.  No difference was found between those mice which were


kept in sunlight and those which were kept in darkness.


     ACUTE DUST INHALATION


     Keplinger, Fancher, Lyman, and Calandra (1973) exposed rats for


four hours to the highest dust concentration achievable (2900-5500


mg/m3) of the following optical brighteners:


(I)    4-(2H-naphtho[l,2-d]triazol-2-yl)-2-stilbenesulfonic acid, sodium


       salt


       Tinopal RBS (Ciba-Geigy Corp.)              .


       Fluorescent Brightener 46


(II)   4,4'-Bis[(4-anilino-6-morpholino-s-triazin-2-yl)aminb]-2,2'-s til-


       benedisulfonic acid, disodium salt


       Tinopal AMS (Ciba-Geigy Corp.)
                                         ••v "* H.

(Ill)  4,4'-Bis[[[4-anilino-6-(2-hydroxyethyl)(methyl)amino]-s-triaziri-
                                  35

-------
       2-yl]amlno]-2,2'-stilbenediaulfonic acid, disodium salt


       Tinopal 5BM (Ciba-Geigy Corp.)


(IV)   2,2'-(4,4t-biphenylybenedivinylene)dibenzenesulfonic acid, disodium


       salt


     Compounds II and IV caused grooming, sneezing, inactivity, and weak-


ness on inhalation by the rats, but induced no pathological changes. • Lung


hyperemia was found in two out of ten rats which inhaled compound I.


Lung consolidation was found in four out of ten rats, and one rat expired;


Compound III induced inactivity in the animals inhaling it.  Slight lung hy-


peremia was found in three put of ten rats and lung consolidation was found


in 2 out of ten rats.


     Fontaine (1968) investigated the oral, intraperitoneal, and intra-


venous LDso values of 4-methylumbelliferone (7-hydroxy-4-methylcoumarin)


in male mice.  These values were 7500, 325, and 250 mg/kg, respectively.


In male rats, the oral and intraperitoneal LDso values were 6200 and


750 mg/kg respectively.  This compound caused ataxia and tranquilization


in both mice and rats.  The i.v. LDioo was 251 mg/kg (respiratory arrest)


and 292 mg/kg (cessation of the QRS complex), following infusion of 5


mg/ml/min into anesthetized rats.  A three month oral administration of


doses of 200 or 40 mg/kg/day to young rats did not affect growth, food


intake, mortality, blood picture, or organ histology.  No blood, acetone,


bile salts, or bile pigments appeared in the urine.


     2.  Sensitization


     No sensitizatipn is reported in any of the published articles studied


irrespective of the type of animal studied, amount of optical brightener

                                                i
administered, route of administration, or duration of experiment
                                  36

-------
(Gloxhuber, Hecht,  and Kimmerle, 1962;  Schneider, 1955; Alexander,  1964;

Glashoff,  1963;  Keplinger, Fancher, Lyman,  and Calandra, 1974).

     3.  Teratogenicity

     Fontaine  (1968) studied the teratological effects of  7-hydroxy-4-

methylcoumarin in rats.  This brightener demonstrated no teratological

effects when administered orally to pregnant rats in doses of  15-1200

mg/kg/day  from the 6th to 15th days of  gestation; to mice  at 50,  200, or

800 mg/kg/day  for 15 days before mating; nor to rabbits at 50,  200, or

800 mg/kg/day  from days 6 through  15  of gestation.

     Keplinger,  Fancher, Lyman, and Calandra (1974) studied the teratogenic

activity of four optical brighteners  in rabbits.  The brighteners were

administered at  dose levels of 10  and 30 mg/kg.  Results are tabulated as

follows:
              SUMMARY OF TERATOGENIC EFFECTS OF FOUR FLUORESCENT WHITENING AGENTS
                                   IN ALBINO RABBITS
Test material
None

Thalidomide


Compound Is

Compound II

Compound III

Compound IV
•'
Dose
(mg/kg)
' —
—
37.5
37.5
75
10
30
10
30
10
30
10
30
No. of
pregnant
females
12
12
10
10
7
14
13
' 17
16
16
11
13
16
No. of
implantations
99
112
70
124
55
118
105
147
140
117
90
91
132'
-No. of
resorptions
8 (8.1%)
9 (8.0%)
13 (18.6%)
24 (19.3%)
15 (27.2%)
10 (8.5%)
10 (9.5%)
16 (10.9%)
19 (13.6%)
20 (17.1%)
24»(26.7%)
17 (18.7%)
15 (11.3%)
No. of
normal
fetuses
91
99
54
85
26
108
95
131
121
97
65
74
107
No. of
abnormal
fetuses
0
4
3
15
14
0
0
0
0
0
1
0
1
           • Test material neutralized to pH 7 with hydrochloric acid.
           ' 15 were from-2~fema1es only.              .
           * 9 were aborted from 1 female.
                                    37

-------
(I)    4-(2H-naphtho[l,2-d]triazol-2-yl)-2-stilbenesulfonic acid, sodium




       salt




       Tinopal RBS (Ciba-Geigy Corp.)




       Fluorescent Brightener 46




(II)   4,4'-Bis[(4-anilino-6-morpiiolino-s-triazin-2-yl)amino]-2,2'-stil-




       benedisulfonic acid, disodium salt




       Tinopal AMS (Ciba-Geigy Corp.)




(Ill)  4,4'-Bis[[[4-anilino-6-(2-hydroxyethyl)(methyl)amino]-s-triaz in-




       2-yl]amino]-2,2l-stilbenedisulfonic acid, disodium salt




       Tinopal 5BM (Ciba-Geigy Corp.)




(IV)   2,2l-(4,4'-biphenylybenedivinylene)dibenzenesulfonic acid, disodium




       salt




     4.  Carcinogenicity




     No evidence was found in the literature to prove that the optical




brighteners are carcinogenic to either humans or animals.




     Bingham and Falk (1970) attempted to demonstrate synergism between




the optical brighteners and ultraviolet light in malignant tumor develop-




ment.  The compounds tested were:   (I) 3-benzyl-4-methyl-7-hydroxycoumarin;




(II) 4,4'-bis(2,4-dimethoxybenzamido)-2,2'-stilbenedisulfonic acid,




disodium salt; and (III) 4,4l-bis(4,6-dianilino-s-triazin-2-yl)amino-




2,2'-stilbenesulfonic acid, disodium salt [Fluorescent Brightener 9].




     Groups of 50 young adult C3H mice were treated with a 1% solution




of optical brightener in DMSO (dimethyl sulfoxide) or with DMSO alone




as a control.  A dose of 50 mg of solution was applied 3 times weekly to




the skin of the intrascapular region, for the lifetime of the mouse or




until a tumour appeared.
                                  38

-------
     Tumours did not occur in any mice receiving topical applications of


the optical brightener alone, but a high incidence of tumors developed


in all three test groups with the addition of ultraviolet light (254 mu).


Histological examination of the tumors revealed that they were squamous


cell carcinomas.


     Optical brightener II appeared to be slightly more active than either


I or III.  Two carcinomas developed in the mice that were treated with


solvent and light.  No tumors developed in the group receiving applica-


tions of solvent alone..


     However, this work has been called irrelevant by Berth, Fischer, and


Gloxhuber (1972), since the wavelength of ultraviolet light used by Bingham


and Falk (254 mu) does not occur in natural light, making the results ob-


tained invalid in practice.


     Neukomm and DeTrey (1961) studied the carcinogenic properties of


the following brighteners:


(I)    4,4l-bis[[4-anilino-6-[(2-hydroxyethyl)methylamino]-s-triazin-2-


       yl]amino]-2,2'-stilbenedisulfonic acid, disodium salt;


(II)   4-(2H-naphtho[l,2-d]triazol-2-yl)-2-stilbenesulfonic acid, sodium


       salt (Fluorescent Brightener 46); and


(III)  4-(7-sulfo-2H-naphtho[l,2-d]triazpl-2 yl)-2-stilbenesulfonic acid,


       disodium salt.


     A group of 50 female mice, aged 3 to 6 months were used as controls.


     A second group of 50 mice of the same sex, age, and strain were


injected subcutaneously with a mixture of 0.2 ml of 8g of talc in 20


g of peanut oil.  These were used as solvent controls.
                                            "*-\_^

     A third group of 50 mice of the same sex, age, and strain were in-
                                  39

-------
jected with 0.5 mg of 3,4-benzopyrene in 0.2 ml of peanut oil.  These



were used as comparison controls in .tumor formation. .



     Fifty test mice, identical in sex, age, and strain to the control



mice, were injected subcutaneously with the optical brighteners at a



dose level of 5 mg of brightener in 0.2 ml of a mixture of talc and



peanut oil, 0.5 mg of brightener per day per animal in food.



     The duration of the experiment was two years.



     The lungs, heart, liver, spleen, and kidneys of each animal were
                                 ' '     '         !


examined both grossly and histologically after expiration.



     No mice receiving the brightener test compounds presented tumors



at the injection site, nor did the talc-oil controls.   The 3,4-benzopyrene



controls developed fibroblasts at the injection site.



     Mammary tumors, ovarian cysts, and incidence of leukemia were not



accelerated by the brighteners when compared with the controls.



     Although there were no general toxic effects noted during these



long-term studies, a few cases of splenic amyloidosis and liver damage



might be attributable to the long-term feeding of brighteners to the



affected animals (comparable doses for humans would amount to 20 tug/kg,



or.1.2 g per day).



     5.  Mutagenicity



     The mutagenic effects of some optical brighteners toward microorgan-



isms are discussed in Section E, TOXICITY TO MICROORGANISMS.



     Keplinger, Fancher, Lyman, and Calandra (1974) tested the following



brighteners for mutagenic effects toward mice:



(I)    4-(2H-naphtho[l,2-d]triazol-2-yl)-2-stilbenesulfonic acid, sodium



       salt

-------
       Tinopal RBS (Ciba-Geigy Corp.)




       Fluorescent Brightener 46




(II)   4,4'-Bis[(4-anilino-6-morpholino-s-triazin-2-yl)amino]-2,2'-stil-




       benedisulfonic acid, disodium salt




       Tinopal AMS (Giba-Geigy Corp.)




(Ill)  4,4'-Bis[[[4-anilino-6-(2-hydroxyethyl)(methyl)amino]-s-triazin-2-




       yl]amino]-2,2'-stilbenedisulfonic acid, disodium salt




       Tinopal 5BM (Ciba-Geigy Corp.)




(IV)   2,2l-(4,4l-biphenylylenedivinylene)dibenzenesulfonic acid, disodium




       salt




     Compounds I,II, and III were administered in dosages of 25 and 50




m§/kg, and compound IV was administered in dosages of 5 and 10 mg/kg.




     The ability of treated males to fertilize untreated females was not




impaired.  The numbers of implantations, resorptions, viable embryos,




prelmplantation losses, and mutation frequencies did not differ from




those of the untreated animals.      -                                   .




     6.  Behavioral Effects




     No relationships between optical brighteners and animal behavior




have been reported in the literature.




     C.  TOXICITY TO LOWER ANIMALS




     Keplinger, Fancher, Lyman, and Calandra (1974) investigated the LCso




values of four different optical brighteners in fish.  The brighteners




used in these studies were:




(I)    4-(2H-naphtholl,2-d]triazol-2-yl)-2-stilbenesulfonic acid, sodium




       salt




       Tinopal RBS (Ciba-Geigy Corp.)




       Fluorescent Brightener U6






                                  Ul

-------
(II)   4,4'-Bis[4-anilino-6-morpholino-s-triazin-2-yl)amino]-2,2'-



       stilbenedisulfonic acid, disodium salt



       Tinopal AMS (Ciba-Geigy Corp.)



(Ill)  4,4'-Bis[[[4-anillno-6-(2-hydroxyethyl)(methyl)amino]-s-triazin-2-



       yl]amino]-2,2'-stilbenedisulfonic acid, disodium salt



       Tinopal 5BM (Ciba-Geigy Corp.)



(IV)   2,2'-(4,4t-biphenylylenedivinylene)dibenzenesulfonic acid, disodium



       salt
                                                •_


     Compound III appeared to be the most toxic, with a twenty-four hour



LCso value of 120 ppm trout and 105 ppm for catfish.  The twenty-four hour



LCso values for compound IV were 160 ppm in trout and 105 ppm for catfish.



Compounds I and II showed equal activity; the twenty-four hour LCso values



for both trout and catfish amounted to 2000 ppm.



     Ciba-Geigy Corp. (Review, 1973/1) reports that the amounts of



optical brighteners which have been measured in domestic effluent in



densely populated areas vary between 0.01 and 0.1 ppm.  Furthermore,



efficient purification plants retain more than 90% of this, so that the



amounts of brightener reaching surface or ground waters would be approxi-



mately .001 to .010 ppm.



     D.  TOXICITY TO PLANTS
                                               f


     Sharma (1963) reports on chromosome breakage in alluim roots after



the roots were treated with natural coumarin and some of its derivatives.



Quereioli (1957) tested twenty-one derivatives of coumarin to study any



toxic effects these might have toward the roots of yellow onion bulbs.  A



considerable degree of fragmentation of the chromosomes was noted.

-------
     Although none of the compounds used in these studies can be designated ..  .




as specific optical brighteners, these studies are mentioned here because




coumarin is the parent structure of several commonly used brighteners.




     E.  TOXICITY TO MICROORGANISMS




     Blankophor FBO (Fluorescent Brightener 206), Uvitex SOF (Fluorescent




Brightener 190), and Uvitex SWN (Fluorescent Brightener 140) were tested for




their ability to induce petite mutants in a diphloid strain of Saccharomyces




cerevisiae.  Fluorescent Brightener 206 induced a high frequency of mutants




when the yeast was incubated for 48 hours in its presence in darkness.




Fluorescent Brighteners 140 and 190 induced photosensitization and a




marked increase in petite mutants after a one-hour treatment with the




brighteners in the presence of light (Gillberg, 1971).




     Gillberg has since admitted that his results are irreproducible




(Kilbey and Zetterberg, 1974).  Kilbey and Zetterberg used the same genetic




system and the same compounds as those used by Gillberg, but were unable




to confirm that the suspected agents acted positively when incorporated




in the growth medium of the organism.  None of their several trials




produced a positive result.




     Darken (1964) determined that ten species of microorganisms showed




increased spore germination of 159%-848% after a two-hour exposure of a




12% solution of 4,4'-bis[4-anilino-6-bis(2-hydroxyethyl)amino-s-triazin-2-




ylamino]-2,2'-stilbenedisulfonic acid, disodium salt (Fluorescent Brigh-




tener 28), in 42% aqueous ethylene glycol monomethy1 ether.

-------
                            APPENDIX'

     Starting on page A-l (follows 148), a compilation of optical
brighteners has been drawn from the Colour Index, from the indices of
Chemical Abstracts, and from manufacturers' data sheets.   The optical
brighteners are listed according to the "C.I. Fluorescent Brightener"
numbers.  All other information with which a correlation  with the  C.I.
numbers could be established is included.
                                        44

-------
                        LITERATURE CITED
Adams, D. A. W. (1954), "Optical Whitening Agents for Detergents",
     Perfumery Essent. Oil Record 45, 303-7   10621

Alexander, P. (1964), "Effect on Skin of Optical Brighteners", Mgf.
     Chemist 35_ (9), 72   12114

Berth, P., Fischer, W. K., and Gloxhuber, C. (1972), "The Development
     of Laundry Aids with Consideration for the Human Toxicity and
     Ecological Requirements", Tenside Det. 9. (5)» 260-267

Bingham, E. and Falk, H. L. (1970), "Combined Action of Optical Brigh-
     teners and Ultraviolet Light in the Production of Tumours", Food
     Cosmet Toxicol 8^, 173-176

Chemical Economics Handbook, Stanford Research Institute, Menlo Park,
     Calif.

Colour Index, Third Edition, 1971, The Society of Dyers and Colourists

Darken, M. A. (1962), "Absorption and Transport of Fluorescent Brigh-
     teners by Microorganisms", Appl. Microbiol 10, 387-93   12620

Darken, M. A., and Swift, M. E. (1964), "Effect of Brightener on Spore
     Germination, Mycologie _56_ (62), 158   12330

Fontaine, L., Grand, M., Chabert, J., Molho, D., Boschetti, E. ."(1968) ,
     "Toxicologies! and Teratological Study of 4-Methylumbelliferone",
     Therapie 23_ (2), 359-71 (Fr.)   12071

Gillberg, B. 0., and Aman, J.  (1971), "Petite Mutants Induced in Yeast
     by Optical Brighteners",  Mutat, Res. 13_ (2), 149-154   10521

Glashoff, E., Stegmann, W., and Schroeder, E. (1963), "The Biological
     Action of Optical Bleaches Used in Detergents and Soaps", Fette,
     Seifen, Anstrich.  65. 42-6 (Ger.)   12244

Gloxhuber, C., Hecht, G., and Kimmerle, G. (1962), "Toxicological In-
     vestigations with Brighteners (Blankophor(R) Series)", Archiv. Toxi-
     kol. 19_, 302-12 (Ger.)   12242

Gouaze, A., and Castaing, J. (1963), "The Tissue Affinity of One Hun-
     dred Forty-Eight Fluorescent Compounds", Compt. Rend. 257 (26),
     4230-4 (Fr.)   12233

Keplinger, M. L., Fancher, 0.  E., Lyman, F. L., and Calandra, J. C.
     (1974), "Toxicologic Studies of Four Fluorescent Whitening Agents",
     Tox. Appl. Pharm. 27, 494-506

Kiger, J. and Bon, R. (I960),. "The Problems of Identification Posed by
     Optical Bleaching Agents", Ann. Pharm. Franc., 18, 853-72 (Fr.)  12211

-------
Kilbey, B. J., and Zetterberg, G. (1974), "Optical Brighteners",
     Science 183, 798   16064

Neukomm, P. S. and De Trey M. (1961), "Study of Some textile Optical
     Bleaching Agents from the Point of View of Their Carcinogenic
     Activity", Med. Exptl. 4_, 298-306 (Fr.)   10557

O'Hare, R. J. (1966), "Optical Brightening Agents", Chem. Ind. (Lon-
     don), 28, 1220-4   10648

Quercioli, E. (1957), "Molecular Constitution of Coumarins and their
     Effect on Vegetable Cells", Pubbl. Centra. Studio Citogenet.
     Vegetale Consiglio Nazi. Ricerche No. 206   12396

Review 1973/1 CIBA-GEIGY

Schneider, W. (1955) "Optical Whitening Agents and Their Influence on
     the Skin and Body Functions", Berufsdermatosen _3_, 201-6 (Ger.)
     10581

Sharma, A. K., Chandhuri, M., Chahraborti, D. T. (1963), "Chemical
     Basis of the Action of Natural Coumarin and its Derivatives on
     Chromosome Breakage", Acta. Biol. Med. Ger. 31 (3), 433-44
     12495

Siegrist, A. E. (1955), "Optical Brighteners in Detergents", Soap.
     Chem. Spec. .31  (11), 44; 31 (12), 58   10592

Snyder, F. H., Opdvke, L., and Rubenkoenig, H. L., (1963), "Toxicolo-
     gic Studies on  Brighteners", Toxicol. Appl. Pharmacol. .5, 176-83
     12601

Stensby, P. S. (1968), "Optical Brighteners as Detergent Additives",
     J. Amer. Oil. Chem. Soc. 45_(7), 497-504   12067

Stensby, P. S. (1967), "Optical Brighteners in Laundry Products",
     Detergent Age,  3_ (9), 20-7   10446

Stensby, P. S. (1967a), "Optical Brighteners and Their Evaluation",
     Sopa. Chem. Spec. 43_(4), 41; (5), 84; (7), 80;  (8), 94; (9),
     96   14167

Stensby, P. S. (1965), "Optical Brighteners in Fabric Softeners",
     Soap. Cham. Spec., May   16498

Taylor, G. G. (1955), "Estimation of Fluorescent Brightening Agents",
     J. Soc. Dyers Colour., 2I» 697-704   10593

Tomura, M., and Akera, T.,  (1971), "Blood Brain Barrier;  Implication
     of Drug Metabolism in  the Penetration of Methylhydroxycoumarin
     in the Rat", Jap. J. Pharmacol., 2J, (5) , 683-5   10505
                                1*6

-------
Ukita, C. (1960), "Triazinylstilbene Optical Bleaching Agents:  I. Tox-
     icity and Change in Urinary Constituents after Administration of
     the Dye.  Shokukin Eiseizaku Zasshi 1 (1), 69-73   10539

United States Tariff Commission, Synthetic Organic Chemicals, United
     States Production and Sales

Weeks, L. E., Harris, J. C., and Lewis, J. T. (1959), "Methods for
     Analysis of Fluorescent Brighteners", Soap. Chem. Spec., May,
     66-70
                               U7"

-------
     METHYL CHLOROFORM, TRICHLOROETHYLENE, AND TETRACHLOROETHYLENE:



     SUMMARY AND CONCLUSIONS








     The status of these three chlorinated hydrocarbon solvents is undergoing



a change at the present time.  The use of trichloroethylene is declining in



industry because of the stringent regulations which are being enforced to



control its use.  This means that there will be bigger markets for methyl



chloroform and tetrachloroethylene.  They will become prominant in those



areas of industrial application where trichloroethyiene was formerly the



solvent of choice.  Tetrachloroethylene is also expected to find continuously



wider application in textile manufacturing and dyeing as these industries



convert from aqueous to non-aqueous systems to avoid water pollution.



     The volatility of these chlorinated hydrocarbons presents a dual



hazard:  they are readily absorbed through the lungs and digestive tract,



and they are easily transported through the air.  In the literature on hand,



there was little or no information specifically reporting on monitoring that



is actually being carried out at the sites where these solvents are used.



Very few figures are reported on actual concentrations of these compounds



found during enviornmental field tests.  One complete study that has been



reported was done in Europe.



     While methyl chloroform is considered to be the most stable and least



toxic of the three solvents discussed here, it may not be considered innocuous.



In fact, a system for grading these compounds according to stability or



toxicity can only be valid when related to specific applications and application



conditions - amount evaporating into the air during use, temperature and press-



ure variables, composition of contact surfaces, and duration of exposure time.
                                     U8

-------
     The danger of toxicity from the inhalation of these solvents is of



fundamental concern.  Their decomposition into toxic products, such as



ph >sgene, occurring under use-related conditions, also presents a hazard.



     The toxicity of the chlorinated hydrocarbon solvents has been est-



ablished from experiments on animals and from observations of exposed



humans.  Acute, heavy exposures result in a depression of the central



nervous system.  Death may occur from respiratory and cardiac failure,



although there is a wide difference between the minimum narcotic dose and



the fatal dose.



     All three solvents discussed in this study induce liver and kidney



dysfunction following repeated, long-term exposures.  However, the function-



ing of these organs returns to normal when the affected subjects no longer



have contact with the solvents.



     The metabolites of these solvents and their excretion have been care-



fully studied.  However, the intermediate breakdown products within the



body, as well as the metabolic sites, seem to remain uncertain.  Since no



information is available, the toxicity of the intermediates in the met-



abolism of these solvents cannot be assessed.

-------
                   CHLORINATED HYDROCARBON SOLVENTS




     (METHYL CHLORFORM, TRICHLOROETHYLENE AND TETRACHLOROETHYLENE)




I.  Physical Properties




     The physical and chemical properties of the chlorinated solvents




methyl chloroform (1,1,1-trichloroethane), trichloroethylene, and tetra-




chloroethylene  (perchloroethylene) qualify_j:hem for continually increasing




use in industry.  Their characteristic non-flammability in air, volatility,




and poor solubility in water make them very useful solvents.  The relatively




low toxicity of methyl chloroform is a special advantage and makes it the




solvent of choice in instances where another solvent might be otherwise more




suitable.




     All three  solvents are clear, colorless liquids with the chloroform




odor characteristic of the group of compounds to which they belong.




     The following composite tables give  the properties reported from various




sources, while  the single tables give data on the pure compound.

-------
        TABLE I.  Chlorinated Solvents, Properties




                         Methyl chloroform    Trichloroethylene
Tetrachlbroethylene
,Formula




 Molecular weight




 Melting Point °C




 Boiling Point °C








 Freezing Point °C




 Decomposition Temp




 Density




 Flash Point




 Relative Rate of




    vaporization




:Solvent Power




 Surface tension




 (dyne/cm2, 20°C)




 Refractive Index




 Vapor Pressure
 Vapor Specific




    Gravity (Air




 Viscosity (cps, 25°C)




 Autooxidation




 Hydrolysis




 Thermal Stability




 (without stabilizers)
C2H3C13
133.41
-50° (1)
74-76° (1)
74.1° (2)
-42° (2)
p. °C 360-440° (4)
1.437 (1)
None
5.0 (3)
124(3)
25.56 (3)
2° 1.4370 (1)
"C mmHg °C mmHg
0 :j7 50 340
10 62 60 470.
20 100 70 600
.".0 150 SO 000

-------
                                   TABLE 1.   Cont'd.



                    Methyl Chloroform   Trichloroethylene    Tetrachloroethylene



Solubility ^  ^     .4420  .-,            O.ll25               0.01525
 water g/lOOg H20

                                        0.12560(4)




(1)   Aldrich Chem. Co.  (97% with  3% p-dioxane)


(la)                     (98%)


(Ib)                     (Spectrophotometric  grade)


(2)   Hooker Chem. Co.


(3)   Dyrenfurth  (1972)


(4)   Klrk-Othmer Encyclopedia of  Chemical Technology,  5^ (1964)

-------
Table 1A - PHYSICAL AND CHEMICAL PROPERTIES OF METHYL CHLOROFORM
NAJ^E Methyl chloroform

Mole Ref. Molecular r ., r. Molecular
% Pur. 99.92 1 Formula <-i"3^13 Weight 133.425

F.P. °C
F.P. 10051
3. P. °C
760 mm
100
30
10
1
Pressure
mm 25°C
«e
Denaity
g/ml 20'C
dt 25
d4 30
a
b
Ref. Index
»D 20.C
50
»C"
MR (Obs.)
• MR (Calc.)
(nD-d/2) .
Dielectric
A 1 -3 to
B 1 1 3 1 "C
c
A*| -3 to
B«i_ 91 -C
K
tk | to"
'xi 'c
A' | to
B'U !£
C'
A'* to
B'» 'C
Ac | It I to
Bc._
-------
Table IB - PHYSICAL AND CHEMICAL PROPERTIES OF TRICHLOROETHYLENE
NAME 1, 1, 2-Trichloroethylene

Mole Ref. Molecular r Hrl Molecular ..
%Pur. Formula C2HO13 Weight 131.399

_F.P. °C
F. P. 100%
B. P. *C ,
760 mm
100
30
10
1
Pressure
mm 25*C
'e
Density
g/ml 20-C
d* 25
"4 60
•
b
Kef. Index
DD ,«
50
»C"
MR (Obs.)
MR(Calc.)
(nD-d/2)
Dielectric
A 1 7 to
B 1 155 *C
C
A*| 7 to
B*|_1 — *—
c
*k 1 to
?! -c
A< | to
B' i_ "C
c- 	
A1* to
B'* *C
Ac| 155 to
Be it,. 'C
Cc l— 	
CryoB. A*
consta. B"
*e'C



- 87.08
31.54
6.90
-11.85
-42. 89
74.31
975.52
1.46422
1.45541
1.39501
1.49948
-0.00174
1.47734
1.47457
1.46056
0.4302
25.37
25.57
0.74523

7.02808
1315.0
230.
1 . 54642
1230.2


7.4675
1675.
280.

95.60
Re I


1
4
5
5
5
5
5
1
1
1
4
4
1
1
1
4
4
5
4

4
4
4.
5
5


5
5
5

5

dt/dP
•C/mm
Z5*C
BP
*.
30 mm
AHm cal/g
oHv cal/g
25'C
30 mm
BP
t'(d.e)
AHv/Te
d 1 7 to
-o.-H6-;f
e' ! 'C
d, g/ml
v£ ml/g
tcc -c
P mm
PV/RT
25'C
30 mm
BP
»e
*c
aHc kcal/m
AHf
AFf
Viscosity
certi stokes
V 20 "C
' 40
60
80
Bv 1 10 to
Av | 70 'C
lB^T| ^
(Av)| .C
«p »q. °K
cp vap. °K
<=v »»P-
0.2890"
d. 04369
0.0359
0.6178

62.33
64.02
56.43
55.61
55. 62
19.81
64.67
0.0946
0.513
1.950
298.
36876.
0.9957
1.0000
0.9578
0.9507
0.265

0. 3844
0.3Z91
0.2867
0.2553
311.03
T. 52395

Ref
5'
5
5
5

5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5

1
L
1
1
4
4

STRUCTURAL FORMULA
CC12=CHC1

f | j to
8 j ' ' IK.
h | .
f ' ' to
g' 1 L "K
h' |
, 	 1 	
ml 'to
n 1 -K
° !
m- I 1 to
n' , 1 -K
°' I
Surface tension
dynas/cm. 20*C
> . 30
40
Parachor [p]
20'C
30
40
Sugd.
Exp. L.l.%/wt.
u.
Dispersion
Flash Point "C
Fire Point
M Spec.
Ultra V.
X-Ray Dif.
Infrared
Solubility in +
Acetone
Carbon tet.
Benzene
Ether
n-Heptan*
Ethanol
Water
Water in





29.28
27.94
26.76
208.7
208.8
209.0
212.8





Ref.




1
1
1
4
4
4
5





TR = 0.75TC * Krarn3/ioo crams solvent
REFERENCES: 1 -Dow 2 -API 3 -Lit. 4-Calc. from det. data 5-Calc. by formula
SOURCE: ' Dow .
PURIFICATION: Distillation
 Source:  ADVANCES IN CHEMISTRY SERIES NUMBER 22

-------
Table 1C - PHYSICAL AND CHEMICAL PROPERTIES OF TETRACHLOROETHYLENE
NAME Perchloroethylene

Mol« Ref. Molecular r _. Molecular
% Pur. Formula ^2^*4 Weight 165.848

P.P. *C
F.P. 100%
B.P. 'C
760 mm
100
30
10
1
Pressure
mm 25°C
«<,
Density
g/ml 20'C
^ 2S
d4 30
a
b
Ref. Index
"D ««
30
"C"
MR (Obs.)
MR (Calc..)
(nD-d/2)
Dielectric
A 1 34 to
B (_187'C
C
A*l 34 to
B*|144'C
K
tk | to"
'x| 'C
A'| 25 to
B'| 34 -C
C'
A1* 25 to
B'* 34 'C
Acl 167 to
-L.'c_-
-------
               -10     0    10   20
                       40     60    80   100  120  140     180   220240
     IOOO
      800
      800
      4OO
      200  £
      100
       80
       60
       40
       20  *
       10  ^
        8
         I
        .8
        .6
           ..T-
±7
                X:
                 +
                       _j	
                                                                 <::
                                                    *f
                                   vapor pressure over a range of —20° G to +240* C.
Source:  GALLANT,  1966
                                  -56

-------
    -150
-140
-130    -120   -110  -100     -80   -SO  -40  -20 0 20  50
  1000
                                vapor pressure over a range of —90° C to +50° C.
Source:   GALLANT, 1966

-------
  120
  100
            -6O
-20
20      60      100     140     180     220    260
          0 CENTIGRADE


 heat of vaporization over a range of —60° G lo | 300° C.
3OO
     O      100     20O    3OO    40O    500    600     TOO     800     900    IOOO
                                     0 CENTIGRADE


Source:   GALLANT,  1966      vapor heat capacity over a range of 0° C to +1,000° C.

-------

                                           50      70
                                        0 CENTIGRADE
                            liquid heat capacity over a range of —30° C to'+150° C.
           -60     -20     20      60     100      I4O      ISO      220     26O    300
                                     0 CENTIGRADE
Source:   GALLANT,  1966
                               liquid density over a range of —60° C to +300° C.
                                         59

-------
 210
 190
 170
 ISO

 130
           -6O
-20
2O      60      100     I4O     ISO     220
       .   ° CENTIGRADE

   vapor viscosity over a range of —60° C to +300° C.
260
300
 2.8 EH

           -6O     -2O     20     60      100     140     180     22O    260     30O
                                       CENTIGRADE
Source:   GALLANT,  1966      liquid viscosity over a range of —60° C to +300° C.

-------
  60

           -60
-20
20      60      100     140     180     220
          0 CENTIGRADE

   surface tension over a range of —60° C to + 300° C.
260    300

            -30
 -10      10      30      50      70      90      110      I3O
                   0 CENTIGRADE

        liquid thermal conductivity over a range of —30° C to +150° C.
                                                        150
Source:  GALLANT,  1966
                                          61

-------
                                  TRICHLOROETHYLENE



U.S. Federal Specification 0-T-634a. Technical Grade Dated April 17.  1956

     Chemical and Physical Requirements
     General (Type I and II)

     Appearance


     Specific Gravity 20°/20°C

     Acidity as HC1:

     Alkalinity as NaOH:

     Water Content:

     Copper Corrosion and
     .  Free Chlorine:

     Color:
     Odor:

     Non-Volatile:

     Spot Test:
     Distillation Range:
       Initial Boiling Point
       At Least 95%
       End Point:

     Acidity as HC1:
Clear and free of suspended natter
  or sediment.

1.450 - 1.475

0.01% Max.

0.01% Max.

No cloud at 0°C


Must pass government test

Shall not be darker than a solution
containing 0.0045 gm potassium
dichromate in one liter of distilled
water.
                                                   Type I
                                 Type II
  No residual odor                —

  0.004 gm/100 ml Max.   0.020 gm/100 ml Max,
  No spot or staia



  86.0°C

  90.0°C
Faintly discernible
spot or stain
85.0°C
Below 90.0°C
95.0°C

0.02% Max.
     Source:  Chemical Economics Handbook
                                       62

-------
                                   TETRACHLOROETHYLENE


U.S. Federal Specification 0-P191a Technical Grade, Dated September 23, 1959,  and

Amendment 1, Dated February 21, 1961:
             Appearance:
             Color:
             Odor:

             Specific Gravity 20°/20°C:

             Non-Volatile Matter:

             pH at 25°C:

             Distillation Range:

             Acid Acceptance:
                  Amine
                  Non-amine

             Spot Test:

             Water Content:

             Copper Corrosion and
                  Free Chlorine:
Clear and free of suspended matter or
sediment.

Shall not be darker than a solution
containing 0.0045 gm. potassium
dichromate in one liter of distilled
water.

Characteristic, no residual odor.

1.615 - 1.630

0.016 gm/100 ml. max.

5.0 min.

118 - 124°C


0.01 max.
0.08 - 0.12

No spot or stain

No cloud at 0°C


Must pass government tests
             Source:   Chemical Economics Handbook

-------
II.  PRODUCTION

     A.  Methyl Chloroform

     The following are the largest reported manufacturers of methyl chloroform in

the U.S.
	Company and Location	

Dow Chemical U.S.A.
     Freeport, Texas

Ethyl Corporation
     Industrial Chemicals Division
        Baton Rouge, Louisiana

PPG Industries, Inc.
     Industrial Chemicals Division
        Lake Charles, Louisiana

Vulcan Materials Company
     Chemicals Division
        Geismar, Louisiana

     Total
   Annual Capacity
As of September 1972
(Millions of Pounds)
      340



       50



      175



       65

      630
Raw Material
vinyl chloride
vinyl chloride
vinylideiie chloride
   ethane
Source:  Chemical Economics Handbook
The overall reactions  for methyl  chloroform production may be represented as follows:

     CH2.= CHC1 +  C12  + CH3CC13

and

     CH2 = CC12 +  HC1 •->• CH3CC13

-------
     No figures on methyl chloroform production are available prior to .1966.
          . -   .                      •            «        "                     •  •

                 Methyl Chloroform (Millions of Pounds)



      '                             Production         .           Sales


     1966                            242.9                       249.7


     1967                              —                        269.7


     1968                            299.4                       288.1


     1969                            324.3                       298.9


     1970                            366.3              ,         327.4


     1971                            374.6                       341.3


     1972                              ™                      .    —


     1973 (p)                        537.3


Jan. 1974 (p)                         45.2  ;                ^     :  —



Source:  United States Tariff Commission


         United States Production and Sales of. Miscellaneous Chemicals


         (p)  Preliminary Report S.O.C. Series C/P-74-1




     Rule 66 which went into effect in Los Angeles County  in 1967 has had a


favorable impact on the methyl chloroform market.  The restricting  of trichloro

ethylene caused 50% of the vapor degreasing industry in Los Angeles to switch


to other chlorinated solvents.  Also, late in 1971, Dow announced that it was


producing vinylidene chloride directly from methyl chloroform, a change which


adds approximately 8-10 million pounds per month to reported methyl chloroform


production (Chemical Economics Handbook).
                                       65

-------
     The Dow Chemical Co. states that methyl chloroform has the best health


and safety picture and is also more readily recovered than other chlorinated


solvents.  It could introduce a savings in consumption of 20-30%.  Dow expects


methyl chloroform to grow by 9-10% per year through 1975, and 5-8% per year after



that  (Chemical Week, November 15, 1972).

                                    '           •''.':




     B.  Trichloroethylene


     During the first part of 1972, the Detrex Chemical Industries, Inc.


closed their plant at Ashtabula, Ohio, which had a production of 100 million



pounds per year of trichloroethylene.  In Mayj 1972, du Pont closed its


Electrochemicals Department plant at Niagara Falls, N.Y., where 250 million


pounds of trichloroethylene were produced per year.
                                    i


      The overall reactions for  trichloroethylene manufacture may be


represented as follows:




      HC  2 CH + 2C12 -»• CHC12-+CHC12


      2CHC12 CHC12 + Ca(OH)2 -»• 2CHC1 =  CC12 + CaCl2 + 2H20
     CHC12 CHC12 	»-   CHC1 = CC12 + HCl

                 Pyrolysis


     CH2C1CH2C1 +  2C12 -»• CHC1  = CC12 +  3HC1
                                       66

-------
     As of September, 1972, the following five companies were reported

.as producers of trichloroethylene in the United States:
     Company and Location
                                 Annual Capacity
                              As of September 1972
                              (Millions of Pounds)
                                 150
                          b.
                    a.
Dow Chemical U.S.A.
     Freeport, Texas

Diamond Shamrock Chemical
Company
     Electric Chemicals
     Division
       Deer Park, Texas           60

Ethyl Corporation
     Industrial Chemicals
     Division
       Baton Rouge, Louisiana     50
                            ^
Hooker Chemical Corporation
     Industrial Chemicals
     Division
       Tacoma, Washington         30
       Taft, Louisiana            40

PPG Industries, Inc.
     Industrial Chemical
     Division
       Lake Charles, Louisiana   200

Total                            530
Raw Material
Ethylene
                                                               Ethylene
                                                               Ethylene
                                                               Acetylene
                                                               Acetylene
                                                               Ethylene
a.  An additional 50 million pounds per year unit was closed in late 1971.

b.  Believed to be producing only small quantities (production was not reported
    to the U.S. Tariff Commission in 1971 or in the first six months of 1972).
    Capacity of the plant will be expanded by April 1973.

c.  A 60 million pounds per year acetylene-based trichloroethylene plant at
    Niagara Falls, New York, was closed in early 1972.

d.  Expanding to 280 million pounds per year by the end of 1973.

Source:  Chemical Economics Handbook.
                                        67

-------
Tfio fn11rnj-fn£ Hat A on production ana SHJ.KS »av^ »«.*... „- 	 	 	
Economics
Handbook and from the United States Tariff Commission TC Publication
C/A for 1971 and Preliminary Report S.O.C Series
for 1973.



1935
1936
1937
1938
1939
1940
1941
1942
1943
1944
1945
1946
1947
-1948
1949
1950
1951
1952
1953
1954
Preliminary figures are indicated "by
Trichloroethylerie (Millions

. Production Siles
12 —
21 - '
33 . ; ' : — • .-••••_ •.- .
27 —
34 —
»
55 —
(82) — '
130 —
(150) . —
' (170) —
185 ~
(186) — ,-
(188) —
190 —
(205) ~
(215) • — ' • x
'(250) 233.2
270.5 241.8
323.3 287.7
296.8 252.4
C/P-74-1 Of
(p).
of Pounds)


1955
1956
1957
1958
1959
I960
1961
1962
1963
1964
1965
1966
1967
1968
1969
1970
1971
1972
1973 '(p)
Jan. 1974 (p)
the same


Production

316.2
346.1
337.7
295.1
360.2
352.8
309.2
356.1
368.2
370.5
434.5
480.2
490.0
519.1
596.8
610.8
514.8
(438.0)
450.5
38.6
source


Sales

284.5
303.2
292.2
243.5
302.2
298.8
325.8
347.9
362^6
370.1
428.1
' 462.9
472.7
527.6
561.5
568.9
532.4
. ~~ .
™ *"
fc—
68

-------
     Producers are curtailing any expansions in trichloroethylene production




since Los Angeles' Rule 66 placed trichloroethylene on the list of restricted




 solvents.  Similar types of legislation have been passed in several states.




     Diamond Shamrock sees a gradual drop in trichloroethylene volume,




conceding it could decline as much as 25-30% by 1975 if all agencies decide




on'rigorous enforcement.  Dow sees trichloroethylene volume going from 600




million pounds per year in 1970 to 400 million pounds per year in 1975, with




the drop continuing (Chemical Week, November 15, 1972).






     C.  Tetrachloroethylene




     Of the companies reported as producers of tetrachloroethylene in the United




States as of September, 1972, Diamond Shamrock, du Pont, and PPG expected to




have undergone considerable expansion in tetrachloroethylene production by the




end of 1973.       .




     It is estimated that about 20% of the tetrachloroethylene produced is from




the acetylene-chlorine method.  The majority, however, is produced as follows:






     CH2C1CH2C1 + 3C12 -»• C12C = CC12 + 4HC1




     C3H8 + 8C12 -»• CCli* '+ C12C = CClz + 8HC1



     2C3H6 + 16 C12 •*•  4CClk + C12C = CC12 + 12 HC1




 Following is a list  of the  major  producers  in the United States.
                                     69

-------
                            Tetrachloroethylene Capacity
	Company and Location

Diamond Shamrock Chemical
Company
     Electro Chemicals Division
       Deer Park, Texas

Dow Chemical U.S.A.
     Freeport, Texas
     Pittsburg, California
     Plaquemine, Louisiana
As of September 1972
(Millions of Pounds)
    100
    120
     20
    105
Raw Material
E. I. du Pont de Nemours & Co.,
Inc.
     Electrochemicals Department
       Corpus Christi, Texas             0

Ethyl Corporation
     Industrial Chemicals Division
      . Baton Rouge, Louisiana           75

Hooker Chemical Corporation
     Industrial Chemicals Division
       Tacoma, Washington               10

       Taft, Louisiana                  35
PPG Industries, Inc.
     Industrial Chemical Division
       Lake Charles, Louisiana         160

Stauffer Chemical Company
     Industrial Chemical Division
       Louisville, Kentucky             70

Vulcan Materials Company
     Chemicals Division
       Geismar, Louisiana              150
       Wichita, Kansas                  40

Total                                  885
Ethylene dichloride
Various
Various
Various
                            Ethylene dichloride
                            Calcium carbide  acetylene
                            generated by Hooker
                            Acetylene generated by
                            Union Carbide  Corporation
                            Ethylene dichloride
                            Various
                            Various
                            Various
Source:  Chemical Economics Handbook
                                    TO

-------
     The  following  data  have been taken from the Chemical Economics Handbook,
from the United States Tariff Commission TC Publication 614
Preliminary Report S.O.C. Series C/P-74-1 of the same source
figures are indicated by (p) .
; Tetrachloroethylene (Millions
1940
1941
1942
1943
1944
1945
1946
1947
1948
1949
1950
1951
1952
1953
1954
1955
1956
Production
12
(13)
15
53.0
75.1
60
(63)
(65)
70
(80)
(93)
109.8
105.7
152.9
158.0
177.9
185.6
* Sales
—
—
—
—
— ' • : .
— '
—
103.0
97.6
136.4
140.6
160.5
169.0
of Pounds)
for 1971
for 1973

Production
1957
1958
1959
1960
1961
1962
1963
1964
1965
1966
1967
1968
1969
1970
1971
1972 (p)
1973 (p)
Jan. 1974
(p)
196.6
187.2
203.0
209.4
225.1
320.5
325.1
365.7
429.4
462.7
533.0
636.5
635.3
706.9
704.7
(745)
693.8
65.8
and from
Preliminary
Sales
168.6
162.3
186.0
187.2
225.4
307.7
278.1
335.6
385.0
424.8
468.7
567.0
611.6
640.2
653.9
—
     Tetrachloroethylene profits from the restriction on trichlordethylene,



although methyl chloroform is favored in metal degreasing because of its lower



toxicity.



     The dry cleaning market is expected to increase its consumption of




tetrachloroethylene at 4-5% per year through 1975.  'It is estimated that the



perchloroethylene consumption for industrial dry cleaning will increase



from about 90 million pounds in 1971 to 200 million pounds by 1975   (Chemical




Economics Handbook).




                                      71

-------
III.  USES




     The chlorinated hydrocarbon solvents find their most widespread appli-




cations as alternatives to water-surfactant systems in dry—cleaning and metal




degreasing (Carbonnier, 1967; Streeb, 1972; Weitbrecht, 1965; Willard, 1972).




     The use of organic solvents as substitutes for water as a medium for




dyeing fabric could eliminate much of the liquid dye wastes from textile




plants, since less actual waste remains after dyeing and this smaller




amount could be used in a variety of ways.  This would have an immediate




effect on the water pollution problem.  Tetrachloroethylene is the subject




of much research in this area (Byeland, 1971; Fielding, 1972; Furness,




1971; Gebert, 1971).




     Methyl chloroform is the principal solvent in wet cleaning applications.




Its use as a vapor degreaser is expected to increase by 10% per year as




trichloroethylene undergoes further restrictions.  The low toxicity of




methyl chloroform, its good evaporation rate, lack of flash and fire points (in air),




and moderately high vapor pressure qualify it as a solvent and carrier for




many of the active materials used in aerosols, specifically in spot removers.



It is used to raise the apparent flash point in-flammable petroleum solvents and




is used as a coolant in cutting oils, printing inks, and shoe polishes.  It




is a resin solvent in adhesives and is used in the'textile industry for




processing and finishing.  Dow Chemical produces vinylidine chloride directly




from methyl chloroform.




     While trichloroethylene has incurred disfavor as a solvent in vapor




degreasing because of its escape into the atmosphere (Dale, 1972;




Greve, 1971), it may find wide application in non-aqueous textile processing




and finishing (Dyhrenfurth, 1972; Willard, 1972).

-------
     Trichloroethylene is used as an inhalation anaesthetic during parturition


and in dentistry (Huff, 1971; Kloos, 1966).  It is used in the extraction of
 I      •                   <*

hops and of soybean oil meal (Kloos, 1966; Pritchard, 1956).


     Tetrachloroethylene is the leading dry-cleaning solvent and is the subject


of much research in the dyeing industry (Byland, 1971; Fielding, 1972; Furners,


1971; Gebert, 1971).  It is used in both cold-cleaning and -vapor degreasing of


metals, as a solvent for silicones, and as an intermediate-in the synthesis of


fluroocarbons 113, 114, 115, 116.                                     .


     In the past, tetrachloroethylene has been used in treating fresh and


dried fruits (Deshusses, 1955) and in controlling rot-producing mold on straw-


berries and on other fresh fruit (Mapers, 1954).  More recently, the brominated


hydrocarbons have replaced tetrachloroethylene in these processes.


     It has been applied medically as an antihelmetic (Jung, I960; Mackie, 1955)


There are no references to this application in the more recent literature,
                                  73

-------
                                    Representative Commercial Products Containing Trichloroethylene
    Brush Top Spot Remover, Regular**
     (Product Sales Co.)
     Espersol 2530 (xylene)     87%
     Trichloroethylene          10*
     Perchloroethylene            1.5
     Methylene chloride           1.5
    Brush Top Spot Remover, Super**
     (Product Sales Co.)
     100% chlorinated solvents
      Triethane (1,1,1 -trichloroethane) 50%
      Trichloroethylene               25
      Perchloroethylene               10
      Methylene chloride               5
    Carbona Cleaning Fluid
     (Carbona Products Co.)
     Trichloroethylene          44%
     Petroleum hydrocarbons    56
    Carbona No. 10 Special Spot Remover
     (Carbona Products Co.)
     1,1,1-trichloroethane       10%
     Trichloroelhylene          40  •
     Petroleum hydrocarbons    50
    Carbona Spray Spot Remover
     (Carbona Products Co.)
     Trichloroethylene
     1,1,1-Trichlorethane
     Cab-O-Sil
     Freonl2
    Crater 2X and 5X Fluid
     (Texaco, Inc.)
     Petroleum lubricating oil
     Trich'.oroethylene
     Pine tat
    DuPont Dry Clean
     (du Pont)
     Trichloroethylene
    Dux
     Water Repellent
     (Detrex Corp.)
       Piccotex 120 Solution      25%
        (synthetic resin)
       Wax (paraffin)
       Trichloroethylene
    Glamorene Dry Cleaner for Rugs
    (Formerly Glamorene Wool Rug Qeaner)
     (Glamorene Products Corp.)
     Chlorinated hydrocarbon
       (trichloroethylene)
  Petroleum distillate  ' •
  Wool flour
 Glamorene Rug Qeaner
  (Glamorene Products Corp.)     t
  Trichloroethylene          t
  Ethylene dichloride
  Heavy naphtha             .
 Helmac Spot Pic-Up         ;
  Aerosol spot remover
  (Helmac Products Corp.).    '        .
  Perchlorethylene
  Methylene chloride
  Trichloroethylene

HH Tree Wound Healer
 Protective seal for pruned and damaged
  tree and shrubs
 (Hubbard-Hall Chem. Co.)
  Asphaltum       '             • ••.  :
  Petroleum oils   '                  v
  Phenylmercury oleate    .    ••••'.•  /:
  Allantoin      ;              •/:',',
  Inert ingredients:
    Dichlorodiiluoromethane     ..  .  ,.
    Trichloroethylene
    Methylene chloride             :  ,
Instant Chimney  Sweep             -
 Aerosol spray application
 (Miracle Adhesives)
  Trichloroethylene
  Active chemicals
  Propellant (Freon)
Joy Solvent**
 (Joy Chem. Inc.)
  Trichloroethylene
Kwik Kleen Drug Shampoo*
 Dry Shampoo
 (Royal Bond, Inc.)
  Trichloroethylene
Lash Bath
 Cleanser for false eyelashes
 (Revlon)
  Naphtha
  Trichloroethylene
O'Cedar Sea-Spray**
 (O'Cedar)
  Methylene chloride
  Trichloroethylene
%w/w
  34
  41
  25
           •  Cellbsolve acetate
             Synthetic detergents
             Wax
             Freon propellent
           Perm-A-Qor NA
            (Detrex Corp.)
             Trichloroethylene

           Sears Air Freshener
           Sears Odor Neutralizer
            (Sears,'Roebuck, & Co.)

             Essential oils
             Perfume
             Trichloroethylene

           Spot Chief**
            Aerosol ring-free spot remover
            (White Frost, Inc.)
           .  Trichloroethylene
             Perchlorethylene
             Solvent 310 (petroleums
  Solvent 310 (petroleum solvent)
  Paradichlorobenzene
  Lanolin
  1,1,1-trichloroethane
  Freon 12

Surfisan Spray*
 Surface disinfection, preservation
  and deodorizing .
 (Koyal Bond, Inc.)
  Chloroform
  Kerosene
  Camphor
  Trichloroethylene

Triad Metal Cleaner
 Trichloroe thy lene
Triad Metal Polish
 Trichloroethylene
Trichlor
 Solvent
 (P.P.G. Industries, Chem. Div.)
  Trichloroethylene    100%
Tri-Qene Dry Clean
  Trichloroethylene
    •No longer contains trichloroethylene but listed since some products may still be in use.
    No longct marketed, but some may still be in use.
    The above product descriptions are not to be construed as current or accurate since changes in product composition are being made
    continually by manufacturers.                                                 •
Source:    Huff,  1971

-------
     The following are data on the consumption of the chlorinated hydro-

carbon solvents in 1971.


                        Methyl Chloroform Consumption

                               Millions of Pounds      Percent
Cleaning solvent
  Cold cleaning
  Vapor degreasing

Exports

Vinylidene chloride

Miscellaneous

Total
200
 50
250



 50

 35

 40

375
  67%



  13
.*""''' •
  9

  11

100%
                        Trichloroethylene Consumption

                               Millions of Pounds      Percent
Metal Cleaning

Exports

Miscellaneous

Total
         •  455

            52

            32

           539
                84

                10

               	6

               100
                 Estimated Perchloroethylene Consumption

                               Millions of Pounds      Percent
Textile Industry                          435

Exports                                   125

Metal Cleaning                            110

Chemical Intermediate                      70

Miscellaneous                             	8_

Total                                     748^

Source:  Chemical Economics Handbook
                           58%

                           17

                           15

                            9

                          	1

                          100%
                                    75

-------
IV.  CURRENT PRACTICE




     Methyl chloroform Is substantially stable under usual handling conditions,




although it ±a sensitive to hydrolysis.  The commercial product always contains




Small amounts of stabilizing substances, the most common of which are:  glycol




diesters, solvent ketone mixtures, nitriles, dialkyl sulfoxides, imines, dialkyl




sulfides, dialkyl sulfites, tetraalkyllead, morpholine, nitroaliphatic hydro-




carbons, 2-methyl-3-butyn-2-ol, tertiary butyl alcohol, tetrahydrofuran, 1,4-




dioxane, sec-butyl alcohol, and monohydric acetylenic alcohols.




     Stabilized methyl chloroform can be stored in mild steel tanks fitted with




a drier to prevent ingress of moisture.  It is transported in lacquer-lined mild




steel drums (.Kirk-Othmer, 1964).






     Hill (1962) investigated the possibility of non-flammable halohydrocafbons




forming explosive mixtures at elevated pressures.  Methyl chloroform liquid




at 24°C pressured to 6 Ib/sq. in. gauge could not be ignited by fusing a




one-inch nichrome wire at 50 or 80 volts.  When the system temperature was




raised to 36°C and the pressure to 26.5 Ib/sq. in. gauge, and fired at 80




volts, a moderate temperature increase and a pressure surge to 65 Ib/sq. in.




gauge occurred.

-------
     The most exothermic combustion reaction which can be written for this
compound is:             .                   .                                   ,
CH3CC13 + 202-»2C02 + 3HC1
 H = -218 Kcal.
     Experimental results indicate that this reaction probably did not occur.
A more likely initial combustion reaction is:
CH3CC13 + 1.75 02 -» C02 + 1.5 H20 + CC13*
 H = ca -33 Kcal.
     This mildly exothermic reaction would be followed by exothermic reaction of
of the CC1 " radical such as:                           -
2 CC13* -> CjClif + C12
resulting in over-all heat release of about 75 Kcal. per mole of pxygen consumed.
     Methyl chloroform will burn, although not energetically, at a tenperatmre
of 36 C and a pressure of 26 Ib/sq. in.
     The flammability of trichloroethylene-air mixtures has been incorrectly
assessed in the literature.  Several reported explosions led to an investigation
by the Bureau of Mines (Perlee, 1966) on the conditions under which such
explosions can occur.  The results of these investigations show that if trich-
loroethylene is handled in the manner prescribed in Chemical Safety Data Sheet
No. 14, published by the Manufacturers and the Manufacturing Chemists'
Association, fires and explosions need not be encountered.   Pertinent data
from these investigations are given here.
                                     77

-------
           £
          CO
          co
          UJ
          ec
          Q.
 1,000

  800

  600


1  400

  300


  200
100
 80

 60


 40

 30


 20



 10
                                      10
                                  TEMPERATURE, * C
                                 20    30  : 40
                                                    60
                                     80
100
               KEY
       •   Air
       o   Oxygen
       O   Nitrogen tetroxide
       A   7-inch-diam tube
      	Experimental curve
      	Theoretical curve
                              Impossible mixtures
                                                                               Nonflammable
                                             11.8 pet
                                             11 pet
                                       7.9 pet
                                                                                10.5 pet
                                                                                -—o—
                                                                                 7.5 pet
                                                      Nonflammable
                                                        UJ
                                                        a:
                                                        O
                                                     100 eg

                                                      80 a. £

                                                      60 < eJ
                                                        LU 
                                                      30 a~
                                                        ui .5?
                                                        O) X

                                                      »li
                                                                                            10
                                                                                   UJ
                                                                                   O

                                                                                  1
50               100
        TEMPERATURE, ° F
                                                                     150
                                                                   200
                                                                           250
                        Temperature Dependence of Vapor Pressure of TCE and Concentration Limits of
                        Flammability of TCE-Air, TGE-Oxygen, and TCE-Nitrogen  Tetroxide  Mixtures.
Source:   PERLEE,  1966
                                                 T8

-------
                                         1              2             3
                                      ELAPSED TIME, seconds

                            typical Pressure History Curve for Gonstont Volume
                            Combustion  of a  15 Volume-Percent TCE-Oxygen
                            Mixture at About 29° C.
              TABLE 2. - Maximum pressure and burning  time for constant
                            volume combustion of near  limit mixtures
                                    of TCE-air and TCE-oxygen.
Mixture composition
(volume percent)
TCE
13
14
15
16
15
15
Oxidant
Air
Air
Air
Oxygen
Oxygen
Oxygen

pmax
(psig)
49
50
51
96
138
129

T
(sec)
5.0
5.2
7.0
.9
.2
.3
Source:  PEKLEE, 1966
                                         79

-------
     The United States Pharmacopeia (1970) states that trichloroethylene



should be preserved in tight, light-resistant containers.  It should be




kept from prolonged exposure to excessive heat.  The containers must




bear the statements "Caution - repeated use may cause liver damage" and




Warning - trichloroethylene must not be used in any closed-circuit rebreathing




system utilizing soda lime or other alkali because phosgene or other




toxic products may be formed."




     The standard container of trichloroethylene is usually 300 ml.  It




is stored and shipped in lined tin or galvanized mild steel drums, fitted




with screw caps or some other suitably tight method of closure.  Lare quantities are



shipped in road or rail tank cars.  Large-scale storage tanks should




be of mild steel, fitted with a dryer.  Vents should, of course, lead to




a safe point outside the storage building.




     Commercial trichloroethylene stabilizers cover a tremendous variety



of chemicals, some of which are:  acetone, aniline, borate esters,




epoxy compounds, hydroxyanisole derivatives, hydrazones, isocyanates,




nitro compounds, phenol, pyrrolinic derivatives, stearates, tetrahydrofuran,




and thiazoles.




     The methods and conditions for the storage and transport of tetra-




chloroethylene closely follow those for trichloroethylene.  Tetrachloro-




ethylene, however, may also be stored in cast iron or galvanized iron




containers.
                                       80

-------
V.  ENVIRONMENTAL CONTAMINATION

     Since the chlorinated hydrocarbons are employed chiefly as solvents,

particularly in metal degreasing and dry-cleaning, their primary escape route

into the atmosphere is by evaporation.  A secondary source of contamination

is the presence of these solvents in effluents.  It has been estimated

(Murray, 1973) that each year in the United States 2 x 105 tons of these

chemicals are lost to the environment.

     There are three mechanisms by which solvent vapors escape from a vapor

degreasing plant:  by external air currents, thermal convection currents,

and molecular diffusion (Greve, 1971).

     Synthetic fibers retain a certain amount of solvent, holding as much

as 5% on the weight of the cloth.  This solvent can volatize in a framing

oven, or in a storage room or warehouse from which it passes to the outside

atmosphere.  •    •  •

     The efficiency of solvent recovery from a variety of sources has been

claimed to be on the order of 95%, which leaves room for pollution problems

in large-scale operations (Willard, 1972).

     In the literature collected, surprisingly little information appeared on

the incidence of methyl chloroform, trichloroethylene, and tetrachloroethylene

in the air, in ground waters, or in surface waters.  No information at all is

available about the levels in the environment of the United States.

     In an introductory study on samples of surface waters collected from the

northeast Atlantic in August, 1972, an average of 7 ng per L of trichloroethylene

and 9.5 ng per 1 of tetrachloroethylene were found.  Molluscs from the rela-

tively unpolluted water around the Isle of Man-had accumulted significant con-
                v'-                     .  • • •        •' •;.'         .        .
centrations of several chlorine compounds, none of which were specifically
                                    81

-------
named in the published report of the studied conducted.




     In air samples taken from over the northeast Atlantic and from the rural




areas of Britain, 6 ng m 3 of trichloroethylene and 5 ng m 3  of tetrachloro-




ethylene were found (Murray, 1973).
                                    82

-------
VI.  MONITORING AND ANALYSIS




     Many of the classical analytical procedures which employ techniques such




as combustion, hydrolysis, and the Beilstein reaction are still used, although




these are nonspecific since they relate total chlorine to the desired com-




ponent.  They are therefore quantitative when a dingle compound is being




tested, but are qualitative only, when a mixture is being tested.




     The colors of the products obtained from the reaction of the chlorinated




hydrocarbon solvents with pyridine and sodium hydroxide (Fujiwara reaction)




are colorimetrically applicable.  The reaction of tetrachloroethylene with




pyridine .aniline, and sodium methylate offers increased sensitivity and more




stable color than the Fujiwara , reaction.  A comprehensive presentation of these




analytical methods is included in The Encyclopedia of Industrial Chemical Analysis.




     Gas chromatography, infrared spectroscopy, and mass spectroscopy can dis-




tinguish between individual compounds and give qualitative and quantitative data




on those present.






A.   Analysis of Mixtures




     In the field sampling of air, Grupinski (1966) mentions the possibility of




error through loss of the higher-boiling solvents by condensation in the gas




sample container during transport.  Drasche (1972) recommends Teflon bags to




store exhaust gases from motor vehicles  (excepting methane and acetylene) for




several days duration.  Initial volumes can be attained by heating the bags.




Saran bags are recommended for long-term storage in the presence of carbon mono-




xide, methane, or acetylene in the air samples.




     However, the use of charcoal tubes for collecting air samples prior to




gas chromatography testing has been shown to be efficient and practical.  The




air to be sampled is aspirated through a standard charcoal sampling tube at an




accurately measured rate of 1 to 2 liters per minute.  The charcoal is trans-





                                   83

-------
ferred to a glass-stoppered Erlenmeyer flask, 3 ml of carbon disulfide is added,




the flask Is stoppered, allowed to stand for 10 min, and gently swirled.  A




10 ml aliquot is injected into the gas chromatograph.  This method gives average




recovery values of 962, 102%, and 100% for methyl chloroform; 88%, 96%, and 100%




for trichloroethylene; and 92%, 95%, and 97% for perchloroethylene (Reid, 1968).




     A rapid field sampling of halogenated hydrocarbons in crude oil is given




by Jordan (1967).  Description of the distillation apparatus is given together




with the experimental details.  Pyridine and NaOH are added to the distillate and




read colorimetrically against standards prepared with kerosene.  The lower




detection limit of methyl chloroform is 90 ppm,' with 1 ppm for trichloroethylene,




and 500 ppm for tetrachloroethylene.                 ..._..




     Methyl chloroform, trichloroethylene, and tetrachloroethylene can be




determined in sewage sludge by either of two methods:  1) the solvents are




isolated  from the  sample by steam distillation, dissolved in n-hexane or




in cyclohexane, reduced with  sodium, and the free chloride ions are deter-




mined titrimetrically; this method has a detection  limit of 0.1 mg of




chlorine  per liter of  sludge.  2) The solvents are  dissolved in ethanol




or cyclohexane, purified with Na2SO^, and  analyzed  by  gas chromatography




(Montgomery, 1967).



     A rapid method for separating and identifying  chlorinated solvents in paint




was developed by Crippen and  Emmerling  (1960).  The volatile solvents are




separated from the paints either  by conventional distillation or  steam distilla-




tion.  The condensate  is injected into gas-phase chromatograph operating between




70-125°F, with a helium flow  rate of approximately  75  ml/min in Perkin Elmer




packed columns.  The identity of  the peaks is determined by time  of emergence



(retention time) of the peak  under given to  temperature, gas flow, and column
                                     8U

-------
packing.  If a peak is questionable, it may be trapped and examined on an infra-




red instrument for positive identity.  These procedures are useful also in




examining blood and body  fluids for inhalation or absorption of chlorinated




solvents.




     Infrafed spectrophotometric methods for determing trichloroethylene and




tetrachloroethylene in various Pharmaceuticals are described by Carol  (1955)




and Healton (1962).






B.  Trichloroethylene




     Campbell (1959) bubbled contaminated air through toluene at 1 L per min.




to test the applicability to air of the method of Seto and Schultze (1956),




which is a modified Fujiwara reaction developed  for determining trichloroethylene




.in urine,  This is a colorimetric prodedure in which the sample is mixed with




toluene, followed by addition of pyridina and ethanolic potassium hydroxide.




The results of this method.used on air were comparable to the results obtained




after dehalogenation with sodium biphenyl and subsequent determination of the




chloride ion by the mercuric thiocyanate method.




     Gage (1959) describes an air sampling system for trichloroethylene deter-




mination, consisting of two tubes connected in series.  The first tube contains




a layer of silica gel impregnated with potassium permanganate and orthophosphoric




acid.  The second tube contains silica gel impregnated with o-toluidine hydro-




chloride and serves to measure chlorine liberated by the first tube by the depth-




of color development.  The life of these tubes is nine months and their precision




is adequate for industrial hygiene air analysis.




     Another application of active charcoal .for...the adsorption of chlorinated




hydrocarbon solvents is demonstrated by Herbolsheimer (1972).  In this case air

-------
is sampled in work areas at the head level of workers.  N-decane is used as




the desorption reagent and the determination is carried out on a gas chroraa-




tograph with a dual flame ionlzation detector.  In testing for trichloroethy-




lene, this method gives reproducibility of 95-100% and is quantitative to



1 ppm.




     To determine trichloroethylene residues in spice oleoresins after solvent




extraction, Roberts (1968) used a microcoulometric gas chromatograph and read




the results against reference standards.




     Using activation analysis, Morgan and Duxbury (1965) developed a method




for determing trichloroethylene in air.  The air sample is drawn through a




saall charcoal pack by means of a battery-operated air flux and the Cl38




formed is determined by y-spectrometry.  The lower limit of detection on




the equipment used was about Img of chloride.




     Versie, Dodinval-Versie, Heusghem, and Moreau (1962) used gas chromato-




graphy to determine the concentration of trichloroethylene in blood following




intoxication.  A 210 ml sample of blood was drawn from 345 of brain tissue.




The sample was treated with distilled water and toluene, before being analyzed




for trichloroethylene under the following conditions:  Instrument, Perken Elmer




vapor fractometer; stationary phase, 25% didecylphthalate on cellite 545;




mobile phase, hydrogen; temperature, 83°C; voltage, 6.5V; flow rate 3.3 1/hr;




pressure, 9.5 kg/cm2; sensitivity, 1 part of trichloroethylene .to 32 parts of




toluene.






C.  Tetrachloroethylene




     The Hygienic Guide Series  (1960) recommends that air to be tested for




tetrachloroethylene should be collected on silica gel followed by hydrolysis




with metallic sodium and determination of halide content.  The alternatives






                                   86

-------
mentioned are expulsion from the silica gel by heat, followed by combustion,




trapping the chloride in sodium carbonate-sodium formate solution and titrating




the trapped chlorine, or a direct combustion method followed by chloride




titration.




     Strawberries which have been fumigated with tetrachloroethylene can be




tested for residue nephelometrically after extracting the tetrachloroethylene




with ethyl ether and evaporating in the presence of ethyl benzene (Mapes, 1954).




Deshusses (1955) extracted the tetrachloroethylene from fruit by thermal




decpnposition and titrated the liberated HC1 with HgN03.






VII..  CHEMICAL REACTIVITY




     Chlorinated solvents in vapor concentrations of a few ppm may decompose




if they contact open flames and/or hot surfaces.  The decomposition products




are hydrogen chloride, carbon dioxide, carbon monoxide and phosgene.






A.  Methyl Chloroform




     Possessing no unsaturation, methyl chloroform is inert to atmospheric




oxidation under normal handling conditions.  It is, however, easily hydrolysed




in an excess of free water, especially at elevated temperatures and in the gas




phase (Dyhrenfurth, 1972).




     Heated at 75-160°C with water under pressure, methyl chloroform decom-




poses in the presence of sulfuric acid or metal chlorides, according to the




quantity of water present, to give acetyl chloride, acetic acid, or acetic




anhydride.  At temperatures over 370°C methyl chloroform is subject to atmos-




pheric oxidation yielding phosgene as one of the decomposition products, with




1,1-dichloroethylene and HC1 also given off."
                                   87

-------
     In contact with iron at 402°Cj copper at 369°C, zinc at 338°C, aluminum




at 354°C, brass at 354°C, and steel at 354°C, the amounts of phosgene in the




decomposition products are respectively, 0.8, 0.4, 1.9, 0.3, and 0.3 mg of




phosgene per gm of methyl chloroform  (Noweir, 1972).




     Methyl chloroform reacts with chlorine in sunlight to give 1,1,1,2-




tetrachloroethane, along with small quantities of penta- and hexachloroethane.




Reaction with anhydrous hydrogen fluoride at 144°C in the absence of a cata-




lyst results in formation of 1,1-dichloro-l-fluoroethane and l-chloro-1,1-




difluoroethane (Kirk-Othmer, 1964).






B.  Trichloroethylene




   .  The unsaturated bonding in trichloroethylene is sensitive to atmospheric




oxidation in light.  However, in the presence of suitable stabilizers, it is




stable to air, moisture, light, and contact with common metals up to 130°C,




where it becomes corrosive to metal.




     Trichloroethylene is not hydrolysed by water under normal conditions




(Dyhrenfurth, 1972).  It reacts with  alkaline hydroxides at 150°C to give




glycolic acid.  Strong alkalies react readily with trichloroethylene to form




explosive chloroacetylehes.  Sodium carbonate and aqueous ammonia do not




react.  In the presence of soda lime  at 37°C, trichloroethylene decomposes




readily to dichloroacetylene, which then oxidizes readily to phosgene and




carbon monoxide.




     Trichloroethylene does not react with cold inorganic acids but decomposes




violently in hot nitric acid.




     In the presence of catalysts  such as finely divided aluminum, or on exposure




to light, thermal decomposition occurs at 120°C  (Smith, 1966).  -In contact

-------
with iron at 450°C, copper at 500°C, zinc at 450°C and aluminum at 425°C,   -




the amount of phosgene in the decomposition products is. 19, 31, 69 and 35 mg




of phosgene, respectively, per gm of trichloroethylene (Noweir, 1972).




     When trichloroethylene is heated to 700°C, the vapor decomposes to give




a mixture of dichloroethylene, perchloroethylene, carbon tetrachloride,




chloroform, and methyl chloride (Kirk-rOthmer).                            :






C.  Tetrachloroethylene




     Unstabilized tetrachloroethylene in contact with water for long periods




slowly decomposes to trichloroacetic acid and HC1.  It is sensitive to atmos-




pheric oxidation on exposure to light, going to trichloroacetyl chloride.




Stabilized tetrachloroethylene is inert to air, water, light, and common




metals to 140°C.                 -




     Strong inorganic acids will oxidize tetrachloroethylene to trichloro-




acetyl chloride and tetrachlorodinitroethane.  With ozone; it is decomposed




to phosgene and trichloroacetyl chloride (Kirk-Ot timer ).




     In contact with iron at 450°C, zinc at 400°C, and aluminum at 400°C,




the amount of phosgene given off in mg of phosgene per gm of tetrachloroethy-




lene is 37, 17, and 3, respectively (Noweir, 1972).
                                  89

-------
VIII.  BIOLOGY

     A.  ABSORPTION

     Methyl chloroform, trichloroethylene, and tetrachloroethylene are

volatile compounds and inhalation is the dominant intake route into human

or animal systems.  They are absorbed very rapidly through the lungs and

gastrointestinal tract.                                                   .

     Skin absorption studies were performed on these three solvents using six

human subjects.  The skin of the hands was exposed to the solvents and the

amount of the compounds in the alveolar air during the skin exposure and in the
post-exposure period was determined by gas-chromatography.  While all the sol-

vents penetrated the skin, it was concluded that they would not be likely to be

absorbed in toxic quantities when in contact with the skin of the hands and

arms (Stewart and Dodd, 1964).

     McBirney (1954) reports paralysis of the thumb and forefinger following

intermittent repeated immersion of the hands in trichloroethylene under industrial

conditions.
                  '-.'•>.•"         - "           :

  .   B.  EXCRETION

       1.  Methyl chloroform

     Studies involving the inhalation of methyl chloroform by human subjects

shows that the excretion of unchanged methyl chloroform via expired air has

an inverse exponential relationship to the time after exposure.
                                     90

-------
70
50
30
20
!*>
7
5
3
2
: ::^

_. ._._










X
t










S











• —











1











\ I.I.I-TRICHLOROETHANE
i CONCENTRATION, PPM
1
.7
.5
.3
.2
.1

















/









' ..-











s










N
s




















j












•)
S •
.
s
1



















. . i. 	 i . ; i iii LI .. j..
	 	 1 • 500 ppm, 78 mm (Exp
_...- 	 : o 496ppm,l86min,(E«p
0 ! ;
r\ ° ' j
\
L Xp
XN
: ->,
x_-
X






i







1
•


























T
y
s
-


-ts
T
>l
TN
1 i.









^



s






i























s

^















--

si


s



















S_ 0
V °
X
\
\









1)
2)

—


j
1







>
j
i

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; o
^




















                     2   3   5  .7   I     23   57  IO
                               HOURS AFTER EXPOSURE
2O 3O 4O
         	  1,1,1-Tric-lilorocthane Expired Air Concentration. Humans were exposed to
       atmospheric concentrations of 500 ppm for 78 minutes (Exp. 1) and 496 ppm for 186 minutes
       (Exp.2).
SOURCE:   Stewart and Gay,  1961 (1)


     Following absorption  of methyl chloroform^  most of the compound ±s excreted

unchanged in the expired air and the metabolites trichloroethanol  and trichloro-

acetic acid appear in the  urine   (Stewart, 1968).

     The  concentrations of methyl chloroform  in  human urine samples taken during

exposure  indicated that some samples possibly contained up to  2  ppm of the compound.

Samples obtained 15 minutes after exposure revealed the presence of a trace amount

in some,  with none being detected in others (Stewart and Gay,  1961 (!))•   .
                                         91

-------
        2.   Trichloroethylene

     The following data are given by Stewart and Dodd (1970),  demonstrating the

excretion of trichlorbethylene in the  expired air  of human subjects after

exposure.
          I
          Q
          a.
          0
          o
          ul
          z
          ul
          J
          ul
          0
          I
          O
                         CO
  108 3ppm. 7hrj /Joy - S d
       6 tubjeett
5 2OOppm, 7hr» - 5lubj»ct»
X 197 7opi>. 3lvi.2Omir> - 2 mbj
  2O2 ppm/ 1 h' - 2 lubj«ctl
• 1OO. 1 ppm, 4hr».- 2 tubjoctt


                             2O     3O . :   4O    'SO     (SO
                                 TIME IN HOURS AFTER EXPOSURE
                        -Following exposure, concentration of trichloroethylene in the expired breath
                 decreased exponentially. Concentration mean and range are plotted. Amount of solvent
                 present related to both duration of exposure and concentration of solvent during exposure.
      Bartonicek (1962) measured the excretion  of trichloroethylene by 9 human

volunteers who  inhaled 1  g/m3 of  the compound  for 5 hours.   He found  the retention

rate to be 51-64%.  The greatest  amount of the trichloroethylene which was

excreted via  the lungs was exhaled  on the 1st  and 2nd days  after exposure, and

in  traces on  the third day.  Of the trichloroethylene retained, 38 to  49.7% was

excreted in the urine as  trichloroethanol and  27.4 to 35.7% as trichloroacetic

acid.  8.4% was excreted  in the feces in the form of metabolites.  The

remainder was excreted in perspiration and in  the saliva in the form  of

metabolites >
                                       92

-------
     Ikeda  (1972)  calculated that only one-third of the trichloroethylene

absorbed  through the lungs was excreted  in  the urine during working time.   His

studies were  performed on urine samples  from 85 male workers from 17 workshops

where the vapor concentration in the air was relatively constant.
      In  an  earlier experiment, the excretion of trichloroethylene was investigated

by Soucek  (1959)  using five human subjects.   A 6% concentration of trichloro-

ethylene was  administered to the subjects by continuous inhalation for five hours.
                                                                         \ •
The subjects  retained 630-1288 mg, representing 58-70% of the amount inhaled

during exposure.   Metabolites were present  in the urine immediately after  the

beginning of  inhalation.  Excretion of  these metabolites in the urine lasted

between  312 to 520 hours.


       3.   Tetrachloroethylene

     Mice were exposed for 2 hours to tetrachloroethylene-C11* vapor.  In 4 days

70% of the  amount inhaled was excreted  in the expired air, and 20% appeared in

the urine in  the  form of metabolites (Yllner,  1961).

     Six human subjects were exposed to tetrachloroethylene vapor, 194 ppm for

187 minutes.   No  tetrachloroethylene was found in the urine.  Following is a

plot of  the exhalation of the compound  in time./

                                 TETRACHIOROETHYUENE EXPIRED AIR CONCENTRATION )
              -Tetrachloro-
      ethylene expired air con-
      centrations following
      vapor exposure.  Mean
      concentration  and range
      are plotted.
                                                 . lo.e
                                                TIME in HOUII*
                                                                       10009
SOURCE:  Stewart and Gay,  1961 (2)
                                         93

-------
     C.  TRANSPORT AND DISTRIBUTION               ,






       1.  Methyl chloroform




     Six subjects were exposed to methyl chloroform at 500 ppm for 78 minutes.




Analysis of serial blood samples obtained during the exposure revealed that the




average concentrations of methyl chloroform in the blood at 30, 60,  and 75




minutes after the start of the exposure were all between 3 and 4 ppm   (Stewart




and Gay, 1961 (1)).




     No studies on the distribution of methyl chloroform or its metabolites in




the tissues are reported in the material at hand.






       2.  Trichloroethylene




     Trichloroethylene tissue uptake after vapor exposure was investigated




on dogs.  Exposures were both acute and chronic with exposure times varying from




25 minutes to 219 hours at trichloroethylene concentrations ranging from 7,000




ppm to 20,000 ppm.  After sacrificing the animals, cardiac blood and cerebral




spinal fluid were removed for immediate extraction, and tissues were frozen until




ready for processing.




     The trichloroethylene concentration was determined colorimetrically after




extraction from the various tissues.  Known amounts of trichloroethylene were




added to various tissues of normal animals as extraction controls.

-------
                            TJUCHLOKUKTHYLKNK RECOVERED FROM TISSUE
                             (Corrected—in milligram* per cent wet weight)
Animal
Number
12
15
1C.
17
20
25
14
2t
1'J
22
24
Anincil
Nuiiitvr
12
15.
10
17
20
2.5
Mtxlr ol Exposure
o Acute
Acute
Acuiu
.Adltl!
Acutu
Acute X3
Chronic-Acute
Chronic-Acute
Chronic
Chronic
Chronic
Moils of Kxpoaiire
Acute
Acute
Acute
Acute
Acute
Acute X3
14 i Chronic-Acute
21
10
22
24
Chronic-Acute
• Chronic
Chronic
1 Chronic
Adrenal
22.4
6.24
—
—
22.5
13.S
60.0
2;u
—
0.94
1.06
Lung
2.8
2.2
0.02
0.92
0.40
10.4
2.0
1.3
0.53
0.20
0.13
Blood
72.5
4ti.O
,r>2.7
22.3
28.4
50.0
4ti.l
50.6
9.6
0.13
0.25
Muscle
2.7
—
0.15
3.3
5.1
9.3
—
3.8
4.1
0.45
0.30
Brain
17.0
15.1
19.7
—
8.2
' 20.9
— .
23.6
2.7
0.22
0.22
Pancreas
—
3.2
9.8
6.4
14.1
43.8
8.1
16.0
2.5
<0.05
0.28
Fat
17.9
14.7
—
4.8
70.4
70.5
—
22.1
30.7
14.4
6.5
Spinal
. Cord
8.8
' —
—
—
—
28.3
—
. —
—
0.13
0.13
Heart.
8.0
5.0
5.4
4.2
18.9
13.9
7.5
12.U
1.2
0.11
0.11
Cerebro
Spinal
Fluid
—
3.8
1.5
0.61
1.7
• —
0.15
1.8
0.15
0.15
O.io
Kidney
1.6
8.2
5.8
3.0
3.2
17.5
21.1
5.3
1.0
0.13
0.25
Spleen
0.71
•• 3.U
1.2
5.4
1.3
5.1
—
8.5
0.71
<0.05
0.12
Liver
27.0
9.6
38.8
10.8
9.2
49.4
.20.6
9.7
3.2
0.12
0.25
Thyroid
—
2.0
6.6
—
3.9
14.1
5.8
7.4
1.1
<0.05
0.63
SOURCE:   Cohen, 1958
        3.   Tetrachloroethylene

     Human volunteers were subjected  to exposures  of tetrachloroethylene vapor

and the  following amounts  of the compound were found in the blood:
«.o
. ».s
J.O

TETRACHLOROETHYLENE CLOOO |
CONCENTRATION DURING EXPOSURE |






lie TBflCm.OBOt TMTLtME I
1 PP« 1
_ z.s
1.0
1.9
1.0
0.5
0





/
/
1
1
1
/
/



T/
/
/'
/





y
/
'
*._«





V
s



.s' -
^. 	



• 1*4 PPM. « HIM.
9i>« rm.ium*.






•— "^™-

,





                                    1.0    1.5    IO
                                       TIME IN HOURS
 SOURCE:
Stewart and  Gay, 1961  (2)
                                            95

-------
       D.   METABOLISM AND METABOLIC EFFECTS


       Five male volunteers were exposed to  500 ppm of  methyl chloroform, 7  hours


 per  day  for  5 consecutive days.   Nine months later the same subjects  were  exposed

 to trichloroethylene vapor,  200 ppm,  7 hours per  day  for 5  days.   Twenty-four


 hour urine collections  obtained before, during, and following these vapor  exposures
                                    .        ' -           •:.•.'    «             •  .
 were analyzed for  trichloroethanol and trichloroacetic acid.   Results were as

 follows:                -.-.- — -     .                 	•„._._.•-...     • •  •         '..' '   . ,  .

                       URINARY EXCRFl'lON OF TRICHtOROACETIC ACID (TAC)  AND TRICHLOROETHANOL (TCE)
              IN FIVE SUBJECTS  DURING AND FOLLOWING VAPOR EXPOSURES TO 1,1,1-TRICHLOROF.THANE AND
                                            TRICHLOROETHYLENE                     . .
              Control value (mean and range)
    1,1,1-Trichloroethane,
        .500 ppm  .
    7 hr/day for 5 days
    TCA        TCE
  (mg/24 hr)   (mg/24 hr)
14,2(8-22,8)  < 1«1-1)
   Trichloroethylene,
       200 ppm
   7 hr/day for 5 days
  TCA        TCE
(mg/24 hr)    (mg/24 "hr)
2(1-4)     <
1st Exposure day
2nd Exposure day
3rd Exposure day
4th Exposure day
5th Day following last exposure
• 12th Day following last exposure
7,5(2,6-10,5) 20,1 ,(7,9-49) 51(34-84) 308(179-430)
10,9 (8,2-19,3) 30,1 (14,8-66,5 175(113-238) 359(294-480)
12,3(5,6-27) 29,3(19,1-51) 229(148-416) 399(296-546)
14,1 (7,8-19,2) 46,6 (23,4-93,6) 306 (231-439) 538 (249-822)
18(13-26) 7(1-14,9) 50(35-61) I5(tf>-18)
17,5(8-22) 
-------
chloroacetic acid appeared in the urine a few minutes after the beginning of




the inhalation of the trichloroethylene vapor.  The total quantity excreted




represented an aver-age of 4% of the quantity of trichloroethylene retained.




Trichloroacetic acid appeared in the urine immediately after the beginning of




the exposure.  The average of the quantities excreted represents 19% of the retained




trichloroethylene.  Trichlbroethanol appeared in the urine very soon after the




start of the exposure, and its excretion corresponded to 50% of the retained




trichloroethylene.  In the various subjects the excretion of monochloroacetic




acid continued for 48 to 168 hours, the excretion of trichloroacetic acid




continued for 312 to 520 hours, and the excretion of trichloroethanol continued




for 312 to 390 hours.  The amount of trichloroethylene which was retained during




the exposure was calculated to be between 58% and 70% of the amount inhaled.




     Bartonicek (1962) determined a retention rate for trichloroethylene to be




51% to 64% of the amount inhaled by nine human subjects.   An average of 45.4% of




the amount retained was excreted as trichloroethanol and 31.9% as trichlbroacetlc




acid.




     The comparison of trichloroacetic acid plus the trichloroethanol in the urine




and the feces (urine average 21.5 mg/100 ml; feces average 17.8 mg/100 ml)




demonstrates that both metabolites pass into the digestive system through bile




and saliva, and are secreted by liver cells and the salivary gland cells in amounts




approximating those found in the urine.




     Excretion of trichloroethanol and trichloroacetic acid in sweat demonstrates




that trichloroethanol-glucuronide circulating in blood and trichloroacetic acid




present in blood in ion form can pass into the parenchyma of sweat glands, and




are not confined to the extracellular fluid.




     Mikiskova (1966) reports that the known trichloroethylene metabolites




possess their own physiological effects.  Trichloroethanol is a central nervous




system depressant, -even when it is conjugated with glucuronic acid.  Monochloroacetic
                                       97

-------
acid has choleretic and laxative action and is hepatotoxic at high doses.




The toxicity of trichloroacetic acid is low.




     The effect of trichloroethylene on tryptophan metabolism was studied  by




determining the 5-hydroxyindole content in the urine of exposed human and  animal
                                                 0



subjects (Corsi, 1963).  A reduction of 5-hydroxyindole in the urine was




determined after administration of trichloroethylene.




     Little is reported on the metabolism of tetrachloroethylene.  Yllner  (1961)




submitted mice to tetrachloroethylene-C11* vapor inhalation and detected the




urinary metabolites:  52% trichloroacetic acid, 11% oxalic acid and traces of




dichloroacetic acid.  An epoxide is postulated as a metabolic intermediate,




with further rearrangement to trichloroacetyl chloride and then to trichloro-




acetic acid.




     Dmitrieva (1967) investigated the metabolism of tetrachloroethylene in rats




and found ethylene glycol to be the dominant-metabolite which was excreted in




the urine.  Trichloroacetic acid and oxalic acid were also determined.




     It is surprising that no follow-up work was found in the literature con-




cerning the presence of the ethylene glycol and oxalic acid in rat urine




following exposure to tetrachloroethylene.  Since it is not justifiable to apply




to man the results from experiments on animals, it would be of prime concern




here to establish that ethylene glycol and oxalic acid actually are metabolites




of tetrachloroethylene in the rat, and to establish whether any specific analysis




for these compound has been run on human urine following exposure to tetra-




chloroethylene.




     When taken internally, ethylene glycol is extremely toxic.  In fatal cases




death has been due to renal failure, with crystals of oxalic acid deposited




in the renal tubules.  In poisoning by any of the glycols or their derivatives,




the outstanding toxic effect is exerted on the kidneys (Browning, 1961).
                                98

-------
     In studies of tetrachloroethylene metabolism in humans, Haag (1958)  reports


trichloroacetic acid in the urine of two workers who had been exposed to


tetrachloroethylene.  Ikeda (1972) discusses the quantitative relationship

  !'••••'     "                  '"'•'"
between exposure to tetrachloroethylene and the concentration of the


metabolites trichloroethanol and trichloroacetic acid.

                  •           ft
                 0   •
IX.  ENVIRONMENTAL TRANSPORT AND FAT°E



     A.  PERSISTENCE AND/OR DEGRADATION


     There are many reports in the literature describing analytical methods for


determining the concentrations  of the chlorinated hydrocarbon solvents in air,


but very little is published giving figures obtained during actual field  tests


or in monitoring the environment in the vicinity of industries in which these


solvents are used.                                          .


     Nothing was found in the literature concerning the persistence or degrada-


tion of the solvents under natural atmospheric conditions.
                                    99

-------
     B.  ENVIRONMENTAL TRANSPORT




     The volatility of the chlorinated hydrocarbon solvents would provide




the mechanism for their transport in air.  Water transport would also




distribute the solvents in the environment if they should escape in




effluents from the cites where they are being used.  Their specif ic^ gravity

                          0                                    «


would tend to maximize effects in the bottoms of water streams or bodies.
                                                         a •






     C.  BIOACCUMULATION




     Murray  (1973) reports on a preliminary investigation which showed




that molluscs from the relatively unpolluted waters around Fort Erin, Isle




of Man, contain significant concentrations of several organic chlorine




compounds in their tissues.  Specific compounds found in these molluscs




are not named in this paper and amounts of chlorine compounds detected

                                                                  . '    1


are not given.
                                 100

-------
X.  TOXICITY
    A.  HUMAN TOXICITY
    1.  Inhalation of Methyl Chloroform
     The principle toxic action of a single vapor exposure of methyl
chloroform is a functional depression of the central nervous system,
proportional to the magnitude of exposure, and typical of an anesthetic
agent (Stewart, 1968).  Humans exposed to 900-1000 ppm experienced tran-
sient, mild eye irritation, light-headedness, and impairment of coordi-
nation.  At a peak of 2650 ppm two of the subjects were unable to
stand (Stewart, 1961 (1)).  Below the current threshold limit value
of 350 ppm no physiological effects have been observed.

Exposure time        Concentration
    (min)             in air (ppm)        Expected effect in humans
     60                  100              Apparent odor threshold
                         500              No detectable effect, but
                                          odor is obvious
                        1000              Very slight loss of equilibrium
                        2000              Loss of coordination
      30                1000              Eye & nasal discomfort, slight
                                          loss of equilibrium
                        2000              Loss of equilibrium        :
      15                1000              Beginning of loss of equilibrium
       5                2000      .        Disturbance of equilibrium

Source:  Stewart, 1968
     Investigating liver and kidney damage suffered by humans after
exposure to methyl chloroform, Stewart, Gay, Erley, Hake, and Schaffer
(1961 (1)) reported the following results:
                                101

-------
                 I, I, l-TriflilonM-tliiiiio I'rc- anil I'cwtoxixmuro Dalit



Normal Value
Experiment 1
500 ppm, 78 niin..




Experiment 2
496 ppm, 186 min.




Experiment 3
U5S ppm, 73 min.

Experiment 4
910 ppm, 35 min.
Experiment 5
900 ppm. 20 min.

Experiment 6
0-2650 ppm. 15 •
niin.





Sub-
ject


1
4
6
6
8
11
1
2
5
6
8
10
5
6
8
3
4
2
7
9.
1
2
3
4
6
6
7
'. SGO-T
exposure
I
20 hr.
Post

7 da.
Post

6-40
22
14
15
16
16
12
20
20
16
23
20
24
16
19
18
14
18
17
18
16
14
16
10
14
14
15
14
10
14
U
10
16
16
20
18
16
20
18
10
18
16
16
16
18
15
20
18
16
15
11
14

15
16
12
in
16
12
14
14
14
16
10
18
19

16
12
15
6
16
14
17
20
15
15
16
18
14
19
20
Urinary Uruhilinngrn
ST
•.
.£
(. hr.
Pout

2(1 hr.
Post

7 Ha.
Post
'
l:40nrl«wi
:IO
:10
-.10
:IO
:IO
:IO
; JO
• |0
:10
:IO
; |0
:10
: 10
:10
:10
1 10
:10
:tO
:10
:10
:IO
:IO
:IO
:IO
:10
:10
:IO

*






:10
:IO
:IO
:10
:IO
:10
:10
:10
:10











1:640

1:640
1:10


1:40
: 10
: 10
: 10
:10
:10
:10
:IO
:10
r 10
r 10
1 10
1 10
:10
:IO
:1U
• |o
! 10
' 10
:IO
:10
:IO
:IU
:IO
:IO
! 10
'. 10
• |Q
; JQ


1:10
1:10
1:10
1:10
1:10
1:10
1:10
1:10
1:40
1:10
1:10
1:10
1:10
1:10
1:20
Urin»ly»i»
Preeipoiure

Alb.

Micro.
'20 hr.
PostexfHMure

Alb.

Micro
0-* RUC/IIPK
neg
neg
neg
neg
nog
neg






neg
neg
neg
neg
neg
neg
neg
neg
neg
neg
neg
neg
neg
neg
neg
neg
neg
rare HOC
1-2 IlUC
rnro RBC
neg •






0-2 RBC
neg
neg
rare RBC
ne«
rare RBC
neg
.neg
neg
neg
neg
neg
neg
neg
neg
neg
neg
tmre
neg
run- HIIC
3-6 KBC
13 min. P.S.P.
Precx-
poture

211 hr.
I'lMt-

Greater tlmn 25%



nrg nire It IK' i
neg nire It TIC
neg






neg
neg
neg
neg
neg
neg
neg
neg
neg
neg
neg
neg

neg
m-g
neg






rare RBC
neg
neg
rare RBC
neg
neg
neg
neg
neg
neg
rare RBC
rare RBC

0-2 RBC
I-S RBC


30%
38%
40%
43%
89%






















44%
31.5%
39%
44%
24%
















     These data show that methyl chloroform has^the capacity  to  exert




adverse effects on the liver and kidneys.  Although in Experiment 6,  it




might seem that the liver dysfunction is transient, subject 1 and sub-




ject 7 exhibited increased urinary urobilinogen values on  the seventh




day following the exposure.  This would indicate  the possibility of




liver damage in predisposed individuals who would be subjected to a




chronic exposure to methyl chloroform.  While  the serum  glutamic oxalo-




acetic transaminase (SGO-T) values and the 15-minute phenolsulfonphalein
                                 102.

-------
excretion values following exposure deviated somewhat from the preexposure




values, they remained within normal limits.




     Death results from the absorption of a toxic quantity of methyl




chloroform, following functional depression of the central nervous




system with respiratory arrest, peripheral vascular collapse, or




aspiration pneumonitis.  The deaths from these causes are reported to




have occurred in unventilated tanks where the concentration of methyl




chloroform was well in excess of 5000 ppm.




     Severe hypotension may be induced by a combination of central




nervous system depression and myocardial anoxia, secondary to poor




oxygen uptake.



     However, no injury to man following repeated exposures to vapor




concentrations of less than 500 ppm has been observed (Stewart, 1968).




     2.  Ingestion of Methyl Chloroform




     Methyl .chloroform is rapidly absorbed from the gastrointestinal




tract and is rapidly excreted, unchanged, via the lungs.  However, the




ingestion of a toxic amount produces the same central nervous system




sequel as does the inhalation of a toxic amount.  If the amount inges-




ted is sufficient to produce loss of consciousness, liver dysfunction




may result.



     One case of accidental ingestion of methyl chloroform has been




reported (Stewart, 1968).  Thirty minutes after a man ingested one




ounce of this solvent, he became nauseated.  One hour after ingestion,




he experienced vomiting and diarrhea; this continued for two and one-half




hours at which time the man became incapacitated.  Laboratory studies




at this time showed a leucocytosis and proteinuria.  A slight eleva-
                             103

-------
tion In the serum bilirubin level was noted forty-eight hours after




ingestion.  Six months following the ingestion, no deviation from the




normal was noted in complete blood cell counts, urinalyses, serum glu-




tamlc oxaloacetic transaminase, serum glutamic pyruvic transaminase,




blood urea nitrogen and electrocardiograms.




     The median lethal oral dose of methyl chloroform in four species




of experimental animals is reported to range from 8.6 to 14.3 gin/kg.




     3.  Skin Contact with Methyl Chloroform




     Prolonged or repeated contact with the skin results in transient




erythema and slight irritation.  Several drops of this solvent splashed




directly on the cornea may produce a mild conjunctivitis which subsides




within a few days (Stewart, 1968).




     4.  Behavioral Effects of Methyl Chloroform




     The daily exposure of humans to gaseous methyl chloroform (350 ppm




or 450 ppm) did not impair performance in psychophysiological tests.




The subjects were tested for perception, memory, reaction time, and




dexterity.




     Although there were some deviations from normal patterns, these




were either not statistically significant or could be attributed to




fatigue and mental strain (Salvini, 1971).




     5.  Inhalation of Trichloroethylene




     Trichloroethylene is classified among the most toxic solvents.




The acute toxicity of trichloroethylene with its predominant effects on




the central nervous system was recognized during the First World War




when it was substituted into degreasing systems.  Individual cases of




liver damage among industrial workers have been reported.

-------
     At trichloroethylene vapor concentrations of 150-250 ppm, workmen




experienced neurologic symptoms, headaches, and fatigue.  Hypoalbuminemia




and hyperglobulinemia were observed in workers exposed for 5-10 months.




When vapor concentrations were 50-100 ppm, the frequency of symptoms




was reduced (Takamatso, 1962).  The maximum permissible level for




trichloroethylene in air was set at 100 ppm in the United States in




1961.




     Ten experimental human exposures to trichloroethylene at a 200 ppm




level were carried out for five consecutive days.  During the exposure




individual subjects complained of lightheadedness, headache, throat




irritation, and mild eye irritation.  Fatigue and drowsiness were experi-




enced.  All neurological tests were normal during exposure, but 50%




of the subjects stated that greater mental effort was required to per-




form a modified Romberg test.  With the exception of the 24-hour urine




samples which contained solvent metabolites, none of the clinical labor-




atory tests performed during or following the vapor exposures were ab-




normal.  Thus, there was no laboratory evidence that even transient




organ dysfunction had occurred.  Urinary urobilinogen tests, a most




sensitive index of hepatic dysfunction, were normal (Stewart, 1970).




     If excessive concentrations of trichloroethylene are inhaled over




extended periods of time, varying degrees of poisoning may result.




Workmen may become addicted to it.  Deaths from acute exposures to




trichloroethylene vapors most frequently result from narcosis to the




point of respiratory arrest or from primary cardiac failure.  Entry




into a degreaser with trichloroethylene present was the most important




single cause of serious injury or death (Morrill, 1963).
                              105

-------
     Longley (1963) states that acute unconsciousness can result from



the inhalation of trichloroethylene in a concentration of 3000 ppm if



the subject has had an immediately earlier, exposure resulting in a mild



intoxication.  The generally accepted level of trichloroethylene required



to cause unconsciousness is 10,000 ppm.



     Capellini and Grisler (1958) studied the liver function in a group



of twelve women who had worked in contact with trichloroethylene for



at least two years.  About one-half of the cases showed dyspeptic syn-
                                                  f


dromes, liver enlargement, and serum protein changes.  All cases had a



slight hyperbilirubinemia.  Serum total proteins, albumin, total and



esterified cholesterol, alkaline phosphatase, blood glucose, and



urea were within normal values.



     A fatal addiction to trichloroethylene was reported by.James



(1963).  A worker who showed evidence of addiction to the inhalation



of trichloroethylene .vapors developed paresis of the olfactory nerves



with intermittant gastric disturbances over a nine-year period.  Sudden



death occurred seventeen hours after the last known exposure.  On autop-



sy, fatty degeneration of the liver, and lung hemmorhage were found.



The concentrations of trichloroethylene in the body were:  2.25 mg/100



ml in the blood, 7.1 mg in the liver, 19.9 mg in the stomach and its



contents, and 14.9 mg in the small intestine and its contents.  The



urine contained 55.5 mg of trichloroacetic acid per 100 ml of urine.



     In another addiction problem, Baerg and Kimberg (1970) found



centrilobular hepatic necrosis and acute renal failure in trichloro-



ethylene "sniffers".  Three cases were involved.  All had been inhaling



fumes from cleaning fluid.  The first patient was admitted to the hos-
                              106

-------
pital with icterus.  Tests of hepatic function were abnormal, but




rapidly returned to normal.  Biopsy of the liver revealed acute toxic




centrilobular necrosis superimposed upon, a previous centrilobular




injury.  The patient had an uneventful recovery and was discharged




from the hospital on the thirteenth day after admission.




     A second patient, who had also inhaled fumes from cleaning fluid




was admitted to the hospital because of anuria of three-days' duration.




The patient had acute tubular necrosis and toxic hepatitis, both secon-




dary to trichloroethylene inhalation.




     6.  Ingestion of Trichloroethylene




     General anesthesia was the outstanding feature in the clinical




course of a human who ingested approximately 50 ml of trichloroethylene




(Fleischhacker, 1956).




     Stentiford and Logan (1956) report that an adult male who swallowed




approximately 130 ml of trichloroethylene was comitose for two days.




The foremost toxic sumptoms were short intermittent periods of very




rapid heart action.  The electrocardiogram showed prolongation of the




P-R interval to 0.26 seconds.  Liver function tests showed no abnormality.




The urine contained no protein at any time during'the course of recovery.




There was no clinical evidence of residual damage to the cranial nerves.




Full recovery ensued.




     Meyer (1965) reviewed fifteen cases of peroral trichloroethylene




intoxication, eight of which were fatal.  All cases displayed central




nervous system disturbances with cerebral edema, central respiratory




paralysis, and psychosis.  The ^electrocardiograms showed a pseudoinfarct




and cardiac arrythmia.  The blood pictures showed a shift to the left,
                               107

-------
with anisocytosis, hypochromasia, polychromasia, and basophilic stip-




pling.  Kidney function disturbances were reversible.  Toxic liver




damage was not detected although degenerative changes were observed.




     7.  Skin Contact with Trichloroethylene




     Although trichloroethylene is not absorbed through the intact skin




in toxic amounts, heavy industrial exposures to this solvent have pro-




duced generalized dermatitis.  Paralysis of the thumb and forefinger




occurred in cases involving intermittent, repeated immersion of hands in




the liquid.  This disability lasted for several months after cessation




of contact.  There was no skin damage in any of the cases (McBirney,




1954).




     8.  Behavioral Effects of Trichloroethylene




     Stopps and McLaughlin (1967) used manual dexterity tests (Craw-




ford Small Parts Dexterity Test), card sorting, and dial display in




measuring changes in psychophysiological function in human subjects




exposed to trichloroethylene vapors.  Four concentrations of trichloro-




ethylene vapor were selected for the exposures:  100 ppm, 200 pp»,




300 ppm, and 400 ppm.  Trichloroethylene showed no significant effect




on psychomotor performance at the 100 ppm level.  There is a slight




decline in performance at the 200 ppm level, which becomes progressively




more pronounced at the 300 ppm and 500 ppm concentrations.




     Salvini, Binaschi, and Riva (1971) conducted studies similar to




those immediately above, and reached similar conclusions.  In these stu-




dies, the following tests were performed:  perception test with tachisto-




scopic presentation, Wechsler Memory Scale, complex reaction time test,




and manual dexterity test.  In all the tests performed, a statistically
                               108

-------
significant decrease in performance ability was seen with increasing
vapor concentration inhaled.  These workers concluded that 100 ppra of
trichloroethylene is very close to the concentration capable of inter-
fering with psychophysiological efficiency.
     9.  Inhalation of Tetrachloroethylene
     Tetrachloroethylene is rapidly absorbed through the lungs and
gastrointestinal tract and is rapidly excreted, unchanged, via the
lungs.  The primary toxic effect of a single vapor exposure is a func-
tional depression of the central nervous system, proportional to the
magnitude of exposure, and typical of an anesthetic agent.  The early
symptoms of acute overexposure (between 200 and 300 ppm) are light-
headedness, and mild eye, nose, and throat irritation.  Below the
current threshold limit value of 100 ppm, no adverse physiological ef-
fects have been observed in man (Stewart, 1969).

Exposure time         Concentration
    (min)             in air (ppm)                Response
    1-4                 75-80              Very slight eye irritation
    4-6                100-120             Soft palate irritation and
                                           dryness
    6-30                 200               Odor not unpleasant
    30+                210-244             Light-headedness

     Following are laboratory studies performed on human subjects
after experimental exposures to tetrachloroethylene:
                              109

-------
                 LABORATORY STUDIES ON  HUMAN SUBJECTS
                  AFTER TETRACHLOROETHYLENE EXPOSURE
                     BOO-T
                                        HOP-T
                                                        Urinary Uroblllnovn
         Subject
Kormnl Value
Pro- 20 llr.
exposure Putt
6-40

7 Dny Pro- 20 llr.
Pout exposure Pott
6-30

7 Day Pro- 8 Hr.
Poet exposure Post
1:40
or Less
20 Hr. 7 Diy
Post Post


Exp. 1
194 ppm,
187 mln.



Kip. 2
194 ppm.
83 mln.

'

Exp. 3
101 ppm,
183 mln.



1
2
3
4 •
6
6
2
3
6
7
8
9
1
2
3
4
6
7
12
18
16 '
16
15
10
16
12
6
16
17
18
16
14
16
14
16
16
18
20
18
23
16
13
16
14
10
17
19
16
12
18
14
10
12
14
18 .... '
14
18 ' ' •
.
14
12
18
12
12
16
20
18
14 16 14 14
14 13 16 -, 14
13 17 16 16
18 20 14 18
16 16 12 14
.17 ,17 12 20
:10
:10
:10
:10
:10
:IO
:10 1:10
:10. 1:10
-.10 1:10
:20 1:80
:tno 1:370
:10
:10
:10
:10
:IO
:10
:10
:10 1:10
:10 1:10
:10 1:10
:10
:10 1:10
:10 1:10
:10 1:10
:10 1 10
:10 1:10
:IO 1:10
:10 1:10
:10 1:10
:10 . 1:10
:10 1:10
:IO 1:10
:10 1:10
:IO 1:10
:IO 1:10
    Source:  Stewart,  R. D., Gay, H.  H., Erley, D. S., Hake, C.'L., and

             Schaffer, A. W.,  1961  (2).
                                   no

-------
     Tetrachloroethylene does not possess great potential for causing




serious liver or kidney injury, but repeated vapor exposures to high




concentrations have produced hepatitis in experimental animals.




     Acute renal failure, occasionally observed in man, is probably a




consequence of the shock produced by the peripheral vascular collapse




secondary to central nervous system depression.




     The SGO-T and SGP-T (serum glutamic oxaloacetic transaminase




and serum glutamic pyruvate transaminase) concentrations are useful




indices of induced hepatocellular injury.  In most cases, the degree




and duration of elevation are related to the extent of liver damage.




     Following are the results of laboratory studies on a man who had




been overcome with tetrachloroethylene while cleaning a tank with




this solvent.  This patient experienced marked central nervous system




depression, followed by transient, minimal liver damage.
Tim*
Alter
Etpotur*
l'/4hr
2 days
3 days
Sdayt
9 days
10 days
SCOT,
Unlit
12
41
31
14
14

SORT.
Unit*
10
10
10
10
10
...
24-hr
Urinary
Uroblll-
nogen,
Ehrllch
Unlit
...
2.4
2.6
2.1
7.2

Total
Scrum
Protein,
gm/
100ml
...
7.1
6.9
6.4

• 6.5
Scrum
Albu-
min. %
...
64
62
69

69
Serum
Dlllrubln
Total/
Direct,
m*;/
100ml
• • •
0.4/0.2
0.4/0.2
0.4/0.1
• • •
0.4/0.1
Alkaline
Phoipha-
tate. King-
Armstrong
Unit*
• • •
11.4
11.4
10
13
11.4
DUN,
me/
100 ml Urlnalytlt
Specific gravity 1.015;
no albumin;
microscopically
normal
... No albumin;
microscopically
normal
No albumin;
microscopically
normal
12 No albumin;
microscopically
normal
... No albumin;
microscopically
normal
...
WBC/
cu mm
10.200
8.700
11.400
10,200
11.900
9.800
Hema-
toc,,,.
45
46
45
44
44
46
Retlcu-
locyt*
Count.
%
...
' ' *
0.7
0.3
0.5
0.4
Source:  Stewart, 1969




     Patel, Janakiram, Johnson, and Elman (1973) described a case of ex-




posure to tetrachloroethylene in which acute pulmonary edema was the




predominant symptom.  The patient was admitted to the hospital in a
                               111

-------
deep coma; the pulse rate was 88 beats per minute; the blood pressure

was 88/20 mm Hg; the temperature was 34.4°C (94°F); and respirations

were 48 per minute.  Bubbling rales were heard over the entire lung

fields.

     After four days of treatment, the patient was well enough to

leave the hospital.  Tests of liver and kidney function, done during the

four-day hospital stay and biweekly for several weeks afterwards, gave

normal results.
                                                >         .      •
     Fatal poisoning by chronic Inhalation of tetrachloroethylene

vapor was reported by Transe and Zimmerman (1969)  .  The symptoms of

pulmonary disease which the patient initially manifested were diagnosed

as miliary tuberculosis.  Later, jaundice and oliguria appeared and

the patient died nine days after the onset.

     On autopsy, the lungs showed fibrin-rich exudate and intraparen-

chymal hemorrhage.  The liver, large and greenish, showed extensive

acute to subacute centrilobular necrosis.  The heart showed fatty de-

generation.

     10.  Ingestion of Tetrachloroethylene

     No reports on human ingestion of tetrachloroethylene were found

in the literature.

     11.  Skin Contact with Tetrachloroethylene

     This solvent is poorly absorbed through the  intact skin (Stewart,

1969) .

     12.  Behavioral Effects of Tetrachloroethylene

     Stewart, Baretta, Dodd, and Torkelson (1970) report an abnormal

modified Romberg test in three subjects within the first three hours of
                                112

-------
exposure  to 100  ppm.   After  five hours of exposure,  the Crawford manual

dexterity tests  and the Flanagan coordination  and arithmetic tests  re-

mained normal.

      A series  of timed, human-skin exposures  to methyl chloroform,

trichloroethylene, and tetrachlbroethylene were run  by Stewart and Dodd

(1964).

      The  results of  these  experiments are as  follows:
            Human Skin Exposure to Chlorinated Aliphatic Hydrocarbon Solvents
Experi-
ment

1
o
4
5
6
1
No. of
Subjects

3
3
•t
i;
l
1
Solvent



Trii'hlnri
M.'tiivln
1. 1. I-T
1. 1. I-T
1, 1. I-T

•llu-l
.• H,l
irhlo
irlil..
irliln
•n<-
irii
or
or
or

!,:,.,,•
liiinr
h:iiii>
LenRlh of
KxpOHure
(niin.)


:lil n i
:<(i n
.'ID n
.'ID n
:il) in






Skin Exposed


.
I hut
thui
llmi
hi.iict
hand t
• .
i n
n
n
i t ii

1 TM
t rn
» rn
SIO
> JJCUl (Up

n)
n)
n)
)
•lifiition)
Mean Peuk Drouth
("onrontrution
After Exposure

_
o.r, P|l
o.:u i>i>
:i.i pp
1.0 pp
2i.r> i>i>




O.iir> ppm
Mean Brtath
li >K>urd Afrer
Kxposure.

O.OH ppm
O.i;9 ppm
0.31 ppm
l.r>.ri ppm
0.31 ppm
                                               I.I.I TRICHLOflOETHAME
                                               TCTRACHLOROCTHVLENE
                                               METHTLfNE CMLO»IDE
                                               CARBON TETRACHLOHlOE
                                 20   2.9   50   35
                                    TIME IN HOURS
     	The mean alveolar air concentrations during skin exposure and in the
      early postexposure period are plotted for the five solvents. The thumb of one hand was
      iimni.TScd in the solvent for the above charted period of time.
                                      113

-------
                      Individual Variation in Alveolar Air Concentration Following 30-Minute Skin Exposures
Experi-
ment
1
2
3
4
5
Solvent
Carbon telrarhloride
Trichloroethvlcne
To;r:ich!orotnyk>ne
Mc'.Jivlrne Chloride
1,1, i-TrichloroL-'.hnne
Solvent Volume
Displaced bv
Thumbs (ml)
15. 15, 17
15. 20. 20
25. 28, 27. 30, 3S
20.21.24
19, 20, 22, 25. 25. 28
RnnRfi of Alveolar Air Concentration, ppm
During Exposure
10 Min.
0.00-1-0.13
0 -0.27
0.02 -0.00
1.4 -2.4
.10 - .10
20 Min.
0.04 -0.05
0.008-0.51
0.11 -0.14
0.14 -0.17
30 Min.
0.11 -O.R3
O.OS'i-O.TU
0.17 -0.17
2.a -n.o
C.'.l -1. 02
Postoxposure
10 Min.
0.27 -0.79
0.01 -0.8
0.2G -0.36
2.1 -4.1
0.24 -0.97
30 Min.
0.45 -0.79
0.10 -0.40
0.2G -0.35
1.1 -fi.G
0.54 -0.77
1 Hour
0.24 -0.49
0.13 -0.32
0.23 -0.39
O.C -4.1
0.46 -0.78
2 Hours
0.19 -0.4S
.05 -0.14
0.1H -0.28
0.26 -1.7
0.18 -0.3^
5 Hours
0.12 -0.14
0 -0.010
0.1G -0.2'5
<0.1
0.03 -'J.tr.
                                                              H»NO- CONTINUOUS IMMCHSION
                                                              THUMB-CONTINUOUS IMMERSION
                                                              H»NO-TOn»L IMPLICATION
                                                  TIME IN HOURS
                             The  alveolar air concentrations for 1,1,1-trichloroetharie during and
                 following 30 minutes of skin exposure are plotted versus time. Topical application of
                 the solvent to the skin of the hand resulted in  far less absorption than when the hand
                 was continuously immersed for a similar period of time.
       It was  concluded,  that although  the solvents penetrated  the  skin,;methyl

chloroform,  trichloroethylene and: tetrachloroethylene  did  not do  so  in toxic

amounts.                   .
                                               liU

-------
     B.  TOXICITY TO NON-HUMAN MAMMALS




     1.  Acute, Subacute, and Chronic Toxicity




     a.  Inhalation




     Mice were exposed to an atmosphere containing 2500-3000 ppm of




methyl chloroform for twenty-four hours.  The animals were then sacri-




ficed and the methyl chloroform concentration in the liver was markedly




greater than that in the blood.  The average methyl chloroform concentra-




tion found in the blood was 94 ± 17 mymol/g and the average concentra-




tion found in the liver was 954 ± 65 mpmol/g (Fuller, Olshan, Puri,




and Lai, 1970).




     Heim (1966) found that the inhalation by mice of 1.8% by volume




of trichloroethylene in air anesthetised the animals.  The animals were




sacrificed at 30 minute and 60 minute intervals after the beginning of




the inhalation.  An analysis of the livers showed decreased levels of




glycogen, glucose, fructose diphosphate, dihydroxyaceteone phosphate,




and lactate.  Glucose-6-phosphate and pyruyic acid levels were not




significantly altered.  Creatinine phosphate, ADP, and AMP were re-




duced while ATP increased, showing that trichloroethylene can dis-




turb the metabolic processes in the mouse liver.




     Tetrachloroethylene was found to disturb the metabolic processes




in the mouse liver by Ogata, Tomokuni, and Watanabe (1967).  After three




hours of exposure to 800 ppm of tetrachloroethylene in air, liver ATP




had dropped to 46% of normal and remained so for twenty hours.  Liver




total lipids increased to 134% immediately after exposure and gradually




increased to 158% after eight hours.




     In comparison studies, trichloroethylene and tetrachloroethylene
                                 115

-------
were inhaled by mice.  Each group of ten mice were given a single


four-hour exposure to a series of different concentrations of each


compound.  Two animals died during trichloroethylene exposure at 6,400


ppm (LDso = 8.450 ppm).  At this concentration there was


no (or only slight) histologically detectable fatty infiltration of the


liver.  Tetrachloroethylene caused fatty infiltration of the liver at


440 ppm, but necrosis of the liver cells could not be detected.  Tri-


chloroethylene did not produce any significant increase in the amount of


extractable liver fat, thereby confirming the histological findings.


Tetrachloroethylene caused an increase of the extractable liver fat with


increasing concentrations in the air.  The authors concluded from this


study that trichloroethylene seemed to be less dangerous to the liver


than tetrachloroethylene (Kylin, Reichard, Sumegi, and Yllner, 1962).


     These same authors (1963) studied this subject further.  On histo-


logical examination of the livers of mice which had been exposed to


trichloroethylene at concentration levels of 1600-3200 ppm, no increase


in liver fat was observed.  Tetrachloroethylene, on the other hand,


induced an increase in liver fat at 400 ppm.  Neither agent increased


the ornithine carbamoyltransferase activity in serum.  The authors


concluded that the hepatotoxic effects of trichloroethylene and tetra-


chloroethylene were in the approximate ratio of 1:10.
                                                s       -.•'".

     Friberg, Kylin, and Nystrom (1953) also concluded from their LDso


studies on mice that tetrachloroethylene is more toxic than trichloro-


ethylene.


     To determine the lethal dose, groups of eight female white mice


were exposed to different concentrations of trichloroethylene  or
                                116

-------
tetrachloroethylene for four hours.  The calculations of LDso showed




8,450 ppm (45.4 mg/L of air) of trichloroethylene and 5,200 ppm




(35.4 mg/L of air) of tetrachloroethylene.




     To determine the effect upon the central nervous system, two




groups of 14 and 15 white mice were exposed to trichloroethylene




(12,200 and 6,800 ppm, respectively) and two groups of 14 and 15 white




mice were exposed to tetrachloroethylene (12,200 and 6,800 ppm, respec-




tively) .  According to the stages of narcosis experienced by the animals,




the narcotic effect of tetrachloroethylene to mice is greater than




that of trichloroethylene.  An analysis of variance showed a signifi-




cant difference (P = 0.001).




     In long-term inhalation studies, mice were exposed to trichloro-




ethylene at 1600 ppm or to tetrachloroethylene at 200 ppm, for four




hours daily, six days per week, for one, two, four, and eight weeks.




No external effect on the animals was discernible.  No animal died as




a result of the exposure.  Histological examinations of the livers




showed only slight fatty degeneration, and this tended to abate after




two weeks.  Fatty degeneration was particularly marked for tetrachloro-




ethylene  and tended to be more severe with longer exposure.  The histo-




logically evaluated degree of fatty degeneration and the amount of




liver fat determined by extraction were in agreement; the correlation




coefficient was +0.74.  The kidneys from the exposed groups and from




the control groups showed no appreciable difference (Kylin, Sumegi,




and Yllner, 1965).




     In a later long-term series of inhalation studies (Prendergast, Jones,




Jenkins, and Siegel, 1967), rats, guinea pigs, dogs, and rabbits were
                                 117

-------
used as experimental animals.




     In a thirty-day series of repeated exposures to methyl chloroform




(12,060 mg/m3), ho animals died and no toxic signs were visible in




the test animals.  Gross and histopathologic examinations of brain,




heart, lung, liver, spleen, and kidney did not reveal any abnormalities




that could be attributed to the exposure.




     Continuous exposure to methyl chloroform (2059 mg/m3) did not




result in death or visible toxic signs in the test animals after




ninety days.  Microscopic examination of tissue showed nonspecific




inflammatory changes in the lungs of all species.




     During continuous exposure to methyl chloroform (754 mg/m3),




2/15 of the rats died on days 27 and 77, and 1/3 of the rabbits died




on day 38.  The survivors exhibited no toxic signs.  Varying degrees of




lung congestion and pneumonitis were noted in all species and in a num-




ber of the controls.  In view of the three deaths and the pneumonitis




present in the surviving animals, no positive conclusion could be drawn




as to whether the effects were associated with the exposure; at the




higher exposure of 2059 mg/M3 no deaths occurred and no pathologic ab-




normalities were noted.




     In repeated exposures to trichloroethylene (3825 mg/M3), animals




were exposed repeatedly for eight hours a day, five days a week, for




thirty exposures over a six-week period.  No mortalities occurred.




Nonspecific inflammatory changes were found on histopathologic examina-




tion in the lungs of all animals, but there was no evidence of specific




chemically-induced changes in any of the organs which could be attributed




to the exposure.  Histochemical studies of enzymatic activity were per-
                                118

-------
 formed on liver tissue from three selected experimental rats; no




changes were  found.                  .




     During continuous exposure to  trichloroethylene (189 mg/M3) for




ninety days,  no animals died and no visible signs of toxicity were




noted.  Histopathologic examination of heart, liver, lung, spleen,




 and kidney tissue showed no indication of chemically induced changes.




     b.  Inges tion




     Trichloroethylene was mixed in olive oil and fed in various con-




 centrations (5-60%; 0.36-4.3 mg/gm) to 200 mice.  The mice were sac-




 rificed 72 hours after exposure.  The results were as'follows:  minimal




narcotizing dose, 10% or 0.72 mg/gm; minimal lethal dose, 40% or 2.92




 mg/gm; minimal hepatotoxic dose, 10% or 0.72 mg/gm; midzonal liver




 fatty  change, 10% or 0.72 mg/gm; central liver  fatty change, 12.5% or




 0.91 mg/gm; moderate liver changes, 20% or 1.46 mg/gm; and severe liver




 changes, none observed (Jones, Margolis, and Stephen, 1958).




     c.  Intraperitoneal administration




     Hepatic  function and kidney function were  determined in mice by




 sulfobromophthalein retention and serum glutamic-pyruvic transaminase




 activity following intraperitoneal  injections of methyl chloroform,




 trichloroethylene, and tetrachloroethylene.  The solvents were adminis-




 tered  in corn oil to deliver a final volume of  0.01 mg/g (Klaassen and




 Plaa,  1966).




     The LDso values after intraperitoneal injection were as follows:




 Methyl chloroform in ml/kg, 3.8; in mmole/kg, 37




 Trichloroethylene in ml/kg, 2.2; in mmole/kg, 24




 Tetrachloroethylene in ml/kg, 2.9;  in mmole/kg, 28
                                 119

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     These three solvents produced liver dysfunction only near the




lethal range when administered intraperitoneally.  Tetrachloroethylene




was shown to produce hydropic degeneration with a minimal amount of




necrosis of the convoluted tubules of the kidneys, while methyl chloro-




form and.trichloroethylene elicited little or no microscopic change.




     In later studies conducted by Klaasen and Plaa (1967), intraperi-




toneal LDso values for dogs were found to be:




Methyl chloroform, 31 mmole/kg




Trichloroethylene, 21 mmole/kg




Tetrachloroethylene, 21 mmole/kg




     By this same route, the EDsg values for the elevation of serum




glutamic-pyruvic transaminase were found to be 8.6 mmole/kg of methyl




chloroform, 6.3 mmole/kg of trichloroethylene, and 7.2 mmole/kg of




tetrachloroethylene.




     The liver dysfunction EDso values as measured by the serum gluta-




mic-pyruvic transaminase activity show that the three solvents are




capable of producing some degree of liver dysfunction.  Tetrachloro-




ethylene can produce kidney dysfunction in dogs at near lethal doses,




as shown by the results of phenolsulfonephthalein excretion tests.




     2.  Sensitization




     No sensitization studies are reported in the literature at hand.




     3.  Teratogenicity




     Nothing is reported on the teratogenic activity of these three




solvents.




     4.  Carcinogenicity




     Nothing is reported on any carcinogenic effects of these three




solvents.
                                  120

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     5.  Mutagenicity




     No mutagenicity studies have been reported on these solvents.




     6.  Behavioral effects




     Trichloroethylene vapor at concentrations of 400-800 ppm reduced




the frequency of the spontaneous alternating behavior of rats.  Their




running speed was significantly increased at 400-600 ppm but was signi-




ficantly decreased at 1600 ppm (Zahner, 1961; Grandjean, 1964).




     Trichloroethylene vapors when repeatedly inhaled daily by rats




produced a specific inhibition of avoidance behavior at concentrations




which did not produce motor imbalance.  No dose-dependent response was




apparent, and results obtained from repeated inhalation of 1568 ppm




did not differ from those with 200 ppm.  Rats exposed to 4380 ppm




were grossly ataxic.




     Tetrachloroethylene produced inhibition of the avoidance response




only at concentrations which caused frank depression and ataxia (Gold-




berg, 1964).




     Four rats were individually exposed to trichloroethylene vapor (400




Y/L) for a period of 72 to 121 days.  In all animals, dynamics of




cortical activity were noted with signs of excitation.  These effects




were demonstrated by a disturbance of differential inhibition and




occurrence of positive reflexes with short latent periods and motor




unrest in the intervals between stimulations (Khorvat, 1959).




     C.  TOXICITY TO LOWER ANIMALS AND INSECTS




     Trichloroethylene was found to be comparatively non-toxic when




applied topically to adult houseflies.  Tetrachloroethylene produced




tremors with subsequent recovery (Kocher, 1954).
                                 121

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     Tetrachloroethylene acts on the nervous system of hookworms by
inhibiting the metabolic enzymes pf muscle fibers and other somatic
cells and induces death by disturbing the respiratory mechanism
(Iwata, 1961).
     D.  TOXICITY TO PLANTS
     Phytotoxicity studies were carried out by making water emulsions
or solutions of the compounds to be tested and applying them to the
foliage of seeding plants with the following results (Cast, 1956):

                     . Bean     Corn    Cotton  Cucumber  Tomato
                     5%  .5% 5%   .5%  5%  .5%  5% .5%  5%  .5%
Methyl chloroform    2    0  2.5   0  0.6   0   101   0
Trichloroethylene   3.5   0  2.5   0  1.5   1   1  0    21
Key:  0 = no inury, 1 = slight injury, 2 = moderate injury,
      3 = heavy injury, 4 = severe injury or dead plant
     E.  TOXICITY TO MICROORGANISMS
     Tetrachloroethylene was found by Horsfall (1955) to reduce
sporulation of Monilinia fructicola.
     Trichloroethylene reduces the survival time of Escherichia coli
to an extent which is generally proportional to the concentration of
the compound used (Horton, Sussman, and Mushin, 1970).
                                122

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                                     130

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       ION-EXCHANGE RESINS:  SUMMARY AND CONCLUSIONS




       Although there are available figures which give the amounts of




resin materials produded annually in the United States, there are no




available figures which give the amounts of ion-exchange resins




specifically.  Neither were there available figures on the amounts of




ion-exchange resins which were used in various applications.




       If ion-exchange resins were released into the environment to




any extent, their physical and chemical properties would indicate per-




sistence under normal environmental conditions.  However, these same




properties would argue against toxic hazards.  It is unlikely that these




resins would find accidental entry into living systems by any route other




than oral.  The many medical studies that were done in the years shortly




following 1950 used human subjects who ingested ion-exchange resins.  No




consequences were noted other than the expected electrolyte imbalance




and the disturbance of acid-base equilibria, and these readjusted to their




starting values after the ion-exchange resin was excreted.




       However, when a certain ion-exchange resin was fed to female mice




during the reproductive cycle, the offspring of these females were below




normal in weight and showed some retardation in tooth eruption.




       Although commercial ion-exchange resins are insoluble and infusible




polymers, they may contain minute quantities of soluble impurities.  In




most cases rinsing with water is adequate to remove the impurities before




certain critical applications.  Nothing was found in the literature collected




to indicate exactly what these impurities are, nor was any mention made of




precautions to be taken in disposing of the rinse water.  There are standard




procedures for obtaining greater purity, and manufacturer's data sheets




contain such information.
                                     131

-------
       According to Food and Drug Regulation 121.1148, extractable sub-




stances must be reduced to certain levels.  There are established proce-




dures for attaining this degree of purity before applying ion-exchange




resins to food treatment.



       The potential toxicity of the ion-exchange resins cannot be




minimized.  Nothing was found in the literature concerning the inhalation




of ion-exchange particles or dusts by humans or by animals.  Therefore,




there is no information on hand relating such inhalation to excretion




of the particles or their fate in the respiratory system.  Experiments




with mice showed that after a suspension of ion-exchange resin was




administered intraperitoneally, granuloma formation was induced at sites




of phagocytosis by one of the resins used.  Particles of other types




of resins were phagocytized without further consequence.




       In summary, until further information is made available concerning




the environmental and biological behavior of the ion-exchange resins, no




statements can be made concerning the potential hazard which these agents




might present.
                                  132

-------
                        ION-EXCHANGE RESINS









I.   PROPERTIES




     An ion-exchange resin is  a  cross-linked polymer which contains either




acidic or basic structural units and which can exchange either cations




or anions on contact with a solution.  Resins are insoluble  in all sol-




vents, due to their infinite molecular size which arises from the cross-




links.  Despite the enormous size of the resin molecules and their com-




plete insolubility, such a polymeric acid or base will exhibit the chemical




activity of a monomeric acid or  base, subject to the restrictive conditions




imposed by the insolubility and  the immobility of the massive organic




ion (Craig, 1953) .  These resins are essentially infusible polymers and




are resistant to common acids and alkalies.  They may also be considered




as insoluble acids or bases, the salts of which are also insoluble.




     These resins are characterized as anion exchangers (with basic




functional groups)  and cation exchangers (with acidic functional groups).




The various matrices to which these functional groups are attached may be




of polystyrene, epoxy-polyamine, phenolic, polyacrylic, and  styrene-di-




vinylbenzene frameworks.  The resins are beads or granules in physical




form with standard mesh range of 16/50 and particle size from 0.3 mm to




1.2 mm.




     Strong-acid cation exchangers are normally supplied in  the sodium




form, weak-acid resins in the hydrogen form, strong-base resins in the




chloride form, and weak-base resins in the mixed salt form.
                                 133

-------
         Types  of  Ion-Exchange  Resins and  Typical'Commercial Products
    Type
         Chemical characterization
                Chemical structure
                                    Selected commercial
                                          products
strong acid . sulfonated styrene-divinyl-
benzene copolymers





CH— CH,— CH— CH,—
nj) |^b
C-50
                                     Amberlite IRC-84
                                     Duolite CS-101
                                     lonac C-270
                                     Dowex CCR-1
                                     Duolite CS-100

                                     Type I:
                                     Amberlite IllA-400
                                     Arnberlifco IHA-401
                                     Amberlite IRA-402
                                     Amberlite iltA-900
                                     Duolite A-101-D
                                     Duolite ES-1V1
                                     Dowex 1
                                     Dowex 11
                                     Dov.ex2lK
                                     lonnc A-o'-tO

                                     Type II:
                                     Amberlite IKA-410
                                     Amberlite IRA-911
                                     Dowex 2
                                     Duolite A-102-D
                                     lonac A-542
                                     lonac A-550
                                     Amberlite IUA-GS
                                     Dowex 44
                                     Duolite A-7
                                     lonac  A-2CO
                                     Amberlite IR-fo
                                     AmberlitoIRA-'j::
                                     Dowex 3
                                     Duolite A-l-t
                                     Dowex A-l
                                                          —CH—CH,—
                                                                          CHX
                                                            ,CH,.COO"

                                                            ^CH.COQ-
  Source:    Snell,  1972

-------
            Characteristics of Typical Ion-Exchange Resins

                          Cation-exchanger3            Anion-exchangers

                    Strongly acidic  Weakly acidic   Strongly basic  Weakly basic

Functional group       Sulfonic        Carboxylic      Quarternary      Amino
                                                       ammon i *fm
Effect of increasing
pH value on
capacity
Independent
Increases
Independent
Decreases
Salts
Stable
Hydrolyse on
washing
Stable
Hydrolyse on
washing
Regeneration of
salts to free acid
on free base
Exesss of
strong acid
required
Readily
regenerated
Excess of
sodium hydrox-
ide required
Readily
regenerated
with sodium
carbonate or
ammonia
Rates of exchange
Rapid
Slow unless
ionized
Rapid
Slow unless
ionized
Source:  Pepper,  1952
                                    135

-------
     The chemical stability  of  the ion-exchange resin as a whole depends




both on the stability of  the main framework and on the stability of the




substituent groups.  The  sulfonated polystyrene resins are stable at




100°C for long periods in the presence of dilute acids and alkalis.  The




salts of the strongly basic  resins are stable up to 50°C and the free




bases possess good stability at room temperature.









II.  PRODUCTION




     The leading producers of ion-exchange resins in the United States




are The Diamond Shamrock  Chemical Company, Resinous Products Division




(the Duolite exchangers); The Dow Chemical Company (the Dowex exchangers);




lonac Chemical, division  of  Sybron Corporation (the Sonac exchangers);




and Rohm and Haas Company (the Amber lite exchangers).




     A styrene-divinylbenzene copolymer is the most frequently used




matrix for ion-exchange resins.  Polystyrene beads cross-linked with




divinylbenzene are modified  by chemical reactions to make ion-exchange




resins.  Cation-exchange  resins are produced by sulfonation of the styrene-




divinylbenzene copolymer.  Anion-exchange resins contain quaternary




ammonium or amine groups.  There are no available specific descriptions




for the manufacture of ion-exchange resins (trade' secrets) .




     Manufacturing sites  and production figures for the ion-exchange




resins are not readily available.









III. USES




     Ion-exchange resins  have many very practical uses.  Their applica-




bility is attributable to their ability to substitute desirable ions for
                                    136

-------
undesirable ions.  Thus, they are highly favored in water softening.

They can eliminate ionic impurities in various media.  They are capable

of isolating ionic constituents and fractionation (as in ion-exchange

chromatography).
                                                                 i
     Water treatment (both softening and deionlzation)  accounts for the

largest single use of these resins.  Their utilization in sugar purifi-

cation is quite extensive.  Nearly all Impurities associated with sugar

in nature are ionic, so the ion-exchange resins are most suitable to

purify sugars obtained from beets, cane, corn starch, etc.

     Chemical processing is another major area where the ion-exchange

resins are used.  They are used in the Isolation and purification of

antibiotics, uranium extraction, and formaldehyde purification.

     The ion-exchange resins are also used in the treatment of waste

liquors from the pulp and paper industry.

     The Federal Food, Drug,,and Cosmetic Act allows many ion-exchange

resins to be used in the treatment of food, including potable water,
                                      •_    I    —,        ^ _
to replace less desirable ions with Cl , H , OH  and S04  , if the

resins are subjected to a preuse treatment by the manufacturer and the

resin results in no more than 1 ppm of organic extractive with H20,

15% EtOH, and 5% HOAc (Anon, 1964).  Sailer (1957) demonstrated the

biological stability of fruit juices which have been treated with ion-

exchange resins.  However, the chemical constitution of the juices was

so modified, resulting from a reduction in mineral content, that the

nutritional value of the juices was substantially minimized.
                                   137

-------
IV.  CURRENT PRACTICES




     No specific regulations were found in the literature collected con-




cerning handling, storage,  or  transport of ion-exchange resins.  The in-




ertness of these resins should make their handling problem-free.









V.   ENVIRONMENTAL CONTAMINATION




     No publications are available which discuss any environmental con-




tamination from the ion-exchange resins.  There seem to be no specific




recommendations in the literature for the disposal of these resins.









VI.  MONITORING AND ANALYSIS




     The organic constituents  of ion-exchange resins can be decomposed




by a wet combustion method  using nitric and perchloric acids as an




alternative to elution when analyzing small amounts of ion exchange




resins for metals (Hoegfeldt,  1954).  This method is suitable for both




cationic and anionic exchangers, since metals can be retained on an ion




exchangers as anionic complexes.  The samples used were Wofatit KS and




Duo lite C-3 as examples of  phenol formaldehyde resins and dowex 50 and




Lewatit S 100 as examples of polystyrene resins.  All are cationic and




contain sulfonic acid groups.  The anion exchanger used was Amberlite-




IRA-400, a polystyrene divinylbenzene copolymer containing quaternary




ammonium groups.  After the wet combustion, the metals were determined




radiochemically and polarographically.




     The total amount of amino groups, the amount of tertiary amino




groups, and the amounts of  secondary and tertiary amino groups were
                                     138

-------
determined by Kopylova (1969) by treating three samples of ion-exchange




feslns with acetic acid, acetic anhydride, and salicylaldehyde.  After being




mixed with 0.1 N HCIO^ the samples were potentiometrically titrated against




0.05 N potassium hydrogen phthalate solution.




     Calmanovici (1965) describes the application of ultraviolet spectro-




scopy to the analysis of cationic exchange resins.




     Ion-exchange resins can be characterized by pyrolysis-gas chromato-




graphy.  Parrish (1973) gives a method for rapid comparisons of pyrograms




of an unknown resin and standard resin using a single resin bead.  Poly-




styrene resins, cation-exchange resins, effects of counterions, effects




of crosslinking, effect of capacity, anion-exchange resins, isoporous



resins, acrylic resins, and miscellaneous resins are discussed.




     Ion-exchangers based on copolymers of styrene and divinylbenzene




may contain fragments which are introduced after manufacture.  The frag-




ments show structural similarity to the resin and have properties associ-




ated with electrolytes.  Mass spectrometry can be used to obtain informa-




tion on the nature of the reactions leading to eventual fragmentations




(Armitage, 1973) .




     The possibility that a given resin preparation may be contaminated




by particles having a different charge was investigated by Burger (1967).




He developed staining methods to detect such a condition and also to




detect variation in cross-linkage.




     A review of the standard methods for analyzing ion-exchange resins




is given by Snell (1972) .
                                      139

-------
VII. CHEMICAL REACTIVITY




     Extremely strong oxidizing agents such as boiling nitric acid or




chromic-nitric acid mixtures will rapidly degrade the polymer matrix.




Slower degradation with oxygen may be catalytically induced, so ions such




as iron, manganese, and copper should be minimized in an oxidizine solu-




tion.  With cation-exchangers attack is primarily on the polymer backbone;




with anion-exchangers attack is on the functional groups.  Amine struc-




tures may be attacked by low-valent sulfur compounds.




     The thermal stability of anion resins is determined by the strength




of the C-N bond.  A low pH favors higher stability.  The quaternary ammon-




ium salts are the least thermostable, limited to 50° C.  The tertiary




amines are stable up to 100° C.  Cation resin stability also depends




on pH.  Sulfonic acid resins in the acid form are not suitable for use




above 150° C in the presence of water.  Depolymerizatlon of anhydrous




cation resins begins at 250-300° C.




     Gamma radiation can cause a variety of simultaneous reactions to




occur - polymerization, depolymerization, oxidation, and rupture of C-S or




C-N bonds.  The results are gas evolution, bead swelling, and weight loss




(Wheaton, 1966).

-------
VIII.  BIOLOGY




       A.  ABSORPTION




           Because of their mqlecular magnitude, the ion-exchange resins




do not pass through the membranes of living systems.  When they are con-




tained within the digestive tract, however, they induce an electrolyte




imbalance by exchanging with those ions which normally are absorbed and




transported through the body.




           This is an advantageous property when the ion-exchange resins




are ingested for the purpose of fixing excess sodium which has caused




edema, or for regulating potassium levels.




           No intestinal damage has been reported from resin ingestion.




No evidence of bone decalcification has been observed, other than that




which would be expected during the course of the disease being treated




(Harthon, 1952).






       B.  EXCRETION/ELIMINATION




          After ingestion, the ion-exchange resins are excreted normally




from the intestinal tract.  The resin remains essentially unchanged with




the only difference at the active sites where ions were exchanged.




          After intraperitoneal injections of ion-exchange resin particles




into mice, Strecker (1956) found that the resin particles were phagocytized




by the mesenchymal cells without substantial cell damage.  This was true




of sulfonic acid resins and weakly acid resins containing phenolic hydroxyl




groups, as well as strongly basic resins.  The exception was the weakly
                                   lUl

-------
acid Amberlite  IRC 50  (carboxylic groups) which induced massive formation



of fibrous  tissue.





       C.   TRANSPORT AND DISTRIBUTION



            Following intraperitoneal injections into mice, the ion-



exchange resins showed no  tendency  to migrate in the capillary fluids



or lymph system (Strecker,  1956).





       D.   METABOLISM AND  METABOLIC EFFECTS



            When ion-exchange resin  particles were introduced into thie



mouse peritoneum  they did  not  enter into metabolic reactions but were



phagocytized, with the exception of the carboxylic Amberlite IRC 50 which



produced tissue reaction in the form of granulomas and fibrous tissue



(Strecker,  1956).
                                                 «


            In human studies during  ingestion of ion-exchange resins, the



only effects reported are  attributable to electrolyte alterations (Levitt,



1953) and disturbance of acid-base  equilibrium (Wolff, 1955; Danowski, 1953),







IX.    ENVIRONMENTAL TRANSPORT AND  FATE



       A.   PERSISTENCE AND/OR  DEGRADATION



            The constitution of the  ion-exchange resins indicates that they



would persist under normal environmental conditions.  There is nothing



reported in the literature, however, concerning the persistence or degrada-



tion of these compounds.
                                     1U2

-------
       B.  ENVIRONMENTAL TRANSPORT




           Nothing was found in the literature to indicate that these




resins are transported through the environment to any extent.







       C.  BIOACCUMULATION




           There are no articles in the literature collected on hand which




report on inhalation of resin particles or dusts.  After ingestion it has




been shown that the resins are excreted essentially unchanged through the




intestinal system.




           Strecker (1956) found that the strongly acidic Dowex 50 (sul-




fonic acid groups), weakly acidic resins (phenolic OH groups), and the




strongly basic Amberlite IRA 410 and Levatit MIH (quaternary ammonium




groups) were phagocytized by the mesenchytnal cells without essential dis-




turbance to the cells after the intraperitoneal administration of resin




particles to mice.




           However, the behavior of the weakly acidic Amberlite IRC 50




(carboxylic groups) demonstrated a possibility of a most hazardous mode




of bioaccumulation.  During the process of its phagocytization, localized




nodular  granuloma formation was noted.









X.     TOXICITY




       A.  HUMAN TOXICITY




           1.  Inhalation




               Nothing is reported in the literature concerning the inhala-




tion of  ion-exchange resin particles or air-borne dust during the manufac-




turing and handling of the resins.
                                      1U3

-------
               However, Astanina  (1969) reports on toxicity occurring


during manufacture of  anion-exchange resins from inhalation of some.start-


ing products.  Workers were  afflicted with headaches, nose and larynx


dryness, dermatitis, disturbed  liver function, and other symptoms.  Air


analysis showed that chloromethyl methyl ether, trimethylamine, dimethyl-


amine, formaldehyde, benzene, hydrochloric acid, methanol, and dimethoxy-


methane were present in the  air.


           2.  Ingestion


               In the many medical experiments reported, during which

                                                  ;
patients ingested various amounts of different types of ion-exchance resins,


it was not the presence of the  resin framework or its contact with the


gastrointestinal tract that  produced toxic symptoms in the body.  The ion-


exchange properties of these resins lead to electrolyte imblance and


disturbance of the acid-base equilibrium (Danowski, 1953; Wolff, 1955;


Levitt, 1953).


               There are no  reports of any instances in which ion-exchange


resins were accidently ingested.



       B.  TOXICITY TO'NON-HUMAN MAMMALS


           1.  Acute,  Subacute, and Chronic Toxicity


               In investigations of anion-exchange resins on experimental


dental caries and tooth eruption in the rat, the experimental animals


received diet supplements of the strongly basic anion-exchange resin


Dowex 2X8 in its chloride form  ("resin 1"), the weakly basic anion-exchange


resin Amberlite XE58 in its  hydroxyl form ("resin 2"), and Amberlite XE58

-------
saturated with chloride to nullify its anion-exchange ability ("saturated




resin 2").




       These resins were toxic when fed to postweaned rats, as evidenced




by varying reductions in the rates of growth  when compared to control




animals.  This symptom was accompanied by retardation in the time of




eruption of the third molars (Shaw, 1963).




           2.  Sensitization




               Rabbits treated subcutaneously with suspensions of




Dowex 50-X4 produced antiserum to this resin.  Serum from untreated




rabbits and from human subjects gave no agglutination reaction with this




resin (Konishi, 1956).




           3.  Teratogenicity - Reproductive Effects




               No teratogenic effects of ion-exchange resins are reported




in the literature.  However, Shaw (1963) noted some reproductive effects.




The offspring of female rats which had been fed weakly basic anion-




exchanger Amberlite XE58 (hydroxyl form) had lower weaning weights and




slower growth rates than the controls.  The offspring of females fed




Amberlite XE58 saturated with chloride had weaning weights approximately




two-thirds those of the controls.




           4.  Carcinogenicity




               No specific carcinogenic studies were reported in the




available literature.




               Strecker (1956) reports on granuloma formation following

-------
Intraperitoneal administration of weakly add Amberlite IRC 50 (carboxylic




groups) and subsequent phagocytosis by the mesenchymal cells.




           5.  Mutagenicity




               No studies relating ion-exchange resins to mutagenicity




are reported in the available literature.




           6.  Behavioral Effects




               No studies were found on the behavioral effects of the




ion-exchange resins.






       C.  TOXICITY TO LOWER ANIMALS




           No studies were encountered on the toxicity of the ion-




exchange resins toward lower animals.






       D.  TOXICITY TO PLANTS




           Ion-exchange resins have been recommended as agents in the




control of aquatic plants, specifically Florida elodea (Martin, 1970).




The resins would achieve the desired effect by sequestering or rendering




unavailable to the plant certain ions such as manganese and iron.  Elodea




died in the presence of cation-exchange resin.  The exact role of the



cation-exchange resin and the identity of the critical metal were not




determined.






       E.  TOXICITY TO MICROORGANISMS




           Nothing was available concerning the toxicity of ion-exchange




resins toward microorganisms.
                                 1U6

-------
                         LITERATURE CITED
Anon (1964), "Food Additives - Ion-Exchange Resins", Federal
     Register 29_, 9708   12322

Armitage, G.M. and Lyle, S.J. (1973), "Mass Spectrophotometric
     Study of the Deterioration of Polystyrene - Based Ion-Exchangers;
     Talanta 20, 315-20   15936

Astanina, F.S. (1969), "Industrial Eygiene in the Production  of
     Anion-Exchange Resins", Gig. Tr. Prof. Zabol. 13 (1), 15-21
     (Russ.).   12191

Burger, C.L. (1967), "Interaction of Dyes with Ion-Exchange Resins",
     J. Chromatogr. 26. (1), 334-6   12373

Calmanovici, B. (1965), "Spectrophotometric Method for the Characteri-
     zation of Ion-Exchange Resins.  I. Cation Exchangers",
     Materials Plas. 2^ (6), 369-71 (Rom.)  10670

Craig, P.N. (1953), "Synthesis of Ion Exchange Resins", Ann,  N. Y.
     Acad. Sci. 57., 67-68

Danowski, T.S. and Greenman, L. (1953), "Changes in Fecal and Serum
     Constituents During Ingestion of Cation and Anion Exchangers",
     Ann. N. Y. Acad. Sci. 57., 273-9    12428

Harthon, J.G;L. and Sigroth, K.I.E. (1952), "A Case of Uremia and
     Hyperpotassemia with Sulfonic Cation - Exchange Resin",  Acta.
     Med. Scand. 144t 230-6   12258

Hoegfeldt, E. and Kierkegaard, P. (1954), "Wet Combustion, and Alter-
     native to Elution when Analyzing Ion-Exchange Resins", Acta. Chem.
     Scand. 8, 585-90   10620          .    •

Konishi, T. and Kitamura, M. (1956), "Serological Studies on  Ion-Exchange
     Resins. I.", Igaku to Seibutsugaku 40_, 195-8   12399

Kopylova, V.D., Asambadze, G.D., and Saldadze, K.M. (1969), "Determina-
     tion of Functional Groups in Anion-Exchangers", Zavod. Lab.
     35  (40), 1180-1 (Russ.)   12077

Levitt, M.F. (1953), "The Interpretation of the Laboratory Data in
     the Clinical Use of the Cation Exchange Resins", Ann. N.Y. Acad.
     Sci. 57, 298-307   12427

-------
Martin, D.E., Doig, M.T., and Millard, D.K.  (1970),  "Potential
     Control of Florida  Elodea by Ion-Control Agents", Nature
     (London) 226  (5241), 181-2   14713

Parrish, J.R. (1973), "Analysis of Ion-Exchange Resin by Pyrolysis -
     Gas Chromatography", Anal. Chem. 45  (9), 1659-62   15941

Pepper, K.W. (1952), "Ion-Exchange Resins",  Plastics Inst.  (London)
     Trans. 20. (41), 68-84   12271

Sailer, W.  (1957), "Ion-Exchange Treatment of Fruit Juices",
     Fruchtsaft-Ind. 2.,  131-5 (Ger.)   12407

Shaw, J.H.  and Griffiths, D. (1963), "Influence of Anion-Exchange
     Resins on Experimental Dental Caries and Tooth Eruption,
     "J. Dental Res. 42_  (4), 1004-14   12509

Snell, F.D. and Ettre, L.S. (1972), "Encyclopedia of Industrial
     Chemical Analysis", Interscience 15, 2-3

Strecker, F.J. (1956), "The Reaction of Tissue to Ion-Exchangers",
     Beitr. Silkkose Forsch., Sonderband 2.,  475-84 (Ger.)   12433

Wheaton, R.M. and  Seamster, A.H. (1966), "Kirk-Othmer:  Encyclopedia
     of Chemical Technology, 2.  C11)* 871-99

Wolff, H.P., Pfeffer, K.H. and Jahrmarker (1955), "The Disturbance of
     Inorganic Metabolism and Its Avoidance  during Treatment with
     Ion-Exchangers", Arztl. Wochschr. 10, 781-8 (Ger.)    12410
                                   1U8

-------
                        APPENDIX
C. I. Fluorescent Brightener 1

    Colour Index Number

    C. A. Registry Number

    Commercial Names


    Chemical Class



    Molecular Formula

    Fluorescence

    Properties
    Applications
C.I. 40630

[15339-39-6]

Tinopal BV, BVA, BVS (Ciba-Geigy
Corp.)

4,4'-Bis[4,6-diamino-s-triazin-2-
yl)amino]-2,2'-stilbenedisulfonic
acid, disodium salt

C20H20N12°6S2 * 2Na ' (CH20)x

Bright blue

Yellowish powder
Good solubility in water.  Stable
to acids and reducing agents.
Fastness:  Chlorine, moderate;
Light, good; Washing, very good

Cellulose
    Ciba-Geigy Corp. reported production and sales of Fluorescent

Brightener 1 to the U. S. Tariff Commission in 1972.  No production fig-

ures are given; they are included in the total brightener production

figures.
                              A-l

-------
C. I. Fluorescent Brightener 1:1

    Colour Index Number              Not given in the literature

    C. A. Registry Number            Not given in the literature

    Commercial Names                 Phorwite GG (Verona Corp.)

    Chemical Class                   Stilbene derivative

    Molecular Formula                Not given in the literature

    Fluorescence                     Blue

    Properties                       Fastness:  Acids, good; Chlorine,
                                     poor; Reducing agents, excellent

    Applications                     Cellulose


C. I. Fluorescent Brightener 2

    This C. I. generic name is discontinued.  The brighteners formerly

    listed under it now appear under C. I. Fluorescent Brightener 1:1.


C. I. Fluorescent Brightener 3

    This C. I. generic name is discontinued.  The brighteners formerly

    listed under it now appear under C. I. Fluorescent Brightener 28.
                               A-2

-------
C. I. Fluorescent Brightener 4

    Colour Index Number              Not given in the literature

    C. A.  Registry Number            Not given in the literature

    Commercial Names                 Calcofluor Yellow HEB (American
                                     Cyanamid Co.)

    Chemical Class                   Naphthalimide derivative

    Molecular Formula                Not given in the literature

    Fluorescence                     Yellow

    Properties                       Insoluble in hydrocarbons and
                                     water, very soluble in formic
                                     acid, soluble in alcohol and
                                     esters

    Applications                     Nylon, acetate
                                     Lacquers


C. I. Fluorescent Brightener 4 is not being manufactured at the present

time.
                               A-3

-------
C. I. Fluorescent Brightener 5

    Colour Index Number              C.I. 36900

    C. A. Registry Number            Not given in the literature

    Commercial Names                 Fluorescent Purple 2G (Allied
                                     Chemical and Dye Corp.)

    Chemical Class                   Stilbene derivative

    Molecular Formula                Not given in the literature

    Fluorescence                     Reddish-blue

    Properties                       Good substantivity for cellulose,
                                     Fastness:  chlorine, poor; peroxide,
                                     good; light, satisfactory

    Applications                     Paper
                                     Cellulose


C. I. Fluorescent Brightener 5 is not being manufactured at the present

time.
                               A-U

-------
C. I. Fluorescent Brightener 5:1

     Colour Index Number

     C. A. Registry Number

     Commercial Names

     Chemical Class

     Molecular Formula

     Fluorescence

     Properties


     Applications


C. I. Fluorescent Brightener 6

     Colour Index Number

     C. A. Registry Number

     Commercial Names

     Chemical Class


     Molecular Formula

     Fluorescence

     Properties

     Applications
Not given in the literature

Not given in the literature

Not given in the literature

Trisazo derivative

Not given in the literature

Reddish-blue

Good substantivity for cellulose
Poor fastness to chlorine

Paper
Not given in the literature

Not given in the literature

Not given in the literature

Calcofluor White B (American
Cyanamid Co.)

Not given in the literature

Blue

Good fastness to chlorine

Cellulose
     American Cyanamid Co. reported production and sales of Fluor-

escent Brightener 6 to the U. S. Tariff Commission in 1972.  No

production figures are given; they are included in the total bright-

ener production figures.
                           A-5

-------
C. I. Fluorescent Brightener 7

     Colour Index Number

     C. A. Registry Number

     Commercial Names


     Chemical Class

     Molecular Formula

     Fluorescence

     Properties

     Applications
Not given in the literature

Not given in the literature

Calcofluor White 4B (American
Cyanamid Co.)

Benzidine sulfone derivative

Not given in the literature

Greenish-blue

Outstanding fastness to chlorine

Cellulose
     C. I. Fluorescent Brightener 7 is not being manufactured at

the present time.
C. I. Fluorescent Brightener 8

     Colour Index Number

     C. A. Registry Number

     Commercial Names


     Chemical Class

     Molecular Formula

     Fluorescence

     Properties

     Applications
Not given in the literature

Not given in the literature

Calcofluor White 5B,  5BT,  P5B
(American Cyananid Co.)

Benzidine sulfone derivative

Not given in the literature

Greenish-blue

Excellent fastness to chlorine

Cellulose
     American Cyanamid Co. reported production and sales of Fluoree-

cent Brightener 8 to the U.S. Tariff Commission in 1972.  No produc-

tion figures are given; they are included in the total brightener

production figures.
                         A-6

-------
C. I. Fluorescent Brightener 9

     Colour Index Number

     C. A. Registry Number

     Commercial Names
     Chemical Class



     Molecular Formula

     Fluorescence

     Properties

     Application
C.I. 40621

[133-66-4]

Blancophor HZP, Tintophen CX
(GAF Corp.); Blankophor HZP
(Farbenfabriken Bayer A.G., Ger-
many) ; Calcofluor White MR (Ameri-
can Cyanamid Co.); Leukophor DNH
(Sandoz Colors and Chemicals);
Ryluz PP (Chemopdl, Czech.);
Tinopal TAS, TASD (Ciba-Geigy
Corp.); Whitex SB (Sumitomo
Chemical Co., Ltd., Japan)

4,4' -Bis[(4,6-dianilino-s-triazin-
2-yl)amino]-2,2'-stilbenedisul-
fonic acid, disodium salt

              • 2 Na

Not given in the literature

Poor fastness to chlorine

Cellulose
Detergents
     American Cyanamid Co., GAF Corp., and Hilton-Davis Div. of

Sterling Drug Corp. reported production and sales of Fluorescent

Brightener 9 to the U.S. Tariff Commission in 1972.  No production

figures are given; they are included in the total brightener pro-

duction figures.

     Production figures which have been reported in the past are:

                         1965     3,749,000 Ibs.

                         1967       318,000 Ibs.

                         1968       234,000 Ibs.

                         1969       254,000 Ibs.
                          A-T

-------
C. I. Fluorescent Brightener 9:1

     Colour Index Number

     C. A. Registry Number

     Commercial Names



     Chemical Class


     Molecular Formula

     Fluorescence

     Properties

     Applications
Not given in the literature

Not given in the literature

Hiltamine White BPK, EPS, EP
(Hilton-Davis Div. of Sterling
Drug Co.)

Bistriazinylaminostilbene deriva-
tive

Not given in the literature

Not given in the literature

Poor fastness to chlorine

Cellulose
C. I. Fluorescent Brightener 10

     Colour Index Number

     C. A. Registry Number

     Commercial Names


     Chemical Class

     Molecular Formula

     Fluorescence

     Properties



     Applications
Not given in the literatura

Not given in the literature

Calcof luor Whit* ZRT (AtttriM*
Cyanamid Co.)

Stilbene derivative

Not given in the literature

Blue

High substantivity, good solu-
bility, good fastness to light,
not fast to chlorine

Cellulose
     C. I. Fluorescent Brightener 10 is not being manufactured at

the present time.
                         A-8

-------
C. I. Fluorescent Brightener 11

     Colour Index Number

     C. A. Registry Number

     Commercial Names


     Chemical Class

     Molecular Formula

     Fluorescence

     Properties

     Applications
 Not given in the literature

 Not given in the literature

 Calcofluor White 4R (American
 Cyanamid Co.)

 Stilbene derivative

 Not given in the literature

 Reddish-blue

 Excellent fastness to chlorine

 Cellulose
     C. I.. Fluorescent Brightener 11 is not being manufactured at

the present time.
C. I. Fluorescent Brightener 12

     Colour Index Number

     C. A. Registry Number

     Commercial Names


     Chemical Class

     Molecular Formula

     Fluorescence

     Properties


     Applications
 Not given in the literature

 Not given in the literature

 Fluorosol AC (Allied Chemical
 and Dye Corp.)

 Stilbene derivative

 Not given in the literature

 Bluish

.. Good substantivity and moderate
 fastness to chlorine

 Cellulose
     C. I. Fluorescent Brightener 12 is not being manufactured at

the present time.
                          A-9

-------
C. I. Fluorescent Brightener 13

     Colour Index Number

     C. A. Registry Number

     Commercial Names


     Chemical Class

     Molecular Formula

     Fluorescence

     Properties

     Applications
Not given in the literature

Not given in the literature

Fluorosol ACL (Allied Chemical
and Dye Corp.)

Stilbene derivative

Not given in the literature

Bluish

Moderate fastness to chlorine

Cellulose
     C. I. Fluorescent Brightener 13 is not being manufactured at

the present time.
C. I. Fluorescent Brightener 14

     Colour Index Number

     C. A. Registry Number

     Commercial Names



     Chemical Class

     Molecular Formula

     Fluorescence

     Properties



     Applications
Not given in the lit«ratur»

Not given in the literature

Leucophor RG (Sandos, Inc.);
Whitex RG (Sumitomo Chemical
Co., Ltd., Japan)

Stilbene derivative

Not given in the literature

Bluish

Greenish-gray powder
Compatible with ionic and nonionic
softening agents

Cellulose
                         A-10

-------
C. I. Fluorescent Brightener 15

     Colour Index Number

     C. A. Registry Number

     Commercial Names
     Chemical Class

     Molecular Formula

     Fluorescence  .

     Properties
     Applications
Not given in the literature

Not given in the literature

Celumyl C (Societe de Produits
Chimiques et de Synthese, France);
Photine BH, 3BS, CM (Hickson and
Welch, Ltd., England); Photine C,
C33, UC (Hickson and Welch, Ltd.,
England; Hickson and Dadajee
Private, Ltd., India; S. A. Rovira,
Spain)

Stilbene derivative

Not given in the literature

Blue

Excellent substantivity, soluble
in aqueous media
Fastness:  Acid, good; Alkali,
very good; Chlorine, very good;
Dithionite, very good; Peroxide,
very good; Light, moderate

Cellulose
Paper
                         A-ll

-------
C. I. Fluorescent Brightener 16

     Colour Index Number

     C. A. Registry Number

     Commercial Names
     Chemical Class

     Molecular Formula

     Fluores'cence

     Properties
     Applications
Not given in the literature

Not given in the literature

Blancol DP (L.B. Holliday and
Co., Ltd., England); Celumyl D
(Societe de Produits chimiques
et de Synthese, France);
Heliofor DP (CZECH, Poland); Pho-
tine D, DK (Hickson and Welch,
Ltd., England; S. A. Rovira,
Spain)

Stilbene derivative

Not given in the literature

Blue

Excellent substantivity.  Slightly
soluble in aqueous detergent solu-
tion
Fastness:  Acid, poor; alkali,
very good; Chlorine, good; Dithi-
onite, very good:; Peroxide, very
good; Light, moderate

Cellulose
Wool
Nylon
                         A-12

-------
C. I. Fluorescent Brightener 17

     Colour Index Number           Not given in the literature

     C. A. Registry Number         Not given in the literature

     Commercial Names              Celumyl S (Societe de Froduits
                                   Chimiques et de Synthese,  France);
                                   Photine S (Hickson and Welch,
                                   Ltd., England;  S. A. Rovira,
                                   Spain)

     Chemical Class                Stilbene derivative

     Molecular Formula             Not given in the literature

     Fluorescence                  Blue

     Properties                    High solubility.  Low substanti-
                                   vity.  Salt^sensitive.  Good
                                   stability to dithionite and per-
                                   borate but poor fastness to chlorine

     Applications                  Cellulose
                                   Paper
C. I. Fluorescent Brightener 17:1

     Colour Index Number           Not given in the literature

     C. A. Registry Number         Not given in the literature

     Commercial Names              Photine DN (Hickson and Welch,
                                   Ltd., England; S. A. Rovira,
                                   Spain)

     Chemical Class                Stilbene derivative

     Molecular Formula             Not given in the literature

     Fluorescence                  Blue

     Properties                    Orange yellow powder
                                   High substantivity.  Dispensible
                                   in water.
                                   Fastness:  Acid, poor; Alkali,  very
                                   good; Chlorine, good; Dithionite,
                                   very good; Peroxide, very good;
                                   Light, moderate

     Applications                  Nylon


                         A-13

-------
C. I. Fluorescent Brightener 18

     Colour Index Number           Not given in the literature

     C. A. Registry Number         Not given in the literature

     Commercial Names              Tinopal SP (Ciba-Geigy Corp.)

     Chemical Class                Benzoyldiaminostilbenedisulfonic
                                   acid derivative

     Molecular Formula             Not given in the literature

     Fluorescence                  Bright bluish

     Properties                    Yellow powder
                                   Moderately soluble in water
                                   Compatible with cationic softeners
                                   Stable to resin finishing
                                   Very good fastness to chlorine,
                                   light, and washing

     Applications                  Cellulose


     C. I. Fluorescent Brightener 18 is not being manufactured at

the present time.



C. I. Fluorescent Brightener 19

     Colour Index Number           Not given in the literature

     C. A. Registry Number         Not given in the literature

     Commercial Names              Uvitex BT (Ciba-Geigy Corp.)

     Chemical Class                Stilbene derivative

     Molecular Formula             Not given in the literature

     Fluorescence                  Yellowish white

     Properties                    Yellowish white powder
                                   Stable to peroxide and dithionite

     Applications                  Cellulose


     C. I. Fluorescent Brightener 19 is not being manufactured at

the present time.

-------
C. I. Fluorescent Brightener 20

     Colour Index Number           Not given in the literature

     C. A. Registry Number         Not given in the literature

     Commercial Names              Fluotex C2B (Compagnie Francaise
                                   des Matieres Colorantes,  France)

     Chemical Class                Stilbene derivative

     Molecular Formula             Not given in the literature

     Fluorescence                  Not given in the literature

     Properties                    Good fastness to perborate
                                   and peroxide, moderate fastness
                                   to chlorine and chlorites

     Applications                  Cellulose


     C. I. Fluorescent Brightener 20 is not being manufactured at

the present time.                                      ,



C. I. Fluorescent Brightener 21

     This C. I. generic name is discontinued.  The brighteners

formerly listed under it now appear under C. I. Fluorescent

Brightener 5.
                         A-15

-------
C. I. Fluorescent Brightener 22

     Colour Index Number

     C. A. Registry Number

     Commercial Names



     Chemical Class

     Molecular Formula

     Fluorescence

     Properties


     Applications
Not given in the literature

Not given in the literature

Tinopal 4BMF Liquid (Ciba-Geigy
Corp.); Whitex 4BM, LSA (Sumitomo
Chemical Co., Ltd., Japan)

Stilbene derivative

Not given in the literature

Clear Bluish

Fastness:  Chlorine, good; Light,
good; Washing, very good

Cellulose
Silk
     Ciba-Geigy reported production and sales of Fluorescent Brigh-

tener 22 to the U. S. Tariff Commission in 1972.  No production

figures are given; they are included in the total brightener pr«4uc-

tion figures.
C. I. Fluorescent Brightener 23

     Colour Index Number

     C. A. Registry Number

     Commercial Names


     Chemical Class

     Molecular Formula

     Fluorescence

     Properties

     Applications
Not given in the literature

Not given in the literature

Fluolite BW,: C (Imperial Chemical
Industries, Ltd., England)

Stilbene derivative

Not given in the literature

Bluish-violet

Good fastness to chlorine

Paper
                         A-16"

-------
C. I. Fluorescent Brightener 24

     Colour Index Number

     C. A. Registry Number

     Commercial Names
     Chemical Class


     Molecular Formula

     Fluorescence

     Properties




     Applications
Not given in the literature

[12224-02-1]

Fluolite HSP Liquid (Imperial
Chemical Industries, Ltd., Eng-
land); Heliofor P (CIECH, Poland);
Kayaphor BSN, SN (Nippon Kayaku
Co., Ltd., Japan); Mikephor BN
(Mitsui Toatsu Chemicals, Inc.,
Japan); Tinopal 2B, 2BF Liquid,
2BP (Ciba-Geigy Corp.); Whitex
BB, BP (Sumitomo Chemical Co.,
Ltd., Japan)

Bistriazinylaminostilbenedisul-
fonic acid derivative

Not given in the literature

Bluish-violet

Yellow powder
Very soluble in water
Fastness:  Chlorine, very good;
Light, good; Washing, very good

Paper
Cellulose
                         A-1T

-------
C. I. Fluorescent Brightener 25

     Colour Index Number

     C. A. Registry Number

     Commercial Names

     Chemical Class

     Molecular Formula

     Fluorescence

     Properties


     Applications
Not given in the literature

Not given in the literature

Blancophor SV (GAF Corp.)

Stilbene derivative

Not given in the literature

Bluish-violet

Very soluble in cool or warm
water

Cotton, wool, mohair
     GAF Corp. reported production and sales of Fluorescent

Brightener 25 to the U. S. Tariff Commission in 1972.  No figures

are given; they are included in the total brightener production

figures.
C. I. Fluorescent Brightener 26

     Colour Index Number

     C. A. Registry Number

     Commercial Names


     Chemical Class

     Molecular Formula

     Fluorescence

     Properties

     Applications
Not given in the literature

Not given in the literature

Pontamine White CL (E.I.  du Pont
de Nemours and Co.,  Inc.)

Thiazole derivative

Not given in the literature

Reddish-blue

Excellent fastness to chlorine

Cellulose
Paper
Nylon
     C. I. Fluorescent Brightener 26 is not being manufactured at

the present time.
                         A-18

-------
C. I. Fluorescent Brightener 27

     This C. I. generic name is discontinued.  Brighteners for-

merly listed under it now appear under C. I. Fluorescent Brightener

5:1.
C. I. Fluorescent Brightener 28

     Colour Index Number

     C. A. Registry Number


     Commercial Names
     Chemical Class
     Molecular Formula

     Fluorescence

     Properties
Not given in the literature

[4404-43-7]
[4193-55-9], disodium salt

Blancol CFB new (L. B. Holliday
and Co . , Ltd . , England) ; Blanco-
phor FB, Tintophen FB (GAF Corp.);
Calcofluor White PMS, BMW, ST
(American Cyanamid Co.); Hiltamine
Arctic White CWD (Hilton-Davis
Division of Sterling Drug Co.);
Paper White BN, BP, Pontamine
White BT, BTS (I.E. du Pont de
Nemours and Co., Inc.); Tinopal
4BM, 4BMA, 4BMT (Ciba-Geigy
Corp.)

4,4'-Bis[[4-anilino-6-[bis(2-
hydroxyethyl) amino ] -s-triazin-
2-yl]amino]-2,2'-stilbenedisulfonic
acid
Pale blue

Canary yellow powder or clear
solution
Readily soluble. in water
Excellent stability under reasonable
storage conditions
Resistant to peroxide and perborate
bleaching action; susceptible to
hypochlorite bleach
Excellent dyeing properties over
temperatures of 80°F to 212°F and
over pH ranges 5-12.
                         A-19

-------
     Applications                  ZEFRAN acrylic and cellulosic
                                   fibers
                                   Shirtings, bed linen, towels,
                                   dress goods
                                   White ground prints, tapes, braids,
                                   white sewing threads, decorative
                                   yarns
                                   Nylon—gives greener (less red)
                                   shade of blue
                                   Cold-water laundry formulations
                                   Liquid detergents
                                   Fabric softeners
     American Cyanamid Co., Cincinnati Malacron Chemicals, Inc.,

E. I. du Pont de Nemours and Co., Inc., Hilton-Davis Chem., Co.,

and the Verona Division of Baychem Corp. reported production and

sales of Fluorescent Brightener 28 to the U. S. Tariff Commission

in 1972.

     Following are production figures for those years in which this

brightener was given separate listing in the U. S. Tariff Commission

Reports.

                  1965     1,515,000 Ibs.

                  1966     1,240,000 Ibs.

                  1967     1,410,000 Ibs.

                  1968     1,420,000 Ibs.

                  1969     1,676,000 Ibs.

                  1970     1,593,000 Ibs.

                  1971     1,574,000 Ibs.

                  1972     1,604,000 Ibs.

     According to the U. S. Tariff Commission Reports, 4,180 pounds

of Fluorescent Brightener 28 were imported into the U. S. in 1972.
                        A-20

-------
C. I. Fluorescent Brightener 29

     Colour Index Number

     C. A. Registry Number

     Commercial Names

     Chemical Class

     Molecular Formula

     Fluorescence

     Properties

     Applications
Not given in the literature

Not given in the literature

Uvitex .P. (Ciba-Geigy Corp.)

Not given in the literature

Not given in the literature

Pure blue

High substantivity for cellulose

Paper
     C. I. Fluorescent Brightener 29 is not being manufactured at

the present time.
C. I. Fluorescent Brightener 30

     Colour Index Number

     C. A. Registry Numbers



     Commercial Names
C. I. 40600

[17118-51-3], cis
[17118-50-2], trans
[2606-93-1], disodium salt

Blancol C (L. B. Holliday and
Co., Ltd., England); Blancophor R
(GAF Corp.); Blankophor R (Far-
benfabriken Bayer A. G., Germany);
Blancofor R (Bayer do Brasil
Industriea Quinicas S. A., Brazil);
Enianil White R (Estabelecimento
Nacional Industria de Anilinas
S. A., Brazil); Glowhite RRN
(Dye-Chem., Ltd., India); Leuco-
phor R (Sandoz, Inc.); Delft White
2RW (Delfland Produkten N.V., Hol-
land); Lumisol RV (Fine Dyestuffs
and Chemicals, Ltd., England);
Phorwite RN (Verona Corp.);
Photine R (Hickson and Welch,
Ltd., England; S. A. Rovira,
Spain); Tintophen R (GAF Corp.);
Whitex R Extra (Sumitomo Chemi-
cal Co., Ltd., Japan)
                        A-21

-------
     Chemical Class



     Molecular Formula

     Fluorescence



     Properties



     Applications
4,4'-Bis(3-phenylureido)-2,2'-
stilbenedisulfonic acid, diso-
dium salt
               2Na
Reddish-violet fluorescence in
daylight; bluish-violet fluores-
cence in ultraviolet radiation

Yellowish powder
Poor fastness to chlorine
Stable to hydrosulfite

Cellulose, protein fibers, nylon,
wool, paper
     GAF Corp. reported production and sales of Fluorescent Brigh-

tening Agent 30 to the U.S. Tariff Commission in 1972.  No pro-

duction figures are given; they are included in the total brigh-

tener production figures.
C. I. Fluorescent Brightener 31

     Colour Index Number

     C. A. Registry Number

     Commercial Names

     Chemical Class

     Molecular Formula

     Fluorescence

     Properties

     Applications
Not given in the literature

Not given in the literature

Uvitex RSW (Ciba-Geigy Corp.)

Not given in the literature

Not given in the literature

Not given in the literature

Good fastness to chlorine

Mixtures of cellulose, protein
fibers, and nylon
     C. I. Fluorescent Brightener 31 is not being manufactured at

the present time.
                         A-22

-------
C. I. Fluorescent Brightener 32

     Colour Index Number

     C. A. Registry Number

     Commercial Names
     Chemical Class
     Molecular Formula

     Fluorescence

     Properties



    _Applications
C. I. 40620.

[1264-32-0]

Blancofor B Extra (Fabricacion
Nacional de Colorantes y Explo-
sives S. A., Spain); Enianil
White B (Estabelecimento Nacional
Industria de Anilinas, S. A.,
Brazil); Heliofor BGC (CIECH, Po-
land); Leukophor B, BCF (Sandoz,
Inc.); Whitex B, 3B (Sumitomo
Chemical Co., Ltd., Japan);
Delft White BS (Delfland Produk-
ten N.V., Holland)

4,4'-Bis[(4-anilino-6-hydroxy-
s-triazin-2-yl) amino]-2,2'-stil-
benedisulfonic acid, disodium
salt

C32H26N10°8S2 * 2Na

Bluish

Yellowish powder
Poor fastness to chlorine
Good fastness to washing

Cellulose, protein fibers, ny-
lon   -  -   —    - -   ....
     According to the U. S. Tariff Commission Reports, 5,181

pounds of Fluorescent Brightener 32 were imported into the U.S.

in 1972.
                         A-23

-------
C. I. Fluorescent Brightening Agent 33

     Colour Index Number           Not given in the literature

     C. A. Registry Number         Not given in the literature

     Commercial Name               Blancophor SC (GAP Corp.)

     Chemical Class                Not given in the literature

     Molecular Formula             Not given in the literature

     Fluorescence                  Blue (peak at 437 nm)

     Properties                    Fair fastness to chlorine

     Applications                  Cellulose, protein fibers,  nylon


     GAF Corp. reported production and sales of Fluorescent Brighten-

ing Agent 33 to the U.S. Tariff Commission in 1972.  No production

figures are given; they are included in the total brightener pro-

duction figures.



C. I. Fluorescent Brightening Agent 34

     Colour Index Number           C. I. 40605

     C. A. Registry Number         [6416-25-7]

     Commercial Name               Pontamine White 2GT (E. I.  du
                                   Pont de Nemours and Co . , Inc . )

     Chemical Class                4,4'-Bis(2,4-dimethoxybenzamido) -
                                   2,2'-stilbenedisulfonic acid,
                                   disodium salt
     Molecular Formula

     Fluorescence                  Not given in the literature

     Properties                    Moderate fastness to chlorine

     Applications                  Cellulose, protein fibers,  nylon
                         A-2U

-------
C. I. Fluorescent Brightener 35

     Colour Index Number

     C. A. Registry Number

     Commercial Names
     Chemical Class

     Molecular Formula

     Fluorescence

     Properties
     Applications
Not given in the literature

Not given in the literature

Celumyl B (Societe de Produits
Chimiques et de Synthese, France);
Photine B (Hickson and Welch, Ltd.,
England; S. A. Rovira, Spain).

Stilbene derivative

Not given in the literature

Blue

Good solubility; moderate sub-
stantivity.  Stable to alum and
size
Fastness:  Acid, very good;
Alkali, very good; Chlorine, good;
Dithionite, very good; Peroxide,
very good; Light, moderate

Paper
C. I. Fluorescent Brightener 36

     Colour Index Number

     C. A. Registry Number

     Commercial Names


     Chemical Class

     Molecular Formula

     Fluorescence

     Properties

     Applications
Not given in the literature

Not given in the literature

Blancol 61281 (L. B. Holliday
and Co., Ltd., England)

Balanced anionic-cationic complex

Not given in the literature

Bluish-violet

Stable to dithionite and peroxide

Protein fibers, acetate, nylon
                         A-25

-------
C. I. Fluorescent Brlghtener 37

     Colour Index Number

     C. A. Registry Number

     Commercial Names



     Chemical Class

     Molecular Formula

     Fluorescence

     Properties




     Applications
Not given In the literature

Not given in the literature

Uvitex RT (Ciba-Geigy Corp.);
Whitex Rt (Sumitomo Chemical
Co., Ltd., Japan)

Stilbene derivative

Not given in the literature

Not given in the literature

Greenish powder
May be used in wash liquors and
oxidizing and reducing discharge
pastes

Mixtures of cellulose, protein
fibers, and nylon
C. I. Fluorescent Brightener 38

     Colour Index Number

     C. A. Registry Number

     Commercial Names

     Chemical Class

     Molecular Formula

     Fluorescence

     Properties




     Applications
Not given in the literature

Not given in the literature

Uvitex TW (Ciba-Geigy Corp.)

Not given in the literature

Not given in the literature

Not given in the literature

Stable to peroxide,  chloride,
and peracetic acid.   Good fast-
ness to light on acetate, polyes-
ters , and acrylics.

Polyester, acrylic,  and protein
fibers
Nylon, acetate
Cellulose
     C. I. Fluorescent Brightener 38 is not being manufactured at

the present time.

                         A-26

-------
C. I. Fluorescent Brightener 39

     C, I. Fluorescent Brightener 39 (Uvitex U, Ciba-Geigy Corp.)

is not being manufactured at the present time.
C. I. Fluorescent Brightener 40

     Colour Index Number

     C. A. Registry Number

     Commercial Names


     Chemical Class



     Molecular Formula

     Fluorescence

     Properties




     Applications
C. I. 40647

[7426-67-7]

Blankophor G (Farbenfabriken
Bayer A . G . , Germany)

4,4' -Bis (6-sulf o-2H-naphtho [1,2-
d] triazol-2-yl) -2,2' -stilbenedi-
sulfonic acid, tetrasodium salt
Blue

Stable to peroxide and hydrosul-
fite
Poor fastness to chlorine
Good fastness to washing

Cellulose, protein fibers, poly-
amide fibers, acetate
     C. I. Fluorescent Brightener 40 is not being manufactured at

the present time.
                        A-27

-------
C.I. Fluorescent Brightening Agent 41
     Colour Index Number

     C. A. Registry Number

     Commercial Name

     Chemical Class

     Molecular Formula

     Fluorescence

     Properties



     Applications
C. I; 49015

[1483-30-3]

Uvitex RS (Ciba-Geigy Corp.)

Z-Styrylbenzothiozole

C15HnNS

Reddish-blue

Orange-yellow powder
Good fastness to chlorine
Stable to hypochlorite

Cellulose, nylon
C. I. Fluorescent Brightener 42

     Colour Index Number

     C. A. Registry Number

     Commercial Names

     Chemical Class

     Molecular Formula

     Fluorescence  •

     Properties


     Applications
Not given in the" literature

Not given in the literature

Uvitex GS (Ciba-Geigy Corp.)

Stilbene derivative

Not given in the literature

Green

Yellow powder
Good fastness to chlorine

Cellulose and Nylon
C. I. Fluorescent Brightener 43

     Application and properties are very similar to those of  C.  I.

Fluorescent Brightener 48.

     C. I. Fluorescent Brightener 43 is not being manufactured at

the present time.
                       A-28

-------
C. I. Fluorescent Brightener 44

     Colour Index Number
     C. A. Registry Number
               '''I'' ••-••  , la-.fe
     Commercial Names
     Chemical.

     Molecular Formula

     Fluorescence -  -

     Properties


     Applications  -



C. I. Fluorescent Brightener 45

     Colour Index Number

     C. A. Registry Number

     Commercial Names

     Chemical Class

     Molecular Formula

     Fluorescence

     Properties


     Applications
                                   Not given in, the literature
                                           •  •-YutfcmjH xsbftT vjLsoIo;

                                   Not given in,the literature
                                       ^^  LJ-'Y f\ *• * .,.,-.*._<_   *.
Blancol W (L. B. Holliday and
Co., Ltd., England)

Aminocoumarin derivative

Not given in the literature

Bluish-violet

Fast to peroxide and to reducing
agents        .  -^vs ^svo;!'!

Protein fibers,
                                   Not  given in the  literature

                                   Not  given in the  literature

                                   Uvitex SIA (Ciba-Geigy Corp.)

                                   Heterocyclic

                                   Not  given in the  literature

                                   Blue

                                   Very good fastness  to chlorine
                                   and  peroxide

                                   Cellulose,  acetate,  nylon
     GAF Corp. reported production and  sales  of  Fluorescent Brighten-

er 45 to the U.S. Tariff Commission in  1972.   No production figures

are given; they are included  in  the total brightener production

figures.
                         A-29

-------
C. I. Fluorescent Brightener 46   *

     Colour Index Number           C, I. 46625

     C. A. Registry Numbers        [4434-38-2]
                                   [6416-68-8], sodium salt

     Commercial Names              Tlnbpal BBS (Ciba-Geigy Corp.)

     Chemical Class                4-(2H-Naphth6[l,2-d]triaz61-2-
                                   yl)-2-stilbenedisuifonic acid,
                                   sodium salt

     Molecular Formula             C^BI 7^038 • Na

     Fluorescence                  Slightly bluish

     Properties              --,.     Very good fastness on polyamldes

     Applications                  Soaps, detergents


     Ciha-Geigy Corp. reported production and sales of Fluorescent

Brightener 46 to the U.S. Tariff Commission in 1972.  No production

figures are given; they are included in the total brightener pro-

duction figures.
                         A-30

-------
C. I. Fluorescent Brightener 47

     Colour Index Number           Not given in the literature

     C. A. Registry Number         Not given in the literature

     Commercial Names              Tinopal GS (Ciba-Geigy Corp.)

     Chemical Class         ,       Stilbyl-naphthotriazole derivative

     Molecular Formula             Not given in the literature

     Fluorescence                  Greenish

     Properties                    Orange-yellow powder
                                   Very good fastness on polyamides
                                   Cellulosic fibers, protein fibers,
                                   polyamide fibers

     Applications                  Soaps, detergents


     According to the U.S. Tariff Commission Reports, 33,951

pounds of Fluorescent Brightener 47 were imported into the U.S.

in 1972.
                         A-31

-------
C. I. Fluorescent Brightener 48

     Colour Index Number           C.I. 40640

     C. A. Registry Number         [30587-99-6]
                                   [6826-44-4], disodium salt

     Commercial Names              Blancol TW  (L. B. Holliday and
                                   Co., Ltdi,  England); Fluorosol
                                   WS  (Allied  Chemical and Dye
                                   Corp.); Ultraphor WT (Badische
                                   Anilin & Soda Fabrik A.G.,
                                   Germany)

     Chemical Class                4 , 4 ' - ( 2-Oxo-4-lmidazolin-4 , 5-diyl) -
                                   dibenzenesulfonic acid, disodium
                                   salt     • .. .

     Molecular Formula             C.l 5^12^20782 * ^a

     Fluorescence                  Blue

     Properties                    Moderate fastness to. chlorine
                                   Stable to peroxide and to reducing
                                   agents

     Applications                  Protein fibers
     According to U.S. Tariff Commission reports, 5,570 Ibs. of

Fluorescent Brightener 48 were imported into the U.S. in 1972.

     Since there is insufficient information to establish correla-

tions between the remainder of the Fluorescent Brightener numbers

and molecular formulas, the molecular formula entry will not appear

in the following tables (C. I. Fluorescent Brighteners 155, 243,

and 245 are exceptions) .

     There are no Colour Index numbers given for the remaining

C. I. Fluorescent Brightener numbers.  This item will not appear

in the following tables (C. I. Fluorescent Brighteners 74, 243,

and 245 are exceptions) .
                        A-32

-------
C. I. Fluorescent Brightener 49

     C. A. Registry Number

     Commercial Names


     Chemical Class

     Fluorescence

     Properties




     Applications
Not given in the literature

Leucophor BS (Sandoz, Inc.);
Rylux BS, BSP (Chemopol, Czech.)

Bistriazinylaminostilbene

Bluish

Maroon-colored liquid
Anion-active, very stable to
acids and alkalis, light-sensi-
tive in solution

Cellulose
Nylon
     Sandoz colors and chemicals reported production and sales of

Fluorescent Brightener 49 to the U.S. Tariff Commission in 1972,

No figures are given; they are included in the total brightener

production figures.

     According to the U.S. Tariff Commission, 5,570 Ibs. of Fluor-

escent Brightener 49 were imported into the U.S. in 1972.       ;
C. I. Fluorescent Brightener 50

     C. A. Registry Number

     Commercial Names

     Chemical Class


     Fluorescence
               i

     Properties





     Applications
Not given in the literature

Leucophor BB (Sandoz, Inc.)

Derivative of 4,4'-diamino-2,2'-
stilbenedisulfonic acid

Bluish

Readily soluble in hot water
Fastness:  Acid, good; chlorine,
moderate; Light, good; Washing,
moderate

Cellulose
                        A-33

-------
C. I. Fluorescent Brightener 51

     C. A. Registry Number         Not given in the literature

     Commercial Names              Ultraphor API (Badische Anilin
                                   & Soda Fabrik A. G.,  Germany)

     Chemical Class                Naphthalic acid derivative

     Fluorescence                  Bright blue

     Properties                    Not substantive to animal fibers
                                   or cellulose.  Unaffected by
                                   hot water.
                                   Fastness:  Alkali, moderate;
                                   Chlorine, light and washing,
                                   very good

     Applications                  Acetate, nylon, acrylic and
                                   polyester fibers


     C. I. Fluorescent Brightener 51 is not being manufactured at

the present time.

-------
C. I. Fluorescent Brightener 52

     C. A. Registry Number         Not given in the literature

     Commercial Names              Blancol WNS (L. B. Holliday &
                                   Co., Ltd., England); Kayaphor
                                   WN (Nippon Kayaku Co.,  Ltd.,
                                   Japan); Leucophor WS, Leucopur
                                   Base (Satido?., Inc.); Mikephor
                                   WS (Mitsui Chemical Industry,
                                   Ltd., Japan); Whitex WS (Sumi-
                                   tomo Chemical Co., Ltd., Japan)

     Chemical Class                Coumarin derivative

     Fluorescence                  Bluish violet

     Properties                    Readily soluble in cold water.
                                   Solution susceptible to prolonged
                                   exposure to light.
                                   Fastness:  Washing, moderate to
                                   gocd; Light, moderate

     Applications                  Prntein fibers, acetate, nylon


     Sandoz Colors and chemicals reported production and sales

of Fluorescent Brightener 52 to the U.S. Tariff Commission in 1972.

No production figures are given; they are included in the  total

brightener production figures.

     According to the U.S. Tariff Commission reports, 3,527 Ibs.

of Fluorescent Brightener 52 were imported into the U.S. in 1972.
                         A-35

-------
C.  I. Fluorescent  Brightener 53

     C. A. Registry Number

     Commercial Names


     Chemical Class

     Fluorescence

     Properties


     Applications
Not given in the literature

Blancol N62532 (L. B. Holliday
and Co., Ltd., England)

Aminocoumarin derivative

Reddish-blue

Stable to acids, peroxide,
and dithionite

Protein fibers, nylon, acetate
Soaps and detergents
     C. I. Fluorescent Brightener 53 is not being manufactured at

the present time.
C. I. Fluorescent Brightener 54

     C. A. Registry Number

     Commercial Names



     Chemical Class

     Fluorescence

     Properties
     Applications
Not given in the literature

Tinopal WG (Ciba-Geigy Corp.);
Whitex WG (Sumitomo Chemical
Co., Ltd., Japan)

Not given in the literature

Greenish blue

Good solubility in water.   Stable
to dithionate
Fastness:  Light and washing
(protein fibers), good; Light
(nylon) good; Washing (nylon),
fairly good

Protein fibers, nylon
     Ciba-Geigy reported production and sales of Fluorescent

Brightener 54 to the U.S. Tariff Commission in 1972.  No production

figures are given; they are included in the total brightener

production figures.
                         A-36

-------
C. I. Fluorescent Brightener 55

     C. A. Registry Number         [12768-90-0]

     Commercial Names              Tiriopal AN (Ciba-Geigy Corp.)
                                   Whitex AN (Sumitomo Chemical
                                   Co., Ltd., Japan)

     Chemical Class                Oxacyanin derivative

     Fluorescence           .       Reddish blue

     Properties                    White powder
                                   Substantive to silk, wook, and
                                   cellulose
                                   Compatible with cationic sof-
                                   teners
                                   Fastness:  Chlorine, poor; Light,
                                   very good; Washing, moderate

     Applications                  Acetate, nylon, and acrylic
                                   fibers


     According to the U.S. Tariff Commission reports, 220 Ibs.

of Fluorescent Brightener 55 were imported into the U.S. in 1972.
C. I. Fluorescent Brightener 56

     This C.I. generic name is discontinued.  Those brighteners

formerly listed under it now appear under C. I. Fluorescent Brighten-

er 61.
                       A-3T

-------
C. I. Fluorescent Brightener 57

     C. A. Registry Number

     Commercial Names

     Chemical Class

     Fluorescence

     Properties



     Applications
Not given in the literature

Uvitex W (Ciba-Geigy Corp.)

Not given in the literature

Not given in the literature

insoluble in water
Soluble in organic solvents and
fatty acids

Protein fibers, acetate,  nylon
     C. I. Fluorescent Brightener 57 is not being manufactured

at the present time.                 .    .
C. I. Fluorescent Brightener 58

     C. A. Registry Number

     Commercial Names

     Chemical Class

     Fluorescence

     Properties

     Applications
Not given in the literature

Uvitex NA (Ciba-Geigy Corp.)

Not given in the literature

Not given in the literature

Stable to peroxide and dithionite

Protein, acetate, nylon,  and
acrylic fibers
     C. I. Fluorescent Brightener 58 is not being manufactured at

the present time.
                       A-38

-------
C. I. Fluorescent Brightener 59

     C. A. Registry Number

     Commercial Names

     Chemical Class


     Fluorescence

     Properties




     Applications
Not given in the literature

Tinopal RBN (Ciba-£eigy Corp.)

Stilbene-triazole-sulfonic acid
derivative

Slightly reddish blue

Greenish-yellow powder
Fastness:  Chlorine, very good;
Light, good; Washing (cellulose),
moderate, (nylon) very good

Protein fibers, nylon
     Ciba-Geigy Corp. reported production and sales of Fluorescent

Brightener 59 to the U.S. Tariff Commission in 1972.  No production

figures are given; they are included in the total brightener pro-

duction figures.
C. I. Fluorescent Brightener 60

     C. A. Registry Number

     Commercial Names


     Chemical Class

     Fluorescence

     Properties

     Applications
Not given in the literature

Blancol 61690 (L. B. Holliday
and Co., Ltd., England)

Cationic-npnionic complex

Bluish violet

Stable to dithionite and peroxide

Protein fibers, acetate, nylon
                         A-39

-------
C. I. Fluorescent Brightener 61

     C. A. Registry Number         [12224-04-3]

     Commercial Names              Blancophor AW, FFG; Tintophen
                                   AW, FFG (GAF Corp.); Calcofluor
                                   White RW, RWP, SD (American
                                   Cyanamid Co.); Uvitex WGS
                                   (Ciba-Geigy Corp.)

     Chemical Class                Aminocoumarin derivative

     Fluorescence                  Bluish-violet

     Properties                    Soluble in aqueous solution
                                   and in alcohol; insoluble in
                                   water

     Applications                  Wool, nylon, acetate, silk


     Ciba-Geigy reported production and sales to the U.S. Tariff

Commission in 1972.  No production figures are given; they are

included in the total brightener production figures.
C. I. Fluorescent Brightener 62

     C. A. Registry Number         Not given in the literature

     Commercial Names              Uvitex NL (Ciba-Geigy Corp.)

     Chemical Class                Not given in the literature

     Fluorescence                  Not given in the literature

     Properties                    Excellent fastness to light

     Applications                  Nylon


     C. I. Fluorescent Brightener 62 is not being manufactured at

the present time.
                         A-ltO

-------
C. I. Fluorescent Brightener 63

     C. A. Registry Number

     Commercial Names


     Chemical Class

     Fluorescence

     Properties


     Applications
Not given in.the literature

Blancol BT (L. B. Holliday
and Co., Ltd., England)

Triazinylaminostilbene derivative

Blue

Effect not cumulative on re-
peated laundering

Cellulose
C. I. Fluorescent Brightener 64

     This C. I. generic name is discontinued.   The brighteners

formerly listed under it now appear under C. I. Fluorescent

Brightener 28.
C. I. Fluorescent Brightener 65

     C. A. Registry Number

     Commercial Names

     Chemical Class

     Fluorescence

     Properties

     Applications
Not given in the literature

Uvitex NSI (Ciba-Geigy Corp.)

Not given in the literature

Not given in the literature

Good fastness to washing

Cellulose
     C. I. Fluorescent Brightener 65 is not being manufactured

at the present time.
                         A-Ul

-------
C. I. Fluorescent Brightener 66

     C. A. Registry Number

     Commercial Names


     Chemical Class

     Fluorescence

     Properties



     Applications
Not given in the literature

Blancophor A-3, Tintophen A3
(GAF Corp.)

Stilbene derivative

Bluish violet

Sparingly soluble in water
Good fastness to chlorine (on
the fiber)

Soaps
C. I. Fluorescent Brightener 67

     C. A. Registry Number

     Commercial Names


     Chemical Class


     Fluorescence

     Properties


     Applications
Not given in the literature

Tintophen CX (General Dyestuff
Co.)

Bistriazinylaminostilbene deri-
vative

Blue (peak at 440 nm)

Sparingly soluble in water
Disperses well in soap

Soaps for laundering cotton
     C. I. Fluorescent Brightener 67 is not being manufactured

at the present time.

-------
C. I. Fluorescent Brightener 68
     This C. I. generic name is discontinued. •  The brighteners
formerly listed under it now appear under C. I. Fluorescent
Brightener 61.
     Cincinnati Malacron Chemicals, Inc. and GAF Corp. reported
production and sales of Fluorescent Brightener  68 to the U.S.
Tariff Commission in 1972.  No figures are given; they are in-
cluded in the total brightener production figures.
     The production figures which have been listed separately in
the past for Fluorescent Brightener 68 are as follows:
                 1960      63,000 Ibs.
                 1961      72,000 Ibs.
                 1962     100,000 Ibs.
                 1964      31,000 Ibs.
C. I. Fluorescent Brightener 69
     C. A. Registry Number
     Commercial Names

     Chemical Class
     Fluorescence
     Properties


     Applications
Not given in the literature
Leucophor DC (Sandoz Colors
and Chemicals)
Coumarin derivative
Bluish-violet
Soluble in hydrocarbons, chlori-
nated hydrocarbons, acetone,
ethyl acetate
All fibers

-------
C.I. Fluorescent Brightener 70

     C. A. Registry Number         Not given in the literature

     Commercial Names,             Tinopal PCR (Ciba-Geigy Corp.)

     Chemical Class                Stilbyl-naphthotriazole deriva-
                                   tive

     Fluorescence                  Bluish

     Properties                    Very good fastness to light

     Applications                  Plastics
                        A-UU

-------
C. I. Fluorescent Brightener 71

     C. A. Registry Number         Not given in the literature
                          ;   ,
     Commercial Names              Blancophor DS-86 (GAtf Corp.);
                                   Calcofluor White RC (American
                                   Cyanamid Co.); Leukophor DU, DUK,
                                   Leukopur PAM (Sandoz, Inc.); Pho-
                                   tine CBV, CBVS (Hickson and Welch,
                                   Ltd., England; S. A. Rovira,
                                   Spain)

     Chemical Class        .        Stilbene derivative

     Fluorescence       .           Bluish-violet

     Properties                    Water dispersible
                     ,              Stable to perborate but not to
                                   chlorine
                                   Fastness:  Acid, poor; Alkali,
                                   very good; Chlorine, very good;
                                   Dithionate, very good; Peroxide,
                                   very good; Light, good

     Applications                  Laundry compositions containing
                                   anionic or nonionic detergents
                                   for use on cellulose


     American Cyanamid Co. and GAF Corp. reported production and

sales of Fluorescent Brightener 71 to the U. S. Tariff Commission

in 1972.  No figures are given; they are included in the total

brightener production figures.
C. I. Fluorescent Brightener 72

     C. A. Registry Number         Not given in the literature

     Commercial Names              Tinopal E (Ciba-Geigy Corp.)

     Chemical Class                Stilbyl-naphthotriazole derivative

     Fluorescence                  Not given in the literature

     Properties                    Fastness:  Light, good; Washing,
                                   very good

     Applications                  Polyester fibers
                                   Plastics

-------
C. I. Fluorescent Brightener 73

     C. A. Registry Number

     Commercial Names


     Chemical Class


     Fluorescence

     Properties


     Applications
Not given in the literature

Blancol SS (L. B. Holliday and
Co., Ltd., England)

Trimethyldihydropyridine deriva-
tive

Blue

Soluble in organic solvents
Insoluble in water

Lacquers and waxes
C. I. Fluorescent Brightener 74

     Colour Index Number

     C. A. Registry Number

     Commercial Names

     Chemical Class

     Fluorescence

     Properties


     Applications
C. I. 45550

Not given in the literature

Fluorol 5G

Xanthene derivative

Greenish-yellow

Soluble in organic solvents
Insoluble in water

Lacquers and coatings
     C. I. Fluorescent Brightener 74 is not being manufactured at

the present time.

-------
C. I. Fluorescent Brightener 75

     C. A. Registry Number

     Commercial Names



     Chemical Class

     Fluorescence

     Properties


     Applications  .
Not given in the literature

Fluorescent Brilliant Yellow R
(L. B. Holliday and Co.,
England); Fluorol 7GA (GAP Corp.)

Xanthene derivative

Green

Soluble in organic solvents
Insolvent in water

Lacquers and coatings
     According to the U. S. tariff Commission reports, 1,200

pounds of Fluorescent Brightener 74 were imported into the U. S.

in 1972.
C. I. Fluorescent Brightener 76

     C. A. Registry Number

     Commercial Names

     Chemical, Class

     Fluorescence

     Properties
Not given in the literature

Fluorol OB (GAF Corp.)

Naphthalimide derivative

Greenish-blue

Insoluble in water and hydrocar-
bons
Soluble in other organic solvents
     Applications
Lacquers and coatings

-------
C. I. Fluorescent Brightener 77

     C. A. Registry Number

     Commercial Names

     Chemical Class

     Fluorescence

     Properties


     Applications   ;
Not given in the literature

Fluorol OBR (GAF Corp.)

Stilbene derivative

Reddish-blue

Soluble in organic solvents
Insoluble in water

Lacquers and coatings
     C. I. Fluorescent Brightener 77 is not being manufactured at

the present time.
C. I. Fluorescent Brightener 78

     C. A. Registry Number

     Commercial Names


     Chemical Class

     Fluorescence

     Properties


     Applications
Not given in the literature

Blancol 62531 (L. B. Holliday
and Co., Ltd., England)

Aminocoumarin derivative

Bluish-violet

Soluble in organic solvents
Insoluble in water

Lacquers, coatings, shellac
Plastics
                         A-U8

-------
C. I. Fluorescent Brightener 79

     C. A. Registry Number

     Commercial Names



     Chemical Class

     Fluorescence

     Properties


     Applications
[12676-63-0]

Leukophor A, AC (Sandoz, Inc.):
Delft White BSM (Delfland Pro-
dukten N.V., Holland)

Not given in the literature

Not given in the literature

Good fastness to acid, alkali,
and chlorine

Cellulose
C. I. Fluorescent Brightener 80

     C. A. Registry Number

     Commercial Names


     Chemical Class

     Fluorescence

     Properties

     Applications
Not given in the literature

Delft White GS (Delfland Pro-
dukten N.V., Holland)

Not given in the literature

Yellowish-green

Not given in the literature

Cellulose
C. I. Fluorescent Brightener 81

     C. A. Registry Number

     Commercial Names


     Chemical Class

     Fluorescence

     Properties


     Applications
Not given in the literature

Delft White BSW (Delfland
Produkten N.V. (Holland)

Not given in the literature

Not given in the literature.

Good fastness to acid, alkali,
and chlorine

Cellulose
                         A-U9

-------
C. I. Fluorescent Brightener 82

     C. A. Registry Number

     Commercial Names


     Chemical Class

     Fluorescence

     Properties



     Applications
Not given in the literature

Delft White RS (Delfland Pro-
dukten N.V., Holland)

Stilbene derivative

Not given in the literature

Fastness:  Acid, good; alkali,
excellent; Heat, good; Light,
good

Cellulose
C. I. Fluorescent Brightener 83

     C. A. Registry Number

     Commercial Names


     Chemical Class

     Fluorescence

     Properties


     Applications
Not given in the literature

Citalba B (Aziende Color! Na-
zionali Affini A.C.N.A., Italy)

Stilbene derivative

Bluish

Poor fastness to chlorine;
stable to dithionite and peroxide

Protein fibers, nylon
Cellulose
     C. I. Fluorescent Brightener 83 is not being manufactured at

the present time.
                        A-50

-------
C. I. Fluorescent Brightener 84

     C. A. Registry Number

     Commercial Names
     Chemical Class


     Fluorescence

     Properties



     Applications
[12224-05-4]

Kayaphor A, AK (Nippon Kayaku
Co., Ltd., Japan); Mikephor BA
(Mitsui Toatsu Chemicals, Inc.,
Japan); Whitex BC, BCK, BO, BT
(Sumitomo Chemical Co., Ltd.,
Japan)

Bistriazinylaminostilbene
derivative

Bluish-violet

Good solubility in water
Good fastness to chlorine, light,
peroxide, and washing

Cellulose
Paper
C. I. Fluorescent Brightener 85

     C. A. Registry Number

     Commercial Names
     Chemical Class


     Fluorescence

     Properties

     Applications
[12224-06-5]

Kayaphor AB, B, BB, BNK, LB
(Nippon Kayaku Co., Ltd., Ja-
pan) ; Leukophor DK (Sandoz Co-
lors and Chemicals); Mikephor
BP, BX, BX Extra 200 (Mitsui
Toatsu Chemicals, Inc., Japan);
Whitex BH, BK, LBH (Sumitomo
Chemical Co., Ltd., Japan)

Bistriazinylaminostilbene
derivative

Bluish-violet

Not given in the literature

Cellulose
Paper
                        A-51

-------
C. I. Fluorescent Brightener  86

     C. A. Registry Number

     Commercial Names
     Chemical Class


     Fluorescence

     Properties



     Applications
[12224-07-6]

Kayaphor FB (Nippon Kayaku Co.,
Ltd., Japan); Mikephor BI
(Mitsui Toatsu Chemicals, Inc.,
Japan); Whitex BN, LSB (Sumitomo
Chemical Co., Ltd., Japan)

Bistriazinylaminostilbene
derivative

Bluish-violet

Good solubility in water
Good fastness to chlorine, light,
peroxide, and washing

Cellulose, paper
Soaps, detergents
C. I. Fluorescent Brightener 87

     C. A. Registry Number

     Commercial Names


     Chemical Class


     Flourescence

     Properties



     Applications
Not given in the literature

Kayaphor S (Nippon Kayaku Co.,
Ltd., Japan)

Bistriazinylaminostilbene
derivative

Bluish-violet

Very good solubility in water
Good fastness to chlorine,
light, peroxide, and washing

Cellulose
Paper
C. I. Fluorescent Brightener  88

     This C. I. generic name  is discontinued.  The brighteners for-

merly listed under it now appear under C. I. Fluorescent Brightener 24.
                          A-52

-------
C. I. Fluorescent Brightener 89

     This C. I. generic name is discontinued.  The brighteners

formerly listed under it now appear under C. I. Fluorescent

Brightener 52.
C. I. Fluorescent Brightener 90

     C. A. Registry Number

     Commercial Names
     Chemical Class


     Fluorescence

     Properties



     Applications
[12224-08-7]

Kayaphor AS, ASC (Nippon Kayaku
Co., Ltd., Japan); Mikephor BS
(Mitsui Toatsu Chemicals, Inc.,
Japan); Whitex BF, EOF, HP (Su-
mitomo Chemical Co., Ltd.,
Japan)

Bistriazinylaminostilbene deri-
vative

Bluish-violet

Fairly soluble in water
Good fastness to chlorine, light,
and peroxide

Nylon
Cellulose
Paper
C. I. Fluorescent Brightener 91

     C. A. Registry Number

     Commercial Names


     Chemical Class

     Fluorescence

     Properties
     Applications
Not given in the literature

Kayalight B (Nippon Kayaku Co.,
Ltd., Japan)

Coumarin derivative

Bluish-violet

Very good solubility in organic
solvents
Poor solubility in water
Moderately fast to light and
washing

Wool, silk
Synthetic resins
                        A-53

-------
C. I. Fluorescent Brightener 92

     This C. I. generic name is discontinued.  The brightener for-

merly listed under it now appears under C. I. Fluorescent Brightener

84.



C. I. Fluorescent Brightener 93

     This C. I. generic name is discontinued.  The brightener for-

merly listed under it now appears under C. I. Fluorescent Brigh-

tener 24.
C. I. Fluorescent Brightener 94

     C. A. Registry Number

     Commercial Names


     Chemical Class

     Fluorescence

     Properties

     Applications
Not given in the literature

Mikephor FP (Mitsui Toatsu
Chemicals, Inc., Japan)

Triazinylstilbene derivative

Bright blue

Not given in the literature

Cellulose
     C. I. Fluorescent Brightener 94 is not being manufactured at

the present time.
C. I. Fluorescent Brightener 95

     This C. I. generic name is discontinued.  The brightener for-

merly listed under it now appears under C. I. Fluorescent Brigh-

tener 85.

-------
C. I. Fluorescent Brightener 96

     This C. I. generic name is discontinued.  The brightener for-

merly listed under it now appears under C. I. Fluorescent Brigh-

tener 85.
C. I. Fluorescent Brightener 97

     C. A. Registry Number

     Commercial Names


     Chemical Class


     Fluorescence

     Properties

     Applications
Not given in the literature

Mikephor BH-2 (Mitsui Toatsu
Chemicals Inc., Japan)

Bistriazinylamino-stilbenedi-
sulfonic acid derivative

Bright blue

Not given in the literature

Cellulose
     C. I. Fluorescent Brightener 97 is not being manufactured at

the present time.
C. I. Fluorescent Brightener 98

     C. A. Registry Number

     Commercial Names



     Chemical Class

     Fluorescence

     Properties
     Applications
Not given in the literature

Fluolite L Tablets (Imperial
Chemical Industries, Ltd.,
England)

Stilbene derivative

Blue

Soluble in water but not in
organic solvents
Fastness:  Alkali, very good;
Chlorine, good; Dithionite, very
good; Peroxide, very good;
Washing, very good

Cellulose
     C. I. Fluorescent Brightener 98 is not being manufactured at

the present time.
                         A-55

-------
C. I. Fluorescent Brightener 99

     C. A. Registry Number

     Commercial Names



     Chemical Class

     Fluorescence

     Properties
     Applications
Not given in the literature

FluoliCe MP Liquid (Imperial
Chemical Industries, Ltd.,
England)

Stilbene derivative

Blue

Soluble in water
Insoluble in organic solvents
Fastness:  Acid, good; Alkali,
very good; Chlorine, good; Di-
thionite, very good; Peroxide,
very good; Washing, very good

Cellulose
Paper
C. I. Fluorescent Brightener 100

     C. A. Registry Number

     Commercial Names


     Chemical Class

     Fluorescence

     Properties
     Applications
[12270-49-4]

Fluolite XNR (Imperial Chemi-
cal Industries, Ltd., England)

Stilbene derivative

Reddish-blue

Soluble in water
Insoluble in organic solvents
Fastness:  Acid, very good;
Alkali, very good; Chlorine,
good; Dithionite, very good;
Peroxide, very good; Washing,
good

Protein fibers, nylon
Cellulose
Paper
                        A-56

-------
C. I. Fluorescent Brightener 101

     C. A. Registry Number

     Commercial Names

     Chemical Class

     Fluorescence

     Properties
     Applications
Not given in the literature

Tinopal ACA (Ciba-Geigy Corp.)

Not given in the literature

Reddish-blue

Fastness:  Acid, very good;
Alkali, good; Chlorine, good;
Dithionite, good; Light, moder-
ate; Peroxide, Moderate; Washing,
good

Acrylic fibers
C. I. Fluorescent Brightener 102

     C. A. Registry Number

     Commercial Names



     Chemical Class

     Fluorescence

     Properties


     Applications
[12224-09-8]

Paper White SP, SPSW, Pontamine
White SP Solution (E. I. du Pont
de Nemours and Co., Inc.)

Stilbene derivative

Greenish

Soluble in water
Stable to alum

Paper
     E. I. du Pont de Nemours and Co. and Verona Corp. reported

production and sales of Fluorescent Brightener 102 to the U. S.

Tariff Commission in 1972.  No production figures are given;

they are included in the total brightener production figures.
                        A-57

-------
C. I. Fluorescent Brightener 103

     C. A. Registry Number

     Commercial Names

     Chemical Class

     Fluorescence

     Properties

     Applications
Not given in the literature

Tinopal BST (Ciba-Geigy Corp.)

Triazinylstilbene derivative

Slightly bluish

Not given in the literature

Cellulose
     According to the U. S. Tariff Commission reports, 220 pounds

of Fluorescent Brightener 103 were imported into the U. S. in

1972.
C. I. Fluorescent Brightener 104

     C. A. Registry Number

     Commercial Names
     Chemical Class


     Fluorescence

     Properties
     Applications
[12224-10-1]

Kayaphor PN (Nippon Kayaku Co.,
Ltd., Japan); Tinopal RP (Ciba-
Geigy Corp.); Whitex RP (Sumi-
tomo Chemical Co., Ltd., Japan)

Bistriazinylaminostilbene
derivative

Bluish-violet

Very good solubility in water
Fastness:  Acid, very good;
Alkali, very good; Chlorine,
good; Dithionite, very good;
Light, very good; Peroxide, good;
Washing, good

Wool, silk, nylon
Cellulose-wool unions;
Cellulose-nylon unions
                         A-58

-------
C. I. Fluorescent Brightener 105

     C. A. Registry Number

     Commercial Names


     Chemical Class

     Fluorescence

     Properties
     Applications
Not given in the literature

Calcofluor White CW (American
Cyanamid Co.)

Triazinylstilbene derivative

Bluish-white

Miscible in water in all
proportions
Insoluble in petroleum solvents
Fastness:  Acid, good; Alkali,
good; Chlorine, poor; Dithionite,
very good; Light, good

Nylon
Cellulose
Paper
     C. I. Fluorescent Brightener 105 is not being manufactured at

the present time.



C. I. Fluorescent Brightener 106

     This C. I. generic name is discontinued.
C. I. Fluorescent Brightener 107

     C. A. Registry Number

     Commercial Names


     Chemical Class

     Fluorescence

     Properties

     Applications
Not given in the literature

Blancophor GS-33, Tintophen
GS-33 (GAF Corp.)

Stilbene derivative

Bright greenish-blue

Levels well

Cellulose
                        A-59

-------
C. I. Fluorescent Brightener 108

     C. A. Registry Number         Not given in the literature

     Commercial Names              Blancophor CB-32, Tintophen
                                   CB-32 (GAP Corp.)

     Chemical Class                Stilbene derivative

     Fluorescence                  Blue

     Properties                    Levels well

     Applications                  Cellulose


     GAF Corp. reported production and sales of Fluorescent Brigh-

tener 108 to the U. S. Tariff Commission in 1972.  No figures are

given; they are included in the total brightener production figures,



C. I. Fluorescent Brightener 109

     C. A. Registry Number         Not given in the literature

     Commercial Names              Blancophor SB, Tintophen SB
                                   (GAF Corp.)

     Chemical Class                Stilbene derivative

     Fluorescence                  Blue

     Properties                    Very good solubility in water

     Applications                  Paper


     GAF Corp. reported production and sales of Fluorescent Brigh-

tener 109 to the U.S. Tariff Commission in 1972.  No production

figures are given; they are included in the total brightener pro-

duction figures.
                         A-60

-------
C. I. Fluorescent Brightener 110

     C. A. Registry Number

     Commercial Names


     Chemical Class

     Fluorescence

     Properties


     Applications
Not given in the literature

Blancophor HL-32, HL-72, Tinto-
phen HL-32, HL-72 (GAF Corp.)

Stilbene derivative

Bright greenish-blue

Water soluble
Insensitive to pH change

Paper
C. I. Fluorescent Brightener 111

     C. A. Registry Number

     Commercial Names



     Chemical Class

     Flourescence

     Properties
     Applications
Not given in the literature

Whitening Agent Wolfen BV, BVP,
BVP 60/100 (Farbenfabriken
Wolfen, Germany)
Bluish-violet

Soluble in water; Anion-active
Fastness:  Acid, sensitive;
Chlorine, moderate; Dithionite,
good; Light, very good; Wash-
ing, good

Nylon
Cellulose
                        A-6l

-------
C. I. Fluorescent Brightener 112

     C. A. Registry Number

     Commercial Names
     Chemical Class

     Fluorescence

     Properties
     Applications
[12270-50-7]

Blankophor ACF (Farbenfabiriken
Bayer A. G., Germany); Ultra-
phor NA (Badische Anilin & Soda
Fabrik A. G., Germany)

Coumarin derivative

Blue

Soluble in hot water
Fastness:  Acid, very good; Al-
kali, very good; Chlorine, very
good; Dithionite, very good;
Peroxide, Very good; Washing,
very good

Acetate
     According to the U. S. Tariff Commission reports, 250

pounds of Fluorescent Brightener 112 were imported into the U. S.

in 1972.
C. I. Fluorescent Brightener 113

     C. A. Registry Number

     Commercial Names


     Chemical Class

     Fluorescence

     Properties
     Applications
Not given in the literature

Blankophor BA (Farbenfabriken
Bayer A. G., Germany)

Stilbene derivative

Bright bluish-violet

Yellowish,white powder
Water soluble
Fastness:  Acid, moderate; Al-
kali, very good; Chlorine, good;
Dithionite, very good; Light,
good; Peroxide, very good;
Washing, very good

Cellulose
                         A-62

-------
C. I. Fluorescent Brightener 114

     C. A. Registry Number         [12270-51-8]

     Commercial Names              Blancofor BBV (Fabricacion
                                   Nacional de Colorantes y Explo-
                                   sives, S. A., Spain); Blankophor
                                   BBV Extra (Farbenfabriken Bayer,
                                   A. G., Germany); Heliofor CAS
                                   (CEICH, Poland); Ultraphor GPB
                                   (Badische Anilin & Soda Fabrik
                                   A. G., Germany)

     Chemical Class                Stilbene derivative

     Fluoresdence                  Bluish-violet

     Properties                    Greenish-yellow powder
                                   Water soluble
                                   Fastness:  Acid, very good; Al-
                                   kali, very good; Chlorine, good;
                                   Dithionite, very good; Light,
                                   good; Peroxide,  very good;
                                   Washing, good

     Applications                  Cellulose


     Verona Corp. reported production and sales of Fluorescent

Brightener 114 to the U. S. Tariff Commission in 1970.  No pro-

duction figures are given; they are included in the total brightener

figures.
C. I. Fluorescent Brightener 115

     C. A. Registry Number         Not given in the literature

     Commercial Names              Blankophor BE Extra (Farben-
                                   fabriken Bayer A. G., Germany)

     Chemical Class                Stilbene derivative

     Fluorescence                  Bluish-violet

     Properties                    Water soluble
                                   Fastness:  Acid, moderate; Al-
                                   kali, very good; Chlorine,
                                   good; Dithionite, very good;
                                   Light, good; Peroxide, very
                                   good; Washing, good

     Applications                  Cellulose

                         A-63

-------
C. I. Fluorescent Brightener 116

     C. A. Registry Number

     Commercial Names
     Chemical Class

     Fluorescence

     Properties




     Applications
Not given in the literature

Blancofor BP (Fabricacion Na-
cional de Colorantes y Explo-
sives S. A., Spain) Blankophor
BP Extra (Farbenfabriken Bayer
A. G., Germany)

Stilbene derivative

Blue

Fastness:  Acid, moderate; Al-
kali, moderate; Dithionite, very
good; Light, good; Peroxide,
very good

Paper
C. I. Fluorescent Brightener 117

     C. A. Registry Number

     Commercial Names
     Chemical Class

     Fluorescence

     Properties
     Applications
Not given in the literature

Blancofor BPN (Fabricacion
Nacional de Colorantes y Explo-
sives S. A., Spain) Blankophor
BPN Extra (Farbenfabriken Bayer
A. G., Germany)

Stilbene derivative

Blue

Water soluble, insoluble in or-
ganic solvents
Fastness:  Acid, good; Alkali,
moderate, Dithionite, very good;
Light, good; Peroxide, very good

Paper
                         A-6U

-------
C. I. Fluorescent Brightener 118

     C. A. Registry Number

     Commercial Names


     Chemical Class

     Fluorescence

     Properties
     Applications
Not given in the literature

Blankophor CE (Farbenfabriken
Bayer A. G., Germany)

Stilbene derivative

Bluish-green

Water soluble
Fastness:  Acid, very good; Al-
kali, very good; Chlorine, very
good; Dithionite, very good;
Light, good; Peroxide, very good;
Washing, moderate

Cellulose
C. I. Fluorescent Brightener 119

     C. A. Registry Number

     Commercial Names
     Chemical Class

     Fluorescence

     Properties
     Applications
[12270-52-9]

Blankophor REV (Farbenfabriken
Bayer A. G., Germany); Ultra-
phor RPB (Badische Anilin &
Soda Fabrik A. G., Germany)

Stilbene derivative

Reddish-violet

Water soluble
Fastness:  Acid, very good; Al-
kali, very good; Chlorine,
good; Dithionite, very good;
Light, good; Peroxide, very
good; Washing, good

Cellulose
     According to the U. S. Tariff Commission reports, 125,040

pounds of Fluorescent Brightener 119 was imported into the U. S,

in 1972.
                        A-65

-------
C. I. Fluorescent Brightener 120

     This C. I. generic name is discontinued.  The fluorescent

brightener formerly listed under it now appears under C. I.

Fluorescent Brightener 104.
C. I. Fluorescent Brightener 121

     C. A. Registry Number

     Commercial Names
     Chemical Class

     Fluorescence

     Properties




     Applications
[12224-11-2]

Blancofor BBH (Fabricacion
Nacional de Colorantes y Ex-
plosives S. A., Spain); Blanko-
phor DCB (Farbenfabriken Bayer
A. G., Germany)

Stilbene derivative

Bright bluish-violet

Fastness:  Acid, very good;
Alkali, very good; Light (acry-
lic) very good, (acetate and
nylon) good; Washing, very good

Acetate, triacetate, nylon,
acrylics
     According to the U. S. Tariff Commission reports, 79,210

pounds, of Fluorescent Brightener 121 were imported into the U. S.

in 1972.



C. I. Fluorescent Brightener  122

     This C. I. generic name  is discontinued.
                         A-66

-------
C. I. Fluorescent Brightener 123

     C. A. Registry Number

     Commercial Names

     Chemical Class

     Fluorescence

     Properties

     Applications
Not given in the literature

Rylux D (Chemapol, Czech.)

Morpholine derivative

Bright blue

Not given in the literature

Not given in the literature
C. I. Fluorescent Brightener 124

     C. A. Registry Number

     Commercial Names


     Chemical Class

     Fluorescence

     Properties

     Applications
Not given in the literature

Blankophor SN (Farbenfabriken
Bayer A.  G., Germany)

Pyrazolone derivative

Bluish

Not given in the literature

Soap

-------
C. I. Fluorescent Brightener 125

     C. A. Registry Number         Not given in the literature

     Commercial Names              Calcofluor White EDW,. PUM (Am-
                                   erican Cyanamid Co.)

     Chemical Class                Triazinylstilbene derivative

     Fluorescence                  Slightly reddish-blue

     Properties                    Amber liquid
                                   Specific gravity 1.23
                                   Fluorescent emission at 440 mu
                                   Compatible with anionic and
                                   nbnionic materials
                                   Miscible with water in all pro-
                                   portions

     Applications                  Padding with resins
                                   Cellulose
  '                                 Nylon


     American Cyanamid Co. reported production and sales of Fluores-

cent Brightener 125 to the U. S. Tariff Commission in 1972.  No

production figures are given; they are included in the total

brightener production figures.
                        A-68

-------
C. I. Fluorescent Brightener 126

     C. A. Registry Number

     Commercial Names



     Chemical Class

     Fluorescence

     Properties
     Applications
Not given in the literature

Hiltamine Arctic Paper White
(Hilton-Davis Div. of Sterling
Drug Co.)

Triazinylstilbene derivative

Bluish-violet

Liquid in form; anionic in na-
ture
Fastness:  Acid, very good; Al-
kali, good; Chlorine, moderate;
Dithionite, good; Light, poor;
Peroxide, good; Washing, good

Suitable for use with practical-
ly all paper-making additives
Cellulose
     Hilton-Davis Div. of Sterling Drug Corp. reported production

and sales of Fluorescent Brightener 126 to the U. S. Tariff Com-

mission in 1972.  No production figures are given; they are in-

cluded in the total brightener production figures.
C. I. Fluorescent Brightener 127

     C. A. Registry Number

     Commercial Names



     Chemical Class

     Fluorescence

     Properties
     Applications
Not given in the literature

Hiltamine Arctic White Acid Sta-
ble (Hilton-Davis Div. of Sterling
Drug Co.)

Triazinylstilbene derivative

Bluish-violet

Liquid in form; anionic in nature
pH 8.5-9.5
Substantive to all cellulesic fibers
Compatible with most anionic and
nonionic textile additives

Cellulose
Textiles, silk, acetate
Exhaust padding
Thermosetting resin finishes
                        A-69

-------
C. I. Fluorescent Brightener 128

     C. A. Registry Number         Not given in the literature

     Commercial Names              Hiltamirie Arctic White DHL
                                   (Hilton-Davis Div. of Sterling
                                   Drug Co.)

     Chemical Class                Triazinylstilbene derivative

     Fluorescence                  Bluish-violet

     Properties                    Liquid in form; anionic in nature
                                   pH 8.5-10.5
                                   Substantive to all cellulosic
                                   fibers
                                   Compatible with cationic, ani-
                                   onic, and nonionic softeners

     Applications                  Cellulose
                                   Paper
                                   Silk, acetate
                                   Fabric softeners


     Hilton-Davis Div. of Sterling Drug Corp. reported production

and sales of Fluorescent Brightener 128 to the U. S. Tariff Com-

mission in 1972.  No production figures are given; they are included

in the total brightener production figures.
C. I. Fluorescent Brightener 129

     C. A. Registry Number         Not given in the literature

     Commercial Names              Hiltamine Arctic White DP
                                   (Hilton-Davis Div. of Sterling
                                   Drug Co.)

     Chemical Class                Stilbene derivative

     Fluorescence                  Bluish-violet

     Properties                    Fastness:  Acid, good; Alkali,
                                   good; Chlorine, moderate; Di-
                                   thionite, good; Peroxide, good

     Applications                  Cellulose, silk, nylon, acetate


     C. I. Fluorescent Brightener 129 is not being manufactured at

the present  time.

                        A-70

-------
C. I. Fluorescent Brightener 130

     C. A. Registry Number         Not given in the literature

     Commercial Names              Calcofluor White LD (American
                                   Cyanamid Co.); Hiltamine Arctic
                                   White N (Hilton-Davis Div. of
                                   Sterling Drug Co.)

     Chemical Class                Coumarin derivative

     Fluorescence                  Violet

     Properties                    Nonionic in nature
                                   Insoluble in water; soluble in
                                   alcohol, glycols, and Cellusolve

     Applications                  Wool, nylon, silk, acetate,
                                   triacetate, and acrylic fibers
                                   Protein fibers


     American Cyanamid Co. reported production and sales of Fluores-

cent Brightener 130 to the U. S. Tariff Commission in 1972.  No

production figures are given; they are included in the total

brightener production figures.
C. I. Fluorescent Brightener 130:1

     C. A. Registry Number         Not given in the literature

     Commercial Names              Hiltamine Arctic White WNOA
                                   (Hilton-Davis Div. of Sterling
                                   Drug Co.)

     Chemical Class                Coumarin derivative

     Fluorescence                  Not given in the literature

     Properties                    Nonionic in nature
                                   Readily dissolves in warm water

     Applications                  Detergent formulation
                                   Polyamides, acetate, triacetate
                        A-71

-------
C. I. Fluorescent Brightener 131

     C. A. Registry Number

     Commercial Names



     Chemical Class

     Fluorescence

     Properties
     Applications
Not given in the literature

Hlltamine Arctic White SP New
(Hilton-Davis Div. of Sterling
Drug Co.)

Stilbene derivative

Bluish-violet

Fastness:  Acid, good; Alkali,
good; Chlorine, moderate; Di-
thionite, good; Light, poor;
Peroxide, good; Washing, good

Cellulose, silk, acetate
     C. I. Fluorescent Brightener 131 is not being manufactured

at the present time.
C. I. Fluorescent Brightener 132

     C. A. Registry Number

     Commercial Names



     Chemical Class

     Fluorescence

     Properties
     Applications
Not given in the literature

Hiltamine White FMC, Mirawhite
White FAC (Hilton-Davis Div. of
Sterling Drug Co.)

Stilbene derivative

Blue

Soluble in glycols and Cellosolve
Fastness:  Acid, poor; Alkali,
very good; Chlorine, very good;
Hydrosulphite, very good;
Light, good; Peroxide, very
good; Washing, very good

Cellulose, silk, acetate, acrylics
                         A-72

-------
C. I. Fluorescent Brightener 133

     C. A. Registry Number

     Commercial Names

     Chemical Class

     Fluorescence

     Properties


     Applications
Not given in the literature

Uvitex A (Ciba-Geigy Corp.)

Heterocyclic

Blue

Very good fastness to light and
washing

Acrylic staple fiber
C. I. Fluorescent Brightener 134

     C. A. Registry Number

     Commercial Names



     Chemical Class

     Fluorescence

     Properties
     Applications
Not given in the literature

Ultraphor BP (Badische Anilin
& Soda Fabrik A. G., Germany);
Uvitex CF (Ciba-Geigy Corp.)

Stilbene derivative

Blue

Good solubility in water.  Sta-
ble to acids, peroxide bleach
liquors and reducing agents
Fastness:  Chlorine, good;
Light, good; Washing, very good

Cellulose, nylon, wool
     According to the U. S. Tariff Commission reports, 25,792

pounds of Fluorescent Brightener 134 were imported into the U. S.

in 1972.
                         A-73

-------
C. I. Fluorescent Brightener 135

     C. A. Registry Number

     Commercial Names



     Chemical Class

     Fluorescence

     Properties
     Applications
[12224-12-3]

Uvitex ERN Cone. P (Ciba-Geigy
Corp.); Whitex ERN (Sumitomo
Chemical Co., Ltd., Japan)

Heterocyclic

Reddish-blue

Excellent fastness to light and
very good fastness to washing
on polyester.  Stable in chlorite
bleach liquors and peracetic
acid

Polyester, acetate, nylon,
polyvinyl fibers
C. I. Fluorescent Brightener 136

     C. A. Registry Number

     Commercial Names

     Chemical Class

     Fluorescence

     Properties
Not given in the literature

Uvitex PRS (Ciba-Geigy Corp.)

Stilbene derivative

Reddish-blue

Very good solubility in water.
Good stability to acid and alkali
     Applications
Paper, cellulose

-------
C. I. Fluorescent Brlghtener 137

     C. A. Registry Number

     Commercial Names

     Chemical Class

     Fluorescence

     Properties



     Applications
Not given in the literature

Uvitex SIG (Ciba-Geigy Corp.)

Not given in the literature

Not given in the literature

Limited build up on repeated
use.  Good stability in hopy-
chlorite and peroxide liquors

Cellulose, acetate, nylon
     C. I. Fluorescent Brightener 137 is not being manufactured at

the present time.
C. I. Fluorescent Brightener 138

     C. A. Registry Number

     Commercial Names

     Chemical Class

     Fluorescence

     Properties


     Applications
Nwt given in the literature

Uvitex S3B (Ciba-Geigy Corp.)

Not given in the literature

Not given in the literature

Good fastness to chlorine and
good stability to acid

Cellulose
     C. I. Fluorescent Brightener 138 is not being manufactured at

the present time.
                        A-T5

-------
C. I. Fluorescent Brightener 139

     C. A. Registry Number

     Commercial Names

     Chemical Class

     Flourescence

     Properties
     Applications
Not given in the literature

Uvitex S2R (Ciba-Ceigy Corp.)

Not given in the literature

Not given in the literature

Considerable build up on repeated
use.  Good fastness to chlorine
and good stability to salts.
Withstands normal spray tempera-
tures when incorporated in
soap or detergents

Cellulose
C. I. Fluorescent Brightener  140

     C. A. Registry Number

     Commercial Names


     Chemical Class

     Fluorescence

     Properties


     Applications
Not given in the literature

Uvitex SWN (Ciba-Geigy Corp.)
Rylux VPA (Chemopol, Czech.)

Heterocyclic

Blue

Good stability to salts.  With-
stand normal spray temperatures

Wool, silk, acetate, nylon
Soaps, detergents
     According to the U.  S.  Tariff Commission reports, 441

pounds of Fluorescent Brightener 140 were imported into the U. S,

in 1972.
                         A-76

-------
C. I. Fluorescent Brightener 141

     C. A. Registry Number

     Commercial Names

     Chemical Class

     Fluorescence

     Properties



     Applications
Not given in the literature

Uvitex SWR (Ciba-Geigy Corp.)

Not given in the literature

Not given in the literature

Good stability to salts.
Withstand normal spray tempera-
tures

Wool, silk, acetate, nylon
Soaps, detergents
     C. I. Fluorescent Brightener 141 is not being manufactured

at the present time.
C. I. Fluorescent Brightener 142

     C. A. Registry Number

     Commercial Names

     Chemical Class

     Fluorescence

     Properties




     Applications
Not given in the literature

Uvitex VR (Ciba-Geigy Corp.)

Stilbene derivative

Blue; reflects green

Orange-yellow powder
Good fastness to washing and
stability to dithionite and
peroxide

Cellulose
                        A-T7

-------
C. I. Fluorescent Brightener 143

     C. A. Registry Number   v

     Commercial Names


     Chemical Class

     Fluorescence

     Properties

     Applications
                                   Not given in the literature

                                   Supra White BN (Dye-Chem,  Ltd.,
                                   India)

                                   Stilbene derivative
                                     i
                                   Bright blue

                                   Not given in the literature

                                   Cellulose, paper
     C. I. Fluorescent Brightener 143 is not being manufactured at

the present time.
C. I. Fluorescent Brightener 144
                                I
     C. A. Registry Number    ,-y
                            
-------
C. I. Fluorescent Brightener 145
               !*_

     C. A. Registry Number

     Commercial Names
     Chemical Class

     Fluores cence

     Properties
     Applications
Not given in the literature

Fluolite SE (Imperial Chemical
Industries, Ltd., England);
Photine BL, CP (Hickson and
Welch, Ltd., England; S. A.
Rovira, Spain); Photine CSP (Hick-
son and Welch, Ltd., England)

Stilbene derivative

Blue

Excellent solubility in cold
water.  Stability to acids
(and resin-catalyst combina-
tions) excellent.  Low substan-
tivity.  Levelling excellent
Fastness:  Acid, very good; Al-
kali, very good; Chlorine,
moderate, Dithionite, very good;
Light, good; Peroxide very good;
Washing, good

Cellulose
C. I. Fluorescent Brightener 146

     C. A. Registry Number

     Commercial Names
     Chemical Class

     Fluorescence

     Properties

     Applications
Not given in the literature

Photine STV (Hickson and
Welch, Ltd., England); White
STV (Hickson and Dadajee Pri-
vate, Ltd., India)

Stilbene derivative

Bluish-violet

Not given in the literature

Not given in the literature
                        A-79

-------
C. I. Fluorescent Brightener 147

     C. A. Registry Number          [12224-13-4]

     Commercial Names              Amar Supra White BRN (Dye-
                                   Chem., Ltd., India)

     Chemical Class                Stilbene derivative

     Fluorescence                  Bright reddish-blue

     Properties                    Very soluble in slightly warm
                                   water
                                   Fastness:  Chlorine, fair;
                                   Light, good; Washing, excellent

     Applications                  Cellulose, paper
  C. I. Fluorescent Brightener 148

     C. A. Registry Number          [12224-14-5]

     Commercial Names              Blankophor RPA (Farbenfabriken
                                   Bayer A. G., Germany)

     Chemical Class                Stilbene derivative

     Fluorescence                  Reddish-blue

     Properties                    Solutions are not stable to
                                   chlorine or chlorite
                                   Fastness:  Chlorine, good; Light,
                                   good; Washing, very good

     Applications                  Nylon


     According to  the U.  S.  Tariff Commission reports, 5,250

pounds of Fluorescent Brightener  148 were  imported into the U. S.

in 1972.
                           A-80

-------
C. I. Fluorescent Brightener 149

     C. A. Registry Number

     Commercial Names


     Chemical Class


     Fluorescence

     Properties
     Applications
[12216-91-0]

Fluolite ttWP (Imperial Chemical
Industries, Ltd., England)

Bistriazinylaminostilbene
derivative

Not given in the literature

Readily soluble in water and
very resistant to acid conditions.
On paper its fastness to light
is only moderate but it is re-
sistant to chlorine, acid and
alkali

Cellulose, paper
     C. I. Fluorescent Brightener 149 is not being manufactured at

the present time.
C. I. Fluorescent Brightener 150

     C. A. Registry Number

     Commercial Names

     Chemical Class

     Fluorescence

     Properties




     Applications
[12224-15-6]

Tinopal IT (Ciba-Geigy Corp.)

Heterocyclic

Blue

Has both reducing and brighten-
ing properties.  It is extremely
sensitive to acid.  Fastness to
light and washing is good

Wool, cotton, nylon
                        A-81

-------
C. I. Fluorescent Brightener 151

     C. A. Registry Number

     Commercial Names

     Chemical Class

     Fluorescence

     Properties
     Applications
[12224-16-7]

Tinopal ABR (Ciba-Geigy Corp.)

Triazinylaminostilbene derivative

Reddish-blue

Soluble in water, ethylene- and
diethyleneglycol and Cellosolve.
Insoluble in benzene, chloroben-
zene, ether, chloroform and
acetone
Fastness:  Acid, very good; Al-
kali, very good; Chlorine, good;
Dithionite, very good; Light,
good; Peroxide, very good

Cellulose, wool, nylon
C. I. Fluorescent Brightener  152

     C. A. Registry Number

     Commercial Names

     Chemical Class

     Fluorescence

     Properties
     Applications
Not given in the literature

Tinopal PG (Ciba-Geigy Corp.)

Coumarin derivative

Greenish-blue

Insoluble in water, soluble
in benzene, chlorobenzene,
acetone and Cellosolve
Fastness:  Acid, very gook; Al-
kali, good; Chlorine, good;
Dithionite, very good; Light,
very good; Peroxide, good

Nylon, acetate, polyester
                         A-82

-------
C. I. Fluorescent Brightener 153

     C. A. Registry Number

     Commercial Names



     Chemical Class


     Fluorescence

     Properties
     Applications
[12224-18-9]

Tinopal CWS (Ciba-Geigy Corp.);
Whitex BWB, Whitex SF (Sumi-
tomo Chemical Co., Ltd., Japan)

Triazinylaminostilbene deriva-
tive

Blue

Soluble in water, ethylene and
diethylene glycols and Cello-
solve.  Insoluble in benzene,
chlorobenzene, ether, chloro-
form and acetone
Fastness:  Acid, poor; Alkali,
very good; Chlorine, good;
Dithionite, very good; Light,
good; Peroxide, very good

Cellulose, wool, nylon
Detergent compositions
   I. Fluorescent Brightener 154

     C. A. Registry Number

     Commercial Names

     Chemical Class

     Fluorescence

     Properties
     Applications
[12224-19-0]

Tinopal UP (Ciba-Geigy Corp.)

Triazinylaminostilbene derivative

Blue

Compatible with cationic soften-
ers.  Soluble in water, ethylene
and diethyleneglycol and Cello-
solve.  Insoluble in benzene,
chlorobenzene, ether, chloro-
form and acetone
Fastness:  Acid, poor; Alkali,
very good; Chlorine, good; Di-
thionite, very good; Light,
good; Peroxide, very good

Cellulose, paper
Wool, nylon
                       A-83

-------
C. I. Fluorescent Brightener 155

     Colour Index Number

     C. A. Registry Number

     Commercial Names

     Chemical Class


     Molecular Formula

     Fluorescence

     Properties
C. I. 45555

[6250-49-3]

Not given in the literature

2 , 8-dimethylnaphtho [3,2, 1-kl ] -
xanthen-9-ol, acetate
     Applications
Green

Soluble in hydrocarbons, the
solutions being stable to heat
and light.  Also soluble in
alcohols, esters, ketones and
plasticisers

Lubricating oils
C. I. Fluorescent Brightener  156

     C. A. Registry Number

     Commercial Names

     Chemical Class

     Fluorescence

     Properties
     Applications
[12224-20-3]

Tinopal ethyl (Ciba-Geigy Corp.)

Coumarin derivative

Blue

Insoluble in water, soluble in
benzene, chlorobenzene, chloro-
form, acetone and Cellosolve
Fastness:  Acid, very good;
Alkali, moderate-good; Chlo-
rine, very good; Dithionite,
good; Light, very good; Peroxide,
moderate-good

Nylon, acetate, polyesters
                        A-8U

-------
C. I. Fluorescent Brightener 157

     C. A. Registry Number

     Commercial Names

     Chemical Class

     Fluorescence

     Properties
     Applications
[12224-21-4]

Tinopal LAT (Ciba-Geigy Corp.)

Coumarin derivative

Greenish-blue

Insoluble in water, soluble in
benzene, chlorobenzene, chloro-
form, acetone, Cellosolve and
dioxan
Stable to chlorite
Fastness:  Acid, very good; Al-
kali, good; Chlorine, very good;
Dithionite, very good; Light,
good; Peroxide, good

Acetate, triacetate, acrylics
C. I. Fluorescent Brightener 158

     C. A. Registry Number

     Commercial Names


     Chemical Class

     Fluorescence

     Properties


     Applications
[12224-22-5]

Calcofluor White Art (American
Cyanamid Co.)

Triazole derivative

Reddish

Excellent stability to chlorite
and excellent fastness to light

Acrylics
     American Cyanamid Co. reported production and sales of Fluores-

cent Brightener 158 to the U. S. Tariff Commission in 1972.  No

production figures are given; they are included in the total

brightener production figures.
                         A-85

-------
C. I. Fluorescent Brightener 159

     C. A. Registry Number

     Commercial Names


     Chemical Class

     Fluorescence

     Properties




     Applications
[12224-23-6]

Calcofluor White ABT (American
Cyanamid Co.)

Azole derivative

Blue

Amber liquid in physical form
Specific gravity 1.10
Miscible in water and in acetic
acid

Acrylic fibers
     American Cyanamid Co. reported production and sales of Fluor-

escent Brightener 159 to the U. S. Tariff Commission in 1972.  No

production figures are given; they are included in the total

brightener production figures.
C. I. Fluorescent Brightener 160

     C. A. Registry Number

     Commercial Names


     Chemical Class

     Fluorescence

     Properties
     Application
[12224-24-7]

Calcofluor White NCV (Ameri-
can Cyanamid Co.)

Benzidine sulfone derivative

Greenish blue

Insoluble in water; very soluble
in methanol, Methyl Cellosolve,
butanol and tetrahydrofurfuryl
alcohol; soluble in methyl
ethyl ketone and acetone; slight-
ly soluble in toluene and ethyl
acetate
Fastness to daylight good and
to artificial light excellent

Nitrocellulose
Cellulose acetate butyrate
Chlorinated rubber varnishes
     C. I. Fluorescent Brightener 160 is not being manufactured at

the present time.
                        A-86

-------
C. I. Fluorescent Brightener 161

     C. I. Registry Number

     Commercial Names


     Chemical Class

     Fluorescence

     Properties
     Applications
[12224-25-8]

Calcofluor White 2RP (American
Cyanamid Co.)

Stilbene derivative

Reddish

Exhausts slowly, has good fastness
to alum and is non-feathering.
Fluorescence little affected
between pH 4«5-6.  Used in paper
coating compositions it is
satisfactory at pH up to 9

Paper
     C. I. Fluorescent Brightener 161 is not being manufactured

at the present time.
C. I. Fluorescent Brightener 162

     C. A. Registry Number

     Commercial Names
     Chemical Class

     Fluorescence

     Properties




     Applications
[12224-26-9]

Mikawhite AT (Nippon Kayaku
Co., Ltd., Japan; Mitsubishi
Chemical Industries, Ltd.,
Japan)

Naphthalic acid derivative

Blue

Usable at pH 3-11 and stable to
chlorite.  Excellent fastness to
light, washing, perspiration
and heat

Polyester, acrylics, acetate
                       A-8?

-------
C. I. Fluorescent Brightener 162:1
     C. A. Registry Number

     Commercial Names
     Chemical Class

     Fluorescence

     Properties

     Applications
Not given in the literature

Leukophor EFR (Sandoz, Inc.);
Mikawhite ATN, (Nippon Kayaku
Co., Ltd., Japan; Mitsubishi
Chemical Industries, Ltd.,
Japan)

Naphthalic acid derivative

Not given in the literature

Not given in the literature

Polyester-cotton blends
C. I. Fluorescent Brightener 163

     C. A. Registry Number          [12224-27-0]


     This C. I. generic name is discontinued.  The brighteners

formerly listed under it now appear under C. I. Fluorescent

Brightener 162:1.
C. I. Fluorescent Brightener  164

     C. A. Registry Number

     Commercial Names
     Chemical Class

     Fluorescence

     Properties




     Applications
[12224-28-1]

Mikawhite BTN (Nippon Kayaku
Co., Ltd., Japan; Mitsubishi
Chemical Industries, Ltd.,
Japan)

Naphthalic acid derivative

Blue

Usable at pH 3-11 and stable to
chlorite.  Excellent fastness
to light, washing, perspiration
and heat

Polyester, acrylics, acetate
                         A-£

-------
C. I. Fluorescent Brightener 165

     C. A. Registry Number

     Commercial Names


     Chemical Class

     Fluorescence

     Properties



     Applications
Not given in the literature

Fluolite HM (Imperial Chemical
Industries, Ltd., England)

Stilbene derivative

Reddish-blue

Readily soluble in cold water.
Stable to acid, alum and rosin.
Good build-up

Paper
C. I. Fluorescent Rrightener 166

     C. A. Registry Number

     Commercial Names


     Chemical Class

     Fluorescence

     Properties


     Applications
[12224-29-2]

Kayaphor 3BS (Nippon Kayaku
Co., Ltd., Japan)

Stilbene derivative

Bright greenish blue

Very good solubility in water.
Stripping with chlorite good

Cellulose, paper
Soaps, detergents
                           A-89

-------
C. I. Fluorescent Brightener 167

     C. A. Registry Number

     Commercial Names


     Chemical Class

     Fluorescence

     Properties



     Applications
[12224-30-5]
                            v
Kayaphor RCS (Nippon
Kayaku Co., Ltd., Japan)

Stilbene derivative

Bright reddish

Good solubility in water.  Good
fastness to chlorine, light,
peroxide and washing

Cellulose, paper
C.I. Fluorescent Brightener 168

     C. A. Registry Number

     Commercial Names


     Chemical Class

     Fluorescence

     Properties



     Applications
[12224-31-6]

Kayaphor C (Nippon Kayaku Co.,
Ltd., Japan)

Stilbene derivative

Bright blue

Very good fastness to chlorine
and good fastness to light,
peroxide and washing

Cellulose, paper
C. I. Fluorescent Brightener 169

     C. A. Registry Number

     Commercial Names


     Chemical Class

     Fluorescence

     Properties


     Applications
[12224-32-7]

Kayaphor PS (Nippon Kayaku Co.»
Ltd., Japan)

Stilbene derivative

Bright reddish-violet

Good fastness to chlorine, light,
peroxide and washing

Cellulose, paper
                        A-90

-------
C. I. Fluorescent Brightener 170

     C. A. Registry Number

     Commercial Names


     Chemical Class

     Fluorescence

     Properties


     Applications
[12236-38-3]

Mikephor EN (Mitsui Toatsu
Chemicals, Inc., Japan)

Oxazole derivative

Bluish

Insoluble in water, soluble in
ethanol

Polyester
C. I. Fluorescent Brightener 171

     C. A. Registry Number

     Commercial Names
     Chemical Class

     Fluorescence

     Properties



     Applications
[12236-39-4]

Mikephor EB (Mitsui Toatsu
Chemicals, Inc., Japan); Pho-
tine EB, EB Liquid (Hickson
and Welch Ltd., England)

Oxazole derivative

Bluish

Good fastness to acid and light,
very good fastness to alkali,
chlorine, dithionite and peroxide

Nylon, Triacetate, polyester
C. I. Fluorescent Brightener 172

     C. A. Registry Number          [12224-33-8]

     This C. I. generic name is discontinued.  The brighteners

formerly listed under it now appear under C. I. Fluorescent

Brightener 185:1 and 185:2.
                         A-91

-------
C. I. Fluorescent Brightener 173

     C. A. Registry Number

     Commercial Names


     Chemical Class

     Fluorescence

     Properties



     Applications
 [12224-34-9]

Whitex 10B  (Sumitomo Chemical
Co., Ltd., Japan)

Stilbene derivative

Bright bluish

Good solubility in water.  Good
fastness to chlorine, light,
peroxide and washing

Cellulose, paper
Soaps, detergents
C. I. Fluorescent Brightener 174

     C. A. Registry Number

     Commercial Names


     Chemical Class

     Fluorescence

     Properties



     Applications
 [12236-40-7]

Mikephor BE  (Mitsui Toatsu
 Chemicals, Inc., Japan)

 Stilbene derivative

 Greenish-blue

 Readily soluble in cold water.
 Fastness:  Chlorine, poor;
 washing, excellent

 Cellulose, paper
 C. I. Fluorescent Brightener 175

     C. A. Registry Number

     Commercial Names


     Chemical Class

     Fluorescence

     Properties

     Applications
[12236-41-8]

Mikephor MX (Mitsui Toatsu
Chemicals,' Inc., Japan)

Stilbene derivative

Bluish

Water soluble

Cellulose, paper
                         A-92

-------
C. I. Fluorescent Brightener 176

     C. A. Registry Number

     Commercial Names


     Chemical Class

     Fluorescence

     Properties

     Applications
[12236-42-9]

Mikephor RFA (Mitsubi Toatsu
Chemicals, Inc., Japan)

Stilbene derivative

Reddish blue

Water soluble

Cellulose
Detergents
C. I. Fluorescent Brightener 177

     C. A. Registry Number

     Commercial Names


     Chemical Class

     Fluorescence

     Properties

     Applications
[12236-43-0]

Mikephor RP (Mitsui Toatsu
Chemicals, Inc., Japan)

Stilbene derivative

Bluish

Water soluble

Cellulose
C. I. Fluorescent Brightener 178

     C. A. Registry Number

     Commercial Names


     Chemical Class

     Fluorescence

     Properties

     Applications
[12236-44-1]

Mikephor RP (Mitsui Toatsu
Chemicals, Inc., Japan)

Stilbene derivative

Bluish

Water soluble

Wool, nylon
                        A-93

-------
C. I. Fluorescent Brightener 179

     C. A. Registry Number

     Commercial Names


     Chemical Class

     Fluorescence

     Properties
     Applications
[12224-35-0]

Fluolite XMF (Imperial Chemi-
cal Industries, Ltd., England)

Triazine derivative

Bluish

Stable to peroxide, salt,
sodium carbonate, sulphonic
acid, anionic and non-ionic
surfactants and some cationic
surfactants.

Acetate, triacetate, acrylic,
nylon
C. I. Fluorescent Brightener  180

     C. A. Registry Number

     Commercial Names
[12224-36-1]

Blancol HR (L. B. Holliday and
Co., Ltd., England)
     This C. I. generic name is discontinued; this brightener is

not being manufactured at  the present time.
C. I. Fluorescent Brightener  181

     C. A. Registry Number

     Commercial Names

     Chemical Class

     Fluorescence

     Properties


     Applications
[12224-37-2]

Uvitex ALN ' (Ciba-Geigy Corp.)

Heterocyclic

Bluish to reddish-blue

Outstanding fastness to light
and washing

Acrylics
                         A-9U

-------
C.I. Fluorescent Brightener 182

     C. A. Registry Number

     Commercial Names

     Chemical Class

     Fluorescence

     Properties

     Applications
[12224-38-3]

Uvitex MP (Ciba-Geigy Corp.)

Triazinylaminostilbene derivative

Bluish  .

Not given in the literature

Nylon
C. I. Fluorescent Brightener 183

     C. A. Registry Number

     Commercial Names

     Chemical Class

     Fluorescence

     Properties

     Applications
[12224-39-4]

Uvitex NB (Ciba-Geigy Corp.)

Triazinylaminostilbene

Blue

Good fastness to light and washing

Cellulose
Nylon
C. I. Fluorescent Brightener 184

     C. A. Registry Number

     Commercial Names

     Chemical Class

     Fluorescence

     Properties

     Applications
[12224-40-7]

Uvitex OB (Ciba-Geigy Corp.)

Heterocyclic

Bluish

Not given in the literature

Acetate, polyvinyl chloride,
triacetate
     According to the U. S. Tariff Commission reports, 551 pounds of

Fluorescent Brightener 184 were imported into the U. S. in 1972.
                        A-95

-------
C. I. Fluorescent Brightener 184:1

     C. A. Registry Number         Not given in the literature

     Commercial Names              Uvitex OB-C (Ciba-Geigy Corp.)


     C. I. Fluorescent Brightener 184:1 is identical to C. I.

Fluorescent Brightener 184, but it is extended with chalk to

facilitate its dispersion in plastics.



C. I. Fluorescent Brightener 184:2

     C. A. Registry Number         Not given in the literature

     Commercial Names              Uvitex OB-P (Ciba-Geigy Corp.)


     C. I. Fluorescent Brightener 184:2 is chemically identical to

C. I. Fluorescent Brightener 184, but contains a softening agent.

Its applications are:  Plasticised poly(vinyl chloride).
C. I. Fluorescent Brightener 185

     C. A. Registry Number

     Commercial Names

     Chemical Class

     Fluorescence

     Properties



     Applications
[12224-41-8]

Uvitex EBF (Ciba-Geigy Corp.)

Thiophene oxazole derivative

Bluish

Outstanding fastness to chlorine,
light, and washing on polyester
fibers

Acetate, triacetate, nylon,
polyester
Polypropylene, poly(vinyl chloride)
                         A-96

-------
C. I. Fluorescent Brightener 185:1

     C. A. Registry Number         Not given in the literature

     Commercial Names              Whitex SNK (Sumitomo Chemical
                                   Co., Ltd., Japan)

     Chemical Class                Thiophene oxazole derivative

     Fluorescence                  Bright bluish

     Properties                    Stable in chlorite bleaching
                                   baths and peracetic acid
                                   Fastness:  (polyester or poly-
                                   propylene), light, excellent;
                                   organic solvents, very good;
                                   washing, excellent

     Applications                  Polypropylene
                                   Polyester, Polyvinyl, nylon


     C. I. Fluorescent Brightener 185:1 is not being manufactured

at the present time.
C. I. Fluorescent Brightener 185:2

     C. A. Registry Number         Not given in the literature

     Commercial Names              Whitex NKR (Sumitomo Chemical
                                   Co., Ltd., Japan)

     Chemical Class                Thiophene oxazole derivative

     Fluorescence                  Bright reddish

     Properties                    Stable in chlorite bleaching
                                   baths and peracetic acid
                                   Fastness:  (polyester or poly-
                                   propylene) , light, excellent;
                                   organic solvents, very good;
                                   washing, excellent

     Applications                  Polypropylene
                                   Polyester, Polyvinyl, nylon
                         A-9T

-------
C. I. Fluorescent Brightener 186

     C. A. Registry Number

     Commercial Names

     Chemical Class

     Fluorescence

     Properties


     Applications
[12224-42-9]

Uvitex SFC (Ciba-Geigy Corp.)

Stilbene derivative

Blue

Excellent fastness to acid and
to perspiration

Soaps, detergents
C. I. Fluorescent Brightener 187

     C. A. Registry Number

     Commercial Names

     Chemical Class

     Fluorescence

     Properties

     Applications
[12224-43-0]

Uvitex SFC (Ciba-Geigy Corp.)

Stilbene derivative

Bluish

Not given in the literature

Paper
C. I. Fluorescent Brightener 188

     C. A. Registry Number

     Commercial Names

     Chemical Class

     Fluorescence

     Properties

     Applications
[12224-44-1]

Uvitex SBRN (Ciba-Geigy Corp.)

Stilbene derivative

Bluish

Not given in the literature

Cellulose, nylon
Detergents
                         A-98

-------
C. I. Fluorescent Brightener 189

     C. A. Registry Number

     Commercial Names

     Chemical Class

     Fluorescence

     Properties
     Applications
[12224-45-2]

Uvitex SK (Ciba-Geigy Corp.)

Heterocyclic

Bluish

Stable in washing liquors con-
taining hypochlorite or chloro-
isocyanuric acid.  Excellent
fastness (on fibre) to acids,
chlorine, light and washing

Detergents
C. I. Fluorescent Brightener 190

     C. A. Registry Number

     Commercial Names

     Chemical Class

     Fluorescence

     Properties
     Applications
[12224-46-3]

Uvitex SOF (Ciba-Geigy Corp.)

Heterocyclic

Bluish

Stable in washing liquors con-
taining hypochlorite or chloro-
isocyanuric acid.  Excellent
fastness (on fibre) to acids,
chlorine, light and washing

Detergents
                         A-99

-------
C. I. Fluorescent Brightener 191

     C. A. Registry Number

     Commercial Names


     Chemical Class

     Fluorescence

     Properties
     Applications
[12270-53-0]

Blankophor CL (Farbenfabriken
Bayer A. G., Germany)

Stilbene derivative

Reddish-violet

Anionic.  Stability (in soln),
acid, very good; alkali, good;
cationic softeners, pptd;
chlorite, very good; dithionite,
very good; heat, very good; hard
water, pptd; hypochlorite, good
at pH 10-12; peroxide, very good

Cellulose, nylon
     According to the U. S. Tariff Commission Reports, 77,975

pounds of Fluorescent Brightener 191 were imported into the U. S.

in 1972.
C. I. Fluorescent Brightener 192

     C . A. Registry Number

     Commercial Names


     Chemical Class

     Fluorescence

     Properties



     Applications
[12270-54-1]

Blankophor PSL (Farbenfabriken
Bayer A. G., Germany)

Stilbene derivative

White

Cationic.  Stable in solution to
acid and dithionite, not stable
to chlorine or chlorite

Acrylic, wool, silk
                         A-100

-------
C. I. Fluorescent Brightener 193

     C. A. Registry Number

     Commercial Names


     Chemical Class


     Fluorescence

     Properties




     Applications
 [12270-55-2]

 Blankophor PSL  (Farbenfabriken
 Bayer A. G., Germany)

 4,4'-Diaminostilbene-2,2'-
:.disulfonic acid derivative

 Slightly reddish

 Good solubility in water,
 extremely good  resistance to
 acid, little substantive to
 cellulose

 Paper
C. I. Fluorescent Brightener 194

     C. A. Registry Number

     Commercial Names


     Chemical Class

     Fluorescence

     Properties



     Applications
 [12270-56-3]

 Glowhite BBN  (Amar Dye-Chem.,
 Ltd.,  India)

 Stilbene derivative

 Bright blue

 Very soluble  in water.   Fastness
 to light good and to chlorine
 and washing very good

 Cellulose,  paper
                         A-ior

-------
C. I. Fluorescent Brightener 195

     C. A. Registry Number

     Commercial Names


     Chemical Class

     Fluorescence

     Properties




     Applications
[12270-57-4]

GlOwhite BRN (Amar Dye-Chem.,
Ltd., India)

Stllbene derivative

Bright reddish blue

Good solubility in water.  Stable
to acids and reducing agents
Fastness:  Chlorine, moderate;
Light, good; Washing, very good

Cellulose
C. I. Fluorescent Brightener 196

     C. A. Registry Number

     Commercial Names


     Chemical Class

     Fluorescence

     Properties



     Applications
[12270-58-5]

Glowhlte NAN (Amar Dye-Chem.,
Ltd., India)

Coumarin derivative

Reddish-violet

Readily soluble in cold water
Fastness:  Light, moderate;
Washing, moderate to good

Protein fibers, acetate, 7\ylon
     Since C. A. Registry Numbers are not available for brighteners

beyond C. I. Fluorescent Brightener 196, this item will be deleted

from the following tables (C. I. Fluorescent Brightener 231 is an

exception).
                        A-102

-------
C. I. Fluorescent Brightener 197

     Commercial Names


     Chemical Class

     Fluorescence

     Properties
     Applications
Ultraphor AL (Badische Anilin &
Soda Fabrik A. G., Germany)

Azacyanine derivative

Reddish-blue

Cationic.  Good solubility.
Stable to cationic softeners and
peroxide, not stable to reducing
agent.  Can be used in chlorite
bleaching baths

Acrylic, triacetate, acetate
     C. I. Fluorescent Brightener 197 is not being manufactured

at the present time.
C. I. Fluorescent Brightener 198

     Commercial Names



     Chemical Class

     Fluorescence

     Properties




     Applications
Pananil Brilliant White G
(Badische Anilin & Soda Fabrik
A. G., Germany)

Stilbene derivative

Greenish-blue

Non-ionic.  Good solubility.
Stable to cationic softeners.
Can be used in chlorite, peroxide
and reduction bleaching baths

Polyester, acetate, nylon,
triacetate
                        A-103

-------
C. I. Fluorescent Brightener 199

     Commercial Names



     Chemical Class

     Fluorescence

     Properties




     Applications
Palanil Brilliant White R
(Badische Anilin & Soda Fabrik,
A. G., Germany)

Stilbene derivative

Reddish-blue

Non-ionic.  -Good solubility.
Stable to cationic softeners.
Can be used in chlorite, peroxide
and reduction bleaching baths

Polyester, acetate, nylon,
triacetate
C. I. Fluorescent Brightener 200

     Commercial Names


     Chemical Class

     Fluorescence

     Properties




     Applications
Blankophor BK (Farbenfabriken
Bayer A. G., Germany)

Stilbene derivative

Bluish-violet

Anionic.  Sensitive to hard
water and cationic softeners.
Stable to acids, alkalies, di-
thionite and heat

Cotton and Polyester-cotton
blends
     According to the U. S. Tariff Commission.Reports, 46, 250

pounds of Fluorescent Brightener 200 were imported into the U. S,

in 1972.
                        A-10U

-------
C.I. Fluorescent Brightener 201

     Commercial Names              Blankophor ACB (Farbenfabriken
                                   Bayer A. G., Germany)

     Chemical Class                Stilbene derivative

     Fluorescence                  Bluish-violet

     Properties                    Cationic.  Good solubility in
                                   water.  Stable to cationic sof-
                                   teners and dithionite

     Applications                  Acrylics
 C. I. Fluorescent Brightener 202

     Commercial Names              Blankophor ACR (Farbenfabriken
                                   Bayer, A. G., Germany)

     Chemical Class                Nitrogen heterocycle

     Properties                    Cationic.  Good solubility in
                                   water.  Unstable in neutral
                                   or alkaline baths

     Applications                  Acrylics
 C. I. Fluorescent Brightener 203

     Commercial Names              Blankophor KL (Farbenfabriken
                                   Bayer A. G., Germany)

     Chemical Class                Coumarin derivative

     Fluorescence                  Bluish

     Properties                    Insoluble in water, soluble
                                   in many solvents.  Excellent
                                   resistance to heat, acid and
                                   alkali, n.p. 70°C

     Applications                  Plastics, resins, plasticizers,
                                   lacquers
                        A-105

-------
C. I. Fluorescent Brightener 204

     Commercial Names


     Chemical Class

     Fluorescence

     Properties
     Applications
Blankophor RA (Farbenfabriken
Bayer A. G., Germany)

Stilbene derivative

Bluish-violet

Anionic.  High substantivity,
riot dischargeable and difficult
to strip.  Not stable in solution
to chlorine and chlorite
bleaching baths

Cellulose, Polyester-cotton
blends, Nylon-cotton blends
C. I. Fluorescent Brightener 205

     Commercial Names


     Chemical Class

     Fluorescence

     Properties
     Applications
Blankophor RKH (Farbenfabriken
Bayer A. G., Germany)

Stilbene derivative

White

Anionic.  Good solubility in
boiling water, good dispersi-
bility in cold water.  Very
good resistance to spray drying,
alkalis and peroxides.   Good
substantivity.  In solution
unstable to chlorine but has
good fastness on the fibre

Cellulose
     According to the U. S. Tariff Commission Reports, 490,665

pounds of Fluorescent Brightener 205 were imported into the U. S.

in 1972.
                        A-106

-------
C. I. Fluorescent Brightener 206

     Commercial Names


     Chemical Class

     Fluorescence

     Properties
     Applications
Blankophor FBO (Farbenfabriken
Bayer A. G., Germany)

Nitrogen heterocycle

Reddish-blue

Non-ionic.  Insoluble in water,
readily dispersible in water
in presence of detergents.  Very
good stability to spray drying,
alkalis and peroxides.  In
solution unstable to chlorine

Acetate, nylon, triacetate
C. I. Fluorescent Brightener 207

     Commercial Names


     Chemical Class

     Fluorescence

     Properties




     Applications
Photine VN (Hickson and Welch,
Ltd., England)

Stilbene derivative

Bluish-violet

Water soluble.  Good substantivity.
Fastness to acid, alkali, chlorine
and light good and to dithionite
and peroxide very good

Nylon
C. I. Fluorescent Brightener 208

     Commercial Names


     Chemical Class

     Fluorescence
                          I
     Properties





     Applications
Photine LTD (Hickson and Welch,
Ltd., England)

Stilbene derivative

Reddish-blue

Water soluble.  Good substanti-
vity.  Fastness to acid and light
good, to alkali, chlorine, di-
thionite and peroxide very good

Cellulose
Soaps, detergents
                       A-107

-------
C. I. Fluorescent Brightener 209

     Commercial Names



     Chemical Class

     Fluorescence

     Properties
     Applications
Photine PT New, Photine Paper-
white P (Hickson and Welch, Ltd.,
England; S. A. Rovira, Spain)

Stilbene derivative

Reddish-blue

Readily soluble in water.  Stable
to high concentrations of alum.
Good sub s tant ivity.  Fastnes s
to chlorine and light good, to
acid, alkali, dithionite and
peroxide very good

Paper
C. I. Fluorescent Brightener 210

     Commercial Names


     Chemical Class

     Fluorescence

     Properties
     Applications
Photine BPM (Hickson and Welch,
Ltd., England)

Stilbene derivative

Blue

Readily soluble in water.  Good
substantivity.  Fastness to
chlorine and light good, to
acid, alkali, dithionite. and
peroxide very good

Paper
C. I. Fluorescent Brightener  211

     Commercial Names


     Chemical Class

     Fluorescence

     Properties
      Applications
                        A-108
Photine BTM  (Hickson and Welch,
Ltd., England)

Stilbene derivative

Blue

Readily soluble in water.  Moder-
ate substantivity.  Sensitive
to electrolytes.  Fastness to
chlorine and light good, to
acid, alkali, dithionite and
peroxide very good

Cellulose
Nylon

-------
C. I. Fluorescent Brightener 212

     Commercial Names


     Chemical Class

     Fluorescence

     Properties
     Applications
Photine CXT (Hickson & Welch,
Ltd., England)

Stilbene derivative

Reddish-blue

Dispersible in cold water, solu-
ble in hot water.  High substan-
tivity.  Fastness to acid poor,
to light good and to alkali,
chlorine, dithionite and peroxide
very good

Cellulose
Nylon, protein fibers
C. I. Fluorescent Brightener 213

     Commercial Names
     Chemical Class

     Fluorescence

     Properties
     Applications
Photine HV, HVS, VHP (Hickson
and Welch, Ltd., England; S. A.
Rovira, Spain; Hickson and Dada-
j ee Private Ltd., India)

Stilbene derivative

Reddish-blue

Readily soluble in water.  Good
substantivity.  Fastness to
chlorine and light good, to acid,
alkali, dithionite and peroxide
very good

Cellulose, paper
Nylon, protein fibers
                       A-109

-------
C. I. Fluorescent Brightener 214

     Commercial Names
     Chemical Class

     Fluorescence

     Properties
     Applications
Photine HVD, RD245D (Hickson
and Welch, Ltd., England; S. A.
Rovira, Spain; Hickson and Dadajee
Private Ltd., India)

Stilbene derivative

Reddish-blue

Readily soluble in water.  Good
Substantivity.  Fastness to
chlorine and light good, to
acid, alkali, dithionite and
peroxide very good

Cellulose
Soaps, detergents
C. I. Fluorescent Brightener 215

     Commercial Names


     Chemical Class

     Fluorescence

     Properties




     Applications
Photine LV (Hickson and Welch,
Ltd., England)

Stilbene derivative

Reddish-blue

Soluble in water.  Medium sub-
stantivity.  Fastness to alkali,
chlorine and light good, to
acid and dithionite very good

Cellulose
Nylon
                        A-110

-------
C. I. Fluorescent Brightener 216

     Commercial Names


     Chemical Class


     Fluorescence

     Properties




     Applications
Kayaphor BR (Nippon Kayaku
Co., Ltd., Japan)

Bistriazinylamtnostilbene
derivative

Reddish-blue

Very good solubility in water.
Fastness to dithionite and light
good, to acid, alkali, chlorine
and peroxide very good

Cellulose
Nylon, protein fibers
Co I» Fluorescent Brightener 217

     Commercial Names
     Chemical Class

     Fluorescence

     Properties.




     Applications
Kayaphor W .(Nippon Kayaku Co.,
Ltd., Japan); Whitex BRF (Su-
mitomo Chemical Co., Ltd.,
Japan)

Pyrazoline derivative

Reddish-blue

Good solubility in water.  Fast-
ness to alkali and light good,
to acid, dithionite and perox-
ide very good

Wool, nylon
                        A-in

-------
C. I. Fluorescent Brightener 218

     Commercial Names


     Chemical Class

     Fluorescence

     Properties




     Applications
Kayaphor N (Nippon Kayaku Co.,
Ltd., Japan)

Bistriazinylaminostilbene

Reddish-blue

Good solubility in water.
Fastness to light good, to
acid, alkali, chlorine, di-
thionite and peroxide very good

Cellulose
Wool, nylon
C. I. Fluorescent Brightener 219

     Commercial Names


     Chemical Class

     Fluorescence

     Properties
     Applications
White WP (Sumitomo Chemical
Co., Ltd., Japan)

Oxazole derivative

Reddish-blue

Insoluble in water but readily
dispersed in cold water.  Fast-
ness to acid, alkali, chlorine,
dithionite, light and peroxide
very good

Polypropylene
Nylon, acetate, poly(vinyl
chloride)
                       A-112

-------
C. I. Fluorescent Brightener 219:1

     Commercial Names


     Chemical Class

     Fluorescence

     Properties




     Applications
Kayaphor OLN (Nippon Kayaku
Co., Ltd., Japan)

Oxazole derivative

Neutral

Readily dispersible in water.
Fastness to chlorine, sublima-
tion and washing good and to
light excellent

Polypropylene
Polyester, nylon, poly(vinyl
chloride)
C. I. Fluorescent Brightener 219:2

     Commercial Names


     Chemical Class

     Fluorescence

     Properties




     Applications
Kayaphor OLR (Nippon Kayaku
Co., Ltd., Japan)

Oxazole derivative

Slightly reddish

Readily dispersible in water.
Fastness to chlorine, sublima-
tion and washing good and to
light excellent

Polypropylene
Polyester, nylon, poly(vinyl
chloride)
                       A-113

-------
C. I. Fluorescent Brightener 220

     Commercial Names



     Chemical Class

     Fluorescence

     Properties




     Applications
Fluolite PS Liquid (Imperial
Chemical Industries, Ltd.,
England)

Stilbene derivative

Bluish

Miscible with cold soft water
in all proportions.  Stable
to alum and strong and weak
acids and alkalis

Paper
C. I. Fluorescent Brightener 221

     This C. I. generic name is discontinued.  The brighteners

formerly listed under it now appear under C. I. Fluorescent

Brightener 146.
C. I. Fluorescent Brightener 222

     Commercial Names
     Chemical Class

     Fluorescence

     Properties




     Applications
Photine SPG (Hickson and Welch,
Ltd., England); White SPC (Hick-
son and Dadajee Private Ltd.,
India)

Stilbene derivative

Bluish-red

Soluble in water.  Fastness
to chlorine poor, to acid, al-
kali, light and peroxide good
and to dithionite very good

Cellulose, paper
                        A-llU

-------
C. I. Fluorescent Brightener 223

     Commercial Names


     Chemical Class


     Fluorescence

     Properties




     Applications
Kayaphor CR (Nippon Kayaku
Co., Ltd., Japan)

Bistriazinylaminostilbene deri-
vative

Bright reddish blue

Good solubility in water.
Fastness to acid, dithionite
and light good, to alkali,
chlorine and peroxide very good

Cellulose, paper
Nylon
C. I. Fluorescent Brightener 224

     Commercial Names


     Chemical Class


     Fluorescence

     Properties
     Applications
Kayaphor HAS (Nippon Kayaku
Co., Ltd., Japan)

Bistriazinylaminostilbene
derivative

Neutral

Good solubility in water.
Fastness to light good and
to acid, alkali, chlorine,
dithionite and peroxide very
good

Cellulose, paper
Wool, nylon
Poly(vinyl alcohol)
                       A-115

-------
C. I. Fluorescent Brightener 225

     Commercial Names
     Chemical Class


     Fluorescence

     Properties




     Applications
Kayaphor LSK (Nippon Kayaku
Co., Ltd., Japan); Whitex
SKC (Sumitomo Chemical Co.,
Ltd., Japan)

Bistriazinylaminostilbene
derivative

Neutral

Slightly soluble in water.
Fastness to dithionite, light
and peroxide good, to alkali
and chlorine very good

Cellulose  '
Nylon
Soaps, detergents
C. I. Fluorescent Brightener 226

     Commercial Names


     Chemical Class

     Fluorescence

     Properties




     Applications
Mikawhite ACR (Nippon Kayaku
Co., Ltd., Japan)

Acenaphthene derivative

Neutral

Readily soluble in cold water.
Very good fastness to acid,
alkali, chlorine, dithionite,
light and peroxide

Acrylics
                        A-116

-------
C. I. Fluorescent Brightener 227

     Commercial Names


     Chemical Class

     Fluorescence

     Properties
     Applications
Mikawhite SIN (Nippon Kayaku
Co., Ltd., Japan)

Acenaphthene derivative

Bluish

Insoluble but readily disper-
sible in water.  Very good
fastness to acid, alkali,
chlorine, dithionite, light
and peroxide

Polyester, acrylic, acetate,
nylon
C. I. Fluorescent Brightener 228

     Commercial Names


     Chemical Class

     Fluorescence

     Properties
     Applications
Photine TCA  (Hickson and Welch,
Ltd., England)

Heterocyclic

Bluish-violet

Insoluble in water.  High
substantivity.  Fastness to
chlorine poor, to acid, dithi-
onite and peroxide good, to
light very good and alkali ex-
cellent

Acetate, triacetate, acrylic,
nylon
                       A-11T

-------
C. I. Fluorescent Brightener 229

     Commercial Names              Blankophor EBL (Farbenfabriken
                                   Bayer A. G., Germany)

     Chemical Class                Coumarin derivative

     Fluorescence                  Neutral

     Properties                    Non-ionic.  Stable in solution
                                   and in the fibre to acid, al-
                                   kali, chlorite, hard water,
   • b                              hypochlorite and reducing agents

     Applications                  Polyester, 'polyester-cotton
                                   blends


     According to U. S. Tariff Commission Reports, 77,160 pounds

of Fluorescent Brightener 229 were imported into, the U. S. in

1972.
C. I. Fluorescent Brightener 230

     Commercial Names              Leukophor AP (Sandoz Colors
                                   and Chemicals)

     Chemical Class                Bistriazinylaminostilbene
                                   derivative

     Fluorescence                  Blue

     Properties                    Not stable to acids and electro-
                                   lytes

     Applications                  Cotton
                                   Paper
                       A-118

-------
C. I. Fluorescent Brightener 231

     C. A. Registry Number

     Commercial Names


     Chemical Class


     Fluorescence

     Properties




     Applications
[12676-64-1]

Leukophor C (Sandoz Colors
and Chemicals)

Bistriazinylaminostilbene
derivative

Blue

Excellent solubility in water.
Stable to acid and alkali.
Heavy metal salts lessen the
fluorescence

Cellulose, paper
C. I. Fluorescent Brightener 232

     Commercial Names


     Chemical Class


     Fluorescence

     Properties



     Applications
Leukophor CK (Sandoz Colors
and Chemicals)

Bistriazinylaminostilbene deri-
vative

Blue

Stable to acid and alkali.
Heavy metal salts lessen the
fluorescence

Paper
                        A-119

-------
C. I. Fluorescent Brightener 233

     Commercial Names


     Chemical Class


     Fluorescence

     Properties
     Applications
Leukophor DT (Sandoz Colors
and Chemicals)

Bistriazinylaminostilbene deriva-
tive

Brilliant blue

Solubility in water at 100°C
10 mg/1.  Stable to perborate
and alkalis.  Looses its fluor-
escence in warm liquors con-
taining hypochlorite but on
the fibre is negligibly affected
by chlorine

Washing powders for cellulose
and nylon textiles
C. I. Fluorescent Brightener 234

     Commercial Names


     Chemical Class


     Fluorescence

     Properties



     Applications
Leukophor PAF (Sandoz Colors
and Chemicals)

Bistriazinylaminostilbene
derivative.

Reddish-blue

Soluble in hot water.  Stable
to acids and alkalis, not
stable to chlorine

Nylon, nylon-wool blends,
nylon-cellulose blends, wool
                        A-120

-------
C. I. Fluorescent Brightener 235

     Commercial Names


     Chemical Class


     Fluorescence

     Properties



     Applications
Leukophor SPA (Sandoz Colors
and Chemicals)

Bistriazinylaminostilbene
derivative

Very brilliant blue

Stable to acids and alkalis
but heavy, metal salts reduce
the fluorescence

Paper
C. I. Fluorescent Brightener 236

     Commercial Names


     Chemical Class

     Fluorescence

     Properties


     Applications
Leukopur EGM (Sandoz Colors
and Chemicals)

Coumarin derivative

Blue

Soluble in hot organic solvents.
Stable to acids and alkalis

Polyester
C. I. Fluorescent Brightener 237

     This C. I. generic name is discontinued.  The brighteners

formerly listed under it now appear under C. I. Fluorescent

Brightener 222.
                        A-121

-------
C. I. Fluorescent Brightener 238

     Commercial Names



     Chemical Class

     Fluorescence

     Properties


     Applications
Lyrcamine White NL (Compagnie
Francaise des Matieres Color-
antes, France)

Naphthalimide derivative

Violet

Cationic in nature.  Soluble
in strong sulfuric acid

Acrylics
     According to the U. S. Tariff Commission Reports, 1,587

pounds of Fluorescent Brightener 238 were imported into the U. S,

in 1972.                                      :
C. I. Fluorescent Brightener 239

     Commercial Names


     Chemical Class


     Fluorescence

     Properties
     Applications
Kayaphor NL (Nippon Kayaku Co.,
Ltd., Japan)

Bistriazinylaminostilbene
derivative

Bluish-violet

Readily soluble in cold water.
Fastness to chlorine moderate,
to alkalis and light good, to
acid, dithionite and peroxide
very good

Cellulose, paper
Protein fibers, nylon
                        A-122

-------
C. I. Fluorescent Brighteher 240

     Commercial Names


     Chemical Class


     Fluorescence

     Properties




     Applications
Kayaphor SFN (Nippon Kayaku
Co., Ltd., Japan)

Bistriazinylaminostilbene
derivative

Bluish-violet

Very good solubility in hot
water.  Good compatibility with
cationic compounds in detergent
compositions

Paper, cellulose
Wool, nylon
C. I. Fluorescent Brightener 241

     Commercial Names


     Chemical Class


     Fluorescence

     Properties
     Applications
Kayaphor CPS Cone. (Nippon
Kayaku Co., Ltd., Japan)

Bistriazinylaminostilbene
derivative

Bluish-violet

Solubility in water 10 g/1
at 75°C.  Esdiausts well on
cellulose from cold solution.
Fostness to chlorine moderate,
to light good and to acid, al-
kali, dithionite and peroxide
very good

Paper
Detergents for wool, nylon,
and cellulose
                       A-123

-------
C. I. Fluorescent Brightener 242

     Commercial Names


     Chemical Class


     Fluorescence

     Properties




     Applications
Kayaphor PBN (Nippon Kayaku
Co., Ltd., Japan)

Bistriazinylaminostilbene
derivative

Bluish-violet

Fastness to chlorine moderate,
to alkali and light good and
to acid, dithionite and peroxide
very good

Cellulose, paper
Wool, nylon
C. I. Fluorescent Brightener 243

     Colour Index Number

     Commercial Names

     Chemical Class
     Molecular Formula

     Fluorescence

     Properties

     Applications
C. I. 40619

Heliofor 2BC (CIECH, Poland)

4,4' -Bis [ (4-amino-6-hydroxy-s-
triazin-2-yl) amino ] -2 , 2 ' -
stilbenedisulfonic acid, diso-
dium salt

              * 2Na
Bluish

Soluble in water

Cellulose
                       A-12U

-------
C. I. Fluorescent Brlghtener 244

     Commercial Names

     Chemical Class

     Fluorescence

     Properties

     Applications
Heliofor 3BC (CIECH, Poland)

Stilbene derivative

Bluish

Slightly soluble in water

Cellulose
C. I. Fluorescent Brightener 245

     Colour Index Number

     Commercial Names

     Chemical Class



     Molecular Formula

     Fluorescence

     Properties


     Applications
C. I. 40615

Heliofor ZSP (CIECH, Poland)

4,4'-Bis[(4-chloro-6-amino-s-
triazin-2-yl)amino] -2,2'-stilben-
edisulfonic acid, disodium salt

C20H1i(Cl2N1006S2  • 2Na

Greenish-blue

Slightly soluble  in water.  Fast
to thermofixation

Nylon
C. I. Fluorescent Brightener 246

     Commercial Names

     Chemical Class

     Fluorescence

     Properties


     Applications
Heliofor SPG  (CIECH, Poland)

Stilbene derivative

Bluish

Soluble in water.  Fast to ther-
mof ixation

Cellulose
Nylon
                        A-125

-------
C. I. Fluorescent Brightener 247

     Commercial Names

     Chemical Class

     Fluorescence

     Properties




     Applications
Heliofor VM (CZECH, Poland)

Stilbene derivative

Bluish

Does not affect the viscosity,
stability or the filtration
and extrusion properties of
viscose solution

Viscose
C. I. Fluorescent Brightener 248

     Commercial Names

     Chemical Class

     Fluorescence

     Properties


     Applications
Heliofor SPM (CIECH, Poland)

Stilbene derivative

Bluish

Soluble in water.  Fast to
thereofixation

Acrylic, nylon
C. I. Fluorescent Brightener 249

     Commercial Names

     Chemical Class

     Fluorescence

     Properties

     Applications
Heliofor V, VP (CIECH,  Poland)

Stilbene derivative

Reddish

Soluble in water

Cellulose, paper
                        A-126"

-------
C. I. Fluorescent Brightener 249:1

     Commercial Names              Not given in the literature

     Chemical Class                Stilbene derivative

     Fluorescence                  Reddish

     Properties                    Not given in the literature

     Applications                  Paper
C. I. Fluorescent Brightener 250

     Commercial Names

     Chemical Class

     Fluorescence

     Properties


     Applications  -          .
Heliofor BDC (CIECH, Poland)

Stilbene derivative

Bluish

Excellent fastness to alkali
and perborates

Cellulose                 .
C. I. Fluorescent Brightener 251

     Commercial Names

     Chemical Class

     Fluorescence

     Properties

     Applications
Tinopal 2BT (Ciba-Geigy Corp.)

Stilbyl-s-triazine derivative

Bluish

Not given in the literature

Cellulose
     According to the U. S. Tariff Commission Reports, 220

pounds of Fluorescent Brightener 251 were imported into the U. S.

in 1972.
                        A-127

-------
C. I. Fluorescent Brightener 252

     Commercial Names

     Chemical Class

     Fluorescence

     Properties

     Applications
Tinopal BHT (Ciba-Geigy Corp.)

Stibyl-s-triazine derivative

Bluish

Not given in the literature

Cellulose
C. I. Fluorescent Brightener 253

     Commercial Names

     Chemical Class

     Fluorescence

     Properties

     Applications
Tinopal WHN (Ciba-Geigy Corp.)

Stibyl-s-triazine derivative

Bluish

Not given in the literature

Polyacrylonitrile
Wool
C. I. Fluorescent Brightener 254

     Commercial Names

     Chemical Class

     Fluorescence

     Properties

     Applications
Tinopal ERT (Ciba-Geigy Corp.)

Coumarinyl-pyrazole derivative

Reddish

Not given in the literature

Polyester
     According to the U. S. Tariff Commission Reports, 1,102

pounds of Fluorescent Brightener 254 were imported into the U. S.

in 1972.
                      A-128

-------
C. I. Fluorescent Brightener 255

     Commercial Names

     Chemical Class

     Fluorescence

     Properties

     Applications
Tinopal NTH (Ciba-Geigy Corp.)

Stilbyl-s-triazine derivative

Slightly bluish

Not given in the literature

Not given in the literature
C. I. Fluorescent Brightener 256

     Commercial Names

     Chemical Class

     Fluorescence

     Properties

     Applications
Tinopal 2RT (Ciba-Geigy Corp.)

Stilbyl-s-triazine derivative

Reddish

Not given in the literature

Not given in the literature
C. I. Fluorescent Brightener 257

     Commercial Names


     Chemical Class

     Fluorescence

     Properties
     Applications
Blankophof ANR (Farbenfabriken
Bayer A. G., Germany)

Coumarin derivative

Reddish

In solution is not resistant
to hypochlorite, peroxide and
alkalis but on the fibre has
very good resistance to them.
Very good resistance both in
soln and on the fibre to
dithionite, acids and hard water

Acrylics
     According to the U. S. Tariff Commission Reports, 1,050

pounds of Fluorescent Brightener were imported into the U. S.

in 1972.
                       A-129

-------
C. I. Fluorescent Brightener 258

     Commercial Names


     Chemical Class

     Fluorescence

     Properties

     Applications
Whitex SNP (Sumitomo Chemical
Co., Ltd., Japan)

Oxazole derivative

Bluish violet

Insoluble in water

Polyolefin, polyester
C. I. Fluorescent Brightener 259

     Commercial Names


     Chemical Class

     Fluorescence

     Properties

     Applications
Whitex AC (Sumitomo Chemical
Co., Ltd., Japan)

Oxazole derivative

Bluish

Soluble in water

Acrylics
C. I. Fluorescent Brightener 260

     Commercial Names


     Chemical Class

     Fluorescence

     Properties



     Applications
Whitex SA (Sumitomo Chemical
Co., Ltd., Japan)

Stilbene derivative

Bluish

Fastness:  Alkali, Chlorine,
Dithionite, Peroxide and Washing,
very good; Light, good

Cellulose
Soaps and detergents
                       A-130

-------
C. I. Fluorescent Brightener 261

     Commercial Names              Whitex SEC (Sumitomo Chemical
                                   Co., Ltd., Japan)

     Chemical Class                Stilbene derivative

     Fluorescence                  Bluish

     Properties                    Fastness:  Acid, Chlorine,
                                   and Light, good; Alkali, Di-
                                   thionlte, Peroxide and Washing,
                                   very good

     Applications                  Cellulose
                                   Spaps and detergents
C. I. Fluorescent Brightener 265

     According to the U. S. Tariff Commission Reports, 450

pounds of Fluorescent Brightener 265 were imported into the U. S.

in 1972.
     No further correlations could be established between C. I.

Fluorescent Brightener numbers and miscellaneous data on the

brighteners, because of a lack of indicative information.
                       A-131

-------
     Following are data on some optical brighteners for which

no C. I. Fluorescent Brightener numbers were obtained.



Hiltamine Arctic Paper White DSA (Hilton-Davis Division of Sterling

Drug Co.)

     Chemical Class                Triazinylstilbene derivative

     Properties                    Liquid in form; pH 9.0-10.0
                                   Anionic in nature
                                   Miscible with water in all pro-
                                   portions !

     Applications                  Paper



Hiltamine Arctic Paper White HMS (Hilton-Davis Division of Sterling

Drug Co.)

     Chemical Class                Triazinylstilbene derivative

     Properties                    Liquid in form; pH 8.6-9.8
                                   Anionic in nature
                                   Miscible with water in all pro-
                                   portions

     Applications                  Paper



Hiltamine Arctic Paper White LG (Hilton-Davis Division of Sterling

Drug Co.)

     Chemical Class                Triazinylstilbene derivative

     Properties                    Liquid in form; pH 6.8-7.8
                                   Anionic in nature
                                   Miscible with water in all
                                   proportions

     Applications                  Paper
                       A-132

-------
Hiltamlne Arctic White GT (Hilton-Davis Division of Sterling

Drug Co.)                                 .

     Chemical Class                Triazinylstilbene derivative

     Properties                    Liquid in form; pH 8.8-9.8
                                   Anionic in nature.
                                   Miscible with water in all
                                   proportions

     Applications                  Textiles; resin finishes
Hiltamine Arctic White SC (Hilton-Davis Division of Sterling

Drug Co.)

     Chemical Class                Triazinylstilbene derivative

     Properties                    Liquid in form; pH 8.2-9.2
                                   Anionic in nature
                                   Miscible with water in all
                                   proportions

     Applications                  Textiles
                                   Liquid detergents, laundry
                                   softeners
Hiltamine Arctic White CC (Hilton-Davis Division of Sterling

Drug Co.)

     Chemical Class                Triazinylstilbene derivative

     Properties                    Liquid in form; pH 9.5-10.5
                                   Anionic in nature
                                   Compatible with cationic,
                                   anionic, and nonionic softeners
                                   Miscible with water in all
                                   proportions

     Applications                  Textiles
                                   Fabric softeners
                        A-133

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Hiltamine Arctic White TX (Hilton-Davis Division of Sterling

Drug Co.)

     Chemical Class                Triazinylstilbene derivative

     Properties                    Liquid in form; pH 8.5-10.5
                                   Anionic in nature
                                   Compatible with cationic,
                                   anionic, and nonionic in
                                   nature
                                   Miscible with water in all
                                   proportions

Applications                       Textiles
                                   Fabric softeners
Hiltamine Arctic White MSO (Hilton-Davis Division of Sterling

Drug Co.)

     Chemical Class                Triazinylstilbene derivative

     Properties                    Powder in form
                                   Anionic in nature
                                   Insoluble in aqueous acidic
                                   solutions
                                   Slightly soluble in aqueous
                                   alkali

     Applications                  Cold water, all-temperature, low-
                                   phosphate, and no-phosphate
                                   laundry formulations
Hiltamine Arctic White CWD  (Hilton-Davis Division of Sterling

Drug Co.)

     Chemical Class                Triazinylstilbene derivative

     Properties                    Powder in form
                                   Anionic in nature
                                   Low solubility at acidic pH
                                   levels

     Applications                  Cold water laundry formulations
                                   Detergents
                                   Fabric Softeners
                       A-13U

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Hiltamine Arctic White SOL (Hilton-Davis Division of Sterling

Drug Co.)

     Chemical Class                Coumarin derivative

     Properties                    Powder in form
                                   Nonionic in nature
                                   Water insoluble
                                   Soluble in alcohol, benzene,
                                   ketones, detergents, and resins

     Applications                  Fine fabric detergent formula-
                                   tions
                                   Textiles; polyamides
Safratone White WNOA (Hilton-Davis Division of Sterling Drug Co.)

     Chemical Class                Coumarin derivative

     Properties                    Powder in form
                                   Nonionic in nature
                                   Readily dissolves in warm water

     Applications                  Detergent formulations
                                   Textiles; polyamides, acetate,
                                   triacetate
 Advabrite BMV (Cincinnati Milacron Chemicals Inc.)

     Chemical Name                 7-Hydroxy-4-Methylcoumarin

     Molecular Formula
     Properties                    Light tan powder        :
                                   M.P. 184-194°C
                                   Outdoor durability
                                   Exhibits strong blue fluorescence
                                   under black light

     Applications                  Pigmented coatings
                                   Solvent and water-based coatings
                        A-135

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 Advabrite MDAC (Cincinnati Milacron Chemicals Inc.)

     Chemical Name                 7-(Diethylamino)-4-MethyIc cm-
                                   mar in

     Molecular Formula

     Properties                    White to light tan powder
                                   M.P. 68-73°C
                                   Excellent heat stability and
                                   outdoor durability
                                   Exhibits strong blue fluorescence
                                   under black light

     Applications                  Pigmented coatings
                                   Solvent and water-based coatings
Advabrite  M-10 (Cincinnati Milacron Chemicals, Inc.)

     Properties                    Clear liquid
                                   Safe for skin contact, but
                                   not recommended for food
                                   packaging

     Application                   Plastic
Calcofluor White A2RT Solution (American Cyanamid Co.)

     Properties                    Reddish-blue fluorescence
                                   Excellent fastness to light
                                   and stability to chlorine bleach
                                   Amber liquid
                                   Specific gravity 1.09-1.10
                                   Miscible in water and acetic
                                   acid

     Application                   Acrylic fibers
Calcofluor White GBP Solution (American Cyanamid Co.)

     Properties                    Characteristics of a low sub-
                                   stantive direct dye
                                   Pale amber liquid
                                   pH 9.8
                                   Slight odor of ammonia
                                   Anionic in reaction
                                   Soluble in water
                                   Specific gravity 1.11

     Application                   Paper

                       A-136

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Calcofluor White LPH Solution (American Cyanamid Co.)

     Properties                    Amber solution
                                   Negligible odor
                                   pH 7.5-8.0    :
                                   Specific gravity 1.2

     Application                   Paper
Aclarat 8678 (Sandoz Colors and Chemicals)

     Properties                    Powder in form
                                   Insoluble in water
                                   Soluble in equal weight of
                                   sulfuric or hydrochloric acid
                                   Soluble in nonionic, anionic,
                                   and cationic surfactants
                                   Soluble in nearly all common
                                   organic solvents
                                   Compatible with acids, reducing
                                   agents, oxidizing agents,
                                   anionics, cationics, and non-
                                   ionics

     Applications                  Nylon, acetate, wool, silk
                                   Shampoo additive
                                   Fabric softeners
                                   Soaps

     Suggested application         Brightening agent in hydrogen
                                   peroxide hair bleaches
Sandoz TH-40 (Sandoz Colors and Chemicals)

     Properties                    Brown liquid
                                   Anionic in nature
                                   Substantive to cotton, rayon,
                                   and nylon
                                   Compatible with anionic and
                                   nonionic compounds, thermo-
                                   setting resins, alkalies,
                                   slightly acidic media, oxygen
                                   bleaches

     Application                   Cellulosic materials
                       A-137

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Leucophor C7002, Leucophor CS, and Leucophor C6902 (Sandoz Colors

and Chemicals)

     Properties                    Clear brown liquids
                                   Anionic in character
                                   Good stabilities to acids,
                                   alkali salts, and hard water
                                   Not compatible with cationic
                                   compounds
                                   Compatible with anionic com-
                                   pounds, nonionic compounds,
                                   fillers and shading pigments,
                                   direct and acid dyes, acid
                                   and alkaline starches, wet
                                   strength resins

     Application                   Paper
                        A-138

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                                   TECHNICAL REPORT DATA
                            (Please read lattaictions on the reverse before completing}
! I. REPORT NO.
   EPA-560/2-75-002
                                                            3. RECIPIENT'S ACCESSIOWNO.
4. TITLE AND SUBTITLE preiiminary Study of Selected  Potential
  Environmental Contaminants  - Optical Brighteners, .
  Methyl  Chloroform, Trichloroethylene, Tetrachloro-
  ethylene and Ion Fxrhangp Rp«;ins .	
7. AUTHOR(S)
             B. REPORT DATE
                 July 1975
             6. PERFORMING ORGANIZATION CODE
             8. PERFORMING ORGANIZATION REPORT NO
9. PERFORMING ORGANIZATION NAME AND ADDRESS
'Science Information Services Department
 Franklin Institute Research Laboratories
 Philadelphia, Pennsylvania  19103
              10. PROGRAM ELEMENT NO.

                  2LA328
              11. CONTRACT/GRANT NOT
                                                                68-01-1897
 12. SPONSORING AGENCY NAME AND ADDRESS

 Office  of Toxic Substances
 Environmental Protection Agency
 Washington, D.C.  20460
              13. TYPE OF REPORT AND PERIOD COVERED
                  Final        .,	
              14. SPONSORING AGENCY CODE
 15. SUPPLEMENTARY NOTES
 16. ABSTRACT
     A  comprehensive review of the literature published from 1953 through
 1973 was  conducted to prepare this preliminary investigation report on
 the physical and chemical properties of optical brighteners, methyl chloro-
 form,  trichloroethylene, tetrachloroethylene and  ion  exchange resins, on
 environmental exposure factors related to their consumption and use, on the
 health and environmental effects resulting from exposure to these substances
 and on any applicable regulations and standards governing their use.
17.
                                KEY WORDS AND DOCUMENT ANALYSIS
                  DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS  C. COSATI Field/Group
 optical  brighteners
 cleaning solvents
 trichloroethylene
 methyl chloroform
 tetrachloroethy1ene
 ion exchange resins
 -chemical properties
 -physical properties
 -environmental effects
 -environmental exposure
06/F,J,P,T

07/A,C,D
18. DISTRIBUTION STATEMENT

 Release  unlimited
19. SECURITY CLASS (ThisReport)

    unclassified	
                                                                          21. NO. OF PAGES
                                              20. SECURITY CLASS (Thispage)
                                                  unclassified
                                                                         22. PRICE
EPA Form 2220-1 (9-73)

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